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REINHOLD PLASTICS
APPLICATIONS SERIES

^POLYPROPYLENE
by

THEODORE

O. J.^^KRESSER

Spencer Chemical

Gompany

Orange, Texas

REINHOLD PUBLISHING CORPORATION

NEW YORK
CHAPMAN &

HALL, LTD.,

LONDON

Copyright

1960 by

REINHOLD PUBLISHING CORPORATION

All rights reserved

Library of Congress Catalog Card

Number 60-53435

Printed in the United States of America

Reinhold Plastics
Applications Series

now grown to greater

The present volume on

This series, which started in 1957, has

proportions than at

"Polypropylene"
or six

more

is

first

planned.

the nineteenth to be published, and five

are in prospect.

The

series,

which started with the

theme, "guidance in application," was designed to devote one

book

to

each of the more important plastics materials, de-

and chemical properties for each material

and its optimum end-product use. Now, however, stimulated
by the industry's wide and cordial acceptance, the series has
been broadened to include books on production processes.
Despite the introduction of volumes on production processes the general character of the books will remain the same.
They will be semi-technical and addressed primarily to engineers, designers, students, and in fact to all practical people
scribing the physical

in plastics.

The new plastics materials, of course, will continue

Books on Alkyd Resins and Polycarbonates

to be covered.

are

now

in preparation.

The process books will include volumes on Premix Molding, Blow Molding, Plastics in Tooling, and on Modern
Methods of Plastics Extrusion.
Production curves in the plastics

an

astonishing rate,

that this

volume

in

field

continue to rise at

and so it is with considerable confidence

the expanded applications series is pre-

sented.

Herbert R. Simonds
Editor

TITLES PUBLISHED

Horn

Acrylic Resins, Milton B.

Amino

Resins, John F. Blais

Cellulosics, Walter Paist

Epoxy

Resins, Irving Skeist

Fluorocarbons, Merritt A. Rudner

Gum Plastics, M. Stafford

Laminated

Plastics,

D.

J.

Thompson

Duffin

Metallizing of Plastics, Harold Narcus

Phenolic Resins, David F. Gould

Plastic Sheet

Forming, Robert L. Butzko

Poly amide Resins,

Don E. Floyd

Polyester Resins, John R.

Lawrence

Polyethylene, Theodore O.

J.

Kresser

Polystyrene, William C. Teach

Polyurethanes, Bernard

and George C. Kiessling

A Dombrow
.

Runnerless Molding, Ernest P. Moslo

SiUcones, Robert N. Meals and Frederick

Vinyl Resins, W.

Mayo Smith

M. Lewis

PREFACE

In this day

some
if

when

suspicion,

new

scientific

advances are looked upon with

and people quite

miracle really

is all

rightly

for the good,

wonder, sometimes,
it is

a great pleasure

be able to write on a subject where no one can deny that

the scientific progress made is for the greater good of mankind.
to

when it
come into volume production is a difficult
job. The technical journals each month bring

Writing a book about a material during the period

is

just starting to

but challenging

out more news of growth and change, and the temptation to

wait and see what the next development will be

is

almost

irresistible.

As time

goes on, however, it becomes obvious that the main

development are following very closely those laid out
by Professor Natta and the publications of the Montecatini
lines of

Company

several years ago.

This book could not have been written without their assistance.

The chapter on

the chemistry of polypropylene

is

taken almost entirely from Professor Natta's pubhcations,

and he has been kind enough

make necessary

to read

it

before pubhcation and

corrections.

Both the chapter on properties and that on processing owe

a great deal to publications of Drs. RanaUi and Crespi of the

Montecatini organization, and permission to reproduce

fully

many

from these publications is grateacknowledged. The Montecatini Company was also very

of the excellent illustrations

helpful concerning applications in Europe.

vii

Preface

viii

The Hercules Powder Company was very kind in making

much of their wealth of experience on applications
in the United States, and the assistance of the AviSun Corp.,
Spencer Chemical Co., Enjay Corp., Eastman Chemical Co.,
Dow Chemical Co., and many others was also most valuable.
The early years in the development of any product are full
available

of problems and difficulties, and polypropylene

is

certainly

no exception. Some of the current problems have led a few

people to doubt that polypropylene will grow in the manner
predicted by its advocates. These problems may be very serious in some fields and may, indeed, change the order and
direction of development; however, they are similar to prob-

lems that have been solved with other materials, and they
will not long delay the

The only
fulfill

development of

this one.

real possibility that polypropylene

present expectations

materials,

made by

propylene,

may be

similar

is

may

fail to

that closely related polyolefin

methods from

olefins other

than

developed so rapidly that they will take

away some of the markets this book predicts for polypropylene.

Even this can hardly change the picture very radically. It will
not be a serious miscalculation on the part of people planning
to

produce polypropylene, because the change in base material

not involve extensive plant revisions, and the chemical

will

and physical research on polypropylene

to other polyolefins.

At

is

equally applicable

the present time there

is

no reason

to

believe that polypropylene will not perform as expected; there

is

much

reason to believe that

it

will

be the most spectacularly

successful thermoplastic ever produced.

The opinions expressed

in this

book

are those of the author

and do not necessarily reflect the conclusions of the Spencer

Chemical Company in certain respects.
The greatest part of the information in this book is from
technical publications here and abroad. Whenever a section
leans very heavily on a single source it has been mentioned

Preface

ix

however, in many cases the information has been

from various sources which are not separately acknowledged. In such a new subject, pubhshed information
must necessarily be supplemented by information drawn from
private conversations and private communications. If any
material which the originator considered confidential has
inadvertently been used, the author asks that consideration
be given to the fact that this book has been written mainly as
a service to the polypropylene industry. It should be a benefit
to all companies in the field to have a "polypropylene primer"
available to assist in orienting the public and any newcomers
in the text;

collected

in the business.

Publications which have been consulted in the preparation

book include Modern Plastics, publications of the

American Chemical Society, Journal of the Society of Plastics
of this

Engineers, Plastics Technology, Plastics World, British Plastics,

Chemical Processing, Chemical Week, Chemical Engi-

neering,

Modern Packaging,
and many

Institute (Britain)

the transactions of the Plastics

others.

Particular thanks are due to the Spencer Chemical Company for permission to undertake this work, and especially to
S. P. Horkowitz, manager of the Spencer Technical Laboratory at Orange, Texas, and Dr. G. Ham, Technical Director

of the Spencer Plastics Division, for their help in the project.

Theodore Kresser
Orange, Texas

November, 1960

CONTENTS
Preface

vii

1.

Introduction

2.

Properties of Polypropylene

3.

Chemistry of Polypropylene

65

4.

Production of Polypropylene

94

5.

Processing of Polypropylene

107

6.

Packaging Applications

163

7.

Applications of Polypropylene in the

Durable-Goods Industries

192

8.

Applications in Soft-Goods Industries

221

9.

Future Developments

246

Index

265

INTRODUCTION

1,

Polypropylene

is

a thermoplastic resin, and in this sense

history starts with the

first

volume of

its

thermoplastics discussed in the

first

this series.

Some understanding

of the major developments that oc-

curred after the great commercial success of polyethylene

is

necessary to appreciate the position of polypropylene.

Introduced in 1941, high-pressure polyethylene has be-

come

the

most widely used

plastic,

and continues

grow

to

at

a tremendous pace. Linear polyethylene, developed in 1955,

has
to

made tremendous

its initial

progress but has so far hardly

come up

promise. At a 1959 consumption of 83 million

pounds, perhaps a quarter of the production capacity

Polypropylene

is

tied in very closely,

commercially, with linear polyethylene.

is

used.

both technically and

The

Ziegler catalysts,

which were originally developed to make linear polyethylene,

were the

we

first

catalysts to

are discussing,

and the

make polypropylenes of the types

now in use for commercial

catalysts

manufacture of polypropylene are direct developments from

the original Ziegler catalysts.

propylene manufacture

is

The

entire technology of poly-

based on work originally done to

make linear polyethylene.

The tremendous penetration

of polyethylene into

long held by traditional materials such as paper, metals,

etc.,

much more open minded regarding

many fields. The general consumer satis-

has caused people to be

the use of plastics in

fields

Polypropylene

faction with polyethylene articles has

done much

to erase the

stigma of "cheap and fragile" that had been associated with

plastics for

many

components of

as

years. Plastics are

now

seriously considered

relatively expensive appliances

and house-

hold goods.
Linear polyethylene manufacturers did a tremendous job

market development for

of

great

demand

stiffness,

and

all

their material.

This created a

and
and water transmission,

for higher heat resistance, greater strength

greater resistance to gas

the other excellent properties of linear polyethylene.

Experience has shown, however, that Unear polyethylene also

has serious limitations which, in
ness,

many

and that there has not been

properties to reach

Polypropylene
the interest built

some

is,

up

cases, restrict

sufficient

its

useful-

improvement

in

large markets.

therefore, falling heir to a great deal of

in linear polyethylene. It has

many

of

good properties of linear polyethylene, but to a greater

them on to a point where the improvement becomes really significant. Polypropylene also lacks
some of the serious faults of linear polyethylene. This will be
discussed in detail in Chapter 2.
the

degree, often carrying

Polypropylene, however,

not as the latest

family but as the

group of

When

is

of greatest historical interest,

member of a fast-growing thermoplastic

first member of an enormously promising

sterically regulated

polymers.

Professor Natta of the Instituto di Chimica Indus-

triale del Politecnico first

polypropylene to the

explained his discovery of isotactic

scientific

world in 1954

with a degree of excitement out of

announcement of a new

all

plastic material.

it

was greeted

proportion to the

Even though

it

was

evident that the material had valuable properties and was

seemed insufficient to justify the

up by the papers. We heard all kinds of en-

potentially inexpensive, this

furor stirred

thusiasm about a major breakthrough in polymer technology,

Introduction

and duplicating processes heretofore impossible except within

the living

cell.

Subsequent events, however, have shown that the most

exuberant enthusiasts were conservative. Natta's work sparked
a

volume of research on polymerization never before apscientific literature was full

proached. Within a short time the

of endless examples

patent literature
effect of this

all

of stereospecific polymerization.

The

over the world also soon showed the

tremendous growth of

scientific effort.

Curiously enough, some of the most startling and perhaps,

most valuable consequences of

in the long run,

resulted not in

rubbers.

The use

this

work

polypropylene but in improved synthetic

of synthetic rubber

had always been limited

because the molecules produced in the factory had a random

or helter-skelter structure. Natural rubber, on the other hand,

known for a
and there has been much speculation as to
the means whereby the living cell was able to direct the
growth of the rubber molecule into this regular pattern.
has a very regular structure. This fact had been
great

many

years,

Professor Natta's

work included some

sterically

ordered

Thousands of researchers all over the world immediately saw that this might be the clue to the long-sought
synthetic rubber that would really duphcate natural rubber.
Without going into detail at this point, subsequent research
proved this to be true. Several pilot plants have made quantities of new types of synthetic rubbers that come up to all
expectations, and large-scale capacity has begun to come on
dienes.

stream. In addition to the types of sterically ordered rubbers

known

in Nature, there are

now

several

new ones

that can

be produced synthetically.
Like

all

great breakthroughs in knowledge,

became necessary
previously
field.

It

known

to

compare

art,

each

was soon proved

this

it

immediately

achievement with the entire

specialist

working

own
monomer

in his

that every unsaturated

Polypropylene

that

was known

to

produce a useful addition polymer by any

other means of catalysis, produced a different kind of polymer

with a stereospecific catalyst, or sometimes several kinds of

polymers with different catalysts or under varying conditions.
At this time we have no idea as to what impact these new

polymers
say that

will

it

will

have on the plastics industry, but

be very great.

it is

safe to

It is also quite clear that the stereospecific catalysts will

strongly affect another great use of synthetic polymers in

The high strength required

had heretofore been possible only with the
expensive monomers. Strongly polar groups

our economy, that of

by a

textile fibers.

textile fiber

use of rather

were needed in the molecule to give the intermolecular forces

necessary for high strength, and

monomers

containing such

groups are expensive. Stereospecific polymerization showed

that relatively simple and inexpensive starting materials, such
as propylene, could

make

fibers that

more complex and expensive

the market. It

is

were

as strong as the

fiber-forming materials

now on

not the purpose of this book to explore the

complicated problems that separate the laboratory discovery

from the general adoption of the

economic facts are so evident that
it is quite impossible for problems of technology or custom
long to delay widespread use.
of a fiber-forming polymer

fiber,

but in

this case the

made a great deal of progress in

yams as fine as 1.5 denier, finer

Montecatini in Italy has

this

field;

than natural
feel very

has spun

it

silk,

much

and has produced blankets and robes that

like wool.

By

a different technology, cotton-

can also be produced from polypropylene.

It is quite impossible to dye polypropylene fiber in conventional ways, but Montecatini has shown polypropylene fibers
like fabrics

dyed in bright
near

Rome

colors. Its 10-million-pound-a-year fiber plant

should soon be in production, and the position

this fiber takes in the textile

market should soon be seen.

Introduction

In

this

country there has been a great deal of interest in

polypropylene
will

fiber; definite

plans that have been announced

be discussed in Chapter

polypropylene fiber has been

9.

made

small amount of coarse

for industrial uses

and

monofilament weaving, such as car-seat covers, but a domestic

textile fiber

seems yet a few years

The entrance
polypropylene

distant.

American Viscose Corporation

of

field in

1959, through

its

into the

subsidiary AviSun,

put a strong textile-fiber organization into

the

Its

field.

commercial product was polypropylene film for packaging

purposes, but it can hardly be doubted that it will also go
first

into the fiber market.

The domestic delay

in the fiber field

is

undoubtedly due to the overcapacity in the synthetic-fiber

field which makes the major companies reluctant to introduce
a
at

new

material. In

1958 the

synthetic-fiber industry operated

something like 70 per cent of capacity, and a considerable

amount of new capacity has come into operation since.

The commercial development of polypropylene resin

is

also closely linked with that of low-pressure polyethylene.

The tremendous success of polyethylene plastic, which started

right after World War II and continues to the present time,
made American industry very receptive to the idea that an
improved polyethylene would have an even more striking
success. When Ziegler in Germany, in 1954, and the PhilHps
Petroleum Co. in

this country, in

1955, announced processes

for producing a higher-density polyethylene,

stiffer

stronger and

than the polyethylene then known, there was a

mendous rush

to obtain licenses to

make

the material.

tre-

By

1958, installed capacity for producing high-density polyethylene exceeded 350 million pounds per year. In that year
sales

probably did not reach 50 million pounds. Although

increased consumption of low-pressure-process polyethylene

continues,

it is

been made

now

evident that a major miscalculation had

as to its

growth and near-term market. As a

Polypropylene

matter of fact

it

now appears that the major use of low-presmay be as a blending agent to upgrade the

sure polyethylene

properties of the high-pressure materials.

The

actual commercial history of polypropylene resin

quite brief. Montecatini

it

began

was the

first

is

commercial producer;

to export polypropylene resin into this country in

1957.

was very active in Europe, and a

European firms obtained Montecatini licenses.
For the first two years it appeared, from announced plans,
that the polypropylene industry would grow more rapidly in
Europe than in the United States.
The first domestic producer of polypropylene was the Hercules Powder Company, which started a 25-million-poundper-year plant in 1957. The reception of the resin was very
favorable, and it has announced the building of a 100-millionpound plant.
The next domestic producer was AviSun, which put facilities, converted from linear polyethylene production, on stream
in the fall of 1959. This plant was leased from Koppers. At
the same time it also started the production of polypropylene
film for packaging purposes. A small number of producers
had previously made polypropylene film from Hercules or
Interest in the material

number

of

Montecatini

resin.

Neither the production nor the marketing

enough to put any great

volume on the market. With a captive source of resin, and
the tremendous marketing organization that American Viscose has built up for cellophane at its disposal, it can be
expected that AviSun will be able to produce and sell a great
facilities of

these firms were large

deal of polypropylene film very shortly.

The remarkable achievement

of the

AviSun Corporation

in

having resin on the market a year after they started in business was

made

Both of
American Viscose and the Sun Oil

possible by a combination of factors.

the parent companies,

Introduction

Company, had been doing extensive polypropylene research

They had both built up a considerable staff
of polypropylene experts and a good volume of technical
information. After the parent-company managements had
decided that it would be more advantageous to work together
than for each to set up separate polypropylene facilities, it
was discovered that the work done by the two companies
fitted together remarkably well. The Sun Oil Company had
concentrated research on monomer and polymer production
up to the finished resin, whereas Viscose had worked mainly
on the processes for making the resin into film and fiber. In
this way AviSun, at its inception, had all the background work
already done. The next important factor was the opportunity
for several years.

to lease part of the

Koppers

linear polyethylene facihties for

conversion to polypropylene. Since the processes are quite

similar, it took only a short time to make the conversion, and
AviSun was operating a plant in advance of other firms who
had announced plans before AviSun was even formed.
The Standard Oil Company of New Jersey announced its
plans to enter the polypropylene field on August 22, 1958,
and its Humble Oil subsidiary started construction on a
40-miUion-pound plant in that year. This facihty went into

production early in 1960. Part of the production of

will

be marketed by the Spencer Chemical

this plant

Company on

4-year contract.

Dow Chemical Company announced in 1959 that

would construct polypropylene production facilities at
Bay City, Michigan, and at Torrance, California; the latter
facility is expected on stream in 1961. No announcement of
The

it

capacity or timing of the

At about

the

announced that

Bay

City facility

is

now

available.

same time, Eastman Chemical Products Co.

it would be supplying polypropylene, but

without any statement of time or capacity. Later

nounced a capacity of 25 million pounds

in

it

an-

Longview, Texas.

Polypropylene

It had been known throughout the industry that this company

had been market testing considerable tonnage of polypro-

pylene in 1959, but without any indication as to source.

It

has since been announced that this had been produced in a

small-capacity plant which wiU continue to produce develop-

mental quantities until the main plant

Firestone has announced that

it

is

completed.

will build a

polypropylene

plant at Hopewell, Virginia.

The

Industrial

in operation in

Since
it

is

it

Rayon Corporation had

1959 and was

a small pilot plant

actively entering the fiber field.

specializes in fabrics for heavy-duty industrial uses,

not as

much concerned

as are other producers,

and

with the dyeing and finishing

it

may have

without such specialized knowledge.

entered the

field

2.

PROPERTIES

OF POLYPROPYLENE

Since polypropylene has yet to find

market,

its

place in the plastics

we must reach our understanding

plications

by considering

its

properties.

of

its

large

major ap-

number

physical and mechanical properties have been used for

of

many

years as guides to the usefulness of plastic materials for

Many of these standard properties have

been determined for polypropylene.
Since polypropylene is by no means a standardized material
it would be somewhat misleading to give single values to
represent the material, and merely stating ranges is not very

various apphcations.

informative.

We

will therefore start this chapter with a

at the physical properties

some commercially

of

look

available

polypropylene as reported by the manufacturer.

These tables are reproduced as received, without any

at-

tempt to correlate them or draw direct comparisons, because

methods of sample preparation and test methods differ
enough to make direct comparison meaningless. These do not,
of course, represent

all

possible polypropylenes,

discussion will include references to

still

and

other resins.

later

They

do, however, give us a convenient starting point because they

represent actual materials

trade

names

now

of the materials

available on the market. The

and designations are included

where given.
For the sake of simplicity we shall not hereafter refer to
any of these specific materials but will consider a representative polypropylene, keeping in mind that it may be possible
that some polypropylenes may differ appreciably from this.
9

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Properties of Polypropylene

Table

2.3.

13

Properties of "Escon'

Various grades of Escon will be offered to permit the processor to

choose the grade best suited for his needs. For this reason, a range
of data

is

shown

for several of the typical

Escon

properties.

As

the

density (crystallinity) of polypropylene increases, the tensile stiffness

and surface hardness of the material also increase. Values for all of
upon how the sample is molded
and what, if any, treatment is given to the sample after molding.

these properties will vary, depending

Data

Property

General Properties
Density (73F) (g/cc)
Melt index (250C)
(g/10 min)

Method

0.897-0.910

ASTM

D1505-57T

1-10

ASTM

1238-57T

(load, 2,160 g)

Environmental
cracking

stress

(100%

"Ige-

None

Bell Labs.

Burning rate
Machining qualities

Slow

ASTM

D635

Mold

0.015-0.030
0.01

ASTM

D570-57T

3,800-5,100

ASTM

D638-58T

2,500-4,900

ASTM

D412-51T

13-18

ASTM

D638-58T

22-315

ASTM D4 12-5 IT

pal

CD-630")

Excellent

shrinkage (in./in.)

Water absorption (%)

Mechanical Properties
Yield strength, psi

(2"/min)
Tensile strength, psi

(2'7min)
Yield elongation,

(2"/min)
Ultimate elongation,
(2"/min)
Impact strength

(ft-lb/in.)

Izod notched
Izod unnotched
Hardness

Rockwell R
Shore D
Elastic modulus, psi
(2'7min)

80-90
70-75

ASTM
ASTM

D785-51
D675-55

45,000-60,000

ASTM

D638-58T

16

14

Polypropylene
Table

Data

modulus

Flexural

(cont.)

2.3

Property

Method

of

111,000-176,000

ASTM

D790-58T

break-max load)
Compressive yield stress,

65,000-81,000

ASTM

D790-58T

psi (O.OS'Vmin)
Compressive strain @
yield,
(O.OS'Vmin)
Compressive elastic
modulus, psi (0.05'V
min)

5,300-6,400

ASTM

D695-54

15

ASTM

D695-54

53,000-63,000
95,000-150,000
100,000-128,000

ASTM
ASTM
ASTM

D695-54
D747-58T
D1043-51

elasticity, psi

(2"/min)

Flexural modulus of rupture

(Flexural strength), psi

(O.OS'Vmin)

(no

Stiffness in flexure, psi

Modulus of

elasticity, psi

Taber abrasion (mg.

loss/ 1000 cycles)
(CS-17 wheel, 1,000 g

29-32

load)

Thermal Properties
Melting point (F)

335

polarizing micro-

scope
Vicat softening point (1
kg) (F)

F @264

Coefficient

ASTM
ASTM

1525-58T
D648-56

ASTM

696-44

psi fiber

131

stress

F @66

266-293

temperature

Deflection

psi fiber stress

188

thermal

of

conductivity

(cal/cm/cm/sec/C)

2.80x10

(Btu/in./ft/hr/F)

1.13

Coefficient of linear

thermal expansion
0.00020

(in./in./C)
Specific

(cal/g)

heat

@73

F
0.46

Properties of Polypropylene

Table

2.3

15

{cont.)

Data

Property

Method

lectrical Properties

Volume
cm)

resistivity

(ohm6.5x10

ASTM

D257-54T

660

ASTM

D149-55T

2.0

ASTM

D150-54T

0.0002-0.0003

ASTM

D150-54T

Dielectric strength

(volts/mil)

short time, V&" thick-

ness
step

by

step,

V&" thick-

650

ness

constant

Dielectric

(10

cycles)

Dissipation

(power)

factor (10 cycles)

In comparing polypropylene with other plastics, one of

striking properties

low density. This

is its

cost standpoint, because

that

more

units of

any given

can be made from a pound of polypropylene than from

size

means

it

its

important from a

is

pound

light

of other thermoplastics. In

many

applications the

weight will be an advantage, quite regardless of cost.

Figure 2.1

is

a bar graph which represents the cubic inches

of material in a

pound

of plastic.

extreme importance. Figure 2.2

shows how polypropylene compares with other common
Tensile strength

is

also of

themoplastics. In this case

still

If

superior to

many

these data are

it is

not so outstanding, but

it is

others.

compared with Figure

per cent elongation at break,

it

will

2.3,

which shows

be seen that polypro-

pylene has a very favorable combination of relatively high

strength with great elongation.

only expensive nylon

strength and elongation
Stiffness will often

is

is

Of

better

all

the materials compared,

when

the

combination of

considered.

determine the plastic to be used for any

particular application. It

is

not always the

stillest

material

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183

Polypropylene

CELLULOSE ACETATE
ACETATE - BUTYRATE
AND PRO PI NAT E

NYLON

POLYSTYRENE
POLYET
LINEAR

YLENE
1

LOW DENS

ITY

POLY PROPYLENE

22
26
30
CUBIC INCHES PER
Figure

2.1.

Volume per pound

of

POUND

common thermoplastics.

LOW DENSITY
POLYETHYLENE
IMPACT STYRENE

HIGH DENSITY

POLYETHYLENE
CELLULOSE
ACETATE-BUTYRATE
POLYPROPYLENE

CELLULOSE ACETATE

STYRENE
NYLON
2

TENSILE STRENGTH
Figure

2.2.

Tensile strength of

10

1000

PS

common thermoplastics.

Properties of Polypropylene

ST

RENE

PACT STYRENE
CELL ULOSE
ACETATE-BUTYRATE
LINEAR
IM

POLYETHYLENE
POLYPROPYLENE

NYLON
LOW DENS

ITY

POLYETHYLENE
200

PERCENT
Figure

that

is

Ultimate elongation of

2.3.

400

ELONGATION

common

thermoplastics.

best for every application. Figure 2.4 shows that poly-

propylene

As with

is

a material of intermediate stiffness.

tensile strength

and elongation,

it is

Some

consider flexural strength with stiffness.

necessary to
of the

com-

parison materials, such as nylon and low-density polyethylene,

cannot be broken in flexure on standard

flexural strength of the others

LOW DENS

ITY

RATE

NYLON

200

FLEXURAL MODULUS
Figure

specimens.

in Figure 2.5.

POLYPROPYLENE
IMPACT STYRENE

STYREN

test

compared

~1

POLYETHYL ENE
LINEAR
POLYETHYLENE

CELLULOSE
ACETATE
CELLULOSE
ACETATE- BUT

is

2.4.

Stiffness of

400
lOOOPS

common thermoplastics.

The

20

Polypropylene
HIGH

DENSITY
POLYETHYLENE

GEL LULOSE

ACETATE
IMPACT STYRENE

POLYPROPYLENE
POL YSTYRE NE

10

12

FLEXURAL STRENGTH I000P5

Figure

2.5.

Strength in flexure of

Surface hardness

is

common thermoplastics.

very important in

many

applications.

Figure 2.6 shows polypropylene to be one of the harder of

the

common

thermoplastics.

Polypropylene has the highest heat-distortion point of any

of the less-expensive plastics;

nylon

is

higher. It

is

among

familiar materials, only

very significant that the heat-distortion

point of polypropylene

is

high enough not merely to allow

exposure to boiling water but even to permit autoclaving

moderate pressures. This opens a wide

field

at

previously closed

LOW DENSITY
POLYETHYLEN E
DENSITY
POLYETHYLENE
HIGH

CELLULOSE

ACETATE-BUTYRATE
POLYPROPYLENE
STYRENE AND
IMPACT STYRENE
NYLON
40

80

120

ROCKWELL HARDNESS
Figure

2.6.

Rockwell hardness of

(R)

common thermoplastics R scale.

Properties of Polypropylene
to thermoplastic materials. Figure 2.7

21

shows the heat-distor-

tion point of several familiar plastics.

Anyone who has had much experience with

plastics has

found that these standard properties can give only a very

rough idea of how well a particular plastic will be adapted to
a given application. There are many new techniques for eval-

LOW DENS ITY

POLYETHYLENE
HIGH DENSITY

POLYETHYLEN
CELLULOSE

ACETATE -BUTYRATE

IMPACT STYRENE

STYRENE
CELLULOSE
AC ETATE
POL

YPROPYLENE

NYLON
200
300
DISTORTION TEMP F

100

HEAT
Figure

2.7.

Heat-distortion temperature of

uating resins that give a great deal

these properties,

and there are

to definite applications.

The

common thermoplastics.

more information than do

which

relate

following pages wiU discuss

some

specific properties

of the special properties that must be considered, as well as

the range of properties that can be obtained from poly-

propylene.

This more detailed study will be carried on in two stages.

First, the general physical properties

of polypropylene, as

they are determined in the laboratory, will be discussed to

22

Polypropylene

what kind of material it really is

under conditions of processing and use.
The second part will describe processing methods and applications, and will explain the special properties of polygive an understanding of

and how

will react

it

comparison with more familiar

propylene.

In

plastics will

be used to maintain perspective.

all

phases,

STRENGTH CHANGE WITH TEMPERATURE

Since polypropylene

a thermoplastic material, one of

is

the most important aspects of

its

behavior relates to

its

change in properties with regard to temperature.

In common with all thermoplastics, polypropylene is an
extremely hard, stiff, but brittle material at very low temperatures, gradually becoming softer, more flexible, and tougher
as the temperature increases, and finally reaching a stage
where it softens beyond the range of usefulness. Figure 2.8
shows how the stilSness of isotactic polypropylene varies with
temperature. In order to give some standard of comparison,
a

similar

curve

is

given

for

high-density

Although high-density polyethylene

very familiar material,

its

is

not, to

polyethylene.

most people, a

properties are sufficiently similar

which to use must

seems a useful comparison to
make. It will be seen in Figure 2.8 that just below room
temperature the two materials have the same stiffness. Upon
warming, polypropylene softens a little more rapidly than
polyethylene, so that through most of the range of ordinary
to polypropylene so that the question as to

often arise. For this reason

use polypropylene

is

the

it

more

ffexible.

As

the temperature

approaches the boiling point of water, however, the two

materials again reverse positions, polyethylene dropping off
rapidly to a negligible strength while polypropylene retains
at least a little stiffness until

somewhat above 212F.

23

Properties of Polypropylene
It

should be pointed out that a wide range

the properties of polypropylene,

used to obtain these data

w30

LI

NCA

is

not as

is

possible in

and the particular sample

stiff as most polypropylene

POLYETHYLENE

20

POLYPROP YLENE

IOF

-300

-150

150

TEMPt RATURE
Figure

2.8.

Comparison of polypropylene and

linear polyethylene at

various temperatures.

now on
stiffer

the market. Typically, polypropylene

is

appreciably

than linear polyethylene in the room temperature

range, even though Figure 2.8 shows

it

to

be

less stiff.

Below room temperature the difference between the two

materials is more marked; polypropylene becomes stiff much

24

Polypropylene

more

rapidly than polyethylene and remains the stiffer of the

two materials

until, at a

very low temperature, the materials

again reverse positions. This means that, for applications

requiring flexibility at low temperatures, polypropylene

is

probably not to be recommended.

The

change in stiffness, such as is

around the freezing point, is
a "glass transition," coupled with the fact that

fact that a very rapid

exhibited by polypropylene
referred to as

certain arbitrary brittleness tests will cause the failure of

polypropylene samples at about

many people

this

temperature has led

to believe that the material

is

entirely useless at

low temperature. This is by no means true, because, even

below its glass-transition temperature, polypropylene is still a
good deal more flexible and tougher than some widely used
materials,

such as polystyrene, at room temperature. At

extremely low temperature polyethylene undergoes transition

and becomes much

stiffer

than polypropylene, whereas in

polypropylene retains a

this region

much more

of flexibility. Polypropylene varies a

eral picture

shown

The problem

good

useful degree

deal, but the gen-

in Figure 2.8 is valid.

of properties versus temperature can also be

studied from the point of view of impact strength,

i.e.,

the

abiUty to withstand a sudden blow. Figure 2.9 shows the

impact strength versus temperature relationship of highdensity polyethylene, polypropylene, and polystyrene. Poly-

propylene
will

is

much

be noted that

tougher above
at

room

low temperature

it

temperature, but

it

does not completely

strength but remains at a relatively low but still useful

between polystyrene and high-density polyethylene.
High-impact polystyrene is widely used in refrigerators because of low-temperature toughness. These data do not exlose

its

level

tend to the extremely low temperatures shown in the previous

figure,

but

it

seems

likely,

from the data shown

there, that

if

25

Properties of Polypropylene

U.7

POLYPROP

o5

LENE

1-2

o
<

LINEAR POLYETHYLENE

POLYSTYRENE

Figure 2.9.

100

100

200

TEMPERATURE

The change

"F

of impact strength with temperature for three

thermoplastic materials.

they were so extended the polyethylene line would ultimately

dip below the polypropylene line.

From

this

we can

see that, although temperature

makes

considerable difference, polypropylene retains a useful degree

of strength over a wider temperature range than do

most

thermoplastics, being particularly outstanding at high tem-

peratures

and

temperatures.

adequate

for

many

applications

at

low

26

Polypropylene

THE EFFECT OF RATE OF LOADING

Another important factor
material

is

ON

STRENGTH

in the physical properties of a

the effect of the rate of application of stress.

Any

material can hold, for a short time, a load that will eventually

and a sharp quick blow may shatter a material that

We have
already mentioned the resistance of polypropylene to quickly

break

it,

could easily withstand a similar load, slowly applied.

We

applied loads.

of long duration.

shall

Much

by Bryce Maxwell

now

consider

how

it

withstands loads

work done

of the following refers to

at the

Princeton University Plastics Labo-

concerned primarily with the phenomenon

ratory.

This

known

as creep, but

is

is

approached by loading the material

with a force, the frequency of application of which can be

varied. It

and

stiff

might be supposed that a material that was strong

to short-term loads

would show

less

creep on long-

time loading than a material that deformed more from fast

loads, but this

is

by no means

ethylene are a case in point.

true.

The

The

properties of poly-

relatively soft low-density

polyethylene deforms easily under short-term loads, whereas

the high-density material

them.

It

is

a good deal

turns out, however, that

when

more

a load

is

resistant to

applied over

a long time, the positions are reversed, and the low-density

material can withstand a greater load than the high-density
material for the

same deformation.

This means that

it

is

essential to understand the time-

dependent properties of a material before using it in any

application. Although long-term creep tests are essential for a
final

determination of the suitability of a material for applica-

tions involving long-term stresses, a great deal can

in a short time

by applying a dynamic

be learned

stress to the material.

These dynamic data can be manipulated to determine actual

creep resistance or stress relaxation; however, what we shall
present here is in terms of loss factor, which measures the heat

27

Properties of Polypropylene
lost in the material

because of the dynamic loading.

high

loss factor gives the material vibration-absorbing qualities,

but this also means that its resilience, or ability to recover

from deformation, is poor. Of special interest is the change
in loss factor with the change in frequency of the dynamic
load. At a high frequency of load application, most materials

0.01

0.1

Figure 2.10.

10

1.0

CYCLES

The change of

PER

SECOND
with frequency of load

loss factor

application for polypropylene and linear polyethylene.

have a low

loss factor, but with

rapidly as the frequency drops

structure of the plastic
load,

and long-term

is

tests

many

materials this increases

oif.

This indicates that the

being permanently deformed by the

would show

that

it

has poor creep

characteristics.

High-density polyethylene

is

a familiar case of this

sort.

Early workers were highly impressed by the strength and

rigidity of this material

and confidently predicted excellent

long-term strength on the basis of these characteristics. Long-

term testing proved quite the opposite; the strong, hard,

28

Polypropylene

high-density polyethylene really had less long-term loadcarrying ability than the soft, weak, low-density material.

This fact could readily have been predicted from dynamic test
data. Figure 2.10 shows the change in loss factor with fre-

quency

at

10C.

30

TEMP

Figure 2.11.

The change

50
OQ

in loss factor at

120

100 cps with temperature

for polypropylene and linear polyethylene.

The sharp

rise

frequency end

shown by

linear polyethylene at the low-

is different, as can
be seen in Figure 2.10, lower curve, which shows a very
moderate increase in loss factor between 100 and 0.01 cycles.
This indicates that polypropylene will resist long-term loads
is

obvious. Polypropylene

well.

Similar curves can be drawn up to and somewhat above

room temperature, where the increase in loss factor for linear
polyethylene is even more marked. At about 40 or 50C

29

Properties of Polypropylene

the loss factor of linear polyethylene, even at high frequency,

increases very rapidly,

and the material

loses

its

resiliency.

which
100 cps against
temperature. The lower curve gives the same data for polyThis

illustrated in Figure 2.11, the top curve of

is

shows

loss factor for linear polyethylene at

propylene.

POLYPROPYLENE

LINEAR

POLYETHYLENE

UJ200

0.1

Figure 2.12.

The change of

in

100

10

1.0

CYCLES

PER SECOND

phase modulus with frequency of load

application for polypropylene and linear polyethylene.

It is

surprising

how moderate

the change in loss factor with

A rapid rise between the

and room temperature concurs with our previous knowledge that polypropylene changes rapidly in this
temperature

10C

is

for polypropylene.

figure

temperature range. The effect of frequency, however, remains

very small.

At room temperature

factor of polypropylene

is

the high frequency loss

greater than that of linear poly-

ethylene, but, unlike the polyethylene, there

frequency decreases.

is

no

rise

as

30

Polypropylene

Even more remarkable is the fact that as we increase the

temperature above room temperature the loss factor of polypropylene again decreases and remains quite low up to
120C. This means that polypropylene remains resilient and
retains its ability to recover from loads even up to high tem2000-

1500-

POLYPROPYLENE
60O0

20.5

GPS

0.1000-

500-

STRAIN
Figure 2.13.

0.001 IN

PER IN

Stress-strain curve for polypropylene at 60 C

and

20.5 cps load application.

peratures, whereas the Unear polyethylene loses

its

resilience

above room temperature.

The modulus of elasticity in phase with the loading, when

at only a little

an intermittent load

is

applied, varies with the frequency of

application. Here, again, a small variation with frequency

gives promise of

good long-term

strength,

whereas a larger

one indicates a tendency to creep. Figure 2.12 gives a plot

modulus versus frequency for polyethylene and
polypropylene showing that polypropylene is less timedependent. At the lower frequencies the modulus of polyof in-phase

Properties of Polypropylene

31

ethylene drops off sharply, but polypropylene changes very

little.

This ability to carry loads for long periods and over a

wide temperature range

is

one of the properties that

will

make

polypropylene very valuable in engineering and other applications.

More than almost any

it can be considered
under severe conditions

other plastic,

for applications that require long

life

of stress and environment.

For engineering purposes there is a very important point

on the stress-strain curve known as the limit of linear response. Figure 2.13 shows the beginning of a stress-strain
curve for polypropylene at 60C and 20.5 cps. Even at this
high temperature polypropylene will take a stress up to about
this

range there should

ON

STRENGTH

1,000 psi perfectly linearly. Within

be no permanent deformation.

EFFECT

OF ENVIRONMENT

Environment includes factors other than those so far considered, one of the most important of these being the effect of
various materials with which the plastic is in contact. Almost
every application involves contact with materials that

weaken the plastic, and in many applications

contain some other substance is critical.
It

is

well

known

its

that polyethylene exhibits

may

ability to

a property

which is characterized
by failure at relatively low but complex stresses in the presence of certain stress-crack-inducing agents. This has been
an important limitation of polyethylene in many applications,
and it is only in recent years, after nearly 20 years of intensive work on the problem, that some polyethylene manufacturers have succeeded in making polyethylene that is substantially free from this weakness.
Polypropylene has shown no sign of this defect, either with
called environmental stress cracking,

32

Polypropylene

agents that induce stress cracking in polyethylene or with a

wide variety of other materials.
The problems of chemical resistance and permeability of
polypropylene cannot be answered in such an easy and categorical manner. The polyolefins all have excellent resistance
to water and to water solutions of many materials, especially
salt and acid solutions that are very destructive to metals.

Table 2.5. Change in Tensile Strength of Polypropylene and

Polyethylene on Immersion in Selected Liquids (3 to 6 Weeks)
Polypropylene

Polyethylene

(per cent crystallinity)

Liquid

Low

density

Turpentine

-30.7
-37.7

Chloroform

-100%

Xylene

Hexane
Commercial bleach

1%

hydrogen peroxide

The use

such agents

56

-12.8
-15.6

-5.3

-1.0
-16.3

6.0

7.9

0.8

2.0

9.3

23.5

-22.8
-13.9

-18.2
-32.7

-6.3
-24.2

-14.8
-20.9
-7.2

is

receive added stimulus

its

63

8.6

of polyolefins in structures which

tact with

with

Linear

must be

in con-

a growing application which should

from the

availability of polypropylene

superior physical propetries. In

chemical resistance of polypropylene

many
is

cases the actual

superior to that of

other polyolefins, but this cannot be taken as a general rule.

The data

in Tables 2.5

and 2.6 represent

results of a series

of tests with high- and low-density polyethylene and poly-

must be remembered that

it is dangerous to
Other grades and
sources of both polyethylene and polypropylene might give
better or worse results; however, the samples used were
representative of some of the most widely used materials.
The contact liquids used were ones that were known or

propylene.

It

generalize

too broadly on these data.

Properties of Polypropylene

33

expected to have particularly drastic effects on poly olefin

materials.

The most

active materials in Table 2.5

were tested

for a shorter time than those in Table 2.6.

Examination of the tables shows that linear polyethylene

As a

has by far the poorest resistance to the materials tested.

Table 2.6. Change in Tensile Strength of Polypropylene and

Polyethylene on Long Immersion in Selected Liquids
(4 Months or More)
Polypropylene

Polyethylene

(per cent crystallinity)

Liquid

Low

Water

1.8

Isopropyl alcohol

1.1

Primol

Methylethylketone

10% sodium hydroxide

10% common salt
10% acetic acid

2.6

-8.1
-6.5
-5.6

Dioctyl phthalate

Corn

oil

oil

Methanol

-100

63

-1.1
-7.1
10.1

13.8

3.2

9.8

13.2

-2.3
-60.5
-50.5

5.9

16.0

2.5

2.3

2.2

"Igepal" *
*

-7.1
-78.0
-11.0
-42.7
-14.0
-6.5

-8.1
-1.5
-5.2
-1.6

Silicone oil

Linseed

Linear

density

1.1

-100

9.8

56

-8.6
-11.3
-20.0
-7.1
-6.0
-4.5
-9.1
-4.7
-3.6
-3.4
-19.8
-7.2
-1.8

surface-active agent used as detergent.

the only sample, in most cases, which

matter of

fact,

weakened

to a point that clearly precludes

it is

density polyethylene

its

use.

and the polypropylene rank

is

The lowdifferently

with the various reagents, sometimes one, sometimes the

other being best.

It

should be remembered that the tables

give per cent tensile change. Since the polypropylene starts

out considerably stronger than the low-density polyethylene,

it

may

still

be stronger even when

it

has lost 10 per cent of

34

Polypropylene

and therefore may be preferable even where its

is poorer. In general, for any application
where prolonged contact with any substance is an important
part of the requirement, tests should be made under condiits

strength,

rating in the table

tions approximating those of actual use.

RESISTANCE TO LIQUID PERMEATION

The situation as regards permeability is even more comMost published literature leads one to believe that the

plex.

Figure 2.14.

Water permeability of polyethylene and polypropylene.

permeability of the available polyolefins

is

about that shown

which shows the water permeability of lowdensity polyethylene to be quite high, that of the linear considerably lower, and that of polypropylene a little lower still.

in Figure 2.14,

This relationship does not hold at

permeants.

all

when we

consider other

35

Properties of Polypropylene
First, there is

a group of materials that have stress-crack-

When these are used as permeants, hnear

high permeability, probably because
shows
polyethylene
are
opened up in it. Permeability to three
microscopic cracks
inducing

activity.

such materials

is

shown

in Figures 2.15

through 2.19.

/
/pOLYETHVLENE

NEAR

LI

:2oo

LESS CRYSTALLINE
POLY PROP YLJ^WT

^^ 9QViy^VtHZ

100

^^^^.^-^^^^^^HIGHLY

Z^

^^^^^^^

CRYSTALLINE

POLYPROPYLENE

80

120

DAYS
Figure 2.15.

polyethylene

and

in the graphs, low-density polyethylene

and

Methylethylketone

permeability

of

polypropylene.

As can be seen
polypropylene

resist these materials

much

the high-density polyethylene. Silicone

ingredient,

was very well

resisted

and polypropylene but not by

oil,

better than does

common

polish

by low-density polyethylene

linear polyethylene. Methyl-

ethylketone, a lacquer solvent, and methyl alcohol permeate

the low-density polyethylene and polypropylene to a lesser

extent than they do the linear material.

The two polypro-

pylene samples tend to bracket the low-density polyethylene

in

some

cases.

Rather surprisingly, methyl alcohol permeates

36

Polypropylene

300-

:200

tflOO-

Figure 2.16.

Methyl alcohol permeability of polyethylene and

polypropylene.

600-

LIN

EAR/POL YETHYL ENE

= 200POLY PROPYLENE

LOW DENSITY

Figure 2.17.

POLYETHYLENE

Silicone oil permeability of polyethylene and

polypropylene.

Properties of Polypropylene

37

DAYS
Pigure 2.18.

Chloroform permeability of polyethylene and

polypropylene.

400-

:200

Figure 2.19.

Isopropyl alcohol permeability of polyethylene and

polypropylene.

Polypropylene

38

higher crystallinity polypropylene

crystallinity.

With substances of

more

readily than lower

this sort,

polypropylene

is

the preferable polyolefin, quite regardless of permeability,

because even low-density polyethylene shows some tendency

toward stress cracking, and the polypropylene

have the longer service life.

would

article

S300

=200

I*'

100

10

DAYS
Figure 2.20.

20

Hexane permeability of polyethylene and

polypropylene.

In the case of chloroform (Figure 2.18), low-density polyethylene shows the greatest permeability and high-density

polyethylene the least, with polypropylene falling between,

but nearer the high density.

There are also substances to which low-density polyis the most resistant. Isopropyl alcohol (Figure 2.19)
is an example. In such a case the low-density polyethylene
would be the preferred material from a permeability standethylene

point.

39

Properties of Polypropylene

There

is

also a

group of solvents that permeate polypro-

pylene more readily than they do other poly olefins. The most
striking of these

the

is

same behavior

an important

hexane (Figure 2.20). Turpentine shows

to a lesser extent.

factor,

Where

permeability

is

polypropylene should not be used with

these materials.

^300

150-

20

DAYS
Figure 2.21.

30

40

Hydrogen peroxide permeability of polyethylene and

polypropylene.

Other materials that must be considered very carefully are

those that give

oS

highly reactive gases.

for instance (Figure 2.21),

Hydrogen peroxide,

shows more rapid permeation of

polypropylene than of other poly olefins.

"Clorox" (a chlorine-containing bleach) perone of the polypropylene samples quite readily

Similarly,

meates

(Figure 2.22).
It

should be observed that the two polypropylene samples

differ

widely in their resistance to those reagents, and that

it

40
is

Polypropylene

the low-crystallinity sample which has the better resistance.

In most other cases the highest-crystaUinity sample

is

better.

This shows that no one type of polypropylene will have the

best resistance to

all

materials, but that a choice will have to

be made in each individual

case.

300

:200.

100-

Figure 2.22.

"Clorox" permeability of polyethylene and

polypropylene.

In Chapter 3 the relationship between crystallinity and

permeability

amorphous
as

is

discussed. Permeation

is

mainly through the

fraction.

The percent crystallinity

shown in Table 2.7.

of the materials in this study

Table

2.7.

Material

7o

crystallinity at

Low-crystallinity polypropylene

56

High-crystallinity polypropylene

63

Low-density polyethyelne
Linear polyethylene

91

61

25C

was

41

Properties of Polypropylene
possible to

It is

make polypropylene with

a crystallinity

both above and below that of these samples, and

it

will then

from them in permeability. In the current state of

knowledge, it wiU be necessary to make simulated service
tests in any case where permeability to some specific liquid is
differ

critical.

OTHER ENVIRONMENTAL FACTORS

In

common

polypropylene
This

with other poly olefins and most other plastics,

is

adversely affected by ultraviolet irradiation.

important only where the material will be subjected

is

to direct sunlight or other sources of ultraviolet light.

Very

effective stabilizers are available

which can protect

polypropylene from such damage. Figure 2.23 shows the

effect of 0.5

per cent of a good ultraviolet-light stabilizer on

80

POLYPROPYLENE
tn

-1

WITHOUT

STABI

LI

ZER

UJ

E20

WITH

STABtLI
50

HOU RS
Figure 2.23.

100

EX PCS

ZER^/^
150

RE

Light stabilizers protect polypropylene against strength

loss

from

light exposure.

42

Polypropylene

the loss of strength of polypropylene fibers

exposed to concentrated ultraviolet

light

when

in

they are

an exposure

The exposure times shown correspond to a long

Where a black

cabinet.

service life under any natural environment.

color

not objectionable, excellent resistance to ultraviolet

is

can also be imparted by the use of carbon black.

POLY PROPYLENE

250
oc
UJ
a.

o
o

40

230
1-

o
^20
<
z

^/

LINEAR
POLYETHYLENE^^"^

iii

o
100

HOURS
Figure 2.24.

AT

250

150

200F

Polypropylene oxidizes rapidly compared to linear

polyethylene.

OXIDATION OF POLYPROPYLENE

A great deal of attention has been paid to the

susceptibility

of polypropylene to oxidation. In fact, polypropylene

useful thermoplastic only because

stabilizing

it

is

means have been found

for

against oxidative attack. Unstabilized polypro-

pylene oxidizes rapidly at relatively low temperature. Figure 2.24 compares oxygen uptake at 200F for unstabilized

polypropylene with that of linear polyethylene.

This

is

not really a matter for concern, because commercial

products will

all

be

stabilized.

Figure 2.25 shows

how

greatly

43

Properties of Polypropylene

an antioxidant can lengthen the time before any appreciable

oxidation starts. There is a 64-hr period before any oxygen
uptake starts, even at this relatively high temperature. This
gives polypropylene an oxidation stability comparable to that
of other thermoplastic materials.

50-

40-

UNSTABI

LI

ZED
STA

Bl L

IZE

20

60

40

20

HOURS AT30 0OF

Figure 2.25.

Antioxidant reduces oxidation of polypropylene at

elevated temperatures.

In service, polypropylene

is

really

much more

heat-stable

than some polymers which are generally considered quite

satisfactory in this respect.

Table 2.8 shows the change in

compared

to

two
110C,

tensile properties of

representative commercial polypropylene resins at

a medium-density polyethylene and a linear

polyethylene resin.

30 days at 110C the linear polyand elongation; the mediumdensity polyethylene, while retaining its strength, no longer
It will

be seen that

ethylene has lost

all

after

strength

44

Polypropylene

and the two polypropylene samples are, if anyand more flexible than at the outset.
One very important fact about the oxidative breakdown
of polypropylene is that it becomes more fluid as oxidation
progresses. This can be shown in a variety of ways. Figure 2.26 shows the effect on melt index and of increased time
elongates;

thing, stronger

Table

2.8.

Tensile Strength

(psi)
Polypropylene

Polyethylene

Time
at

(days)

110C

Medium
density

Linear

2,330

4,550

4,630

4,990

2,830

4,840

4,870

5,070

14

2,890

4,890

4,750

5,090

30

2,220

180

4,870

5,000

Elongation

(%)

275

110

45

105

155

190

14

150

90
75

85
75
65

110

30

75

of preheat at the comparatively low temperature of 190C.-

Polyethylene tends to

stiffen

and become

less fluid

under

the influence of heat and oxidation. This causes a crust of

decomposed polymer

to

form on the surface of equipment

in

contact with the molten polymer. This crust carbonizes and

flakes off in a

molding machine, or builds up and disrupts

the flow in an extrusion die. Problems related to this characteristic constitute a fairly large

item of cost in polyethylene

processing.

Polypropylene, by becoming more fluid as

it

decomposes,

be squeezed out before it has a chance to carbonize; thus

equipment will be kept clean much more easily. Polystyrene

will

45

Properties of Polypropylene

becoming more
fluid as it
who has had experiwith
polystyrene
polyethylene
ence
both
and
is well aware of
the increased carbonization problems encountered with the
is

similar to polypropylene in this respect,

breaks down. Every processor

0.57

MELT INDEX RISE

0.56

I90OC

0.55

0.64

0.53

0.52

10

HEATI N&
Figure 2.26.

20

15

Tl

ME

The melt index of polypropylene

at

25

Ml N
increases with time

190C.

This effect is discussed in more detail under

Molding and Extrusion of Polypropylene," in

latter material.

"Injection

Chapter

4.

CHARACTERIZATION OF POLYPROPYLENE RESINS

Up
eral,

to this point
as

compared

we have
to

considered polypropylene in gen-

and the behavior of

which seem to be reasonably

other plastics,

particular polypropylene resins

representative of the material.

46

Polypropylene
has been mentioned that polypropylene

is an extremely
can be made in many modifications.
It is essential to the understanding of the material that a few
simple standard tests should be made to show what can be
expected from a particular sample. Chapter 3 will discuss

It

versatile material that

the relationships between molecular configuration and phys-

but here

ical properties,

we

are concerned only with simple

physical tests which reflect these molecular configurations.

The

and most comprehensive method of characwas worked out in the Montecatini

earliest

terizing polypropylene

laboratories.

The

following pages reflect various publications

of G. Crespi and F. Ranalli of that organization, which give

the best information currently available regarding the range

of properties of polypropylene.
Isotactic

What
will

Index

this

term means in regard to molecular configuration

later. For the present it will represent

be considered

the percentage of the resin that

heptane. This
in

many ways

is

is

insoluble in boiling n-

a very important value for polypropylene,

resembling the effect of density on the physical

properties of polyethylene.

Melt Index of Polypropylene

Much

caused by the use of the term grade or

melt index to characterize the flow properties of polypropylene, because it is natural to expect that this is the same
confusion

is

value used to characterize polyethylene.

When

the usual commercial grades of polypropylene are

run in a melt indexer in the manner used for polyethylene, a

very low value results. Flow is so little under these conditions
that it cannot be accurately measured. For this reason it is
common practice to modify the conditions in order to get a
measurable value. At this time there is no industry-wide

47

Properties of Polypropylene

standardization of the conditions to be used, so that data

sometimes refer to different modifications.

In this book the term grade or melt index

will refer to

determinations run on the standard melt indexer at

under a load of 22
for polyethylene.

lb.

This

is

190C

about 10 times the load used

The other most common modification

is

to

use the standard load at 230C. These methods give values

in the

same general order of magnitude, but they are by no

means

directly comparable.

5000

J
1/
y

'h

'

1\
J

7S

4000

In 7
2
>-

Ten

//

3500

)0

90

100

Isotactic index (%)

Figure 2.27.

and melt index.

Montecatini)

Variation of tensile yield stress with isotactic index

(Left: grade over 5; right: grade

below

1.)

{Courtesy

48

Polypropylene

Yield Strength

Perhaps the most striking

index

effect of

changing the isotactic

that increased isotactic index increases the yield

is

strength of the resin very sharply. Figure 2.27 shows this.

The four lines represent

1 on the right, to above

differences in melt index

on the

left.

Note

from below

that at any given

110

100

/'
90

80

/'

//

/
/

100

90
Isotactic index

Figure 2.28.

(%)

Variation of surface hardness

(Rockwell R) with
5; bottom: grade

index and melt index. (Top: grade over

isotactic

below

1.)

{Courtesy Montecatini)

level of isotactic index, the higher melt index, that is the

easier-flowing resin, has the higher yield point. This

is

directly

contrary to experience with cellulosics and plasticized vinyls,

where

easier flow

means a more

yielding resin.

The reasons

for this rather unexpected behavior will be found in Chapter 3.

Hardness
Rockwell hardness also increases with increased

isotactic

index and increased melt index, as shown in Figure 2.28.

Again, the easier flowing material

is

the harder.

49

Properties of Polypropylene
Stiffness

The
tic

stiffness of

polypropylene

index and melt index, in

point and surface hardness; that

greatly affected by isotac-

is

much

the

is,

and the higher melt index give the

same way

as are yield

the higher isotactic index

stiff er

The data on

resin.

220,000

180,000

160,000

140,000

120.000

100,000

90
Isotactic index

Figure 2.29.

Variation in stiffness

isotactic

(flexural

elastic

modulus) with

index and melt index. {Courtesy Montecatini)

this relationship

They

100

(%)

cannot adequately be expressed in a few

by the area shown in Figbounded on the top by the high-melt-index

material and on the bottom by the low-melt-index material.
At very high isotactic index, melt index has no influence,
lines.

are best expressed

ure 2.29 which

is

50

Polypropylene

whereas

at

material

is stiffer.

lower isotactic-index

levels, the

high-melt index

Tensile Strength and Elongation

These factors are strongly influenced by melt index. If the

is over 10, elongation is below 100 per cent; as the
sample does not extend enough to orient it, failure occurs at
comparatively low values. If the melt index is low, elongation
may go up to 900 per cent, and the resulting orientation gives

melt index

Lower

a high breaking point.

isotactic index also gives higher

elongation, but in this case orientation

strength lower.

The

strength and elongation; at a low rate there

of elongation,

and the break

less

is

rate of straui also greatly influences the

and the break strength

is

is

high.

a great deal

At high

rates

of elongation the yield point will be higher, but the sample

will elongate less

and

will

break well below the yield point.

Shear Stress
In polypropylenes of high isotactic index, shear
off

stress falls

with increasing melt index, as shown in Figure 2.30.

400

5000

\^

^ 360

^
5500

\^

p
S

4500

J^

280
-0.4

Figure 2.30.

0.8

0.4
O.i

2
Mel

og grade
20

grade

inde X

Variation of shear stress with melt index, isotactic index

95 to 96 per cent. (Courtesy Montecatini)

51

Properties of Polypropylene

Impact Strength

The

and melt index

relationship of isotactic index

pact strength

is

somewhat complex,

as

shown

to im-

in Figure 2.31.

Material with a low melt index has a uniformly high impact

strength, quite regardless of the isotactic index. Material with

a higher melt index, however, has high impact strength only

when

the isotactic index

is

relatively low.

^100
I

50

80

00

60

40

\V

^^

^^

20

S
_E

20

10

100

90

80

Isotactic index

(%)

Figure 2.31. Variation of impact strength with isotactic index and

melt index. (Top: grade below 1; bottom: grade above 5.) {Courtesy
Montecatini)

Softening Temperatures

The

shows a relationship to isotactic

we are by now quite familiar.
The higher isotactic index and the higher melt index give the
highest vicat point (see Figure 2.32). It is perhaps a little
difficult to accept at first, but the material which flows most
easily is the hardest in almost all respects. It must be kept in
mind, however, that it is not the strongest or toughest.
vicat softening point

index and melt index with which

52

Polypropylene

100

y^

y^
^

^^

80

//

y
'/

90

100

Isotactic index

Figure 2.32.

(%)

(vicat) with isotactic

bottom: grade below 1.)

Variation of softening point

index and melt index. (Top: grade above

5;

{Courtesy Montecatini)

Low-Temperature

One
its

Brittleness

of the much-discussed properties of polypropylene

is

low-temperature brittleness. This has been mentioned in

comparison with other

same

plastics,

but

it

is

by no means the

for all polypropylene, varying a great deal with melt

index and to a lesser extent with isotactic index. Figure 2.33

shows that the

rises

brittle

point (as defined by

ASTM

D746)
when

very rapidly as the melt index goes up, especially

the isotactic index

makes
brittle

it

is

high

(left

curve)

A lower isotactic index

possible to go to a higher melt index before the

point

is

reached. This fact will limit the use of highly

isotactic materials with a high melt index in

tions, in spite of the

The previous

many good

many

applica-

qualities of this combination.

discussion should give a reasonable idea of

what kind of material polypropylene

is.

It

has a few prop-

53

Properties of Polypropylene

20

/,'

^,0

i
^
y
,/

810

100

Grade

Figure 2.33.

Variation of brittle point

(ASTM:D

746) with melt

index and isotactic index. (Left: isotactic index 80 to 90 per cent;

right: isotactic

erties

index 70 to 80 per cent.) {Courtesy Montecatini)

that relate especially to particular applications,

and

these are discussed in the following pages.

POLYPROPYLENE-FILM PROPERTIES

The polypropylene-film
be assumed that the

film

industry

now

is

so

new

that

it

cannot

available represents the ultimate

properties attainable; however, the currently available films

are our best guide to an understanding of what kind of film

can be made from polypropylene.

Biaxial orientation greatly improves the strength of poly-

propylene

film,

and many

authorities believe that the future

of polypropylene film lies in a product so oriented.

polypropylene film

made by

However,

the simple chill-roll extrusion

54

Polypropylene

method, which gives very

little

orientation across the sheet,

has properties that appear to be good enough to ensure a

wide market.
It

has been the experience in the plastic-film industry, so

far, that the

only resins to appear only as biaxially oriented

film are those

whose

properties,

when not

so oriented, are

not adequate to assure substantial markets. Polystyrene and

polyester resins are such materials. Other resins, such as

polyethylene, are improved considerably by biaxial orienta-

most of the polyethylene film on the market is made

by methods that do not take advantage of this fact. This is
because polyethylene film has adequate properties for most
tion, yet

uses, even

when not

and vinyl

fully oriented. This is also true of cellu-

which are generally not oriented.

initially, this will also be true
of polypropylene film. For this reason two types of unoriented
polypropylene film, both made on chill-roll equipment of
conventional design, were selected for description here.
These films differ in that the resin used to make type 1
has a low melt index and a high isotactic index, whereas the
resin used for type 2 has a high melt index and a low isotactic

losics

It is

films

probable that, at least

index.

The properties of these films are shown in Table 2.9 in

comparison with properties of polyethylene and cellophane
films.

Certain factors not included in the table are worth discussion.

The lower-melt-index

film retains

its

strength at

lower temperatures than does the higher-melt-index

much
film.

Poor low-temperature properties are often cited as a weakness of polypropylene film, and the higher-melt-index film
should not be recommended for applications such as frozenfood wrapping where low-temperature resistance is needed.

The lower-melt-index
such purposes.

film,

however,

is

entirely adequate for

c
4,400-18,000

18-20

15-45

150-200

4,400-8,100

3,400-3,600

29-30

2,800-3,100

29-31

2,400-2,600

29-31

2,800-4,400

3.5-6.8

0.4

5-10

10-300

29-30

1-3

0.05

0.25

125

580

0.7

280

990

100-125

1,000-2,000

50-70

1,500-3,500

300-375

45-50

1,500-2,000

2-3

0.65

200-250

100-115

350-450

2-3

0.65

a
'o
Ph

5-10

75-225

11

97

280

1a
97

280

sq

10^)

F)

75

(g/100

100F)

psi)

cc/100

at

X
(psi

F,

(NTP
permeability

at

hr/mil

(psi)

(75
103
hr/mil

(%)
modulus

impact
permeability

strength

vapor
factor

(%)

in./atm./24

in./24
Elongation

Spencer
Tensile

CO,

Tensile

Water

Area

Haze

sq

o.,
Gas

56

Polypropylene

The other important

polypropylene film

by the

is

difference

between the two types of

that the stiffness, indicated in the table

rial. It

modulus, is much greater in the type-1 matecan be seen in the table that the type-2 polypropylene

film

in the

is

tensile

same

stiffness

range as medium-density poly-

polypropylene is more
on a par with high-density polyethylene or cellophane.
Present markets show that both stiffness ranges have wide
areas of usefulness. This is one example of the great versatility
of polypropylene resins, which will make it possible to adapt
them to almost any application.
Although the main reason why these films differ is the
difference in isotactic index between the two base resins, this
ethylene film, whereas the type-1
nearly

does not completely determine the properties of the

The

film.

physical properties of the film are determined over a

considerable range by conditions of extrusion.

The

stiff

cello-

phane-like film or the flexible polyethylene-like film can be

made from the same resin under

different extrusion conditions.

have poor tear strength and

poor impact strength, whereas the flexible film will be excellent in these properties. This means that most of the many
property compromises, which require dozens of different
resins to achieve with polyethylene, will be possible with one,
or at most a few, polypropylene resins.
In general, the

The area

factor

stiff

is

film will

the

number

of square inches of 1-mil

can be made from a pound of resin. Polypropylene

film has the highest area factor of any plastic film now available. This means that at any given price per pound the polypropylene film will be cheaper, for the same area, than any
film that

other film at the same

polyethylene film

is

pound

price.

The advantage over

small, but over cellophane

it

is

very

significant.

The tensile-strength figures are rather low compared to

some that have been quoted for polypropylene film, but, even

57

Properties of Polypropylene
so, the type-1 material

exceeds polyethylene by a consider-

able margin, and approaches that of cellophane.

tively high elongation that

accompanies

The

rela-

this tensile strength

shows that the polypropylene film is much tougher than the

competitive films, even though it is stiffer than most of them.
This combination of stiffness and toughness is very valuable
and should open many markets.
The stiffness enables the polypropylene film to be processed
easily on high-speed wrapping machinery, and the high
elongation makes the resulting package very durable.
Polypropylene film is readily heat-sealable by the same
equipment used for polyethylene film. It requires about 50
higher sealing temperature but is not any more critical as to
control and requires no longer time to seal. Although this
may mean that some sealing equipment will have inadequate
heating capacity to maintain maximum rates, relatively minor

machine modification should make

it

possible to obtain ade-

quate speed.

Water and gas permeability of these films was in the

same range as that of polyethylene, which we know is
adequate for

many

barrier, but in the

ture-vapor

purposes.

Cellophane

uncoated form

transmission.

To

it

has a

a better gas

is

much

higher mois-

equal polypropylene

respect, the relatively expensive coated cellophane

in

this

would be

needed.

Although no data appear in the

table,

polypropylene film

has outstanding grease resistance.

Biaxially Oriented

Film

The following data

some experiThe great im-

represent the properties of

mental biaxially oriented polypropylene

film.

provement in tensile strength over the unoriented film is

evident by comparison of Table 2.10 with Table 2.9. It
should be noted that this increase in strength is accomplished

58

Polypropylene

without any drastic reduction in elongation. Although

film

both directions
so

much

Table

in the

2.10.

this

can be seen that orientation in

not the same, because properties differ

biaxially oriented,

is

is

two

it

directions.

Properties of i/i-MiL Oriented Polypropylene

Film
Tensile strength

Room

temperature

300F

Along sheet

Across sheet

15,000 psi

60,000 psi

4,000 psi

8,800 psi

Elongation at break (room tempera-

35%

200%

ture)

Elmendorf tear strength

Mullen burst strength
Moisture-vapor transmission (25 C)
Gas permeability

Oxygen, 25 C, 1 atm
Carbon dioxide 25 C,

12g
13g
37 psi
0.28g/10C sq in./24 hr

200 cc/100 sq in./24 hr

730 cc/100 sq in./24 hr

atm

Yield

61,000 sq in./lb

Along sheet

Shrinkage

None

200F
250F
300F

Across sheet

None

5%

8%

12%

28%

Much

depends on the relative costs of oriented and unIt was about ten years from the time biaxially
oriented polystyrene film was first introduced until it could be
oriented films.

produced

at a price that

the techniques for

it

may

could attract a large market.

making such

be possible to produce

it

By now,

film are highly developed,

at prices competitive

large-volume films such as polyethylene and cellophane.

the other hand,

it

may

The

no valid judgment
differences

in

On

some time compete only with

such as nylon and polyester. At

for

special high-strength films

present,

and

with the

is

possible.

moisture-vapor transmission and in

gas transmission (Tables 2.9 and 2.10) are in part due to

Properties of Polypropylene
the various temperatures used
variations. It

them

greatly.

is

and

in part

59

probably to resin

not likely that orientation would influence

Note

also that

Table 2.10 refers to Vi-mil

film,

Table 2.9 to 1-mil film.

Table 2.11 gives data furnished by a commercial producer

and concerns the properties of the polypropylene film he

had available. The strength of this film is much better than
Table

2.1

I.

Film properties

Values

Specific gravity

0.885-0.895

Yield (theoretical) sq in./lb/l mil

30,900-31,300

Water-vapor transmission rate g/100

sq in./24 hr/1 mil
Maximum use temperature before

0.45-1.10

300F

softening

Impulse and radiant bar

3 50-425 F

Types of heat seal

Heat-seal range
Tensile strength (average) (psi)

Machine

7,600

direction

4,600

Transverse direction
Elongation (average) (%)

Machine

741
730

direction

Transverse direction

Tear strength (average-mod. Elmendorf)

Machine

82
426

direction

Transverse direction

O2 transmission (cc/100

sq in./l mil/

180-260

atm)

CO2

transmission

(cc/100

sq

in./l

586-870

mil/atm)
Clarity, haze, gloss

Excellent optical properties

Dimensional

Excellent

stability

up

to

max.

use

temp.
Printability

Equivalent to polyethylene

Resistance to acids

Excellent

Resistance to alkalies

Excellent

Resistance to organics

Variable

60

Polypropylene

that

shown

in

Table 2.9 but nowhere near that of the oriented

film in

Table 2.10.

or not.

The

not stated whether this is oriented

improvement could come from a slight
degree of orientation or simply from differences in resin and
processing. This probably reflects more nearly what may be
expected of good commercial film than does the information
It is

strength

in Table 2.9.

ELECTRICAL PROPERTIES OF POLYPROPYLENE

Like

the hydrocarbon polymers,

all

excellent electrical resistivity.

Some

polypropylene has

are better than those of

polyethylene or polystyrene; for instance, polypropylene has

Power factor
by the preparation

the lowest dielectric constant by a small margin.

is

also very

low but

of the resin.

Power

is

strongly influenced

factors similar to the best electrical-grade

polyethylene could be obtained only at additional processing

costs.

Resistivity,

both volume and surface, are excellent, and

dielectric strength

is

extremely high. The following data were

obtained on Vi-mil biaxially oriented film.

Table

Power

2.12.

Electrical Properties of Polypropylene Film

AT 90% Relative Humidity

factor

30C

150C

0.0011

0.0063

Dielectric constant (60 cps)

2.11

Volume

4.9

resistivity

(ohm-cm)

Surface resistivity (25 C)

Dielectric strength (25 C)

1.86

IQi*
1.4

3.6

10i5

10^2

ohms

740 volts/mil

It can readily be seen that the high dielectric strength,

accompanied by the heat resistance, makes it an excellent
material for insulation of motor windings.
The low dielectric constant recommends it for communica-

Properties of Polypropylene
tion-wire insulation.

Many

now

people

61

believe that

its

rela-

low brittleness temperature is a serious obstacle in

this field. For thin coatings, however, it is quite possible that
it will have sufficient flexibility at low temperatures. The
extraordinary low brittleness temperature of polyethylene has
set a standard for this property that may, in fact, have no
valid relation to performance in service.
These figures are rather different when molded slabs are
used instead of thin film. Table 2.13 gives values determined
on Vs-in. molded slabs.
tively

Table

2.13.

ASTM

Property

differences in dielectric strength

and volume resistivity

form of the sample.

Dielectric constant (106 cps)

The

Value

770-820 volts/mil

Dissipation factor

Volume

method

D149
D150
D150
D257

Dielectric strength (short time)

resistivity

2.0-2.1

0.0002-0.0003
1016

ohm-cm

are probably due to the different physical

From

either table, however,

it is

evident that polypropylene

has electrical properties equal to the best of other dielectric

materials.

PHYSICAL PROPERTIES OF POLYPROPYLENE PIPE

The

first

criterion of a pipe

is its

burst strength. Since one

main advantages polypropylene has over other plastic

materials is its temperature resistance, it is helpful to compare
of the

the change in burst strength of polypropylene pipe, over a

range of temperatures, with that of other plastic pipe.

Figure 2.34 shows four

performance of

rigid

below, this pipe

is

PVC

lines, the

pipe.

upper

extremely strong, but

in strength with temperature

is

line giving the

At room temperature and

its

very rapid.

rate of decrease

The

line

is

shown

62

Polypropylene

7100

2840 i

200

40

20

60

80

100

120

Temperature (C)

Change of burst

Figure 2.34.

strength with temperature for several

types of plastic pipe. (Courtesy Montecatini)

as dotted

above about 60C, as

it is

not considered practical

to use this material at higher temperatures.

Lines

and

represent polypropylene pipe, line

having

the higher isotactic content. Although strength at low tem-

peratures

is

considerably less than

strength with temperature

ticular, the

is

PVC,

the decrease of

also considerably less. In par-

strength-temperature slope becomes quite

mod-

63

Properties of Polypropylene

60C, which makes

erate above about

up

100C. This

to

may make

it

its

use practical even

suitable for domestic hot-

water systems.

The bottom
not only

This

line refers to low-density polyethylene.

much lower

starts

than polypropylene but

loss of

its

is so great that it has little use above about 60C.

Although polypropylene has not been in existence long
enough for long-time strength to have been established,
preliminary testing shows that the embrittlement that sets in
so rapidly when linear polyethylene is held for extended

strength

periods at high temperatures does not seem to be a factor

with polypropylene. Spherulite growth under laboratory conditions

its

can be carried to the point where the material loses

strength. This

may

prevent the use of the most highly

isotactic polypropylenes for services requiring protracted ex-

posure to high temperatures. The presence of stereo blocks

in

the molecule prevents

crystallization

beyond a certain

The use

point and limits spherulite growth.

molecular-weight material can also solve this

does

but

with high-density polyethylene,

may

processing problems that

provement

is

of very high-

problem, as

this

it

introduces

be more costly than the im-

worth.

Polypropylene pipe for hot water would have the additional advantage (besides those of corrosion resistance, lack

of taste

and odor,

etc.)

that

it

has in any service:

thermal conductivity of polypropylene

of metal, so heat loss

Since piping
tinuous stress,

is

much

less

from the water would be reduced.

last for a long time under con-

is

expected to

it

is

important to consider the long-term

shows the hoop

of polypropylene pipe. Figure 2.35

required to burst plastic pipe as a function of time.

the samples

is

the

than that

polypropylene and one

ethylene pipe material.

At 120F

is

life

stress

One

of

a special linear poly-

the polypropylene pipe

withstands considerably higher stresses than special linear

64

Polypropylene
i

Polypropylene

3000

120F

~^

2000

Special linear Polyethylene

1000

900
800

__^

iq4F
~"

Special

700 ^..^
00

500

400

300

-^

Polypropylene
'

__
__

inear Polyethylene

^..^.,_^

194 F

~^

200

100

HOURS TO FAILURE

Figure 2.35.

Hoop

stress required to burst plastic pipe as a function

of time and temperature.

material; however, at

194F the decrease

of strength with

time becomes considerably more severe for polypropylene.

This means that this particular polypropylene pipe

is

not

recommended

for continuous service at temperatures as high

194F.

has previously been mentioned that polypro-

as

It

pylene can be modified greatly, and other samples might be

better.

3.

CHEMISTRY OF POLYPROPYLENE
NEW WORDS FOR NEW POLYMERS

No
is

discussion of the molecular structure of polypropylene

number

possible without a clear understanding of a

of

new

terms, which were introduced by G. Natta of the Instituto di

Chimica Industriale del

Politecnicio, Milan, Italy,

and

first

publicly discussed at a meeting of the Geselleschaft Deutscher

Chemiker at Bad Nauheim, Germany, on April 25, 1956.

These terms describe the order of the molecular configuration
of a high polymer.

Tacticity

The

first

and most general of these terms

"tactic" with

its

the adjective

is

corresponding noun "tacticity."

A tactic polymer is a polymer consisting of molecules

whose monomeric, or basic structural, units follow one another in the chain with their respective spatial configurations
in

some

particular order. This order

may be

quite complex, partial or complete. All that

that the arrangement

is

very simple or
is

essential

not random or accidental.

It is

is

also

possible to have progressive arrangements of tacticities along

and varieties of tacticity

and complex molecule are very great, and
a considerable literature has grown up describing them. This
shall
is, however, beyond the scope of this chapter. We
discuss only the two kinds of tacticity needed to understand
polypropylene, and mention a few others very briefly.

the molecule. Evidently, the kinds

possible in a large

65

66

Polypropylene

Before going into the various kinds of tacticity, however,

define one other word that gets into all these discus-

we must

and

sions,

which also appears

this is the adjective "steric"

as a prefix "stereo-."

This

is

used by the chemist to designate the position of

molecules in space. "Spatial"

is

more

a fairly good but

A steric configuration therefore a configuration in space. A steric regularity

a regularity of posi-

general synonym.

is

is

and a molecule with

tion in space,

steric regularity

can be

said to be stereoregulated.

Atactic Polymer

To

return to tacticity, the easiest term to define

This means having no

tacticity,

is

"atactic."

or no steric order, the parts

of the molecule being randomly disposed in space relative to

Isotactie

The

Polymer

really important

term as regards polypropylene

In simplest terms an isotactie polymer

is

one
whose basic building blocks are unsymmetrical, and in which
the building blocks are so arranged that, if one passes along
the chain from one block to the next, it will be found to be
"isotactie."

in the

To

same

is

relative position in space.

explain this definition

we

shall

have to go back to some

of the fundamentals of stereochemistry.

stereochemistry of organic molecules

a carbon atom

will, if possible,

is

The

basic fact of the

that the 4

bonds of

arrange themselves as

if

they

came out of the apexes of an equilateral tetrahedron, with the

carbon atom in the center of the tetrahedron. In Figure 3. -la,
if

we imagine

that

we

tetrahedron, then there

from
ing

us.

at.

each other.

The other
line

are looking directly at a face of a

is

one

line

which goes

straight

three apexes are on the plane

we

away

are look-

from the center of the tetrahedron through the

Chemistry of Polypropylene
apexes, however, does not he in this plane

upward toward us

slants

It is

very convenient,

67
but each line

shghtly.

when

trying to represent this three-

dimensional figure on a sheet of paper, to have two of these

bond

lines

on the plane of the sheet of paper. When we

shift

our point of view to look directly at the plane of two

bond lines, we find that they form an angle of about

130 deg, and that of the other two bonds one comes up away

of the

ABC

Figure

3.1.

Bond

directions in the carbon atom.

from the paper at a certain angle, and the other goes down
away from the paper at the same angle. If we look directly
at the plane now, the bonds above and below the paper
would be directly over each other, so, to get a projection
that we can visualize, we can shift our point of view down to
get Figure 3.1b.
If

we now

discard the tetrahedron, leaving only the

we

The

bond

from
and 3 are in the plane of the paper. The line
from the center to 2 comes up toward us from the paper, and
the line from the center to 4 goes down away from us at the
same angle. Figure 3.1c is a very convenient way of representing how a carbon atom in a long molecule is arranged in
space. If we take the bonds represented by 1 and 3 in Figure 3.1c to be the ones that go to the main chain of the
molecule, we can then represent this chain by a zigzag line
lines

through

the center to

its

apexes,

get Figure 3.1c.

lines

68

Polypropylene

across the paper, with the bottom

resenting another carbon

atom

pomts of the zigzag repsame way but upside

in the

down.

Figure

Schematic representation of part of the main carbon chain

3.2.

of a long hydrocarbon molecule, showing

bond

directions.

We now

have a means of putting down on paper a repwhat isotactic means. The first part of the
definition is that the molecular building block must be unsymmetrical. Now, the main chain bonds are necessarily the
same. Therefore, to get an unsymmetrical building block it is
necessary for the atoms attached to the other two bonds of
our carbon atom to be different.
Keeping to the simplest case and avoiding, for the present,
any discussion of the many fascinating ways in which giant
resentation of

molecules

may be

built

up from smaller ones, an unsym-

metrical building block can be discussed.

Figure

3.3.

Diagram showing ethylene entering a long-chain molecule.

The simplest way for a polymer to form is by the direct

polymerization or joining together of small molecules containing a double bond. The simplest such molecules are the
olefins,

and the simplest of these

is

ethylene. If

we make

Chemistry of Polypropylene

69

diagram for ethylene, we see that, to get a double bond,

of the carbon atoms must be bent or strained,
perhaps as in Figure 3.3a.
steric

the

bond angles

When

bond opens up and

the double

make

with others to

seen that the chain building block

This means that ethylene cannot

The

simplest

joins this molecule

a polymer, as in Figure 3.3b,

monomer

is

it

can be

entirely symmetrical.

make an isotactic polymer.

make an isotactic polymer

that can

^"3

Figure. 3.4.

Diagram showing propylene entering a long-chain

molecule.

is

propylene.

If

we

the previous figure,

to the
its

double bond

represent propylene as

we
is

we

did ethylene in

find that one of the carbons attached

attached to a methyl group by one of

other bonds and to a hydrogen by the other (Figure 3.4a),

is attached to two hydrogens.

becomes part of the chain, one of the carbon
atoms in the chain is now unsymmetrical, i.e., it is bonded
to a hydrogen on one side and to a methyl on the other.
The next part of our definition is that, if we go from one
building block to another along the chain, it will be found
in the same relative position in space. If we draw a few
more propylene molecules similar to the first one we
drew (see Figure 3.5), we have represented an isotactic

while the second carbon

When

this

portion of a polypropylene molecule.

methyl

is

If

the unsymmetrical

examined it will be seen that the attached

always on the bond coming up from the paper

chain carbon

is

70

Polypropylene

toward the viewer, while the hydrogen

on the bond

is

extending down. Therefore, they always have the same relative position in space.
If

we had

methyls

a similar portion of the molecule, but with the

fashion, this condition

k^1^
1

T^
"3

Figure

and sometimes down

would be called atactic.

sometimes up

3.5.

>^^^
1

H
1

in

random

T
""3

"

'z

Diagram of part of an

'"z

isotactic

'z

polypropylene molecule.

Syndiotactic Polymer

Another term that is of interest, although less important

can very readily be explained now. "Syndiotactic" is
the term used to describe the polymer where methyls (or in
general the unsymmetrical groups) alternate up and down
regularly
one up, the next down.
This method of representing the main polymer chain on
the plane of the sheet of paper, and the groups bonded to the
chain carbons above and below the plane, is a very convenient
way to show what these various tacticities mean. It is, howto us,

ever, misleading

if

we

think of this as representing the experi-

mental work that Natta announced

at that historic

meeting

at

Bad Nauheim.

We

have been working backwards toward a point

where we can understand what the experiments showed and
how an isotactic polymer molecule is disposed in space.
If we take one of our plane diagrams, say Figure 3.5, and
visualize now that the atoms on this skeleton are so large
that they really crowd each other, and that the main chain,
really

Chemistry of Polypropylene
while

it

resists

distortion of the

71

bond angles and

about a bond, does have a certain

flexibility,

it

will

rotation

be seen

polymer would not stay in this stretched-out

position by itself. In particular, those methyl groups sticking
up all along one side, because of their mutual repulsion,
would tend to take positions as far from each other as posthat an isotactic

sible.

In the case of isotactic polypropylene, the equilibrium

position has the methyls arranged around the

spiral fashion,
It

is

this

main chain

completing one spiral in three propylene

in

units.

first drew Natta's

was examining an unusual mate-

three-group-length spiral that

attention to the fact that he

rial. It is this spiral

molecule that interlocks with other spiral

molecules to form the crystals which are so important in the

behavior of polypropylene.
Figure 3.6 shows a diagram of the two possible spiral

arrangements for a polypropylene molecule, one right-handed

and one left-handed.

In

the

crystals,

the

two enantiomorphous

spirals

are

present in equal quantities. There are two possible orienta-

one with the CH-CH bond in the

and the other with the CH-CH bond in the
down direction. Isomorphous spirals differing in the orientation of the CH-CH bond occupy about the same space and
can substitute for each other in a crystal.
The upper part of the figure represents a side view of a
short segment of polymer chain. The numbers to the right
tions for each of them,

up

direction,

refer to the

monomer

units.

Each monomer

3 carbon atoms, 2 in the chain

unit

is

one

is

and

outside.

unit consists of

Each monomer

rotated 120 deg from the next one, so that the fourth

placed identically with the

first.

This sequence will

continue indefinitely until the tacticity of the molecule

is

changed, or something else interferes.

The lower part of the figure represents an end view of the

same segment of molecule, showing very clearly how the

72

Polypropylene

unsymmetrical carbon atoms have been located to give the

The manner in which the right- and left-

least interference.

handed

helices tend to

crystallize in pairs, as

Figure

3.6.

fit

together

shown

is

apparent.

They always

in the illustration.

Diagram of the

position of the carbon atoms of isotactic

polypropylene in space, when crystallized.

Stereoblock Polymers
In addition to isotactic, syndiotactic, and atactic polymers,
it is

tic

also possible to

and then,

make polymers

that start off being isotac-

after maintaining this condition for a while,

and continue again being isotactic, but

Such polymers are called
stereoblock polymers, and they differ in properties from
reverse their position

in the opposite position in space.

the previously discussed types. Stereoblock polymers can, of

course, differ from each other greatly, because the length of
the blocks can vary

from very short

to very long.

Chemistry of Polypropylene

73

Depending on how often the order of a stereoblock polymer

more or less

reverses along the chain, the polymer shows

elastomeric properties.
Generally, infrequent inversion in a long chain causes

only a slight lowering of the melting point and a slight increase in elastic elongation. Tensile strength and yield point
will

be about the same. The properties of these polymers are

essentially

the

same

high-molecular-weight

as

isotactic

polymers.

In the same way, small isotactic blocks in an atactic chain

do not

alter the properties appreciably.

When

enough to produce
some new and interest-

there are isotactic blocks long

partial crystallization of the polymer,

ing characteristics appear.

The

material remains elastomeric

but begins to have some of the properties of vulcanized elastomers.

The

crystallized portions act similarly to the cross

and prevent the cold-flow

Such polymers can
be partially stretched to produce crystallization, and will then
have a reversible elongation of 50 to 100 per cent or more.
These materials have tensile strengths higher than most vullinks in a vulcanized elastomer

characteristics of unvulcanized elastomers.

canized rubbers.

This vulcanization-like effect of crystallinity, of course, dis-

appears

when

the material

is

heated above the melting point

of the crystals.

The

revolutionary technical possibilities of an elastomer

that can be injection molded, or handled

plastic

by any other thermo-

technique, to yield a product with the properties

of a vulcanized rubber, without any kind of cure or after-

treatment, almost stagger the imagination.

Polymers of

more
tic

readily

this

type are of particular interest as they are

made by

direct polymerization than pure isotac-

polypropylene. Although certain catalysts under some

conditions can produce mostly isotactic polymers, the usual

74

Polypropylene

catalysts,

under operating conditions most suitable for ecoof isotactic, atactic, and

nomic production, produce mixtures

stereoblock polymers.
It is

not

difficult to

thus producing a
isotactic

keep the purely

raw polymer

atactic portions low,

consisting of a mixture of

and stereoblock chains. This raw polymer would

evidently be cheaper than a pure isotactic polymer produced

by the solvent fractionation of the raw polymer.

It also

appears that for

many

applications the presence of

these stereoblock fractions will have

many

advantages.

When

more complex than propylene are polymerized there

are many more types of possible polymers, but a full discussion of these is beyond the scope of this book.

olefins

Optical Activity

Although

it

is

not a

new

term, the general problem of

steric configurations leads to the question of optical activity.

It is

well

known

that

some organic compounds have

erty of rotating the plane of polarization of

the prop-

beam

of

polarized light passed through a solution of the compound.

These are called optically active substances.

The science of stereochemistry is based upon this property. When a steric model of optically active compounds
was developed it turned out that two models, differing only
in steric configuration, could be made.
It was then determined that the substance having one of
these steric configurations rotated a

beam

of light to the

and the other rotated it to the left. These are called

dextrorotary and levorotary, respectively, and in chemical
literature are indicated by writing d- and L- in front of the
right,

name

of the substance, as D-glucose.

Because of the close connection between stereochemistry

and optical activity, the optical activity of these sterically
ordered polymers was investigated. It was found that most

75

Chemistry of Polypropylene

them are not

of

forms

lized

Some

optically active in solution, although crystal-

affect polarized light, as will

be discussed

later.

optically active substances, however, are capable of

forming polymers. Ordinary atactic polymers of these mate-

show

rials

little

or no optical activity, but

it

was found that

properly ordered polymers of these materials were optically

In

active.

some cases the polymer

monomer.

is

a hundred times as

optically active as the

THE EFFECT OF STEREOREGULARITY

ON

POLYMER PROPERTIES
Crystallinity

and Tacticity

was mentioned

It

the

in

discussion

of

isotactic

poly-

propylene that the regular location of the methyl group on

the polymer chain gave

it

a spiral configuration. There are

really four possible spiral configurations,

two

left

hand.

One

of each

was shown

two

right

hand and
Such

in Figure 3.6.

a regular chain can evidently interlock closely with other

chains to form a crystal, whereas any lack of regularity interferes with crystal formation.

This means that an isotactic polymer will be highly crystal-

and an atactic polymer will not. The percentage of

polymers in any given sample will be reflected in

line,

isotactic
its

degree of crystallinity, but this

there

is

is

not intended to

mean

that

a simple numerical relationship between the two.

Crystallinity

is

affected

by many

factors other than the

percentage of isotactic material. For instance, the heat history

of the sample

is very important. If a sample is cooled rapidly

from a melt, the chains do not have time to align themselves

into

the proper position for crystal formation before the

viscosity of the melt

into place. In this
a

low

becomes so high

way

that they "are frozen

a highly isotactic sample could have

crystallinity percentage.

76

Polypropylene
Also,

a relatively

makes

short chain

it

for the

easier

molecules to assume a crystalline position than does a long

chain.

a lower-molecular-weight sample might

Therefore,

show a higher degree

weight

of crystallinity than a higher-molecular-

even though the percentage

sample,

of

isotactic

polymer were the same.

This discussion

is

necessary because the properties of

polypropylene samples are sometimes described with reference to percentage of isotactic polymer and sometimes with
reference to per cent crystallinity.

Natta and other European sources prefer to use per cent

isotactic.

They

ordinarily determine this

by extraction with

boiling n-heptane, assuming the insoluble portion to be a

pure isotactic polymer. This

is

not, of course, the definition

on material so
makes a quite reliable
and atactic polypropylene. The

of an isotactic polymer, but repeated tests

extracted have

shown

that this reagent

separation between isotactic

analysis

is

a classic gravimetric procedure requiring only rela-

tively simple laboratory

entirely

equipment, and the results depend

on the properties

of the basic polymer, not

physical history of the sample.

It is,

on the

however, quite time con-

suming, and requires considerable skill in its execution.

American sources prefer to use percentage crystallinity, as
it involves an instrumental procedure which requires little
time and can generally be carried out by laboratory technicians. The instrument is complex and expensive, generally
an X-ray spectrograph, although the value can also be determined by infrared. American laboratories generally have such
instruments available, and their use saves much time. If care
is

taken in sample preparation to assure

crystallinity,

and

if

samples that

maximum

possible

differ little in factors

other

than percentage of isotactic polymer are compared, then the

percentage crystallinity can be taken, at least relatively, as a

measure of percentage of

isotactic

polymer.

77

Chemistry of Polypropylene

Since the data which will be discussed are only qualitative

and represent polymers that are by no means absolutely representative of any polymer that may be encountered commercially, the terms percentage crystallinity and percentage
of isotactic polymer will be considered essentially as different
measures of the same thing. For the present purpose, no

confusion should result

if

the foregoing discussion

is

kept in

mind.

The

Effect of Stereoregularity on Permeability

The degree

of crystallinity of a sample of polypropylene

also very important in determining

As with
is

its

is

permeability to liquids.

other partly crystalline materials, solvent penetration

almost entirely through the amorphous areas. The relation-

Figure

3.7.

Effect of degree of crystallinity of polypropylene

n-heptane permeability.

on

Polypropylene

78
30C

Figure

3.8.

Effect of degree of crystallinity of polypropylene

on

toluene permeability.

Figure

3.9.

Effect of degree of crystallinity of polypropylene

carbon tetrachloride permeability.

on

Chemistry of Polypropylene
ship between solvent penetration

and

crystallinity

very clearly in Figures 3.7, 3.8, and 3.9.

are materials

The degree

79

The

is

shown

solvents used

which penetrate polypropylene very

rapidly.

of crystallinity for the samples of polypropylene

is ^, 66 per cent; B, 64 per cent; and C, 63 per cent. It can

be seen that this rather small range of crystallinity may

produce a three- or fourfold change in permeability characteristics,

although the results are not quite the same with the

various materials. With n-heptane, for instance, the differ-

ence between

and

is

greater than the difference between

and C, whereas with toluene the opposite

is

true.

The

solvent action of the test liquid appears to be an important

factor in permeability.

Many

solvents actually extract soluble

from the plastic, and this facilitates passage of the

liquid. Although crystallinity is the main influence in these
tests, it cannot be inferred that other samples having the
same crystallinity will quantitatively reproduce these results.
fractions

Other Properties Related to Crystallinity

As we have seen
lar configuration

shown

as

before, solubility

and can be related

is

a function of molecu-

to per cent crystallinity,

in Figure 3.10.

This graph represents the results of extracting 10-mil film

for

22 hr

at

75F with

toluene.

polymers in the most useful

The

crystallinity

soluble fraction of

range

is

quite small.

Practically all other physical properties also are profoundly

influenced by crystallinity.
strong,
soft,

and

The

polymer is stiff,
amorphous polymer is

crystalline

resistant to heat, but the

weak, and rapidly softened by heating.

Any

practical

polymer which

is

a mixture of the two has

properties intermediate between them, depending

on the per-

centage of each present.

The polymer

of greatest commercial interest at present

is

80

Polypropylene

highly crystalline one, but this

is

not necessarily the best one

for all purposes.

The
in

physical properties of commercial polymers, discussed

Chapter

2, reflect,

among

other things, the judgment of the

producers in balancing properties by controlling

figuration

and

steric

con-

crystallinity.

<6

50

PERCENT
Figure 3.10.

60
RYSTALLI NUT

Effect of degree of crystallinity

on toluene

extractables

in polypropylene.

STEREOSPECIFIC CATALYSTS

The

basic discovery that

made

possible isotactic polypro-

pylene, and the whole group of sterically controlled polymers,

was the

fact that certain catalysts

monomer

have the

ability to

add a

unit to a growing polymer chain in a particular

position relative to the previously added group. These are

called stereospecific catalysts.

of research sparked by Natta's

announcement of ordered polymers has disclosed a

The tremendous volume

original

Chemistry of Polypropylene
vast

number

81

of catalysts which have this property.

Both

patent and technical literature in this field have been full of

and catalyst combinations.

had been studied previously in
relation to their usefulness for making polyethylene by the
low-pressure process. Because of its symmetry, ethylene cannot polymerize in a sterically ordered manner, but the fact
that the same catalysts that made linear polymers with
descriptions of different catalysts

Many

of these catalysts

ethylene also
olefins in
It

some

made

isotactic

cases has led to

polymers with unsymmetrical

much

confusion in this matter.

should be understood that the catalysts discussed here are

stereospecific because of the ordered

with unsymmetrical olefins. They

polymers they can make

may

also

make

linear poly-

do with their stereospecificity.

Natta's original work had been done with catalysts rather
similar to the Ziegler type, e.g., an aluminum alkyl (triethyl
aluminum or triisobutyl aluminum) and have been widely
used in conjunction with titanium IV chloride. Although
titanium is one of the most effective metals in such catalysts,
almost any of the elements of the fourth, fifth, and sixth
groups in the periodic table are useful, and have been menethylene, but this has nothing to

The metal is essential,

aluminum chloride has no practical catalytic
activity in these reactions. For stereospecific activity it was
found that titanium in the trivalent state was more effective.
Organometallic compounds other than the aluminum alkyls
are also effective; for instance, dimethyl magnesium, propyl
magnesium chloride, diethyl zinc, phenyl magnesium bromide, and tetrabutyl orthotitanate have been described. A
number of substituted aluminum hydrides are also effective.
tioned in the literature or patented.
since diethyl

All the above materials belong to the class generally called

some differ a great deal from those

by Ziegler. There are two other broad classes
that have stereospecific properties and were orig-

Ziegler catalysts, although

originally used

of catalysts

82

Polypropylene

by their ability to make linear polyethylene.

These are usually designated by the names of the companies

inally discovered

The Phillips catalysts consist of

chromium III oxide catalysts supported on silica
alumina. Numerous promoters modify the action of these

holding the original patents.

calcined

Typical are nickel, thorium, iron, manganese,

uranium, vanadium, molybdenum, tungsten, and zirconium.
In contrast to this relatively simple group of substances, the
catalysts.

Standard Oil Co. of Indiana has a

clude

many

series of patents that in-

materials, for instance, combinations of

an

alkali

metal and an oxide of Periodic Group VIA, an alkali metal

hyride with the same group of oxides, nickel-cobalt alloy

supported on activated carbon, partially reduced nickel and

aluminum hydride and

cobalt oxides, lithium (or sodium)

an oxide of Group
The purpose of

VA, and many

other combinations.

this listing is to show the complexity of

and to illustrate the tremendous amount of work
that has been done on the stereospecific catalysts.
It must not be thought that practically anything will work
in this manner; quite the contrary is true, for only very specific combinations show any activity, and frequently small
this subject

traces of other materials will completely inactivate the catalyst.

For instance, small amounts of

nickel, cobalt,

and other

metals in Ziegler catalysts will cause them to form dimers

or other very low polymers instead of high polymers.
It is

much

too early in the development of this field for

there to be a very

One

suggestion

is

good theory
as follows:

approaching the aluminum

as to

how

these catalysts work.

Visualize an olefin molecule

triethyl as

C2H5

C2H5

= CHR
+

C2H5--Al
1

C2H5

CH2

>

-f

C2H5--Al

-c = CHR

Chemistry of Polypropylene

The presence

83

aluminum activates the olefin as inis then complexed with the alkyl. This
complex is stabilized by the shift of an ethyl with its electron
pair, and the process can start over. If the olefin is unsymdicated,

metrical,

of the

and the

it is

olefin

easy to see that the position of the molecules

during the complexing might be such that the olefin would

always have to present

itself in

a certain specific orientation

in order to react.
It is interesting

that there are a

number of Ziegler-type
makes it possible

catalysts that are hydrocarbon-soluble. This

produce polymers with no solid catalyst phase present.

to

This has obvious advantages in the separation of catalyst and

polymer.

It

has been found, however, that these catalysts are

not stereospecific, so the polymer produced

Evidently a solid phase

is

ordered polymers. Therefore,

is atactic.

essential to the formation of

it

may be

that

it is

not a single

catalyst molecule that forces the olefin to present itself in a

specific orientation, but a crystal structure consisting of a

relatively large

number

of molecules.

Natta has shown that there are catalytic complexes containing transition metals

and metal organic groups which

alone do not polymerize the alpha olefins and are not stereospecific catalysts

but

become

when adsorbed on amorphous

highly

stereospecific

on

certain

substances,
crystalline

supports.

He

reported

polymerization

carried

out

with

triethyl

aluminum and various titanium compounds at 70 to 80C

with n-heptane as solvent and the percentage of polypropylene produced which was not extractable in boiling n-heptane. This is the usual way of determining the isotactic fraction.
Ti(OC3H7)4 alone or adsorbed on silica alumina gave less

than 10 per cent isotactic polymer.

this to

CoCL

support raised

35 to 45 per cent.

When

TiCls was used, the yield of isotactic polymer de-

84

Polypropylene

pended upon the crystal structure of the TiCls. This compound exists in three crystalline forms. The two that are of
interest here are the alpha, or violet form, and the beta, or
brown form. When the violet form was used as catalyst support, the polymer was 80 to 90 per cent isotactic. With the
brown form the polymer was only 40 to 50 per cent isotactic.

STEREOREGULATED DIOLEFIN POLYMERS

These two forms of TiCls are also very interesting

in that

they order diolefins in a very remarkable way. Although this

concerns only the synthetic-rubber industry and

cidental to the polypropylene problem,
ical interest

specific

and

known

of

is

only in-

of great theoret-

illustrates clearly the potentialities of stereo-

catalysts.

When

may be

double bond

it is

which are

diolefins

polymerize,

the

second

positioned in several ways, the best-

cis

and

trans.

These are represented by

plane diagrams, shown in Figure 3.11, and differ only in the

way

the double bonds are located relative to each other in

the chains.

The double bonds

are in the chain in both cases,

the butadiene being attached by

its

end carbons or in the

1,4 position.

The interesting point relative to the TiCls crystal form is

that when polybutadiene is made using catalysts containing
the alpha form of TiCls the polymer is 1,4-trans, and when
the beta

form

is

used, 1,4-cis results.

Diolefins can also polymerize in the 1,2 position with only

two carbons actually attached

to the double

chain, while the other double

chain. This

is

bond

bond remains out

joining the
as a side

called the vinyl configuration. This type of

polymer was not known before the discovery of the stereospecific catalysts. Figure 3.11 also shows vinyl polybutadiene.
This kind of butadiene can be formed in isotactic configura-

85

Chemistry of Polypropylene

and the syndiotactic form is also possible. The atactic

is not represented but can also be made.
The importance of this discovery can only be understood

tion,

form
if

we remember

isoprene,

that natural rubber

and that the

is

almost pure c/5-poly-

rubber to match

failure of synthetic

^C=C

/C=c

CIS

TRANS

CHj

CHj CH2

VINYL

ISOTACTIC

"2

Sh,

"2

i^

en*

"2

U^

OH,
Sh

ij

VINYL
S

YN DIOTACTI
"2

Figure 3.11.

the low heat build-up

uct

was due

duplicate this

to

the

Sh,

"2

"2

"2

l^

Four-ordered polybutadienes.

and high resihence of the natural prodinability of the polymer chemist to

natural structure.

The use

of stereospecific

catalysts has resulted in the synthesis of practically

polyisoprene.

High-cis

polybutadiene

has

pure

tendency

cis-

to

low temperature, but this can be prevented by

reducing the cis content to 80 per cent without serious loss

crystallize at

The vinyl dienes are still too new to deterThey produce rubbers of interesting but not

of other properties.

mine

their uses.

outstanding properties and offer a possible variation for the

86

Polypropylene

new high-polymer types for specific appHcations.

The many unsaturated side chains offer obvious sites either

production of

for reaction with inorganic substituents or for the grafting

Much work

is being done on exploring

by the structural features of
these polymers. Although no commercial products have yet
been announced as a result of these studies, it can hardly be
doubted that the results will eventually have a major influence

of other polymers.

the

many

possibilities indicated

not only on the synthetic-elastomer industry but quite possibly

on the

plastic

and

fiber industries as well.

CHEMICAL REACTIONS

The polypropylene molecule

molecule in that there
other carbon

atom

is

differs

from the polyethylene

a methyl group attached to every

in the polypropylene chain,

whereas linear

polyethylene has practically no branches on the chain, and

low-density polyethylene has perhaps two or three side chains

per hundred chain carbon atoms.

Oxidation
It is

well

known

to a tertiary carbon

other carbons, as

more

it

hydrogen atom which is attached

atom (one which is connected to three
would be at a branch in the chain) is

that a

reactive than hydrogen attached to carbon atoms

which

are connected with only one or two other carbons.

One

of the results of this

polypropylene

At 200F

is

much

is

that the

oxygen uptake of

greater than that of polyethylene.

unstabilized polypropylene will absorb oxygen at

0.117 cc/g/min after an induction period of 11 hr, whereas

linear polyethylene has a 164-hr induction period and then
only absorbs at 0.0031 cc/g/min. This requires the use of
antioxidants

in

polypropylene.

further in later chapters.

This

subject

is

discussed

87

Chemistry of Polypropylene
Sulfochlorination

High-molecular-weight polypropylene can be

made

vul-

by sulfochlorination and then vulcanized with

polyvalent bases. These rubbers have highly reversible deformation values, or good rebound. In many respects their
canizable

technical properties are far superior to those of sulfochlorin-

ated polyethylene, which has

some

industrial applications.

Unlike polyethylene, which requires considerable (25 to 40

per cent) chlorination in order to break up the crystal struc-

and form an elastomer, polypropylene can be made subamorphous to begin with, if atactic polymer is used.
This means that a small amount of sulfur (less than 1 per
cent) and only enough chlorine to produce the equivalent
sulfochlorination are needed to make the polymer vulcanizture

stantially

able.

The vulcanized product has

better elastic properties

than sulfochlorinated polyethylene, and, because of the small

amount

of chlorine introduced,

it is

much

lighter.

Sulfochlorinated polypropylene represents a class of sat-

urated elastomers which have better properties than other

known

saturated rubbers and should have wide applications.

MOLECULAR WEIGHT OF POLYPROPYLENE

Polypropylene

an early stage of development

borrowed from studies of
more famiUar materials. Routine determinations of the
molecular weight of polyethylene usually have been accomplished by means of solution- viscosity measurements. One of
the commonest means of calculation was the Harris equation [Harris, /. Polymer Sci., 8, 353 (1952)].
When work on polypropylene started, it was natural to
is

in such

that techniques are largely

still

attempt to use the same type of equation, with coefficients

changed to

fit

the

new

material. Several experimenters

have

88

Polypropylene

reported results which agree quite closely [R. E. Hughes and

B. Kansinger, ACS Meeting, New York, September, 1957;

J.

/. Polymer ScL, 28, 235 (1958)].

These equations relate the intrinsic viscosity

R. Chiang,

weight average molecular weight

Mw,

to the

(?y)

as follows, using the

average of the two references.

(^)=

1.04

X 10-4 MwO.80

135C, "Decalin"

Mw

Determining
difficult,

from an equation of
shown

so a graph of the form

usually used for

its

Determining the

this sort is rather

in Figure 3.12

intrinsic viscosity of a material requires

made

the extrapolation of several viscosity determinations

As

time consuming,

different

concentrations.

common

practice to use the inherent viscosity

this

is

place of the intrinsic viscosity in this equation;

tive viscosity

solution

^y
fj

is

solution.

at

it

is

i-yr-]

in

f]r is

the rela-

jj^^ inherent viscosity requires only

solvent

one determination made on a solution of a very low concenused is low enough, there is no

tration. If the concentration

substantial difference

between inherent and

intrinsic viscosity.

In calculation of concentrations for use in these equations,

concentration

is

in

grams per

the test. If solutions are

deciliter at the

made up

at

temperature of

room temperature,

the

volume measured must be corrected for thermal expansion.

Polypropylene presents a problem not found in polyethylene because of its rapid oxidation at relatively moderate
temperatures. It is necessary to protect the solution from
oxidation, or results will be erratic and the viscosity determined will be low. The easiest way to do this is to add a little
antioxidant to the solution. If the entire preparation

is

carried

Chemistry of Polypropylene

on

in

89

an atmosphere of nitrogen, similar results can be

obtained.
It

ary

must be kept in mind that viscosity is, at best, a secondmethod of determining molecular weight and must be

0.2

0.3

0.6

INTRINSIC
Figure 3.12.

The

1.0

3.0

2.0

VISCOSITY

relationship between molecular weight and intrinsic

viscosity in polypropylene.

calibrated

by reference

to

some primary method such

as

osmotic pressure changes, boiling-point raising, or freezingpoint lowering.

As
if

in other high polymers, average

molecular weight, even

accurately determined, has only limited value for charac-

terizing the polymer.

90

Polypropylene

Molecular-Weight Distribution

Any sample

of a high polymer consists of chains of

many

The average size of the chain means little

that make up the average are not known. A mategiven average molecular weight, made up entirely

different lengths.
if

the sizes

rial

with a

of molecules very nearly aUke, will be very different from a

material of the

same average molecular weight but made up

The details of the

of very short and very long molecules.

molecular-weight distribution are very important in determining the properties of the polymer.

The

fractionation of polypropylene

is

more complex than

that of polyethylene because the solubility of a polypropylene

molecule depends not only upon

its

length but also on

its

tacticity.

Natta reports that the percentage of isotactic polypropylene

is

nearly the percentage which

is

not extracted by boiling

heptane. Further extraction of the residue with

more

active

solvents produces a series of fractions differing in molecular

weight but not appreciably in

tacticity.

This means that both

and the

isotactic

fraction will have a

the atactic fraction

molecular-weight distribution as well as an average molecular

weight, and quite probably

all

these figures will be required

in order to characterize a sample.

It is

not possible at this time to explain specifically

how

these factors affect the important properties of the plastic,

but, judging

from experience with other polymers, it is quite

polymer properties will neces-

certain that close control of

sitate a better
It

may be

pylene than

understanding of these

effects.

that this will be less important with polyproit

has been with other polymers, because the

proportion of isotactic to atactic polymer

riding effect

on many properties.

It

may have an

over-

appears, even at this

stage of development, however, that low-temperature prop-

91

Chemistry of Polypropylene
erties are to

a considerable extent influenced by molecular

weight,

higher-molecular-weight

the

having

materials

the

better properties.

CRYSTALLITE SIZE OF POLYPROPYLENE

Crystallite size as well as percentage of crystallinity influ-

ence the properties of a plastic material. In general, small and

uniform crystalhtes are preferable to larger or varied ones,

because the large crystallite tends to produce points of stress

The

concentration which cause premature failure.

crystaUite size has

control of

been a major source of improved physical

properties in polyethylene.

Polypropylene has a

150

disc about

which
and 50

crystallite

in diameter

roughly a circular

is

to

60

thick.

The

polypropylene molecule (c-axis) runs in the direction of the

thickness.

This size
erally

is

shghtly smaller than the value of 190

accepted

for

low-density

smaller than values of 360 to 390

linear polyethylenes,

gen-

and much

polyethylene,

reported for various

showing that polypropylene should be

from the stress-raising effects of large crystallites

which are the source of premature failure, especially in hnear
polyethylene. This appears to be due to the numerous methyl
side chains on the polypropylene molecule, which restrict

quite free

crystallite size.

Rapidly cooled polypropylene has smaller

slowly cooled samples.
size

found

samples

which

after

may have

will

The

than

maximum

relatively

long

crystallite

diameters from 110 to 120 A,

grow with

age,

annealing.

Typical

film

depending on conditions of storage.

Certain treatments, such as

celerate the

crystallites

figures given refer to

gamma

radiation, tend to ac-

growth of crystaUites, and

this

is

particularly

92

Polypropylene

marked

in the case of oriented film. This could cause deterio-

ration of properties in such environments.

Spherulites in Polypropylene

Like other poly crystalline

form

relatively

are readily studied

plastics,

polypropylene crystals

spherulites. These
by means of polarized Ught because they

large

aggregates

called

exhibit birefringence. Unlike the other poly crystalline plastics,

polypropylene forms

which

differ

at least

four distinct types of spherulites

not only in amount but even in the sign of their

birefringence.

There are also many mixed types which show

same spherulite.
work has been done on this problem by

birefringence differences within the

great deal of

more recently by Keith, Padden, Walter, and

Wycoff of American Viscose. The main significance of this
work is achieving an understanding of the formation of the
Natta, and

spherulite.

Two
the

of the kinds of spherulites found consist of crystals of

most

common

in polypropylene
sist

type,

which were described by Natta early

development. The other two seem to con-

of quite a different crystalline form.

occurs,

it

though

all

generally

known what

applies

surrounding

to

When

this

form

an entire spherulite, even

crystallites

are

normal.

causes these two forms; apparently

It
it

is

is

not

mostly

due to an accident of starting, although the temperature at

which the spherulite is grown appears to have some influence.
Under certain conditions spherulites can be grown to quite

When this is done, cracks begin to appear between the spherulites, and also within them. The dark areas
between spherulites were first believed to be amorphous
polymer, but it has now been found that they are mostly
voids, and very large spherulites can be separated from one
another with little effort. This clearly shows the great imporlarge sizes.

Chemistry of Polypropylene
tance of controlling spherulite growth

if

strength

93
is

be

to

maintained.
If

a sample of polypropylene

is

partially crystallized

then rapidly quenched, a feathery growth of crystals

is

and
ob-

among which is a considerable amount of amorphous

material. As the structure of this feathery crystallization is
tained,

extremely

fine,

it

does not interfere greatly with light trans-

mission, and a clear film can be obtained.

Once

the material has been cooled to the point where

solid, further crystal

growth

will continue to progress,

it

is

may

it is

quite slow, and, although

it

take sufficient time to permit

a reasonable lifetime for the plastic.

If

individual spheruhtes are separated out and their density

it will be found to be as high as 0.919 from a

polymer originally 0.905. The same polymer rapidly quenched
from +300 to -77C will have a density of only 0.897

is

measured,

g/mil.

PRODUCTION OF POLYPROPYLENE

4.

PROPYLENE PRODUCTION

The

first

step in the production of polypropylene

is

to

monomer, propylene.
Over 90 per cent of the propylene consumed today is
polymerized to high-octane gasoline. This demand is satisfied
by propane-propylene mixtures easily separated from refinery
obtain a supply of

its

Polypropylene

off-gases.

requires

pure

substantially

pro-

pylene, and this requires extra processing steps.

It

is

estimated that 20 billion pounds of propylene are

produced, 80 to 85 per cent of which are recovered from

refinery

off-gases;

the

rest

are

by-products

of

ethylene

production.

In addition to aviation gasoline, propylene

is

used in a

wide variety of chemicals; however, it does not appear that

there is likely to be any shortage in the near future. Certainly
the amounts needed for even a large polymer production
should be no strain on the available resources.

PROPANE-PROPYLENE SEPARATION

Cs fraction can be isolated rather easily by fractional

Adsorption and absorption techniques have been

distillation.

described but are not currently of very great importance.

Usually two distillations in

series,

94

each having 30-40

stages,

Production of Polypropylene
will isolate a

mixture with

less

95

than 2 per cent outside the

C3 range.
Separating propane from propylene

than

most

volatility

commercial

data

given

distillation

Figure 4.1

in

psi the relative volatility

is

very low.

is

rather

more

separations.
indicate
It is

that

difficult

Relativeat

300

convenient to op-

erate at this pressure to permit condensation of reflux with

cooling water.

.10

1.20

1.30

RELATIVE VOLATILITY PROPYLENE TO PROPANE

Figure

4.1.

Relative volatility of propylene-propane mixtures.

96

Polypropylene

The use

of an extractive distillation agent to improve the

relative volatility

dling

is

possible, but the extra expense of han-

and separating the extracting agent

is

more, generally,

than the cost of the increased height of column required to

make

The

the separation without the agent.

propane

ratio in the feed

may

fact that the

vary appreciably adds to the

problem of designing a system for propylene purification.

For polypropylene manufacture, particular care must be
taken to remove all traces of water, which will destroy the
catalyst. Methyl acetylene must also be completely removed,
as it is a cross-linking agent which will produce infusible
polymers.
If

the distillation

column

is

operated at 300

psi, the re-

covery of 99 per cent plus propylene requires a column height

of about 140 ft, so it is generally more convenient to have
two shorter columns operated in series.
A vapor-recompression cycle makes it possible to operate
in the 100 to 200 psi pressure range with a single column.
Overhead vapor is compressed and then condensed as heating medium for the column reboiler. In a large refinery it is
often possible to use a refrigeration unit, which also serves

other processes, to provide condensation at lower pressures

where the

relative volatility

is

more

favorable.

All things taken into consideration,

it

appears that neither

technical nor economic problems are likely to limit the supply

of propylene to the expanding polypropylene industry.

POLYMERIZATION OF PROPYLENE

The manufacture
manufacturer
ess,

and there

is still
is

of polypropylene

is

so

new

that each

very secretive about his particular proc-

no standardization of production procedures.

Certain basic methods of operation, however, are apparent

from the

literature.

97

Production of Polypropylene

The

first

step in the manufacture of polypropylene

monomer

purification of the

to avoid variation in product properties

ing of the catalyst,

it is

is

the

discussed previously. In order

and possible poison-

necessary to refine the propylene to a

Some plants perform their own purification, others

depend on the monomer supplier. Purification is carried out
in a rectifying column with, in some cases, selective absorption of specific impurities. Special care must be taken to be
high purity.

sure the gas

When

is

dry.

the gas

is

obtained, present processes are of two

distinct classes, depending on the type of catalyst employed.

These differences are similar to those in linear polyethylene
production, although the catalysts may not be the same.
The first class, which covers all current production facilities, is

similar to the Ziegler process for polyethylene, in that

the catalyst used

formed

produced in situ by the reaction of its

minor modification of this the catalyst is

is

constituents. In a

in a separate vessel just before entering the reaction

vessel. It

may be

subject to

some aging before use or

to

some

degree of grinding for the control of certain properties, but

basically

it

is

made

as required,

and cannot be stored or

transported between manufacture and use.

These catalysts are generally formed from transition metal

and organometallic compounds. One such composition

salts

that

is

particularly suitable for the production of isotactic

polypropylene
butyl.

is

Catalysts

Chapter

titanium trichloride and aluminum

of this

triiso-

type were discussed in detail in

3.

The second

class uses catalysts generally referred to as

preformed catalysts because they are made outside the reaction vessel at some earlier time. These are the Phillips-type
(chromium oxide on silica alumina) and the Standard Oil
catalysts (molybdenum oxide, cobalt molybdate, and other
molybdates on a variety of refractory bases). The activity of

98

Polypropylene

these catalysts can be modified

calcium hydride,
in

Chapter

This

etc.

is

by promoters such as sodium

more detail

also discussed in

Catalysts of this sort are not

3.

now

being used

commercially, but some of them can polymerize propylene to

form

largely isotactic polymer.

All the catalyst types used for linear polyethylene can,

with some modification, be used for polypropylene, with the

exception of the soluble complex types. For stereospecific

polymerization a solid phase appears to be essential.

The process
of three steps

of

making polypropylene

consists essentially

the polymerization proper, the separation of

the catalysts and solvents from the polymer, and the pelletizing of the polymer to

make

granules suitable for use in plastic

conversion equipment.

Linear polyethylene can be

made

in

two ways. The tem-

perature of the reaction can be kept high enough to keep the

polymer as

formed in solution, or it can be low enough

polymer to precipitate out as a suspension.

it is

to cause the

For polypropylene the suspension process

is

generally

indicated because, unlike linear polyethylene, the properties

of the polymer are greatly influenced by the temperature, and

high temperatures produce

soft,

rubbery atactic polymers

rather than the desired isotactic form.

Catalyst composition, however,

determining

developed that
operation.

is

also very important in

tacticity, so it is possible that

will

It is also

which can use

a catalyst

may be

permit the more convenient solution-type

atactic

possible that applications

may

develop

polymers or polymers with appreciable

atactic content.

All the factors involved in the control of polypropylene

polymerization are not

known

at this time.

form of the

In addition to
is

very

important. Molecular-weight distribution, in particular,

may

catalyst composition, the physical

catalyst

be influenced quite markedly by grinding the catalyst

after

it

Production of Polypropylene
is

formed. Aging before use

this property.

may

also

99

have an influence on

This means that catalyst production must be

very closely keyed to plant operation so that the age and

condition of the catalyst

is

always the same at the

moment

of use.

Gas composition

on polymer
must be quite pure, but
controlled amounts of other gases may be deliberately added
to change polymer properties. Hydrogen, for instance, is
added to reduce molecular weight, and thus improve the flow
properties. Other unsaturated gases may also be added to
propylene to produce copolymers of many types.
properties. It

also

is

a strong influence

true that the gas

is

In the suspension-type operation,

of about 100

atm

is

added

monomer

at a pressure

to a well-agitated reactor contain-

ing a dispersion of catalyst in a liquid hydrocarbon.

reaction temperature

is

The

well below the softening point of the

polymer. Polymer granules form around the catalyst particles

and are kept

in suspension

by the

agitator. This

can be

continued until the polymer content reaches about 40 per

which is the maximum that can be conveniently pumped.

Although early processes were batchwise, most current procent,

duction

is

on a continuous

basis.

The solvent-polymer-catalyst slurry is then pumped to a

flash drum where a reduction in pressure removes the unreacted monomer, which is then recycled. A purification step

may be

required in the recycle system to prevent build-up of

impurities.

From

here the slurry

remove the

is

run into a centrifuge or

filter

to

Proper choice of diluent and temperature

leave the majority of the atactic polymer in

diluent.

at this point will

the solvent phase, and the solid matter wiU be mostly isotactic.

The

solvent

is

then

distilled to separate

and low-molecular-weight material, which

the system as a by-product.

it

from the atactic

removed from

is

100

Polypropylene

The polymer is then reslurried with an extractant, for

weak HCl in methanol, to decompose the catalyst.

instance

This must be done before the mixture

is

exposed to

any previous operations must be carried out

closed system.
centrifuge or

The

extractant

is

air,

hence

in a completely

then removed in another

filter.

The polymer

is

steam-distilled to

then washed with water to remove the HCl,

remove

final traces of solvent,

dried, ex-

truded, and formed into pellets.

The complete removal

of

HCl and

chlorine containing

reaction by-products of the catalyst decomposition reaction

is

essential to

keep the polymer from corroding processing

equipment.

For some end

tions,

it

is

uses, such as

more convenient

most injection-molding appUcato add a corrosion inhibitor

which absorbs the corrosive materials rather than attempting

to remove the very last traces.

which demand the best electrical properties require complete removal of all residues, and film
grades which must have the greatest possible clarity must
be free from all extraneous material. This method of catalyst
removal is evidently effective only in the case of Ziegler-type
catalysts, whose residues are entirely acid-soluble. When
catalysts on a refractory-type substrate are used, it is necessary to dissolve the polymer in a solvent at elevated temperature (xylene at 130C, for instance) and centrifuge or filter
the hot solution to remove catalyst residues.
Electrical grades

In order to obtain a colorless polymer, this solution

be decolorized by treatment with suitable clays,

other decolorizing agents.

It

is

oxidants to the polymer before

may

silica gel,

also necessary to

add

or

anti-

it is exposed to the air.

Although a rough separation of isotactic from atactic
polymer may have been made earlier, it is generally at this
point that final separation is made. The hot, filtered, and

101

Production of Polypropylene
antioxidant-protected solution

which precipitates out the

tic in

is

cooled to

room temperature

isotactic fraction, leaving the atac-

solution.

Another filtration or centrifuging separates out the isotactic

material which is, however, saturated with xylene, a rather
difficult solvent to

remove.

The xylene wet cake may be extracted with

more volatile solvents to remove xylene. Final

a series of

solvent re-

may be by steam distillation, or devolatilizing

may be used to remove solvent and form the pellets

moval

extruders
at the

same

time. Figure 4.2

is

a flow sheet of this process

These vary a great deal in

detail
often some may be combined, and in other cases
the steps may be split up into more subdivisions. As the
discussion indicates, the final dissolving and filtration steps
may not be necessary when the catalyst is of such a nature as
to be completely extractable in the earlier steps.
It is evident that this is a complex process involving the
interrelation of numerous steps, each of which can cause loss
showing the essential

steps.

of product or of quality. In spite of this complexity,

it

is

straightforward process that does not involve a great deal of

labor cost.

Once

the design and

settled, the plant will

method

of operation are

run automatically and economically.

Unlike the high-pressure polyethylene process which uses

pumps, valves, piping, autoclaves, etc.,

equipment familiar to every chemical

special high-pressure
this

process

uses

engineer.

The

is a closed tank with an agitator. It

depending on operating pressure, but this

reactor

in detail,

will differ
is

usually

below 100 atm, so that no unfamiliar construction is required.

The same is true of all other items of equipment; centrifuges

may be

substituted for the

for maintaining a dry

and

filters

inert

shown. Except for the need

atmosphere in the first one,

no unusual problems are involved.

102

Polypropylene

The

first

removing

solvent recovery

must have

special provision for

traces of water, since water destroys the effec-

all

tiveness of the catalyst.

MONOMER
MONOMER

CATALYST

REACTO

RECYCLE

STORAGE
SOLV ENT

FLASH DRUM

RECYCLE

FILTER

A^A CTTC
AND LOW POLYMER
I

AGITATOR

EXTRACTANT

FILTER

RECOVERY

Fl

CAT ALYST
RESIDUE

WATER

AGITATOR

LTER

WATER AND
TaTALYST RESIDUE

^ATER

STEAM STILL

ANTI 0X1

STILL

DANX

DECOLORIZER

DISSOLVER ]

RECOVERY

ST0RA6E~|

SOLVENT

FILTER

CL

CATAL YST

COOLER

RESI DUE

FILTER

^RECOVErTIaTAC TIC
POLYMER

EXTRACTION

RECOVERY

SOLVENT
STO RAGE
SHI

Figure

The

may

4.2.

Flow

PPING

sheet of polypropylene manufacture.

devolatiUzing extruders used in the final operation

These consist of long screw exmachines used in extruding plastic

film or pipe, except that they are longer. At one or several
not be famiUar to

all.

truders, similar to the

places along the barrel length, there are openings or vents.

The screw

is

modified at these points to assure a low pressure

103

Production of Polypropylene

on the polymer. The polymer

is

heated and melted as

it

progresses forward in the barrel, which heats and volatihzes

When

comes to one of the vents,

The evaporation of solvent
is generally assisted by drawing a vacuum on the vent. These
machines have been improved until they can remove a great
deal of solvent, but their best function is to remove the last
traces. When film-grade polymer is being produced, it may

the solvent.

the polymer

the solvent flashes out of the vent.

be necessary to provide inert-gas blanketing to exclude

all

oxygen from the process.

The product leaves the extruder through a die, forming a

number of small rods; on cooling, these are cut with rotary
knives or more often with a flying knife at the die face. The
whole operation may be performed under water. This method
produces a pellet that ranges from lentil-shaped to nearly
and has excellent flow properties in the processing
equipment used to put the resin into its final form. Round
pellets are also much better suited to the pneumatic transfer
systems being installed in most modern processing plants.
spherical,

Unlike low-density polyethylene, which

is

useful for

many

purposes as essentially pure polymer, the usefulness of polyis dependent upon

and oxidation. Although the

propylene

is

quite new,

The

it

being stabilized against heat

polypropylene

has a highly developed tradition to draw from.

fact that for

stabilized

its

art of stabilizing

some purposes, polyethylene must be

the linear variety for almost

all

purposes

has

led to the development of stabilizers particularly suitable for

poly olefins.

Many

of the stabilizers used for vinyl chlorides

are also effective in polypropylene, despite the fact that the

nature of the degradation

Many

is

so different in the two cases.

of the materials used in the protection of rubber

The

years

of experience with antioxidants in this industry have

been

against oxidation are also useful in polypropylene.

very helpful in developing similar materials

for

polypro-

104

Polypropylene

pylene. In

some cases where rubber antidoxidants had

serious

drawbacks, related materials were found to be suitable.

In spite of

its

novelty,

stabilizing polypropylene,

much
and

has been found out about

this is

an important part of

polypropylene technology. In the process, some stabilizer

must be added

to the resin before

it

is

subjected to any

elevated temperature. Additional stabilizer, or special stabi-

Uzer for

some

specific purpose,

may

also be

added in a subse-

quent operation.

COLORING OF POLYPROPYLENE
Colors can be incorporated into polypropylene by any of

methods used for polyethylene and thermoplastics the

mill, Banbury mixer, or compounding extruder.
These types of equipment are generally used ( 1 ) for applications where color dispersion is critical, for instance where
carbon black is to be incorporated to improve the resistance
to light exposure; (2) where a particularly even color or an
accurate color match is needed; (3) for reworking scrap and
the

two-roll

off-grade material, with the incorporation of color.

Economic

factors,

however, cause a large proportion of the

colored polypropylene to be dry colored. In

this

process the

various colors and pigments are blended with the resin in a

tumbling barrel or other dry mixer. This dry blend

is

then

used as feed for the processing equipment, depending on the

turbulence of flow in the processing step to complete the
mixing. This

method

of coloring

injection-molding industry.

Some

is

particularly useful in the

difficulty

has been encoun-

tered with the dry coloring of polypropylene.

It

has been

common

practice

in

the injection-molding

industry to insert a wide variety of dispersion aids into the

The nozzles vary in design

same general purpose of increasing the

nozzle of the molding machine.

but

all

serve the

Production of Polypropylene

105

turbulence of flow, and so improving the dispersion of color.

Many

of these devices have been quite successful in produc-

ing excellent color dispersions in polystyrene

ethylene, but have been

of polypropylene.
erties of

markedly

The previous

polypropylene makes

would be the

case.

and

in poly-

less successful in the case

discussion of the flow prop-

easy to understand

it

The sharp break

why

this

in the viscosity of poly-

propylene with increased temperature means that when the

resin

heated in the molding machine the portion near the

which gets hot first, becomes fluid, and the mass moves
through the cylinder without any great degree of tum-

is

walls,

easily

bling or turbulence.

The

sensitivity of the viscosity to rate of

shear aggravates this tendency.

The

first-melted portions flow

are subjected to the greatest shear, and

first,

more

become even

and the material away from the walls has no

tendency whatsoever to mix in with the material near the
fluid,

walls. This flow pattern persists to a considerable degree

even

through the rather complicated and tortuous passages of the

various dispersion devices in the injection machine.

In order to get color dispersion in polypropylene melts,

it is

to

necessary to force the wall and center layers of the melt

mix

together, regardless of their natural tendency to remain

One successful device for doing this was developed

by the Plastic Color Division of the Ferro Corp. This is
apart.

called a spherical Venturi,

and

its

operating principle

is

just

the opposite of that of an ordinary Venturi tube. Instead of

changing

fluid velocity efficiently

and without turbulence, the

by a

spherical Venturi deliberately uses the energy produced

change

in velocity to shatter the

laminar flow of the plastic

and create turbulence.

This

is

accomplished by forcing the plastic through a small

hole 0.030 to 0.050

in diameter

small hole.

in. in

diameter into a sphere about V2

in.

and then immediately forcing it through another

These two successive, rapid-velocity changes

106

Polypropylene

create a great deal of turbulence. Figure 4.3 shows a typical

spherical Venturi. Exact dimensions will, of course, vary with

the type and size of machine.

With dispersion

aids of this sort

^-plEce TO BE
THIS

IKI

TU;o

secTioMs- HALVED

OKI

DIA.SPHEI2.E

-N^ 63(.029D1A )

DRILU THRU

Figure

4.3.

Spherical Venturi plate for dispersing color in

polypropylene. (Courtesy Ferro Corp.)

it

is

possible to get entirely satisfactory dry-blended color

with polypropylene.
It

must be kept

in

mind

higher temperatures than

that polypropylene will

many

mold

at

other plastics; thus extremely

heat-stable colors are required. In general, however, colors

that

have been successful in polystyrene and polyethylene

also be satisfactory in polypropylene.

will

PROCESSING OF POLYPROPYLENE

5.

The processing

of polypropylene closely

resembles the

processing of polyethylene and other thermoplastics, but

has certain special characteristics that modify

requirements somewhat, and

its

it

processing

responds particularly favora-

it

bly to certain modifications of conventional methods. These

be discussed in detail
mention of the basic process

special processing characteristics will

in this chapter, with only such

as

essential to

is

Where

reference

is

the understanding of the

made

ethylene, further details

from the

first

book

modifications.

equipment used to process polyof this equipment may be obtained

to

in this series.

EXTRUSION OF POLYPROPYLENE
Although the greatest present use of polypropylene is in
market research and the history of other

injection molding,

thermoplastic materials

make

it

very clear that the largest

ultimate market will be for extrusion purposes.

General Considerations
Polypropylene
will

is

a relatively easy material to extrude and

perform reasonably well in any machine designed

to

extrude polyethylene.

As with

the other poly olefins, a relatively long extruder

produces better-quality melt.

An L/D
107

ratio of

20:1

is

good

08

Polypropylene

practice, although satisfactory resuhs

ratios ranging

from 16:1

can be obtained from

to 24:1.

Relatively high compression screws are also

recommended,

with a 4:1 compression (preferably produced by increase of

root diameter) being a

minimum.

or more) metering section

Double-screw as well

is

relatively long (4 turns

desirable.

as single-screw

machines have been

used successfully on polypropylene.

Screen packs and valving in the melt channel are generally
less effective

with polypropylene than with polyethylene be-

cause of the great sensitivity of the viscosity of polypropylene

melts to rate of shear.

Back pressure

built into the die

by

way

to

increased land length appears to be the preferred

control the extrusion.

An

increase of land length restricts

flow without increasing the rate of shear as does a valve or

a screen pack. In

many

cases this will require a consider-

able change in die design

from that used for other

land length 50 times part thickness

is

plastics.

not unusual, and

approach to the land should be long and shallow. It is easy

understand that if the flow is a little more rapid in one
area, the rate of shear wiU be higher, and hence the viscosity
will be lower in this area, resulting in uncontrolled flow.
Streamlining of the die is very important because of the decrease in melt viscosity that results from too long exposure
to

of the polypropylene to heat. Material delayed in relatively

stagnant areas will soften and behave very differently

it

when

leaves the die.

The above discussion should not discourage the use of the

same dies for polyethylene as for polypropylene, since perfectly satisfactory results can often be obtained from them;
however, if a new die is to be built, the considerations mentioned should improve quality and output. If the proper die
is

used, really remarkable extrusion rates can often be ob-

tained with polypropylene.

It

appears likely that familiar ex-

109

Processing of Polypropylene
trusion economics will be completely upset

of polypropylene to extrude rapidly

is

when

the abihty

thoroughly understood.

Polypropylene does not absorb moisture,

except for

so,

compounds containing carbon black or other hygroscopic

fillers, no drying is needed. The quahty and output of an extruder, however, can frequently be improved by the use of a
hopper dryer which will deliver material to the feed section
of the extruder at a uniform temperature around 190F.

The

susceptibility of polypropylene to oxidation

enough, in spite of advances

is still

great

in stabilization, that the extru-

sion of the highest-quality film, or other critical products,

from the exclusion of oxygen from the process. This

conveniently done by displacing the air between the granules

benefits
is

being fed to the extruder with an inert gas.

POLYPROPYLENE-FILM PRODUCTION

The
to

greatest

volume of extruded polyproplene

is

expected

go into thin film for packaging. Polypropylene can be

made into film by any of the processes used

from other thermoplastics.

new

material

is

produce film

first on equipment
and polypropylene has

inevitably tried out

originally designed for other materials,

been no exception.

to

When

the polypropylene resins

now

avail-

on the kind of equipment used to make polyethylene blown tubing, it is not difficult to obtain film, but it
able are run

is

not very attractive in appearance.

It

does not have gloss

or clarity equal to polyethylene blown tubing, except at thicknesses below 0.3 mil (0.0003 in.), and
are not

much

its

physical properties

better than those of polyethylene film.

the development of resins that are better for this

processing

is

of

not impossible, at present the main promise of

polypropylene as a film material

chill-roll

Although

method

extrusion method.

lies in its

adaptability to the

110

Polypropylene
Extrusion of Polypropylene Film

Chill-roll

In this method the hot plastic

slit

and the resulting web

die,

polished steel roll that

two general

falls into

ment
is

is

is

is

extruded through a long

brought into contact with a

water-cooled. Chill-roll equipment

classes

which are adaptations of equip-

originally designed for other purposes.

The

first

of these

the equipment used for coating paper with polyethylene. In

STRIPPER ROLL
TO
Wl

01 E

NDER

A( R

KNIFE

igure 5.1

Chill-roll casting, vertical-extrusion

method.

(Courtesy F. W. Egan Co.)

this,

web

the

with the

is

chill roll

extruded straight

The coating equipment

nearer the

down and makes

contact

while traveling almost vertically downward.

is

modified either by moving the die

chill roll, so that film falls

upon

it,

or by removing

or drawing back the rubber pressure roller. After following

the chill roller through 180 deg or more, the cooled film

can be taken off onto a stripping roll, from which it goes to a

trimmer, and then through tensioning rolls, to a windup. The
chill rolls used in this equipment may be quite large, up to
3 or 4
finish.

ft

in diameter,

Figure 5.1

is

and are usually polished

thin polypropylene film the mirror finish

the film

makes no

The

the film takes

is

not essential, as

real contact with the roll but rides

air film, giving excellent gloss

chill roll.

to a mirror

arrangement. For

a diagram of this

and

clarity,

on an

even from a dull

transition from roll contact conditions, where

on the imprint of the roll surface, to air film

Processing of Polypropylene
condition,

where the

roll

surface

immaterial

is

gross imperfections, depends mostly

111

on

if

thickness, although other factors also influence

has no

it

and

linear speed

film

Thicknesses

it.

below 2 or 3 mils generally run on an air film at speeds

above 100 fpm. High extrusion temperature and high roll
temperature are influences favoring contact, whereas thin film
and high linear speeds favor air-film conditions. Commercial
operations will probably be under air-film conditions, in most
cases, to obtain
roll is

economical production

commonly used

may be

and

single chill

stripper roll

or a steel roll spaced out a httle. Test runs have

been made employing the rubber pressure

roll

The

a siHcone-rubber roll which runs in contact with the

chill roll,

ing. It is

rates.

in this arrangement.

roll

used in coat-

necessary to adjust the point of contact between

been on the

film so that the film has

a foot before the pressure roll hits

it.

have positive cooling on the pressure

hot and stick to the

film.

Some

chill roll

It is also
roll,

or

it

chill

about

necessary to
will

become

coating equipment provides

and

for wetting the pressure roll as

it

leaves the chill

dry before

it

contacts the product.

then squeegeeing

roll,

can also be provided by means of a furnishing

film of water
roll,

it

as in printing.

roller cool. In

These methods can keep the pressure

any event, the pressure

age to the high gloss

of

roller

does some dam-

polypropylene

the

film,

but

it

and
allows considerably higher operating speeds. Depending on
the film and use, it may sometimes be advantageous. As
shown in Figure 5.1, an air knife may also be used to assure
contact of film and roll.
stabilizes

On

improves uniformity of the

a chill-roll casting unit,

the die
roll as

operation,

it

is

desirable to bring

when
it

the

film,

web emerges from

into contact with the chill

soon as possible. The distance between die lips and roll

is determined by the construction of the equipment;

surface
if

possible

it

should be

less

than an inch, and one-half inch

112

Polypropylene

or less

is

with the

even better. The film

roll at the

not generally

will

make

contact

nearest point, except for heavy film, at low

speeds. Thin film run at high speed will not really contact the
roll at all,

an

except at the edges, but will ride

air film, as

previously mentioned.

distance between die and roll

is

One

all

reason

necessary

is

the

way on

why

a short

to prevent the

edges of the film from drawing in excessively, reducing the

usable width and building up a heavy "bead" at the edges.

more severe with polypropylene than with polyits low melt viscosity. Not only does the
narrow excessively, but, under some conditions, the width

This effect

is

ethylene, because of
film
is

extremely unstable. Short gap and high take-up speed favor

stability.

The most important reason why

is essential to have a
and chill roll is that the
clarity and gloss of the film are dependent upon extremely
rapid chilling of the melt from extrusion temperature to some
temperature below the crystaUization point. If the film is
drawn through the air for any considerable distance before
contacting the roll, it cools too gradually, and large crystals
form which make it dull and cloudy.

very narrow gap between the die

The

it

lip

film take-up speeds attainable with polypropylene film

The best film resins, run at recommended temdrawn down to 0.1 mil without tearing off,
high as 500 fpm. Most of the factors that limit

are very high.

peratures, can be
at speeds as

the speed of polyethylene-film casting units do not appear to

affect

much

higher. Poly-

chill-roll

temperatures

polypropylene film until speeds are

propylene permits the use of very low

which give more rapid chilling of the film, and this pushes
the limitation on speed up to higher levels as well. The lower
heat content of polypropylene also serves to reduce the time
required to chill the film to handling consistency.

Horizontal Extrusion. The other general type of equipfor chill-roll extrusion is a development from

ment used

Processing of Polypropylene

113

equipment designed for other thermoplastic film or sheeting,

such as polyethylene, cellulose acetate, butyrate, or styrene.
In this equipment the film
a

down around 180 deg

another pohshed
type

is

or more, where

it

is

Equipment

roll similar to the first.

it

picked up by
of this

There may be as many as four

succession, and then the film goes on to trimming

shown

chill rolls in

extruded horizontally, or just

is

contacts the top of the chill roll and follows

little less. It

in Figure 5.2.

KNIFE
DIE

CASTING^

ROLLS

^TO

>-< r^

Wi NDER
Figure

5.2.

Chill-roll casting, horizontal-extrusion

method.

{Courtesy F. W. Egan Co.)

and

roll up, as

shown. Increasing the number of

rolls assures

a cool film at the take-up and prevents troubles caused by

thermal contraction of the film after

it is

rolled up.

Rolls in this equipment are generally smaller than in the

diameter being common, and

equipment often has a polished roller
above the first chill roll, which can be brought down on the
film. When extruding heavy sheeting this serves to improve
the top surface, but it cannot be used for thin film; 10 mils is
probably the thinnest sheet benefited by the top roller. This
equipment may not be capable of as high speeds as the
previous type because of the smaller chill-roll diameter, but
previous type, 18

in. to 1 ft in

8 in. not unusual. This

it

may make
It

better film.

appears very likely that

roll plants set

up

many

of the high-speed chill-

for the extrusion of polyethylene film will

114

Polypropylene

attain the high

if

web speeds

for

which they were designed only

they are converted to the manufacture of polypropylene

film.

Die Design
Although

slot or

manifold dies of conventional design are

usable for making polypropylene film by the chill-cast method,

there are certain design features that are very important for
successful operation. Figure 5.3,

which

is

adapted from a

drawing of a die cross section furnished by F.

W. Egan and

Figure

5.3.

Cross section of die for extrusion of polypropylene

film. (Courtesy F. W. Egan Co.)

flat

115

Processing of Polypropylene
Co., shows one

way

in

which most of these features can be

obtained.

Die hps tapered

( 1 )

to permit very close

approach

to roll

surface.

Long land and gradual approach to land.

Solid jaw on roll side to make leaks on

(2)
(3)

this

side

impossible.

(4) Die passages streamlined and well finished.

(5) Adjustment perpendicular to land to prevent one jaw
projecting out ahead of the other.

In addition to these features,

that,
is,

provided

it

it

should be kept in mind

has the essential features, the simpler a die

the better. Every joint

is

a potential leak and a potential

source of hang-up. Every unnecessary bolt or screw

of extra maintenance

An

work and down

extrusion die must be

made

is

a source

time.

of high-grade tool steel,

heat-treated to relieve strains at well above the highest ex-

pected operating temperature.

All surfaces in contact with the plastic should be well

and chrome-plated. It is not necessary to poHsh the

smooth but dull surface appears to be
easier to keep clean. The plating must be free from porosity
or pinholes which will catch and hold polymer.
finished

surfaces highly; a

Control of

With

Web

by Air Flow

either type of

stream of

equipment

it

is

desirable to provide a

air to force the film against the chill roll shortly

must be rather low in

and accurately controlled, or it will cause flutter in
the web and will cool the die lips. A well-controlled lowvelocity air stream will, however, stabilize operations and
permit higher speeds in most cases.
The "air-knife" technique is even more effective than the
low-velocity air stream. In this method an air duct is fitted
after

it

velocity

leaves the die. This air stream

Polypropylene

116
with a set of adjustable

lips

which are the same length as the

used and have a narrow opening between them, of

the order of 0.050 in. Air is passed through this duct at
considerable pressure, 5 to 10 psi being common. The narrow
chill roll

jet

or "knife" of air which emerges presses the molten poly-

Figure

5.4.

Commercial

chill-roll casting unit

with

air knife in place.

Die not shown. (Courtesy F. W. Egan Co.)

mer

against the chill

no considerable
knife

is

Much

roll.

Since the volume of air

directed properly, flutter of the

skill is

is

chilling of the die lips results, and,

web

will

not

involved in the use of the air knife, and

small,
if

the

result.

many

have become discouraged because of poor initial results. The

knife must be well constructed of rigid material, and means
for adjusting the position and direction must be accurate and
positive.

The

knife should be directed at the roll surface,

and should

111

Processing of Polypropylene
contact the

web

as soon as practical after the film leaves the

Figure 5.4 shows a

die.

place. It

with the
this is

is

chill-roll

unit with

air

knife

in

quite possible to cut the hot film off entirely

air knife if

blows against unsupported

it

film,

and

perhaps what has discouraged more users than any

if the jet blows directly at the roll

narrow enough to avoid setting up air currents at a distance, no trouble should be encountered. For greatest effect,
the lips of the air knife should be quite close to the film

other difficulty; however,

and

is

surface.

One advantage

of the air knife

development of an

up

is

side of the

web

it

chill

can prevent the

roll and the web

web speeds and down

possible without

polished, a smoother surface

on the

that

between the

air film

to considerably higher

film thicknesses than

is

it.

to thinner

If the roll is

highly

and higher gloss are obtained

that contacts the roll.

Puckering of Film

Good

contact with the chill roll also

venting the very

common

is

effective in pre-

defect of chill-cast film

known

as

puckering or seersuckering.
In extreme cases the appearance closely resembles that of
seersucker cloth. There will be longitudinal strips in the film

which are perfectly

flat,

and between these

be puckered or wavy. This

effect

lines the film will

appears to be due to

differ-

ences in cooling rate caused by imperfect contact with the

Although the air knife will not prevent the formamarks under all conditions, it does appreciably
extend the range of operating conditions over which flat film
can be made.
It should be noted that the linear speeds at which these
defects appear are considerably higher for polypropylene
chill roll.

tion of these

than they are for polyethylene. Early work indicated that

118

Polypropylene

there

would be no puckers

in polypropylene film, but this

was

before the possibility of extremely high linear speeds was discovered.

One

of the reasons for the better performance of poly-

propylene in
is

rial

on the

formation of the puckers

this respect is that the

made much more

serious

by the build-up of oxidized mate-

which causes gauge variations

die lips,

at very

short intervals. These gauge variations contribute greatly to

uneven

With polyethylene these

up very rapidly and are apparent even after

contact of the film.

roll

deposits build

only a few hours of operation.

If

the extrusion

is

uninter-

rupted and at a rapid rate, the amount of oxidation de-

and a reasonable period

do continue to grow, and it is necessary to stop the machine every
few days, at best, in order to remove the accumulation. The
posit tends to stabilize after a while,

of operation

is

possible. Nevertheless, the deposits

tendency of polypropylene to break

rather than a

more

down

to a less viscous,

viscous, material prevents the formation

of these oxidized deposits. Polypropylene-film dies

may be

operated for months without shutdown caused by die deposits.

This not only reduces

down

time and maintenance costs on

the machine but eliminates the progressive deterioration of

film quality

between cleanings.

Gel Streaks in Film

The same

reaction of polypropylene to heat also eliminates

another source of defective film that can be very serious in

the case of polyethylene. If die passages are not perfectly

streamlined, or

if

the inner die surface

is

roughened

in

any

manner, polyethylene may build up oxidized material within

the die or in polymer passages elsewhere in the machine. This
build-up periodically peels

off,

causing streaks in the film.

Polypropylene has no tendency to do

this.

119

Processing of Polypropylene

Gels in Film
It is

not possible at

this

time to form a firm conclusion

regarding the problem of gels in polyproplene film. Gels are

a serious source of trouble in polyethylene film, and they

have generally been attributed to an oxidation cross-linking

phenomenon similar to the one which causes the annoying
surface deposits referred to above.

On

the basis of the fact

that polypropylene does not cross-link in such a manner,

it

has been assumed that the gel problem would be eliminated.

From

time to time remarkably gel-free polypropylene film has

been exhibited, but current production resins do not appear
to be uniformly gel-free. There apparently is some other
mechanism of gel formation in polypropylene, and it cannot
be certain at present how completely these gels can be eliminated.

Flat Film

by the Water-Bath Method

Polyethylene film has long been

material out of a narrow

method has

slit

made by

extruding molten

die into a water bath.

of the largest plants using

it

some such equipment is still in operation.

The first attempts to apply this process
film gave rather

poor

results,

to polypropylene

especially as to appearance.

Further work on the process, however, has shown that,

water tank

This

and several
have closed down; however,

recently been considered obsolescent,

is

carefully baffled

and

rigidly

if

the

supported to pre-

vent the formation of surface wavelets, the water level can

then be brought up very close to the die opening, and this will
produce clear film. The distance between die lip and water
surface required to get this effect is about Va in. Figure 5.5
shows a water bath with necessary baffles in place.
The water carry-over problem that limits the speed of
water-bath polyethylene film appears to be easily controUed

120

Polypropylene

in the case of polypropylene,

and web speeds

as high as those

obtainable in cast film are possible.

Figure

5.5.

Small water-bath film unit showing baffles on water bath

waves in water. (Courtesy F. W. Egan Co.)

to prevent

It should be kept in mind that these speeds are higher than

any obtainable with polyethylene. Generally available machine speeds are the limiting factor, and machines have not

yet been built that will exceed the ability of the resin to ex-

trude and

draw down.

General Considerations in Film Extrusion

Contrary to experience with other thermoplastics, polypropylene extrudes better at the highest screw speed and out-

Processing of Polypropylene

121

Also contrary to other experience, the use of a

pack or other method of producing back
pressure on the screw does not improve the appearance of
put

rates.

restricted screen

polypropylene

film,

nor does

it

steady the operation of the

extruder.

long extruder barrel

is

a greater advantage in poly-

propylene extrusion than in that of any other thermoplastic.

In general, an extruder with a 15:1 ratio of screw length to

diameter will extrude less polypropylene at any given speed

than

it

will, say,

polyethylene. If the ratio of length to diam-

above 20:1, however, quite often the output of polypropylene will be greater than that of polyethylene.
eter

is

The reason for this is that polypropylene shows a sharper

drop in viscosity as it heats up than do most other thermoplastics. This means that the frictional heat build-up is smaller,
so a larger part of the heat required to reach extrusion tem-

peratures must be provided by thermal conductivity from

the cylinder walls. This

is

partly, but not entirely,

compen-

sated for by the fact that polypropylene requires rather less

heat per pound to reach a given temperature than do most

plastics.

ter 2.

This situation was discussed more fully in Chap-

Extrusion temperature for polypropylene film

is

usually

from 525 to 575 F. Below this the film is not clear, and
above 600 F the resin degrades. Table 5.1 shows typical
conditions. One of the most common problems encountered
in

polypropylene-film

extrusion

is

generally

described

surge. This appears as variations in film thickness

as

and can

usually also be observed as variation in film width as

it

is

The normal reaction of those familiar with extruders is to slow down or to put in a heavier screen pack.
These expedients usually make the situation worse, since this

extruded.

variation does not appear to originate in the screw, as such

fluctuations

do with other

plastics,

but in the die

itself,

due

to the low melt viscosity of the material, which does not allow

122

Polypropylene

build-up of enough pressure in the die to estabHsh a positive

flow pattern.

Corrective action

is

to increase extruder speed, lengthen

and decrease the die opening. Die lands of 1 in.

or more are recommended, and lengths below V4 in. are
almost inoperable. A die opening from 15 to 25 mils is genthe die land,

erally satisfactory with a reasonably long land. In addition to

Table

5.1.

Recommended Processing Conditions for

Two Polypropylene Film

Low

Resins

melt index

High

melt

index

Die temperature
Stock temperature
Chill-roll temperature

450-550F
525-550F
550-575F
40-100F

450-550F
500-550F
525-550F
40-100F

Screen pack

None

None

Cylinder temperature

finer

than

100 mesh

Extruder L/D ratio

Die gap (mils)
Die land
Air gap (in.)

finer than
100 mesh

20/1 min
15-25

20/1 min
15-25

V2 to

1 in.

V2 to

1 in.

1/2

Va to

1/2

1/4

to

promoting surge, wider die openings also tend to increase the

unidirectional orientation of the film and aggravate its tendency to tear easily in the direction of extrusion.
Biaxial Orientation

great deal has been said about biaxial orientation of

polypropylene

film.

This consists of drawing the film out

sidewise as well as in the direction of extrusion. Extremely

high film strengths can be developed in this way. Table 5.2

shows how stretching increases the strength of polypropylene

film.

The strength of polypropylene film made by the chill-roll

method is probably adequate for the principal uses it will
have. Chill-roll film may receive a small amount of stretch

123

Processing of Polypropylene
across the web, because, while the film as a whole
firm contact with the chill

when

usually stick to the roll

temperature

remain

and the

in place,

linear-expansion

It

between is stretched. The high

polypropylene makes this

can also be extended somewhat

in

Effect of Stretching on Strength of

Polypropylene Film

5.2.

Ultimate
stretching

the chill-roll

if

it

the film cools, the edges

of

coefficient

stretch appreciable.

Table

film

they touch

As

above 160F.

is

makes no

the edges do, and they will

roll,

(%)

strength

None

tensile
(psi)

Elongation

8,400

500
250

14,000

115

22,400
23,800

40
40

5,600

200
400
600
900

the longitudinal direction by increasing

web

(%)

tension. If the

below 160F, there will generally be

no sticking of the edges and no transverse stretch. Numerous
devices have been suggested for the biaxial orientation of
polypropylene film but only one will be mentioned here as a
chill-roll

temperature

is

guide.

textile tenter is a device

long used in that industry to

control the width of cloth, especially after washing or dyeing

operations.

found

It

consists of a series of clips, not unlike those

at the top of the

common

"clip

board" used to hold

on two endless chains which run on two

These tracks are horizontal and can be arranged so

papers, arranged
tracks.

that the clips grasp the edge of the plastic film as

from the

die or

comes from a cooling

roll.

The

slightly so that the clips pull the film sideways.

it

The

the tracks can be regulated to produce any desired

of stretch,

emerges

tracks diverge

and the whole tenter can be mounted

in

angle of

amount
an oven

124

Polypropylene

which the stretch occurs. This

used to orient other plastic films and should prove

to control the temperature at

device

is

suitable for polypropylene.

SHEET EXTRUSION

made
equipment commonly used

Polypropylene can be
the

heavy sheet by means of

into
to

make impact

styrene sheet.

Extrusion temperature will vary with the kind of polypropylene, but most current resins would require 420 to

550F stock temperatures. Die temperature is preferably 10

to 20 F below stock temperature, and small temperature differences across the die

may be used

to obtain

even flow across

the die, as with other thermoplastics.

Die

lip settings

should be approximately the same as the

desired sheet thickness; a

drawdown not above 10 per

cent

is

permissible.

This equipment generally has three rolls set vertically

above one another, with the sheet passing between the top
two. The upper roll, which is adjustable, should be set to

maintain contact with the sheet, without, however, causing an

excess of material to build

up

in the nip.

build-up in the

nip will cause surface defects in the sheet.

The polypropylene

will generally take the

same

finish as

the roll surface. Its ability to reproduce roll surface

is

con-

siderably greater than that of polyethylene. Roll-surface tem-

peratures are generally 180 to 190F, or just cool enough

to prevent sticking. Cooler rolls will reduce the effect of roll
is glossy the sheet wifl be
and vice versa. The cold roll may
also cause mottUng of the surface and may stiffen the sheet
so that it wrinkles. Various surface finishes or embossed designs are easily produced by modifying the roll surface in an
appropriate way.

the roll surface

surface;

i.e.,

duller

the roll

if

if

is

cool,

125

Processing of Polypropylene
PIPE

AND MISCELLANEOUS EXTRUSION

The equipment used for polyethylene pipe can generally be

used for polypropylene pipe, although the sizes produced on
a die may not be identical for the two materials because
of the difference in flow properties.

monly used

The equipment most comwhich permits

for this purpose consists of a die

the passage of plastic through the annular space between a

central core or pin

and an outer bushing. These dies

only in the manner in which the core

is

differ

supported, which, of

course, determines the flow path of the plastic material.

Two

general methods are used. In the

the core

first,

ported on two or more radial members at

is

sup-

which are
rigidly fastened to the die body. In recent years it has been
more usual to use an offset die in which the pin goes right
through the die body, while the plastic enters on the side,
and turns at right angles. The most important practical difference between the two dies is that the offset die is particu-

and supports the pipe as

it

leaves the die.

Polypropylene, like any other plastic,

the extrusion die,

own

and

it

pipe extrusion

is

is

its

to support

shape.

when

it

leaves

The major problem

and cool the pipe

In the internal-mandrel method the

it

soft

quite incapable of sustaining

is

weight or maintaining

front of

base,

adapted to the use of the "internal-mandrel" method

larly well

of sizing

its

die

its

in

at this point.

pin holds

in

a water-cooled mandrel which supports and cools

and at the same time finally fixes its internal diamis most easily done with the offset-type die, because
this permits water lines to be run through the die core to
the mandrel, without excessive difficulty. This method is very
difficult to operate with heavy-walled polypropylene pipe and
the pipe,

eter.

This

should generally be used only for thin-walled tube.

The other currently popular method is the vacuum sizing

chamber. This method was brought to a high state of de-

126

Polypropylene

velopment in Europe and

is becoming popular here. In this

taken from the die into a water-cooled
metal cylinder, which has a perforated section in its center

method the hot pipe

is

which communicates with a passage that can be evacuated.

By drawing
drawn up

vacuum on

this center section, the soft

close to the walls of the cylinder. This

the outer diameter of the pipe while cooling

where it can be handled.

and sizing pipe are also

Many

it

pipe

method

is

fixes

to the point

other methods of supporting

two are the most

in use, but these

common.
Polypropylene resin makes

method. After the

initial

satisfactory

the pipe

sizing,

pipe by
is

either

carried under

streams of water and immersed in a water tank to cool

it

completely.

In small

sizes,

polyethylene pipe

polypropylene pipe can be coiled the way

is,

but for larger sizes

it

must be cut

into

lengths for transportation.

Extruder cylinder temperatures should be regulated to give

a stock temperature from 375 to 500F, depending on resin

and equipment. Die temperature may be the same

as stock

temperature or slightly above or below. Which gives the

best results

must be determined in each individual case.

3 to 4 in. of water is adequate for maintain-

A vacuum of

ing proper contact with a

vacuum

die.

The cooling water in the internal mandrel may be run

slightly warmer than is generally done with polyethylene, to
prevent premature cooling and seizing.

probably produce

slightly smaller

given mandrel will

polypropylene pipe than

polyethylene, because the polypropylene sets at a higher tem-

perature and therefore shrinks

more on cooling

to

room

temperature.

Most shapes can be made from polypropylene without

much

modification of current practices, but

it

is

generally

127

Processing of Polypropylene

preferable to use longer land lengths, and the approach to

the land must be very gradual.

must be remembered that polypropylene is a considerably stiff er material and sets up more rapidly than polyIt

150

Polyethylene

/
Polyethylene

High density

^^^/

Low density^,''

100

/l
,''

yAv

Polypropylene

50

'^'^''^\
1

TEMPERATURE

Figure

5.6.

Specific heat

v^'.

temperature curves of leading polyolefins

compared.

ethylene. This

means

that the outer skin of a heavy-walled

shape can become so rigid by rapid cooling that

give

when

the interior cools and shrinks.

it

will not

Those who have

extruded styrene or acrylic will understand that shrinkage

causes voids to form in the body of the plastic. In order
to prevent this, the extrusion

must be cooled more gradually.

128

Polypropylene

and gradually moving into

one good method. For some shapes, air flow

Starting out with a hot-water bath

cooler water

is

or contact with cooled metal guides or plates

Polypropylene requires considerably

ethylene because

its

is

adequate.

less cooling

than poly-

heat content (specific enthalpy)

in the critical cooling regions. This

means

lower

is

that cooling

from

a given extrusion temperature to a lower temperature requires

the removal of considerably fewer calories of heat.

capacity
are

is

generally higher

much

As

cooling

frequently the limiting factor in extrusion, outputs

higher.

with polypropylene

in

some

cases,

Figure 5.6 shows specific-heat-content

(en-

thalpy) curves for polypropylene and other poly olefins. Note

particularly that the linear polyethylene has a very

much

greater change in heat content during the critical cooling

when it is changing from the molten state to a rigid

Low-density polyethylene does not change as much,

period
solid.

but

it still

requires a great deal of cooling to bring

point where

it

becomes

it

to the

self-supporting.

EXTRUSION COATING

The

mend

excellent barrier properties of polypropylene recom-

an extrusion coating material.

When polypropylene is used in equipment designed for extrusion coating polyethylene, it is generally possible to have a
good coating operation without excessive trouble; however,
the two polymers are, for all practical purposes, incompatible.

When

it

as

polypropylene follows polythylene in the extruder,

the transition will be better at slow screw speed and low

pressure.

The opposite

transition

is

easier at high speeds

and

high pressure.

The use of an extended die jaw which reduces the gap

between the die lips and the point of contact with the substrate appears to have even more importance with poly-

Processing of Polypropylene

129

propylene than with polyethylene. Provision for heating the

is essential, because otherwise its temperature will
drop below die temperature, and the main purpose of the extension, which is to maintain melt temperature, is lost.

extension

The thermal
ture regulation

polypropylene makes tempera-

sensitivity of

somewhat more

critical.

The usual

relation

of improved adhesion with increased stock temperature

served with polypropylene.

625

is

ob-

stock temperatures in the region

If

650F, which are not unsual with polyethylene,

wiU be obtained, which has excellent adhesion but no value. This
means that the speed, adhesion, thickness, and temperature
balance must be achieved at a somewhat lower temperature
of

to

are used with polypropylene, a blistery coating

with polypropylene. Since the type of resin, residence time at

melt temperature,

etc., all

influence the decomposition rate,

no top temperature can be quoted, but, ordinarily, temperatures of from 575 to 600F will give adequate adhesion
without excessive loss of polymer properties.

Any
until

it

of the famihar techniques for keeping the plastic hot

passes through the nip are helpful. These comprise

heating the an: gap, heating the paper, and the afore-mentioned extended die Hps. In

some

cases,

merely speeding up

As

processors gain ex-

the machine will improve adhesion.

perience with polypropylene,

it

appears probable that very

high speed will be possible. The rec-

economical operation

at

ommendations

machine design

as to

for fihn

making apply

equally well to coating operations.

MONOFILAMENT PRODUCTION
Extruded polypropylene monofilament comprises the seclargest market for the material in this country at the pres-

ond

ent time. Nevertheless, the

number

and information about the process

of producers
is

is

not large,

meager. Most of the

130

Polypropylene

from experimental work reported by

of the Enjay Corp.
The general plan of monofilament extrusion equipment is
shown in Figure 5.7. The extruder used is essentially the same

following information

is

Mclntyre, Craven, and

Figure

5.7.

Heumann

Diagram of Monofilament production

Extrusion die

E
F

B Quench tank

First

Godet

unit

Orientation oven
Second Godet

Spooling unit

as that used for other polypropylene extrusion, except that

the machines are generally smaller.

The

die

is

a straight manifold type, generally similar to the

tee-type die used in

opening

is

openings.

flat

film extrusion, except that the die

not a continuous

The

die openings

slit

but a series of small round

commonly

After the filament leaves the die,

tank containing water.

It

downward.
run through a quench

face

it is

then passes over a set of driven

which determine its initial speed. These are termed

"godets," and it is customary to take several laps around
them to assure that there will be no slippage. From here the
rollers

Processing of Polypropylene

131

filament enters an orientation oven where

its

be accurately controlled, then to another

going faster than the first set.

set of

temperature can

drawing

rolls

This means that the filament has been elongated several

hundred per cent under accurately controlled temperature conditions. This elongation is the most critical part of the process,
as it produces the orientation essential to good strength.
After leaving the second set of pull rolls, the filament may
be annealed by raising its temperature somewhat, either while
maintaining a constant length or while permitting a slight
retraction. This stabilizes

it

against shrinkage, at least

up

to

annealing temperature, without any great loss of strength.

This step

is

omitted in the figure for simplicity, and

be used in some cases. The filament

up. Generally, each filament

is

is

wound on

Monofilaments are relatively coarse

of

from 0.003

denier.

The

0.012

to

denier

grams, of 9,000

from

is

in.

it

may not
wound

then cooled and

a separate spool.

fibers

with a diameter

In textile terms this

is

40

to

1000

a unit which represents the weight, in

of fiber. Textile fibers have a denier of

to 15.

In a typical commercial monofilament setup, a P/i-in. extruder

may

carry a die with 18 orifices. Die orifice

may

vary

somewhat with the size of fiber, but a hole diameter of about

0.050 in. will do for all but the finest fiber. This setup will
produce about

The

5 lb of fiber /hr.

strongest fibers are

made from

resins of high molecular

weight and high isotactic index, or density. Although the com-

now

good fiber, which is

monofilament uses, experimental resins
with higher molecular weight and higher tacticity than those
available commercially have shown that, when special resins
mercial resins

very successful in

for this purpose

can be expected.

available produce

all

become

To

available, considerable

improvement

get the greatest strength, extrusion tem-

perature should be as low as practicable with the available

132

Polypropylene

With a resin of high isotactic index, this will be around

425F.
The quench-bath temperature should be as high as possible
without boiling where the filament enters the water. This is
generally around 120F. Some benefit can be obtained by
adding glycols or other materials to increase the boiling point
resin.

of this bath, but this introduces carry-over problems.

The orientation-oven temperature should be

as high as

possible without melting the fibers. This will be about

350F

with the most suitable resins.

The speed ratio between the two godets is set by the

amount of elongation necessary to obtain full draw of the
fiber. This will vary with resin and processing conditions and
must be determined experimentally. At a given speed on the
first

godet, the speed of the second godet

the fibers start to turn white or break;

it is

is

increased until

then slowed

down

until the fibers are clear again. This gives the point of maxi-

mum orientation and strength.

The
in the

air gap between the die and the surface of the water
quench tank appears to have Kttle effect on the fiber

properties.

Polypropylene

monofilaments,

made

as

recommended

above, show very sharp spots in an X-ray diffraction pattern, which means they have a high degree of axial orientation.
They show a low elongation and little shrinkage below the

temperature at which they were oriented.

POLYPROPYLENE MULTIFILAMENT YARN PRODUCTION

The
yarn

is

difference

multifilament
1

between monofilament and multifilament

only in the diameter of the individual filaments.

is

so

much

finer, 1.5 to

The

6 denier against 40 to

,000 denier for the monofilament, that the entire technology

133

Processing of Polypropylene

is different. The number of holes necessary to make a die that

would take the capacity of even a small extruder would be
entirely impractical to handle. The dies used are called spinnerets and usually consist of a number of very fine holes arranged in a circular pattern. The hole diameter bears about
the same relation to filament diameter as it does in monofilament, which means it may be as small as 0.005 in. for fine
fiber. The small diameter of these holes requires the resin

to be

much

hotter for multifilament production

than for

monofilament production and places a great strain on the

stability of the polymer. A temperature of 650 to 700F is
required, which is well above the point where polypropylene
breaks

down

means

of inert-gas blanketing

The complete exclusion

rapidly.

zation of the polymer

is

is

essential,

of oxygen by
and special stabili-

also needed.

The temperature required

to reduce the viscosity to the

point where the plastic will extrude through such a small

orifice

can be reduced by the use of a solvent, and the means

its removal profoundly affect the nature of the fila-

used for

ment. This

is

one of the ways in which widely

different poly-

propylene filaments can be provided. The solvent

may be

removed by evaporation, merely by passing the hot filament

through heated air. It may also be removed by extraction,
by extruding the filament into a bath which dissolves out
the solvent but does not weaken the polypropylene, and then
drying out the filament. In either case, orientation of the fiber
to

produce

maximum

strength

must be carried out

after

solvent removal.

Linear speeds in these operations are very high, generally

above 1,500 fpm for economical operation.
In spite of these high speeds the amount of material passis quite small, and it is not pracproduce the pressure in a screw extruder. This is

ing through one spinneret

tical to

134

Polypropylene

particularly so since a screw extruder does not operate well

at

such low viscosity. Pressure can be produced by the use of

by a small gear pump.

not practical to wind up the
individual fibers, but the whole group produced from a single
spinneret is assembled together. They are usually given a
twist so that the group of fibers makes a single thread, hence
inert gas at high pressure or

Unlike the monofilament,

the

name

multifilament.

Multifilament

change

it is

its

may be crimped in different patterns to

and may be cut into lengths to pro-

characteristics

duce staple which can be handled by the techniques used for

natural fiber. It may, also, be given coatings of different kinds
to vary

its

handling characteristics.

INJECTION MOLDING OF POLYPROPYLENE

Since the largest present use of polypropylene

is

for injec-

one field where there is plenty of

production experience, and techniques have been developed

tion

molding, this

is

to a considerable extent.

Physical Properties Related to Injection Molding

The

physical properties of polypropylene have been dis-

way

Chapter 2. It is worth while, howwhere polypropylene fits among

injection-molding materials, so that it can be determined what
kinds of articles should be molded from it.
cussed in a general

in

ever, to consider specifically

All molded parts require

some degree

gradation from rigid to flexible

plastic.

Polypropylene

is

is

of stiffness,

a useful

way

and the

to classify a

a relatively rigid plastic, with flex-

ural strength near that of cellulose acetate plastics. General-

purpose polystyrene
polystyrene is slightly

is

much more

more

rigid.

in the stiffness gradation, being

rigid,

This

is

whereas impact

a very useful area

now occupied mainly by

the

135

Processing of Polypropylene
relatively expensive

propylene will permit

The

acetate plastics.
it

wall thickness and retain practically the

should be noted that polypropylene

density polyethylene, with which

over most of

its

Tensile strength, as such,

the

is

it

same

much

is

same range

is

more

stiffness.

stiffer

It

than high-

frequently compared,

rarely a

molding

resin,

major considera-

but polypropylene

in this property as in the previous one.

Surface hardness of polypropylene

more than

of poly-

usable temperature range.

tion in the selection of a

falls in

stiffness

impact styrene of the same

to replace

is

similar to or slightly

that of cellulose acetate or butyrate.

The

poly-

and impact, have a higher surface

hardness. This is one property where the difference between
polypropylene and high-density polyethylene is particularly
styrenes, both straight

striking.

The

surface hardness of polypropylene

is

more than
"R"

twice that of high-density polyethylene on the Rockwell

scale.

This should greatly improve the resistance of the sur-

face to accidental marring and denting. In

some

cases this

hardness range appears to provide more durability than

The

either the harder or softer surfaces.

slight resiUence of

from Ught scratching that so easily

mars the surface of harder plastics, and it does not show indentation from pressure as easily as softer ones. This property has long been understood as an advantage of acetate and
butyrate resins, as against their cheaper harder and softer
competitors. In polypropylene we have the same advantage
at more moderate cost. This must be qualified somewhat bethe surface protects

it

cause the polypropylene part

that very small scratches are

One

is

tures.

Only nylon

is

better.

glossy

visible.

property where polypropylene

other moderately priced plastics

much more

often so

more

is

It is

clearly

exceeds

all

heat-distortion temperaquite significant that the

66-psi heat-distortion temperature of polypropylene

near the boiling point of water. This

means

is

very

that polypropy-

136

Polypropylene

lene not only does not soften appreciably at boiling tempera-

amount of stiffness. This is in

marked contrast to "boilable" polyethylenes which retain
form but have little useful stiffness at the boiling point.
Once the decision has been made that polypropylene would
tures but even retains a useful

make

a useful part, the cost must be considered. In addition

to a relatively

density that

pound

low

it is

would

price

initial price,

polypropylene has such a low

appreciably cheaper per part than the perindicate.

Polypropylene has one property that

tance to the molder, so

was discussed

it is

is of special impormentioned again even though it

earlier in this chapter. This is the fact that

its

specific-heat content does not increase with temperature as

rapidly as that of other polyolefins (see Figure 5.6).

To explain what this means

when going from polystyrene

in a practical

way,

to polyethylene,

all

made

molders,
the dis-

covery that it is necessary to put more heat into a given

weight of polyethylene to get it to some particular molding
temperature, and, conversely, to take more heat out in order
to cool it down again. This, of course, puts greater demands
on the heating and cooling systems of the machine and reduces speed and capacity.

When high-density polyethylene was introduced,

hoped

because of

that,

resistance,

which allows

this capacity loss

trary

its
it

greater stiffness

it had been
and temperature

to be taken out of the

mold

hotter,

could be reduced. Of course, quite the con-

was found that the high-density

was
when it was heated through its melting

was observed, and

it

material was even harder to heat and cool rapidly. This

due to the fact

that,

range, a very sharp increase in specific-heat content occurred.

Therefore,

put into
It

it

relatively

to raise

it

great

amount

of

heat has to be

a few degrees in this range.

might be expected that polypropylene with its very reguwould exhibit a similar need for a great amount

lar structure

137

Processing of Polypropylene
of heat in

its

melting range. This

propylene, because of

its

its

less

it

true.

Poly-

heat input than can polyethylene. Since

molding temperature

polyethylene,

all

can be heated to a higher

tent with increasing temperature,

temperature with

not at

is

lower increase in specific-heat con-

is

higher than that of low-density

does not have a practical advantage over

material in the heat-input requirement, but

it

this

does have a

very valuable superiority over the high-density material.

It

has the advantage in cooling that might be expected. Since

it

can be removed from the mold hotter than can low-density

polyethylene,

it

requires appreciably less cooling.

In estimating the effect of these differences on machine

capacity, it should be kept in mind that, because of the higher
molding temperatures needed and the low density of polypropylene, no advantage in shot capacity or even hourly plastifying capacity can be expected.
very appreciable reduction

in cycle, however,

is

possible because of the faster setting-up

Both the lower heat

amount of cooling needed to

time.

capacity,

which decreases the

and

get to a given temperature,

the higher heat resistance, which permits ejection at a higher

work together to cause rapid setting up. It is

mold an article from polypropylene in half
the time it takes for a high-density polyethylene. This makes
it a much more profitable material to mold.
The viscosity of a polypropylene melt drops sharply betemperature,

often possible to

tween 450 and 525 F, so

it is

best to aim at a molding tem-

perature in this range. Figure 5.8 shows that at

450F

the

sample was softer than the harder of the

two polypropylene samples, but at 550F this was reversed.
The softer polypropylene and the low-density polyethylene

linear polyethylene

show a

similar relationship. This rather sharp viscosity gradi-

ent in the narrow temperature range

concerting to those
useful

when

who

may be somewhat

are not used to

the temperature

is

it.

It is

just right.

dis-

actually very

The main

flow

138

Polypropylene

should occur while the material

is

in the low-viscosity

still

range and should be timed so that the temperature has

dropped out of that range

just as the

mold

fills.

Under

these

temperature conditions, a polypropylene molding shows very

httle

tendency to

flash,

but

fills

the

mold

easily

and

reliably.

450
500
CYLINDER TEMPERATURE "F

Figure

5.8.

Flow

vs.

temperature curves for polyolefins.

This also makes polypropylene very responsive to temperature changes in this region; however,
sensitive,

it

is

not excessively

so normal control fluctuations cause no more

trouble than with other plastics.

can readily be seen that the polypropylene flow curve

a point where the product wifl fiU much more
rapidly than polyethylene, and long flows in thin sections can
easily be made. Generally, cylinder temperatures above
600 F are not recommended for polypropylene, because the
material begins to decompose; however, the very easy flow
It

is

rising to

139

Processing of Polypropylene
of the resin

characteristics

make

higher temperatures un-

necessary.

Another feature of the flow properties of polypropylene

that is very helpful, when understood and properly manipulated,

when

the fact that

is

it is

viscosity

Most
haps

it

its

melt viscosity drops very sharply

caused to flow, and the faster

it

plastics

have

merits a

this

little

its

property to some extent, and per-

description. If a true fluid like water

gives a certain flow at a certain pressure,

fast

flows, the lower

becomes.

under twice the pressure.

It

it

will flow twice as

known

has long been

that

respond to increases in pressure with more than proportional flow increases. It has also been well understood
plastics

that this

more than proportional flow increase

property for obtaining short cycles.

is

a very useful

Acetate formulations

have been modified to increase this property, and such increase has been a major goal in the development of polyethylene resins.
It is

often represented in the form of shear-rate versus

shear-stress curves. In these curves the rate of flow (shear

rate)

is

plotted against the pressure required to produce the

flow (shear stress). Figure 5.9 shows such a curve for poly-

propylene and high-density polyethylene.

slope of the polypropylene curves

phenomenon

tical effect of this

is

melt leaves the sprue and runners, where

and enters the mold

cavity,

melt tends to

up even before

tends to be
the fluidity

Although

mold

stiffen

more
is

this

design,

its

does

make
less

the

it is

moving

rapidly,

speed slows down, the

it

cools at

fluid in restricted areas of the

through a mold, with

larly

where

most needed, and less

should not be taken
it

It is clear that

much greater. The practhat, when a polypropylene

is

all.

Also,

it

mold where

wider openings.
an excuse for poor

fluid in

as

the material flow

more evenly

tendency to spurt ahead irregu-

where there are variations

in the path available to

it.

140

Polypropylene

PRESSURE

Figure

5.9.

Shear-rate-shear-stress curves for polyolefins.

This also means that polypropylene

the

maximum

benefit

signed to obtain

is

ideally suited to get

from the new techniques which are de-

maximum

effective pressure in the

mold.

Melt-Compression Techniques
These techniques are called by various names such as
molding, sequential-impact molding, and

precompression
others.

The

essential feature of these

molding methods

is

that a

placed either in the nozzle or in the gates of the

valve

is

mold

itself.

The

valves are closed

when

the plunger starts

forward and remain closed until full ram pressure has built
up on the plastic behind the valve. The valve is then opened,
allowing the plastic to spurt into the mold under full pressure.

Processing of Polypropylene
In the form called valve gating, the valve
itself.

141
is

in the

mold

In the form called sequential-impact molding, there

are two or more valved nozzles that are opened in sequence

by mechanisms located in the machine itself, each being

opened long enough

after the previous

pressure to have reached a

maximum

one for the

plastic

again.

Plunger

10,000

psi

10 cu in/sec

Granular Region
408, 11.7 cu in.

AVp
Figure 5.10.

AVg

Melt Region
50 Cu in

AVm

+ AVs

Schematic diagram of injection-molding process.

These techniques were, of course, developed for use on

than polypropylene; however, the steep slope

plastics other

of the shear-rate-shear-stress curve of polypropylene

makes

them so valuable,

worth

specifically for this material, that

while to discuss the principles involved.

it is

To understand what

happens during the injection stroke of an ordinary injectionmolding machine. Figure 5.10 should be referred to. Consider a plunger which can produce 10,000 psi at a speed of
10 cu in./sec. Pushing the loose plastic granules in the
feed section of the machine forces them ahead to create
pressure on melted material farther forward, which then flows

through the nozzle and into the

terial

die.

has to be compressed from

final density of the plastic.

its

The

loosely

This will require a displacement

of the piston about equal to one full shot, just to

air.

In addition to

this,

packed ma-

loose bulk density to the

remove the

the melted plastic in the cylinder

is

142

Polypropylene

quite compressible

so that

merely to compress the

much

plunger motion

is

used

plastic.

It is possible to calculate all these factors exactly, but

such calculations are beyond the scope of this book. Suffice
it to say that, to inject 5 cu in. of material, the plunger may

have

to displace

material

is

12 cu

in.

flowing into the

or more. During

mold under

the 10,000 psi which the plunger can produce.

seen, this will

make

this time,

all

a pressure well below

As we have

very inefficient use of the pressure, be-

cause, at the relatively slow injection rate, the response of

the melt to pressure
If,

is

very poor.

instead of following the above sequence,

we move

the

plunger forward with a closed valve in the nozzle, the granules

will

be fully compressed and, as pressure builds up, the melt

be compressed up to the capacity of the plunger.

will also

When

at this point the valve is

flow through the nozzle at

its

opened, material

maximum

through the nozzle exceeds the speed of plunger

compression of the melt

in extremely fast flow at
est possible

will

add

maximum

its

starts to

pressure. If flow
travel, de-

surge of flow, resulting

pressure, taking the great-

advantage of the pressure sensitivity of the melt

viscosity.
filling. In one test reported, the effecwas six times as fast from the precompressed
melt as it was from the same machine used in the conventional manner. This makes possible the filling of thin-wall
sections that would be impossible by older techniques, because the melt would set up before filling was complete. Core
shifting is reduced because the melt viscosity remains so low
that no pressure gradients develop around the core, and weld

This gives very rapid

tive filling rate

lines are eliminated.

Of course
very

much

by the use of
pumps, producing more rapid plunger

similar results could be obtained

larger

Processing of Polypropylene
travel,

but the cost of

this

143

would be very much greater than

the cost of the valving arrangement.

typical valve for this purpose

high-speed hydraulic cylinder. Total

activated by a small

is

movement

of the valve

from full shut to full open is very small and takes something
on the order of 2 milliseconds (msec). The time of opening
can be very accurately controlled, and this gives very precise
control of the

When

amount

of material entering the mold.

using such a system

it is generally unnecessary to
have temperature variation within the mold to control the
flow; maximum coohng can be used to give minimum cycles.

In this respect also, polypropylene

is

especially suited to

take fullest advantage of the technique, because good surface

finish

is

obtained even with a very cold mold.

If

melt tempera-

and pressure is high

enough to ensure smooth filling, a good surface can be obtained with the mold as cold as 60 to 8QF. With precompression molding it may be possible to use a mold as cold
as 40 F with even faster cycles.
ture

is

in the range previously indicated

Shrinkage of Moldings

The average shrinkage

of polypropylene

(0.01 to 0.02 in./in.). This

is

less

linear or low-density polyethylene,

times that of polystyrene.

of polypropylene permits

The

but

relatively

quite

is 1

or 2 per cent

than half that of either

still two or three
wide molding range

a considerable control of

shrinkage by changing conditions. In most molds there

is

one injection temperature which gives minimum shrinkage,

the shrinkage increasing above or below this. Low mold
temperature and efficient cooling of the mold, high injection
pressure, and longer ram-forward time all reduce shrinkage.
Polypropylene is remarkably versatile in this respect, and
pieces can often be made of it on molds designed for other

144

Polypropylene

plastics,

maintaining dimensional tolerances merely by con-

trolled cooling.

Moldability Area

very informative

way

of

comparing the

relative

ability of various plastics is the moldability-area

mold-

method. The

following data were furnished by Montecatini.

Cycles (sec)

40

50 60 70

High impart polystyrene

Figure 5.11.

30

40

50

60

Polypropylene

70

30

40

50

60

Low-density polythene

Moldability areas of thermoplastics. (Cowr^e^y

Montecatini)

Figure 5.11 shows the moldability areas of high-impact

and low-density polyethylene, using

same machine and the same mold in each case. The

styrene, polypropylene,

the

shaded area represents the range of time-temperature conditions over which satisfactory moldings can be made. The
upper line represents the maximum temperature which can
be used without overheating and decomposing the plastic.
The lower line is the lowest temperature at which the mold

145

Processing of Polypropylene
is

completely

filled.

The

left-hand point of the area

is

the

which a satisfactory molding is possible, and

arbitrarily ended at the right side at a cycle twice

shortest cycle at

the area

is

the shortest cycle.

The shape and

size of the

shaded area give a clear idea of

the relative ease of molding the materials. It can

be seen

not only that polypropylene gives shorter cycles than high-

impact polystyrene but that the temperature range over which

reasonably short cycles are possible

is

much wider

for poly-

propylene.

The low-density polyethylene shows up more favorably in

comparison, but it must be kept in mind that the low-

this

temperature molding range of

this material is of little prac-

use because of warpage and other defects that appear

tical

molded cold. When the molding conditions that

from a production point of view are considered,
polypropylene compares quite favorably with polyethylene.

when

it

is

are practical

Mold Design

Good mold
all

design

is

other plastics, but

worth while
it

is

not at

mold. Polypropylene molds well in

two and

mold

in polypropylene, as with

as to type of

all critical
all

conventional kinds of

three plate, hot runner, runnerless, or valve-

gated.

In multiple-cavity molding

it

is

particularly important to

balance runner lengths to each cavity, and to have equal

cavities per runner.

This goes back to the same pressure

sensitivity of the flow properties. If the

mold

is

unbalanced,

the parts affording the freest flow will receive a disproportionate share of the flow, even

most other

Relatively large runners

down

more

so than

is

the case with

plastics.

{V4- to %-in. diam)

stepped

each branch are desirable, and the cross section

should be as nearly round as practicable. Fine-machined
at

146
surfaces

Polypropylene

on the runners are

surface of the molding

off a polished

better than polished ones, as the

may be marred

if

cooled material

slips

runner surface into the mold.

In small multiple-cavity

work 0.040-

to 0.060-in.

gates

are generally adequate, but large pieces should be given large

Gate land lengths should be kept small, preferably

below 0.040 in.
gates.

Jump

gates, tab gates, or gates in the center of the

of the piece, which are

commonly used

bottom
by

to prevent jetting

impingement of the entering plastic on a mold wall, should

also be used for polypropylene, but this practice does not
differ from that used with other plastics.
Large parts should be multiple-gated, as with other materials, with careful selection of gate locations to minimize
jetting, sinks, weld marks, etc.
Warpage caused by differential shrinkage in large flat
pieces is a problem with polypropylene, but by no means to
the same extent as with polyethylene, and the commonly

known

techniques for minimizing

it

are usually quite suc-

cessful.
It should be kept in mind that it is most advantageous to
mold polypropylene at the highest pressure possible. This
means that mold construction should be very solid to with-

stand the pressure without distortion.

an excellent injection-molding material.

new material he will for
some time be rather doubtful about its molding characteristics. Practically every molder who tries a suitable grade of
polypropylene is very pleased with its performance almost
from the first shot. This does not mean that any of the factors
of good molding practice, described in the previous paragraphs, can be neglected, but it does mean that special problems that come up with many other materials do not arise
Polypropylene

Generally,

when

is

a molder tries a

with polypropylene.

Processing of Polypropylene

147

Fluidization on Heating

There

is

no moisture problem such

countered in nylon or acetate.

One

as that

considered a problem with polypropylene

increase in melt index

when

which

is

en-

been
tendency to

fact that has often

is

its

subjected to heat. This must be

POLYSTYRENE

MINUTES

Figure 5.12.

Change

IN

INJECTION

CYLINDER

in flow with increased holding time in injection

cylinder.

kept in mind

when molding polypropylene.

It

does, for in-

it is by no
means the new or special problem that people have implied.
The ability of polyethylene to withstand prolonged heating
without increase of fluidity is seldom required and it is, at

stance,

best,

somewhat

limit the reuse of scrap,

but

a doubtful advantage. Polypropylene behaves in this

respect

much

like polystyrene or acetate.

Figure 5.12 shows

the change in spiral-flow distance with cylinder residence

time at 550F.

It is

apparent that the polypropylene samples

148

Polypropylene

are very similar to polystyrene in increasing flow with longer

residence time. Far from being a problem, this tendency to

on prolonged heating is a great advantage. When

molding polyethylene, the material against the cylinder walls
and heaters (that material which has had the longest heat
fluidize

history)

is

the least fluid; therefore

decompose

until

it

it

tends to stay there and

forms a black crust which flakes

causes black spots in the moldings.

When

off and
molding polypro-

pylene, that material with the longest heat history

more

hence

fluid,

it

is

fresh material. This prevents

heat-transfer
plastic slip

surfaces

more

easily

is

much

rapidly forced out and replaced by

further decomposition, keeps

its

clean and efficient, and

makes

the

through the machine.

Good shutdown practice is still desirable, but the penalty

down a machine hot is half a dozen sloppy paleyellow shots when you start up again which is much better
for shutting

than a whole day of carbonized moldings.

Resin variables as well as machine variables affect the

molding of polypropylene and the properties of the resulting
pieces. Table 5.3 summarizes some of these variables. These
modified to some extent by the parmachine and mold used, but they should give some

effects are, of course,

ticular

guidance.

Machines for Molding Polypropylene

Injection-molding machines are
panies and in

many models and

chine for molding polypropylene

ciples as for

pends on the
in

mind

that,

any other

plastic.

made by numerous comThe choice of a ma-

sizes.
is

The

size of the shot to

based on the same prinsize of the

be molded.

It

machine demust be kept

because of the low density of polypropylene,

a molding machine will not be able to produce as heavy a

shot as

it

would of a denser

plastic.

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150

Polypropylene

The

special advantage gained

by

fast injection

makes

it

very desirable to use a machine with a fast injection speed

and capable of producing a high injection pressure. This

means that a high clamping pressure is desirable.

also

Sequence of the Molding Operation

The
resin
this

flow of material through the press

is

right to left

pump

The

as follows:

From

right.

feeds through a volumetric feed-measuring

it

into the throat of the cylinder below.

from

is

placed in a feed hopper at the upper

mechanism

A plunger, which travels

under hydrauHc pressure produced by a

machine, pushes the resin granules

in the base of the

into the heater.

The heater

is

encircled

by

electrical

band

heaters which provide the heat necessary for melting the

granules.

The

interior of this heater contains a torpedo or

spreader which distributes the polymer mass into

thin layers for uniform heat penetration.
After being melted in the heater, the plastic

through the nozzle, which

is

located to the

left

relatively

is

forced

of the heater,

into the mold.

powerful, hydraulically operated toggle clamp holds the

mold together while

molding has cooled
the piece is removed.

The duration

the plastic

is

sufficiently,

injected into

the

mold

of each element of this cycle

it.

When

the

is

opened and

is

controlled by

automatic timers, and the temperature of the heater

is

con-

by means of a thermoregulator. In many installations,

positive means for removing the piece from the mold can be
provided. In this case the operation can be completely automatic, requiring the services of an operator only to fill the
feed hopper and remove finished pieces. In large plants, even
these operations are taken over by conveyors, and the plant
requires labor only for adjustment and repairs.

trolled

Processing of Polypropylene

151

THERMOFORMING OF POLYPROPYLENE
This

is

the oldest of plastic processing methods; the cellu-

was thermoformed from plastic sheet in the very

infancy of the plastics industry. Thermoforming was superseded by injection molding 25 years ago, and has only recently resumed an important position among plastic processloid doll

ing techniques.

Thermoforming
ess

is

broad term used

wherein a plastic sheet

contact with a

mold

to

is

to describe

any proc-

heated and then forced into

produce a shaped

article.

It is

dis-

tinguished from blow molding by having cold sheet as a

starting material,

which

is

whereas blow molding

starts

with a tube

usually hot.

As might be expected from its age, thermoforming is a

complex of a tremendous number of special techniques for
special purposes. It is not our intention to go into any considerable number of these here. We will concentrate on a few
that offer the greatest potential for polypropylene.

Vacuum Forming
Most important of these is the complex of related techvacuum forming, where the heated sheet is

niques called

forced into conformity with a die by vacuum. These tech-

vacuum forming, where the sheet is

mold of the proper size. This is perhaps

niques include straight

drawn

into a female

the simplest method, and

is

draw does not exceed one

satisfactory

where the depth of

half the opening.

When

deeper

where
drawn over a male form of the proper shape,
final shaping being assured by vacuum. A hybrid of these is
called drape-assist or plug-assist vacuum forming, in which
the sheet is first stretched into approximate shape by a male
draws are desired,

the sheet

is

it

is

better to use drape forming,

152

Polypropylene

form and then drawn from the male form into contact with
by vacuum.
This group of techniques is extremely versatile and can
make a wide variety of thin-walled shapes. Rapid improvements in equipment for vacuum forming have shortened the
cycles and allowed automatic operation to the point where

a female die

this

method

is

now

often the cheapest

way

of

making a given

piece.

The current resurgence

of

vacuum forming

is

based mainly

on impact styrene sheet, although acrylics, cellulosics,

and vinyls are also used. Polyolefins have heretofore had little
application in this
is

its

ability to

The

field.

make

principal virtue of this process

thin-walled articles. Since this puts a

premium on stiffness of the material, low-density polyethylene

fails on the first count; articles drawn from it simply are not
stiff enough. It was expected that high-density polyethylene
would eliminate this objection because it is so much stiffer.
It was found, however, that this material required excessive
heating cycles. The reason for this can easily be seen in the
heat-content curve of Figure 5.6. Stated simply,

much

it

takes too

heat to raise linear polyethylene to softening tem-

perature.

Polypropylene, as can be seen from Figure 5.6,

improvement

in this respect.

The

is

a great

practical value of this heat-

content difference can be seen in Table 5.4.

Table

5.4.

Heating time (sec /mil)

Heater temp
(F)

Polyethylene
(60 mil)

Polypropylene

Polyethylene
(125 mil)

1200-1125
1100-1025

0.30

0.25

0.32

0.27

0.40

0.33

0.40

0.32

Polypropylene takes

5 to

20 per cent

less

Polypropylene

time to heat to

forming temperature than does linear polyethylene.

similar

Processing of Polypropylene
time saving will also be

made

153

in the cooling cycle. This im-

provement does not make polypropylene competitive with

impact styrene in this respect, but it does narrow the gap.

Figure 5.13.

Modern thermoforming machine. (Courtesy

Auto-Vac Co.)

Pressure Forming

is

Another development in the thermoforming field, which

by no means new but has only recently been incorporated

into high-speed automatic equipment,

is

pressure forming,

where compressed air is used to force the plastic sheet against

the die. Vacuum forming is, by its nature, limited by atmos-

154

Polypropylene

pheric pressure, and no

vacuum can

exert

more than

atm of

pressure on the plastic. In pressure forming, this limitation

removed, and any desired pressure can be obtained. Cur-

is

no
and

rent practice indicates that pressures above 125 psi have

particular advantage, but

up

to this pressure faster cycles,

some cases, better parts can be obtained.

The use of pressure substantially eliminates one very
critical problem usually found in vacuum forming; this is the

in

sagging of the heated sheet. In order to soften a sheet for

forming by vacuum alone,

it

to the point

may

This sag

where

it

it is

sometimes necessary to heat

no longer can support

its

own

weight.

cause folds or wrinkles or merely thickness

The use

makes it possible to form the

and easier to control. This, of
course, also shortens both heating and cooling cycles.
Heavy sheeting is necessarily fed into a forming machine
one sheet at a time, but modern machines are now equipped
variations.

sheet

when

it is

of pressure

slightly stiffer

to roll-feed the lighter gauges.

Polypropylene sheets can be economically thermoformed

in

modern high-speed forming equipment. Figure 5.13 shows

modern automatically controlled forming machine with dual

heaters.

Skin Packaging

Another thermoforming technique having even greater potentialities for

polypropylene application

is

skin packaging.

In this process, articles to be packaged are arranged on a

may be printed for brand identificaand other information. This assembly is then placed on
a perforated plate which can be evacuated from underneath.
A softened plastic sheet is placed over the assembly, and
sheet of cardboard, which

tion

vacuum

drawn. This forces the hot plastic against the

be packaged and against the cardboard backing.
In the case of polypropylene, the hot plastic will adhere to
is

articles to

155

Processing of Polypropylene

cardboard and similar materials quite adequately, without

special treatment of the board or other special techniques.
Since this

method usually

heating time

enough

is

requires film thinner than 5 mils,

not very long and over-all cycles can be rapid

for economical production.

BLOW MOLDING
Development

of Blovs^

Molding

The blow-molded squeeze

bottle

is

the application

many

people consider most characteristic of polyethylene, in spite

of the fact that the

employed

volume used never approached the amount

in other ways.

Linear polyethylene

quickly

showed

adapted to blow molding, even though

it

itself

to

be

well

lacks the resilience

or snapback characteristic needed for a squeeze bottle. Poly-

propylene
resilience

is

also very easily blown, and, because of better

and stress-crack

linear polyethylene in

resistance,

many

it

will

probably replace

applications.

For a long time the development of a blow-molding induswas hampered by a patent condition which
gave a very few relatively large firms an almost monopolistic
control of the industry. These firms were interested only in
making containers and so prevented recognition of the fact
that blow molding is an excellent and economical method
try in this country

of producing hollow articles of

Influence of European

all

kinds.

Equipment

Blow-molding equipment imported from Europe has estabblow-molding industry in this country, and
recent cross-licensing agreements have freed the industry
from the patent difficulties that have heretofore hampered it.
It appears, therefore, that blow molding will account for
much more material in the coming years than previously.
lished a thriving

156

Polypropylene

Polypropylene in Blow Molding

Polypropylene is very well adapted to blow molding. It
has an excellent chance of benefiting from the success of
linear polyethylene in this field.

The thermal

properties of

polypropylene permit considerably shorter cycles than linear

polyethylene allows, and the physical properties are also generally better.

How Blow

Molding Works

AU

blow-molding machines operate on the same principle.

heavy-waUed tube is produced, and, while it is still hot, it
is closed at one end and then inflated with compressed air to
conform to the inside of a hollow mold. The most common
way to produce the original tube, called a parison, a term
derived from glass-blowing practice, is to extrude it, although
some firms utilize injection molding.

Main

DiflFerences

The

Between Blow-Molding Machines

basic problem in using an extruded parison

extrusion

is

is

that

a continuous process, whereas blow molding

is

an intermittent one. The multitude of variations in blowmolding machines results from the different approaches used
to correlate the continuous extrusion with the intermittent

blowing.

The most used techniques

stop

and

start

the

are as foUows:

Some companies

extruder for each parison,

use a continuously operating extruder.

The

first,

most

but

and

still

very popular, means was a direct adaptation of conven-

A series of split molds is carried

around on a circular table which indexes them successively
under the extruder nozzle, where the parison is being formed.
tional glass-bottle blowing.

When

the parison reaches the right length, the

cutting off the parison but holding

it

mold

closes,

in position inside the

157

Processing of Polypropylene

It then indexes to the next position where the parison

blown into conformity with the mold, and at the same time
an empty open mold is placed under the extruder nozzle. At
successive locations the part is cooled and ejected from the

mold.
is

mold.

A minor modification of this method uses only two molds

which are reciprocated between the loading position and a
cooling and ejection position. While a parison is being extruded into one mold, the other one is being cooled, and the
piece

is

ejected just in time for the

mold

to receive the next

parison.

In another

common method

fold leading to a

number

the extruder feeds a mani-

of dies, usually four.

valving

arrangement directs the flow to each of the dies in turn,

forming a parison at one station, and, when it is done, starting another at the next station.

Each mold goes through

and

cycle of closing, inflation, cooling, opening,

the

same place underneath the

die

its

ejecting in

which forms the parison.

In the older machines the parison was pinched shut at the

lower end by the closing of the mold and inflated either

through an

air

hole in the extrusion die or by a needle thrust

through an excess amount of material above the bottle proper,

which had been pinched enough

to collapse the hole of the

parison. Inflation through the die, of course,

in those

machines which stop

plastic flow

is

only possible

through the

die,

by stopping the extruder or by valving the flow.

These methods closely resemble the glass-blowing operation, making the bottle right side up, and result in a bottle
neck that has to go through some sort of finishing operation

either

before use.

More recent machines blow the bottle upside down. The

open end of the parison slips over a pin in the base of the
mold, which is the same size as the desired inside of the
bottle neck. This pin is hollow and is used to inflate the bottle.

158

Polypropylene

When
forms

mold

the

the pin

is

it

closes, the material

which has slipped over

caught between the pin and the closing mold, which

into the exact finished size

and shape of the

bottle

At the same time the parison is cut off by the part of

the mold forming the bottom of the bottle, and this end is
pinched shut by the mold. In this way a bottle is made that is
neck.

completely finished at the end of the cycle and requires no

further operations.

need for pinching the parison in the mold

and having the cut end open to slip over the pin in the bottom
of the next mold requires parisons to be cut twice, leaving a
little piece of scrap which is usually left joined to the bottle
by a thin web of plastic. The machine operator has to pull

The

conflicting

this piece of scrap free of the bottle,

but

this is the

only

finishing operation required.

Special Considerations in BIov^ Molding Polypropylene

Any machines
perform

blow polyethylene bottles will

on polypropylene bottles. The polyprorequire somewhat higher temperatures. It will be
that will

just as well

pylene will

necessary to adjust cycles to obtain the right parison length,

and, of course, a given extrusion die will not give quite the

same weight and thickness to the parison.

The superior strength of polypropylene will make it possible to use thinner walls and less material per piece. Even
though polypropylene is more expensive per pound, it should
make cheaper bottles than polyethylene. This means not only
that polypropylene

that

it

may be

substituted for polyethylene but

should expand markets into

fields

now

held by metal

cans or glass bottles.

Blow Molding

Articles

Other Than Containers

Recent expansion in the blow-molding field has resulted

from the recognition that blow molding is by no means limited

159

Processing of Polypropylene
to bottlemaking but
articles of

many

is

a versatile

kinds.

Many

method

articles

for

making hollow

now made by

injection

molding two halves and fastening them together to make a

hollow part can be blow-molded more conveniently. Toys, in
particular, are very suitable for blow molding; for instance,
doll parts, or the bodies of toy automobiles, blocks, balls,

and a variety of other articles.

A blow-molded article must have some sort of opening
to admit the blowing air, but it need be only large enough
to admit a hollow needle, and can easily be closed up later.

MISCELLANEOUS PROCESSING METHODS

Hot Gas Welding

The

best

way

to

make

tanks and relatively large structures

out of polypropylene, particularly

if only one or a few of

one kind are to be made, is hot gas welding. This technique
has been widely used on rigid vinyl, polyethylene, and other

rigid thermoplastics.

Relatively heavy sheeting Vs

in. and up is cut and welded

by techniques closely resembling those used in

together

metal-plate fabrication.

an oven just warm

enough to make
it lose its shape entirely. With polypropylene this is about
310F, which is considerably hotter than for any other
thermoplastic. This creates a problem where ovens are heated
with low-pressure steam, because they cannot maintain such
a high temperature. Gas or high-pressure steam, however,
Pieces are bent by placing

enough

to

make

them

in

the sheet easily bent, but not

easily reaches this temperature.

After the pieces are cut and bent to the proper size and
shape, they are clamped in jigs to hold the edges together
firmly,

and then welded.

The welding "torch"

consists of a device

which heats a

60

Polypropylene

stream of inert gas to about 700 F.

trically or

contact the plastic.

about Vs

It

may be

either elec-

gas heated; in the latter case the flame does not

welding rod

diameter

made

of polypropylene

both the
rod and the edges of the joint are being heated by the torch.
A butt weld can also be made by heating the two edges of
in. in

is

laid into the joint while

by pressing them against a heated metal bar until

The bar is then removed, and the
edges are pressed together. Either method makes joints that
are quite adequate for sound structural fabrication. Table 5.5

the joint

they are soft and sticky.

Table

5.5.

Weld Values for Butt-Welded "Agile-Prolene"

(per cent of parent material strength)

Material
thickness (in.)

Type weld

Weld value (%)

1/8

l^

Double-V 5 beads
Double-V 5 beads
Double-V 2 beads
Double-V 2 beads

l^

Heated-tool butt

95-100
95-100
85-96
70-85
80-100

V4
1/8

shows results reported by the American Agile Co. on

brand of polypropylene sheet.

their

Machining Polypropylene
machined by regular metalworking
equipment. Tools must be very sharp, and overheating must
Polypropylene

is

easily

be avoided, but, in general, the problems are

with other thermoplastics. This

is

fabricating models, prototypes, or parts

number

will

less severe

a very convenient

than

way

of

where only a small

be required.

Pov^der Techniques

There are several ways in which articles can be made out

powdered polypropylene: flame spraying, fluidized powder
dipping, and the "Engel" process. The first two are methods
of

Processing of Polypropylene

161

of coating metals with a corrosion-resistant layer of poly-

propylene.

Flame Spraying.
pylene

In this technique powdered polypro-

sprayed through a gas flame onto the surface to be

is

coated. Careful regulation of flame temperature

melt the powder to the point where

coating without degrading
coats are necessary to

it.

bond

it

is

needed

to

will flow into a solid

Generally, one or

more base

the polypropylene to the metal.

Atactic polypropylene, or a mixture of atactic polypropylene

with a

little

coat. It

and

it

is

may be used as the base

have the base metal heated,

of the isotactic material,

also advantageous to

must be

free of oil, dirt, or other materials that interfere

with bonding.

Fluidized Powder Dip. In

propylene

this

process powdered poly-

placed in a box, and an inert gas

is

through the powder until

is

blown up

mobile or fluidized state.

Hot metal parts are then dipped into the fluidized powder.
it is

in a

The metal must be hot enough to melt the polypropylene

particles that come into contact with it. The metal temperature and the length of time it is left in the powder determine
the thickness of the coating. After the part has been removed
from the bath,

it

may be

reheated in an oven to smooth the

outer surface of the coating.

"Engel" Process. This

ing large polypropylene

shape
boat

is

is

a very versatile

articles,

method

particularly

for

mak-

those whose

not well adapted for welding, for instance, pleasure-

hulls, bathtubs, etc.

The powder used

in this process does not

have to be

as fine

as in the two previous methods, a fine pourable granule being

suitable.

light

metal mold

is

filled

with powdered poly-

propylene, covered with an insulating cover, and placed in a

heated oven.

It is

heated long enough to cause the desired

thickness of polypropylene to melt and adhere to the inside

of the mold.

162

Polypropylene

The mold

is

then removed from the oven, the excess poly-

dumped

out, and the mold is returned

open to smooth out the inside
surface. An oven temperature around 700F is required for
this process. After the inside has flowed smooth, the mold is
removed from the oven and cooled, and the piece is stripped

propylene powder

is

to the oven, with the top

out of the mold.

It

appears likely that the highly isotactic polypropylene

most other purposes will not be very

powder techniques. The relatively severe temperature treatment causes a breakdown of the polypropylene
which increases its crystallinity to the point where it becomes
quite brittle. Material with a lower isotactic index is more
successful, and improvements in stabilization will probably
which

is

desirable for

useful in these

be made before long.

6.

PACKAGING APPLICATIONS
POLYPROPYLENE-FILM APPLICATIONS

Although polypropylene-film applications are

infancy, people

vinced that

who

market

this

still

in their

are familiar with the material are conis

due for a tremendous growth

in

the very near future.

Film

clarity

(which has always been a

with polyethylene film, in

many

critical

problem

cases determining equip-

ment construction, operating conditions, and choice of resin)

is no problem at all with polypropylene. Before polypropylene
had been commercially available a year, film resins were on
the market that could not only match cellophane in clarity
but even exceed

it.

Polypropylene embraces a wide variety of materials which

differ

much more

than, say, polyethylene,

and

this

means

that

very different films for a wide variety of applications can be

made. The kind that has shown the greatest promise so

far is the clear, stiff film made from the most nearly atactic
grades of polypropylene. When made by the chill-roll process,
these films are as clear or clearer than cellophane and show
greatly superior physical properties.

Although polyethylene film has often been discussed as a

it has never really been that, and
the great volume of polyethylene film has been used in
applications for which cellophane could never be considered.
competitor to cellophane,

163

64

A
is

Polypropylene

breakdown of the packaging market

shown in Table 6.1.
It

and

for polyethylene film

can be seen that fresh produce is the largest category,

not a field where cellophane is a possible

this certainly is

factor.

Many

of the other large categories are also essentially

noncompetitive with cellophane.

Table

6.1.

Consumption of Polyethylene Film

in Packaging

(Millions of Pounds)
End

use

Tobacco

0.5

Candy

4.5

Baked goods
Meat and poultry

3.0
5.5

Snacks

1.5

Frozen foods
Dairy products
Fresh produce
Other foods

6.5

5.5

68.0
5.0

Textiles

12.0

Drugs

1.0

Garment and

shirt

bags

30.0

All others

37.0

180.0

The rapid growth of polyethylene has had a tendency to

make people forget that, of the 600 million pounds of transparent film used in 1958, 400 million were cellophane.
this

two

thirds of the

polypropylene

film.

market that

It is

the natural target for

Unless polypropylene takes a substantial

cannot obtain any real market.

part of

this, it

does

have of doing so?

it

is

What chance

Cellophane users are characterized by a surprising willingness to pay extra money for a better package. A large proportion of the cellophane market is in special premium grades,
which cost more than ordinary cellophane but have better

165

Packaging Applications
properties. It

therefore a great oversimplification to say

is

made cheaper than

that because polypropylene film can be

cellophane

it

will replace

Cellophane holds

its

it.

present position because of the ability

of the cellophane producers to adapt

rial for

and modify

their

mate-

each application. The number of kinds and grades

is

and each one represents a cooperative

effort between the producer and some consuming industry.
Machinery has been designed in a similar manner, so that
the entire equipment and packaging concept of many industries is tied in directly to this one material. The idea that a
saving of a few cents a pound will penetrate this structure is
truly

bewildering,

naive.

On

the other hand, polypropylene film has

other than price.

are

what may prove

where turnover is not rapid

cellophane, and
articles

Its tear resistance is far

much

its

advantages

superior to that of

greatest advantage in

the aging characteristics

better.

Polypropylene film

a better barrier material than

is

many

grades of cellophane; moisture resistance, for instance

much

is

greater.

The advantage cellophane holds

in having

had high-speed

packaging machinery specifically designed for

being lost by the appearance of

it

is

rapidly

new machinery which can

handle polypropylene film just as rapidly.

As

already stated, a few cents a

displace cellophane

from

its

pound premium

will not

firmly entrenched position in the

be assumed that the packagpay 30 to 100 per cent more

for a packaging material that offers no advantages either in
package quality or in operational economy. This is not inpackaging

field,

but neither can

it

ing industry will long prefer to

tended to

mean

that these markets will either inevitably or

rapidly fall to the

propylene

film.

first

person astute enough to make poly-

Penetration will be slow and irregular, and

66

Polypropylene

undoubtedly

many

polypropylene-film manufacturers will be

sadder and wiser before any great volume develops.

The

facts of physical properties

and economies seem

to

point inevitably, however, to a polypropylene-film market as

large or larger than the present cellophane market, and, unlike the polyethylene-film

market,

it

will

be largely carved

out of the present cellophane market. Certain fringe areas

of the polyethylene-film market,

where

are primary considerations, will also

clarity

fall to

and

stiffness

polypropylene.

In addition to the above markets, about 50 million pounds

a year of specialty films such as "Pliofilm," vinyl, saran,

etc.,

These hold their position because of

certain special properties, most of which would probably not
be satisfied by the cellophane-replacement type of polypropylene film under discussion. The versatility of polypropylene
is so great, however, that, as production experience grows, it
seems highly probable that these markets, which are generally
characterized by very high material costs, will also be penetrated in large part by it. Polypropylene film will also open
up many new markets on the basis of its own special
enter the packaging

field.

properties.

Let us

now

consider in a

little

more

polypropylene film will penetrate most

do

this,

detail exactly

a brief review of the advantages which

cellophane

is

where

readily. In order to
it

holds over

in order.

Dried Products
Perhaps the greatest weakness of cellophane is its moisture
Although moisture proofing improves its moisture
resistance, it is still true that cellophane must have a moisture
content within narrow limits for optimum properties. A wide
sensitivity.

variety of dried products tend to

cellophane, causing

it

draw the moisture out of

and break in use. Such

to embrittle

167

Packaging Applications

products are more suitably packaged in polypropylene, for

example
Dried milk
Flour products

Cake,
Rice

biscuit, roll

Dessert powders

Noodles

Powdered starch

Spaghetti

Cellophane
age, to

also limited,

is

packages weighing

packaged

less

by

mix

tendency toward break-

its

than 3

lb.

Materials ordinarily

in larger units are better off in polypropylene.

Specific applications for polypropylene film will

be

dis-

cussed as regards packaging ten major categories of materials,

in the following order:

Baked goods

Dairy products
Miscellaneous food items

Fresh produce
Frozen foods

Textile products

Meat and poultry

Tobacco products

Confectionery

Paper products

we shall assume that

improvements will be made in the handling of
polypropylene film on medium- and high-speed automatic
wrapping machinery. The progress already made in the use
of polyethylene film in such equipment should lead to its
In considering these applications

significant

rapid adaptation to polypropylene. This

of direct-wrap

is

particularly true

and carton-overwrap machinery where the

superior stiffness of polypropylene film, as

compared

make the conversion

handling equipment much less of a problem.
ethylene film, should

It also

to poly-

of cellophane-

seems that the problem involved in sealing poly-

propylene film at high speeds, especially through several

layers as
for

is

necessary for sealing an overwrap, will be solved

many packaging

The problem

applications.

of opening a polypropylene overwrap easily

168

Polypropylene

and conveniently
easy to

also well

is

make polypropylene

on

its

way

to solution. It

film in such a

way

is

quite

as to offer

the "built-in tear tape" feature that has been highly publicized

an advantage of linear polyethylene film. In polypropylene

however, it is a real practical advantage, since it can be
controlled to any degree, or even be eliminated, rather than
being an inherent feature of the film, as it is in linear polyas

film,

ethylene. In general,

problem are found

much more

practical solutions to the

embedded

tear tapes or strings, per-

in

forations, peelable seals, or extruded beads.

It is also assumed that present problems involving Food
and Drug Administration approval for the use of Polypropylene film in contact with food will be solved.
Many of the markets we shall discuss have already been
penetrated to a considerable degree by cast medium- or highdensity polyethylene film and may be shared for a consider-

able time with these materials.

view, however,

many

polypropylene

films

of

them

From

the long-range point of

will ultimately fall largely to

because of their

inherently

superior

properties.

Baked Goods
The baking

industry

is

the largest single market for trans-

parent flexible packaging materials. In the past year about

150 million pounds of flexible packaging materials were used

by this industry. Despite a phenomenal growth in the use of
polyethylene film in this field, and a minor amount of polyfilm, 85 per cent of this was cellophane.
Bread Wrap. Approximately half this amount was used to
wrap bread. Out of 8 or 9 miflion loaves of white bread, only
IVi to 2 million loaves were wrapped in cellophane; the

propylene

remainder are
Since

it

still

waxed-paper wrapped.

has been found that %-mil polypropylene will

handle in bread-wrapping equipment just about as weU as

169

Packaging Applications

1-mil polyethylene or cellophane, polypropylene should be

price-competitive not merely with the

premium wraps but

with waxed paper as well. Under these circumstances

it

should be just a matter of time before the approximately

7 5 -million-pound cellophane market, plus three or four times
this

amount

as a replacement for

waxed paper, should be

available for polypropylene film.

It

should be understood that price

is

by no means the

primary consideration which

will force this revolution.

main consideration
wrapper, and price

superiority

is

used.

is

will

The advantages

the

of

the

The

polyolefin

merely determine which polyolefin

of the polyolefin wrappers are:

(1) Longer preservation of freshness. This means not

only that the consumer receives a superior product but that
life before it becomes unsalable,
and the producer has much more flexibility in scheduUng
production, as he is no longer held to such a brief inventory
period. By extending the production day the output of a
bakery can be substantially increased without added investment; equipment which now stands idle a substantial part of
each day can be operated practically continuously, if desired.
(2) A package which has an inherently "fresh" feel.
Although polypropylene film is stiffer than polyethylene film,
the thinner film that can be used still results in a soft-feeling
package, and the consumer associates this with freshness.
(3) A package which resists accidental tearing.

the product has a longer shelf

(4)

A package

that can be reclosed

by twisting or folding
opened loaves.
preserving flavor and

the film, thus preserving the freshness of

(5) Equal to any other wrapping in

retarding mold.

(6)
brittle.

Can be

stored under refrigeration without becoming

In regard to

this,

much

has been said about the low-

temperature brittleness of polypropylene.

sections of

molded polypropylene become

It is

true that thick

brittle at

low tem-

70

Polypropylene

made

peratures, but film

of selected resins by the chill-roll

technique retains strength and

flexibility

even

at deep-freeze

temperatures.

Wrapping machines, and attachments

now

machines, are

for modifying older

available to use polypropylene film at

v^rapping speeds equal to those possible with any other

material.

At

present

it

appears that the

Food and Drug Administra-

polypropylene film used in wrapping

bread does not transfer anything whatsoever to the bread,
and hence does not come under the food-additive provisions
of the law. Further study will be required to determine if the
tion

satisfied that

is

same
more

bakery products which contain

which might extract material from

fact holds for other

sugar, fats, oils, etc.,

the wrapper.

If

any degree of extraction

is

found,

it

will

be

necessary to identify the material extracted and prove conclusively that

difficult

it

has no potentially harmful

effects.

This

is

task which could delay the use of polypropylene film

in such applications for a long time.

Other Baked Goods. Although bread wrapping is the largwrapping baked goods, more than

est single use of film for

half of the cellophane

packaging of cake,

now used

rolls,

in this industry goes for the

crackers, biscuits,

and miscellaneous

items.

The importance

of impulse buying in these items has

made

the

transparent

package especially valuable. This

by the polymer-coated grades of

market

is

largely served

cellophane which are 30 to 90 per cent more expensive than

ordinary cellophane. This means that the price advantage of

polypropylene film

To

is

even more important.

no penetration of polyolefin
in
large
part to the wide variety
due
films in
purpose,
and
the lack of any single
of equipment used for the
not, as yet, been
It
has
large target, such as bread wrap.
date, there
this field.

is

practically

This

is

found worth while to produce the machines, or adaptations

Packaging Applications

111

of machines, to use polypropylene film in these packages.

The problems

are

no more complex than those involved

bread wrap; as a matter of

fact,

and the common use of cardboard boxes or

speeds,

in

because of lower packaging

trays

under the wrapper, the problems are really much simpler,

and

their solution is

The advantages
erally slower

and

merely a matter of time.

are just as great, and, because of the gen-

less accurately predictable -turnover of

products, the advantages of longer shelf

are even

life

such

more

important. Polyethylene has not been able to penetrate this

field

because the

oils, fats,

and sugars that are present create

a greaseproofness problem. Polypropylene film has inherently

superior greaseproofness which should obviate this difficulty.

The

fact that polyethylene film lacks the gloss

cellophane has also hampered

film has

The

its

and

clarity of

acceptance. Polypropylene

no such problem.

cost advantage of polypropylene film

important in the baking industry because

is

particularly

operates on a

it

very low profit margin, and because the cost of packaging

much

industries.

showed

that,

is

most
recent survey by Modern Packaging magazine

greater part of the sales price than

among

is

true in

the bakers surveyed, packaging costs

ranged from IV2 to 32 per cent of factory

selling price. It

showed that companies packaging the same kind of

goods had very nearly the same cost ratios. These conditions
also

should

make

this industry

move very

quickly into a packag-

ing material showing a cost advantage.

In summary, the baked-goods industry should offer a

market which, even at the present size of the industry, should
take up to about 400 million pounds of transparent films.
There seems to be little reason why the largest part of this
should not eventually be polypropylene film.
It will

require a great deal of time, effort, and money,

however, to develop

this

market. Cooperative programs be-

172

Polypropylene

tween film producers and consumers

be needed to match

will

made by waxed-paper and cellophane

this market. The list below gives a partial

the efforts that will be

producers to retain

enumeration of baked goods that could advantageously be

packaged in polypropylene film.
Bread
Bread crumbs

Cracker meal and crumbs

Poultry stuffing

Fruit cake

Pretzels

Iced cakes

Ice

cream cones
Marshmallow-topped

Cookies
Saltines,

soda crackers

Doughnuts

Sugar wafers

Melba

Zweiback

Rolls and buns

biscuits Muffins

toast

Fresh Produce
is currently the largest market for polyconsumes about 75 miUion pounds a year,
growing rapidly. In certain applications such

Fresh produce
ethylene film.

and

It

this total is

as the potato or carrot bag, polyethylene

Industry practice

is

these commodities,

comparative
at a

is

firmly entrenched.

well established for the use of a bag for

and

difficulty of

this

is

a convenient process. The

blowing polypropylene film puts

it

disadvantage in bag production. This disadvantage, how-

ever,

may be

a temporary one, as high-speed machinery

being developed which will

is

make

a bag out of flat film

economically
one
almost as
as
can now be made out of
tubing. Under these circumstances it seems probable that
the superior clarity and high strength of polypropylene film
will

make

it

polyethylene

possible to replace a considerable part of the

now

used.

There are also many fresh-produce items that do not lend

themselves very conveniently to bagging and which are not

now

very generally packaged.

A partial

list

follows.

Asparagus

Chicory

Cabbage

Escarole

Broccoli

Cherries

Cauliflower

Sweet corn

Green beans
Green peas

Grapes

Kale
Mustard greens

Celery

Packaging Applications

173

Several of these items require packaging rather different

from the usual bag. Irregular shape and size, for instance, is
much more easily compensated for by an overwrap package.
For overwrap, the superior stiffness of polypropylene film will
have a great advantage. Cellophane is hardly a contender in
this field

because of

its

moisture sensitivity.

Table
Average
annual
supply
thousands

Crop

6.2.

Estimated
Estimated

Estimated

potential for

per cent

per cent

pkg

pkg

of lbs

1960

1965

polypropylene
thousands
of pounds

3,379

35

35

4.5

Beans, snap

542

50

2.6

Beets

137

20

50

0.4

Carrots

1,250

90

50

3.9

Celery

1,435

20

40

5.0

Corn

1,339

10

25

2.4

Grapefruit

Apples

1,732

20

20

1.3

Grapes

846

Lemons

589

20

20
20

0.4

10.0

1.3

3,280

50

26

15

20

0.2

Onions, dry

1,785

35

35

2.5

Oranges

4,796

20

20

3.5

parsnips

65

35

35

0.1

Peas, green

66

25

0.8

Potatoes, white

17,158

55

25

7.8

Potatoes, sweet

1,306

30

1.2

Radishes
Tangerines

236
337

75

0.8

30
20

0.5

Turnips

393

50

30

0.5

Lettuce

Limes

Total
Retail level packaging and items not listed

Liners

Estimated total potential for polypropylene

49.5
5.0
5.0

59^5

174

Polypropylene

Another trend in fresh-produce packaging that should

is the tendency to do the packaging

favor polypropylene film

at larger distribution centers rather

The bag
costs

is

than at the

retail level.

a natural package for retail use, since labor

are less important than the

minimum

ability

perform the

to

As

the

operation increases in scale, the labor assumes greater

sig-

operation with a

of special equipment.

and high-speed equipment requiring a minimum of

more attractive. A bag is not, in general, a
good choice for high-speed automatic packaging; overwrap
nificance,

labor becomes

is

usually

distinct

in

more

practicable. This gives polypropylene film a

advantage because

it

has superior handling qualities

such equipment.
In order to

make

a reasonable estimate of the market

available for polypropylene film, detailed estimates of the

1958 polyethylene film consumption for produce packaging

Stokes, United States Department of Agriculture, were studied. Considering the over-all tendency to increase the percentage of produce packaged, and the competitive positions of the various packaging materials, the
estimates in Table 6.2 seem to be reasonable. In view of these
figures, and the fact that the volume of produce shipped is
constantly increasing, it does not seem overoptimistic to
predict a fresh-produce market for polypropylene film in
excess of 50 million pounds within the next 5 years.

made by D. R.

Frozen Foods
Before discussing frozen-food markets for polypropylene
film,

it

is

worth repeating that the often-discussed low-

temperature brittleness of polypropylene does not occur in

thin film,

which retains a great deal of

toughness

down

resin

is

its

to deep-freeze temperatures,

flexibility
if

and

the proper

used and proper processing methods are employed.

The frozen-food market today

includes about

,000

differ-

Packaging Applications
ent items with a yearly
If

we exclude

volume of 6 or 7

175
billion packages.

frozen juices, the packaging of which in poly-

propylene film would require very considerable technological

changes which are not in the immediate offing, the frozenfood retail-packaging market will shape up approximately as
follows
Billions of

packages annually

Produce

Vegetables and fruits

1.5

Precooked foods and specialties

Seafood
Meat, meat products, poultry

0.5

Frozen foods

1.5

2.0

at present are generally

packaged

in a paper-

board carton covered with a printed, waxed-paper wrap. This

is

an attractive package, well adapted to stimulating impulse

buying, but

relatively expensive, wastes space,

it is

and does

not offer very good protection to the contents.

The

protest against the deficiencies of this package has

already started a

movement toward

a polyethylene-bag pack,

especially for the so-called "free running" vegetables such as

peas, corn, carrots, lima beans,

and mixed vegetables.

Unlike the polyethylene bag for fresh produce,

these bags are

made

in continuous sealing

chines which start with

flat film.

and

Machines of

many

filling

this

of

ma-

type are

capable of very rapid, completely automatic operation suit-

With equipment of
and gloss of polypropylene film

able for the large-scale freezing plant.

this sort the superior clarity

should

make

it

a strong contender.

Although this method of packing frozen foods has not yet

achieved any very great volume, it is increasing rapidly. It has
the following strong advantages over present packs
(1)
(2)

It costs

Its

considerably

less.

lighter weight saves shipping costs.

176
(

Polypropylene
3)

The

rolls of film

take up

much

less

space in the plant

than do the cartons and overwrap.

(4)

The consumer can use

part packages and reseal for

further storage.

In addition to the frozen foods

now common,

others are

being investigated that should be very suitable for packaging

in a polypropylene

item.
ing,

The

bag or pouch. Baby foods are one such

amount desired, resealthe freezing compartment with full reten-

possibility of using just the

and storing in
and quality

tion of flavor

is

The

the big feature here.

savings

over glass jars or cans will be considerable.

The

boilable

pouch which can serve both

as container for preparation of the

cates for

some

as

food has had

package and
many advo-

time. Its use has been retarded because of

its

questionable strength retention at boiling-water temperature.

This has, in general, resulted in the use of very expensive

films such as polyester resins. Polypropylene film has

ample

strength at the temperature of boiling water for this application,

and

it is

very likely that the availability of polypropylene

film will spark a big expansion in this line.

Two

other frozen-food items are of interest.

packaging of frozen baked goods, such as

One

is

the

rolls.

This

is

being done, to some extent, with polyethylene

film,

but poly-

already

propylene film would be better.

There

is

development work going on in the freezing of

candies to retain freshness. Polypropylene film has particular

advantages here because of

its

superior resistance to greases.

completely moistureproof package

condensation of moisture

The

on

is

essential to prevent

the candy during thawing.

current polyethylene consumption for frozen foods

is

only 7 or 8 million pounds a year, and polypropylene can

hardly be expected to displace polyethylene entirely. Developments now in progress, however, should raise the total to 25

Packaging Applications

111

or 30 million within 4 years, half of which could go to

polypropylene.

Meat and Poultry

Commercial meat production is at present about 26 billion
pounds yearly, about 16 billion of which is sold as fresh red
meat.

At

the present time about half of

all

fresh meats sold are

prepackaged, mostly from self-selection meat cases, and the

trend

is

to increase prepackaging.

prepackaged meat

Cellophane dominates the

by virtue of special coated grades

which give the meat packer the proper relationship between
moisture control and oxygen transmission. Polyethylene film
is

field

used to some extent, very thin films having desirable pro-

needed strength. "Pliofilm" is also used to a considerable extent in fresh-meat packaging, in spite of its high cost and low oxygen transmission.
tective characteristics but lacking the

It is difficult to

evaluate the position of polypropylene film

in this industry because any large penetration of the

market

depends on the development of films with the desired transmission properties at practicable thicknesses, and also of
better

wrapping and sealing techniques. The great

versatility

of polypropylene leads to the hope that such developments

might be forthcoming, but in

its

present form

it

does not

appear that polypropylene film would be a strong contender.

The

potential market

is

probably above 50 million pounds a

year.

Poultry packaging consumes a good deal of transparent

film, especially

some

relatively expensive products

such as

and "Cry-o-vac." These films have a particularly good ability to conform to the contour of the poultry,
making a very neat and attractive package. Polyethylene film
"Pliofilm," saran,

is

used only to a small extent in spite of

its

lower price, be-

178
cause

Polypropylene
it

does not have

this form-fitting

extent. Polypropylene film

property to the same

can be made with considerably

higher elongation than polyethylene film, and

that a suitable film for this purpose

without

much

it

seems

likely

could be developed

trouble.

Present successful applications of polyethylene film, such

ham, and processed meats, are fully

open to market penetration by polypropylene film because of
its superior appearance and strength.
as with sausage, bacon,

Confectionery

Almost 3

pounds of confectionery products were

last year. About 5 miUion
pounds of polyethylene film were used for packaging it. Polyproduced

billion

in the

United States

ethylene film has almost ideal protective characteristics for

confectionery packaging, but

its

appearance generally leaves

something to be desired. Confectionery depends to a great

extent on impulse buying, and even a little haze in the film

can be an obstacle.

The

superior

gloss

and

make

it

of

clarity

should be an important factor in

this

polypropylene

film

market, and should

possible not only to take over present polyethylene-

film uses but to double or triple this

amount

in a short time.

Paper and cellophane have a large market in the direct

wrapping of hard candies, caramels, and chewing gum. This
apphcation depends on the use of extremely high-speed machinery, some of which can wrap 1,200 pieces a minute. Such
equipment is generally limited to the type of film for which it
is designed, so no rapid replacement is possible. Work to
date, however, shows that polypropylene film has excellent
characteristics for handling

on high-speed machinery, so

it

should be possible to develop suitable equipment. This will

require close cooperation between film producers and machine

179

Packaging Applications

manufacturers.

cellophane a year

manner

this

market now using 35 million pounds of

is

involved.

list

of products

wrapped

in

shown below.

is

Caramels

Lozenges

Chewing gum

Marshmallows

Chocolates

Mints

Hard candy

Jellies

Lollipops

Gum

Hygroscopic types
(butter mints, etc.)

Candy-coated nuts
Peanut brittle
Candy-coated popcorn
Candy sticks and canes

drops

Dairy Products
In

this industry, plastic film is

used mainly for the com-

mercial shipment of dry powdered milk and liquid cream.

Polyethylene

is

generally used. Polypropylene film should be

a strong competitor because of

its

superior strength. This

should permit a reduction of film thickness, which

is

generally

in the 3- to 4-mil range with polyethylene, to 2 mils, result-

ing in a cheaper package with superior handling and sealing

characteristics

is

and equivalent product protection.

The only other major use for plastic film in this industry
in window tops for containers of cottage cheese, ice cream,

prepared salads, and other refrigerated specialty foods. This

now

by polyvinylidine chloride film, used

because of its high gloss, clarity, and toughness. Polypropylene should provide equally good properties at considerably
use

is

largely filled

lower cost.

The

use in this industry should be up to 10

pounds within 5 years, and polypropylene film may
be taking half by that time, with greater percentages later.
total film

million

Miscellaneous

Food Items

wide variety of food items not falling into the previous

be excellent candidates for polypropylene film

classes should

180

Polypropylene

packaging. Without going into detail on each one, the following partial

list is

presented for consideration.

Bouillon cubes (prewrapped)

Dried

Cereals [candy or honey coated,

puffed rice and wheat,

flakes,

and uncooked (oatmeal,

etc.)]

Chocolate (cooking)

Cocoa
Coffee (beans)

Dehydrated foods (eggs, fruits,

soup mixes, and vegetables)
Dessert and drink powders (fruit
drinks,

gelatin,

ice-cream

fruits

dates,

figs,

(apples,

apricots,

pears,

peaches,

prunes, and raisins)

Dried vegetables (beans, peas.

and rice)
Flour (wheat, corn, etc.)
Noodles and macaroni
Nuts (unshelled)
Popcorn (popped, unpopped)
Sandwiches
Sugar

mixes, malted milk, and pud-

Tea

dings)

Yeast (wet and dry)

Dog

food

(dry

and

biscuits

pellets)

must be remembered that the use

of polypropylene film will be contingent upon proving either
that the food extracts nothing from the film or that the substances extracted are harmless. This may delay development
of these fields. The following applications have no such
In

all

food packaging

it

limitations.

Textile Products

The use of transparent-film wrap in the textile field has

grown very rapidly in the last few years, and the future looks
very promising.

Some

of the

tecting the item

from

soiling,

article

(4)

to

low

help selection,
cost,

many

advantages are: (1) pro(2) allowing inspection of the

(3) promoting impulse buying,

and (5) giving the package an appealing

appearance.
Until a few years ago cellophane dominated this market,

Packaging Applications
it

has lost good deal of ground recently, mainly because

its

poor aging characteristics, which give the package a

life. Polyethylene and vinyl film have moved into

but
of

181

short shelf
this

field

in

volume, and polystyrene film has had some

success.

Polyethylene film

is

a major factor in packaging blankets,

sheets, pillowcases, shirts, sweaters, infants' wear, children's

wear, women's gloves, pillows, and draperies.

in

It is also

used

packaging yard goods, men's hosiery, napkins, tablecloths,

pajamas, underwear, and household furnishings.

The use of polyethylene film in these applications has been

hampered by just those characteristics that polypropylene
will improve. These are: (1) gloss and clarity; (2) strength,
especially on heavier articles; (3) stiffness; and (4) the
ability to handle on high-speed machinery.
The film with the above-mentioned characteristics, that
manufacturers have been trying unsuccessfully to get
from polyethylene-film manufacturers, is almost a perfect
description of polypropylene film, and it seems inevitable that
the greatest part of this market will go to polypropylene as
textile

rapidly as suitable film

Vinyl film holds

is

much

available.

of the sheet-

and pillowcase-pack-

aging market because of acceptance a good

when no
aware
seems

many

years ago,

other suitable film was available. Present users are

of. the

changes occurring in transparent

likely that

films,

and

it

polypropylene can easily be a replacement,

because, on an area basis, vinyl film

sive as polypropylene film should

is

almost twice as expen-

be when

it is

available in

volume. There will also have to be some modification of

wrapping machinery.
Considering the advantages of polypropylene film in

this

market, and the rapid rate of growth of the market, 25 million

pounds should be consumed within 5 years. The following

list

182

Polypropylene

some

gives

products suitable for packaging in poly-

textile

propylene film:
Bandages

Hosiery

Blankets

Infants'

Shirts

wear

Shoelaces

Bolt goods

Linens

Sweaters

Children's wear

Tablecloths

Draperies

Napkins
Pajamas

Gauze

Pillowcases

Underwear

Gloves
Handkerchiefs

Pillows

Washcloths
Yarns

Towels

Sheets

Tobacco Products
Cigarettes are by far the most important tobacco product,
and the 40 million pounds of cellophane used yearly to
package cigarettes is a natural market for any new film.

At

this time,

cellophane

is

firmly entrenched in this market,

largely because the extremely high-speed

used are geared to

wrapping machines

this film.

Polypropylene film appears to have the characteristics

necessary to take over this market eventually.

machine-handling characteristics

should

make

Its excellent
it

easy

to

develop the necessary equipment. The protective characteristics

of polypropylene film are superior to those of cello-

phane, and the price should be appreciably lower.

Several million pounds of cellophane are also used as
cigar wrappers

boxes.

should be less
field,

and as over wrappers on five-packs and larger

The problem

of replacing this with polypropylene film

difficult

than that of penetrating the cigarette

because the mechanization of the packaging lines

is

not

market for pouch

material for pipe tobacco. At present, laminates of paper and
polyethylene are used. Polypropylene film should be strong
enough to use without the paper reinforcement, and also
so extreme. There

is

also a small potential

moisture-resistant

enough

such as aluminum

foil,

to

make

unnecessary.

other barrier materials,

183

Packaging Applications

These markets might grow

to 3

or 4 milUon pounds in

5 years.

Paper Products

The number

of packages or units of paper products sold

many

annually totals

The major

billions.

to perhaps half the market,

item,

is toilet tissue.

products are paper wrapped, but certain

packaged

which amounts

In general, these

premium grades

are

in cellophane. Polypropylene film should easily re-

place the cellophane and, because of

its

lower cost, should be

able to extend the market to replace a good part of the paper

wrapping.
Polyethylene film
kins.

Annual

used to wrap quite a few paper nappaper napkins amount to about 500

is

sales of

milUon packages. About a third of these are premium grades

which polypropylene-film wrapping should be immediately adaptable. The remainder of the market is in low-cost
grades which will probably continue to be paper-wrapped
for

for

some

time, purely

on a

A potential market up

cost basis.

20 million pounds should not be

following list gives some paper
products that could well be wrapped in polypropylene film.
to

The

unrealistic in 5 years.

Confetti

Napkins

Cups

Plates

Toilet tissue

Doilies

Sandwich bags

Envelopes
Garbage bags

Sanitary napkins

Towels
Typing paper

Shelf paper

Writing tablets

Gift wraps

Stationery

Tissues

Miscellaneous Items
In addition to the categories discussed above, there are

almost innumerable other items that are regularly sold in

quantity at retail and

wrapped

would therefore be advantageously

in polypropylene film.

Many

of these are

now

cello-

184

Polypropylene

phane wrapped, and many are packaged

in

paperboard

cartons, with or without a film overwrap. In these cases a

better

package can be made

Some

at

lower cost with polypropylene

of these products are

still sold in bulk or packaged in paper. These products should benefit greatly from

film.

the use of polypropylene-film wrapping.

A few of these prod-

ucts are listed below.

Bottle wraps

Friction tape

Rubber goods

Candles
Clay (modeling)
Decalcomanias

Games and

Sanitary items

Glassware
Golf balls
Leather goods
Matches

Deodorants
(unscented)

Dyes (egg and household)

puzzles

Moth

repellents

Slide fasteners

Soap
Sponges
String and twine
Thread

Plastic articles

Tire patches

Flowers, bulbs

Play balls

Tire wrapping

Flowers, cut blooms

Flower seeds

Powder

Wood

Razor and blades

puffs

products

Polypropylene-film applications today are very small in

volume and must be considered experimental, so present consumption figures would be meaningless even if they were
available. Our estimates, therefore, are based on potential
markets and the known properties of polypropylene film,
compared to competitive materials. The timing of the development of these markets depends, to a great extent, on
factors that cannot be assessed accurately at this time. Merely
to give an idea of the magnitude of the market that can reasonably be expected, however, a summary of the previous
discussion

is

presented in Table 6.3.

POLYPROPYLENE BOTTLES

When

was first introduced, it was exwould compete with low-density polyethylene

linear polyethylene

pected that

it

Packaging Applications
for the squeeze-bottle business.

The

stiff er

185
resin should

make

a strong enough bottle with considerably less material, thus

reducing the cost.

It

turned out that linear polyethylene

does not have the resilience necessary for a squeeze bottle.

It

may be

enough, but

stiff

Table

6.3.

it

does not recover

when

squeezed.

Estimated Consumption of Polypropylene

Film in Packaging Uses
Millions of pounds

1965

1970

Baked goods
Fresh produce
Frozen foods
Meat and poultry
Confectionery
Dairy products

80
50
20
20

250
200

10

Textile products

20

40

30
30
80
40
50
200

265

1,020

Tobacco

Paper products
Other

15

Total

We

80
60

have seen in our study of polypropylene properties that

polypropylene has considerably better resilience than has

linear polyethylene. Since

it

also processes well

by the blowing

method, a good quantity of polypropylene should find its way

into squeeze bottles. There is no considerable commercial
output of these bottles in

this

country yet, but

been produced experimentally, and there

production in Europe.

The
feature

is

many have

some commercial

found many uses where the squeeze

The fact that it is both light and
an advantage over glass. Polypropylene

plastic bottle has

is

not

essential.

unbreakable gives

it

has a strength superiority that should give

applications.

Where

cost

is

it

many

of these

a factor, a polypropylene bottle

186

Polypropylene

can be made enough thinner and

to

make

it

will process

enough

faster

the least expensive plastic bottle available. Fig-

ure 6.1 shows a polypropylene bottle.

Where
needed

strength

is

enough

is

a factor, the

less

amount of polypropylene

than most other plastics to give

it

an

advantage.

:^^-^

Figure

6.1.

typical polypropylene bottle.

Powder Co. )

(Courtesy Hercules

Packaging Applications

187

POLYPROPYLENE AEROSOL CONTAINERS

One of the most recent polypropylene applications has

been in aerosol containers. This field has been dominated by
metal cans, and strength considerations have prevented the
use of plastics.

The

wall thickness required to get adequate

strength in a polypropylene aerosol bottle generally

as expensive as the

makes

it

metal can. In some applications, however,

where style and appearance are dominant factors, the design

freedom that is possible in the polypropylene container outweighs economic factors. This is particularly true in smallsized containers, where the material cost is not a great factor,
and in applications where a relatively low pressure gives adequate dispersion of the aerosol.

These considerations have led

to

the

first

use of poly-

Only 7 years
and perfumes were nonexistent, but in
1959 they accounted for 77 per cent of the entire fragrance
market. In terms of the aerosol market, colognes and perfumes accounted for only about 8 to 9 per cent of the total
propylene arerosol bottles in the perfume

field.

ago, aerosol colognes

aerosol containers produced, but, because of the luxury nature of the trade, they constitute about

20 per cent of the

industry's dollar volume.

One
this

of the drawbacks to the use of aerosol containers in

field is

more

that the traditionally fancy

perfume

bottle

is

can be done to an aerosol

can. This is why polypropylene has been able to invade the
field successfully. There are many problems in this field reattractive than anything that

lated to the compatibility of

perfume components with the

polypropylene container, and long

to

test

periods are required

be certain that the scent does not deteriorate on storage;

however, considerable success has been already achieved.

It is

probable that the invasion of the perfume

field

by

polypropylene will be slow and gradual rather than spectacu-

188
lar,

Polypropylene
but, as experience

is

built up,

should be possible to

it

reduce the cost and displace the metal can in

many

aerosol

applications.

POLYPROPYLENE BOTTLES
Polypropylene
field.

It

AND CLOSURES

already well established in the closure

is

has a very valuable combination of characteristics.

where the price is hmited

stamped metal closures and
phenolic caps. Unlike most compression moldings, bottle
caps are manufactured on automatic machinery that is almost
as economical to operate as is injection molding. The very
lowest price range is, at present, not open to polypropylene.
Many consumer items are, however, packaged in ornamental
containers that require a light-colored and attractive closure.
Here polypropylene competes with the more expensive urea
and melamine resins among the thermosets, and with a numThis

a highly competitive

is

by the

field,

availability of inexpensive

ber of other thermoplastics.

The thermoplastics have

closure

field,

a great advantage in the specialty

because the thermosets are limited by the com-

pression-molding technique to relatively plain and simple

The injection-molding technique gives the designer

make the closure any shape he wants,

shapes.

complete freedom to

and

ornament

to

it

in

any way. Injection molding

is

also a

very economical method of molding, and polypropylene reinforces this advantage

by molding

in exceptionally short

cycles.

The

light

weight and high strength of polypropylene

it

possible to compete very favorably

is

so tough and impact resistant that

it

on a price
is

make

basis.

It

superior to poly-

and it is enough stiff er than polyethylene to give it

an advantage here, too. The surface gloss and abrasion re-

styrene,

189

Packaging Applications
sistance are also superior to polyethylene,
resilience so that

of requiring, at most, a

Polypropylene
thermoplastics in

is

and

it

has enough

shares with polyethylene the advantage

it

minimum

of gasketing.

superior to both of the other widely used

its

resistance to solvents

and other envi-

ronmental factors that are likely to cause crazing,

stress

cracking, and other premature failure.

INJECTION-MOLDED CONTAINERS

The

fast

molding cycles possible with polypropylene and

made possible by its strength and stiff-

the thin wall sections

ness

make

it

a very attractive material for injection-molded

containers.
It has already had some success in this field. An injectionmolded ointment or cosmetic jar is currently in production.
This is molded with double walls, so that it closely resembles
the heavy milk-glass jar that has been standard in this field
for many years. It weighs only a small fraction of what the

glass jar weighs, thus saving shipping costs. Its light weight

and impact resistance mean that it can be shipped with much

packing than can the glass jar. Its wide base
makes it very stable in use.
The main jar with its double walls is molded in one piece,
with the hollow wall open at the bottom. A separately molded,
flat, bottom plate snaps into the bottom to close it off.
A wide variety of injection-molded boxes, cases, etc., now
molded in polystyrene will probably gradually be taken over
by polypropylene because of its improved impact resistance.
The main limitation will be in those cases where clear polystyrene is used in order to display the contents. Because of
its crystalline nature, molded polypropylene pieces are not
entirely clear, so that some color or pigment will be necessary
less protective

190

Polypropylene

for an attractive appearance. Since a large part of the boxes

and cases now made

in other resins are colored, this limita-

tion should not be serious.

VACUUM-FORMED TRAYS AND BOXES

Inexpensive, thin-walled yet rigid, vacuum-formed trays

and boxes have been increasing

They

in popularity for

for small packages of jams, jellies, catsup,

more complex shapes they

toys, paints,
unit.

some

years.

are used for food packaging, especially of meats, and

This

is

and the

and the

like, to increase the size

In

is

now

of the sales

and hobby

field

where

offered in "set" form,

many

especially true in the craft

a wide variety of materials

like.

are used to assemble "sets" of

on vacuum-formed plastic trays.

The main materials of construction are impact styrene and
rigid vinyl. These materials give some dissatisfaction, especially breakage in those applications where the package must
support considerable weight.

There

is

a great deal of interest shown in polypropylene by

manufacturers in

this field,

and

tests indicate that it

may

in-

crease the usefulness of these packaging forms.

SKIN

The
rapidly.

display

plastic skin

AND

BUBBLE PACKS

and bubble packs have been growing

They make a very attractive package, with

of contents, and at the same time protect

excellent

the mer-

chandise completely against atmosphere and handling.

It is difficult, at present, to

tirely clear,

drawback

make polypropylene

except in the thinnest gauges. This

in the

is

films en-

a serious

bubble pack, where the merchandise

lies

an

appreciable distance below the film, and where the film has to

be thick enough to be self-supporting.

Packaging Applications

more favorable; thinner

on the item
not visible. The polypropylene

In the skin pack the situation

displayed, a slight haze
film

is

can be used, and, as the film

films

is

ance.

is

191

lies directly

quite glossy, so the package has an attractive appear-

The

fact that

uncoated board can be used as a base for

polypropylene skin packs gives

it

some advantage.

APPLICATIONS OF POLYPROPYLENE
IN THE DURABLE-GOODS
INDUSTRIES
The

fact that

we can even

talk about the use of a plastic

material in the durable-goods industries

the

of

significant

strides

plastic

is,

in itself, evidence

materials

toward greater acceptability in the past decade.

ety of plastics has

shown

in

recent years

have made
wide vari-

that with

the

proper part and design, and under the right conditions, plastics

can be more

and longer

reliable

of any other material.

lasting than a part

made

study of the properties of poly-

propylene leads to the conclusion that

this material

can ben-

from the experience with older plastics, and build a large

market in the durable-goods industries.
Durable goods are divided into two categories producer
durables and consumer durables.
efit

The producer durables consist of industrial-plant machinThey present some of the severest re-

ery and equipment.

quirements on a material found in any application, and the

standards

of reliability

and permanence are the

highest.

Nevertheless polypropylene has already had a very considerable

amount

of acceptance in just this field.

POLYPROPYLENE IN CORROSIVE-CHEMICAL SERVICE

The

strength, rigidity, temperature resistance,

cal resistance of polypropylene naturally

192

and chemi-

recommend

it

as a

Applications in the Durable-Goods Industries

193

material for the production of chemical-process equipment

that

must be

resistant to corrosive chemicals or biological

attack.

The use

of vinyl chloride resins for such purposes received

Germany during World War

great impetus in

II,

and

this

experience has been widely adapted elsewhere since that time.

In the United States polyethylene has been widely used for

such purposes, and the linear polyethylenes extended the

range of usefulness. This long history of successful use of
thermoplastics in process equipment

and a disadvantage

is

both an advantage

new

material seeking to

to polypropylene.

The disadvantage

is

that

it

is

replace other materials which already have a history of success.

The advantage

the parts have been

is

that techniques for the production of

worked

and many designs adapted

Perhaps

out,

to the efficient use of thermoplastics are available.

even more important

is

the fact that engineers and designers

have started to think about thermoplastic components. Until

very recently, the idea that a durable piece of equipment

made out of plastics would not even be considered

by most designers, but excellent service in a variety of very

could be

adverse environments

has changed their thinking in this

respect.

One

of the

equipment

is

main

limitations of thermoplastic processing

the low softening temperature of the material.

Polypropylene extends the usefulness of thermoplastic parts

quite appreciably in this respect.

very

significant

one,

because

it

The

difference

withstands

peratures well above the boiling point, which

ful for

containing boiling-water solutions of

chemicals.

The

is

really a

service

makes

many

it

temuse-

corrosive

superior strength, stiffness, temperature re-

and resistance to stress cracking often make it possible to produce a vessel for some particular service with
considerably less polypropylene than any of the competitive
sistance,

194

Polypropylene

plastics.

For

this

reason the polypropylene piece

may be

ap-

preciably cheaper.

considerable line of standard sizes of tanks

polypropylene
tanks.

is

available.

Figure 7.1

made

of

shows two typical

These have had wide success in the electroplating

in-

dustry as containers for acid and corrosive solutions, and

Figure

in the

7.1.

Polypropylene tanks for corrosive chemical service.

(Courtesy American Agile Corp.)

manufacture of chemical

specialties.

In addition to

tanks, a wide variety of fabricated parts, such as

and

ducts, pipe fittings, etc.,

is

fume hoods

available.

A very interesting piece of chemical equipment that has

been successfully made of polypropylene is a plating tank
complete with an attached fume hood. Electrolytic cells
24 in. ID, 48 in. deep, with a 50-in. over-all height, have
been made, using V^-in material for the shell and a 2-in.
bottom. These cells are reinforced at top, middle, and bottom
and have an outlet welded into the side near the bottom.

Applications in the Durable-Goods Industries

The use

of plastic liners in steel tanks has been

some

practice for

rapidly.

subjected to temperature changes

expansion of the plastic

is

much

is

the fact that the thermal

greater than that of the steel,

leading to buckling and even breaking after

Figure

7.2.

common

where the metal

serious problem in installations

years, in kinds of service

would be corroded

end construction

195

polypropylene liner in a
to allow for expansion.

many tempera-

steel tank, showing open{Courtesy American Agile

Corp.)

ture cycles. A very ingenious solution to this problem was

found by the American Agile Co. The tank involved was
for use in handling sulfuric acid. It was 15 ft long, but
narrow and relatively shallow. Calculations showed that differential expansion in the 15-ft length would lead to variations

up

liner

made

to

%
it

or

1 in.

The high

strength of the polypropylene

omit one of the small sides

accommodating the expansion withshown in Figure 7.2.

entirely practical to

of the steel tank, thereby

out trouble. This

is

196

Polypropylene

POLYPROPYLENE VALVES,

The use

PIPES,

AND

FITTINGS

of polypropylene tanks and industrial containers

it a demand for valves and fittings to
go with

carries with

them.

supply

Figure

is

7.3.

considerable variety of these is available, and the

growing. This is another case where the rapid de-

valve

made

of polypropylene, showing internal con-

struction. (Courtesy Montecatini)

velopment of a polypropylene item was made possible by

previous success with rigid polyvinyl chloride. The two materials are similar

enough

in properties so that valve designs

could be readily adapted, the polypropylene has as its main

advantage much better heat resistance, and throughout most
of the temperature range better impact resistance as well.
Styrene copolymers have also been used for this service, but
their

heat

chloride.

resistance

is

no

better

than that of polyvinyl

Applications in the Durable-Goods Industries

197

Polypropylene should replace these materials even in applications

where temperature

a better valve can be

some advantage
is

made

is

not a factor, simply because

at a

lower price. The vinyl has

pound, but

in cost per

so high that the cost per piece

is

its

specific gravity

higher. It

an

also

is

expensive material to fabricate because of the thermal in-

melt and the fact that

stability of the

means

leases hydrochloric acid. This

its

that

decomposition remolding conditions

are determined mainly by the temperature the resin will stand,

and not by the requirements of economical operation. It also
means that all equipment must either be corrosion-resistant
or be subject to high maintenance costs. The styrene copolymers are more satisfactory molding materials but are high
in cost.

Polypropylene, on the other hand,

into

complex shapes on

density,

is

is

very easy to mold

fast cycles, and, considering its

low

relatively inexpensive to begin with.

Figure 7.3 shows a typical polypropylene valve for industrial use.

Polypropylene Pipe

The

industrial use of polypropylene pipe for corrosive-

liquid service

is

starting,

and

it

appears likely that

it

will

gradually replace rigid polyvinyl chloride and styrene co-

polymers in

and lower

The

this service,

on the

largest

polyethylene.

volume of thermoplastic
This

is

used

supplies, water-well piping,

chemical resistance
its

basis of superior properties

cost.

is

low cost and ease of

in

pipe,

however,

and similar

not a factor. In these applications

installation are important factors. Its

particular advantage, as far as installation goes,

that

it

is

and farm-water
applications where

irrigation

is

the fact

can be readily coiled, so that long continuous lengths

can be transported and laid into position without the use of

198

Polypropylene

couplings. Polypropylene pipe

vantage in

this respect,

because

is

something of a disad-

at

a good deal

it is

cannot be coiled except in the smallest

stiffer

and

sizes. It is also difi&-

cult to join polypropylene pipe with the simple

clamp-type

used for polyethylene pipe.

Polypropylene has entered into

fittings

this field in one respect,

used for joining polyethylene pipe.
These have generally been made of high-impact polystyrene,
but polypropylene fittings are stronger and cost about the

in the

molded

fittings

same. Figure 7.4 shows such

fittings.

Inexpensive and very satisfactory welding techniques are

and it is likely that

main use joined in this manner.
The largest amount of pipe is for domestic water and gas
pipe. Plastic pipe has had no great popularity m these fields,
partly because of the mass of regulations that necessarily
available for joining polypropylene pipe

it

will find its

limit

such uses, but mainly because

all

previous plastic piping

was really marginal in its properties for this service.

Although long-term service proving tests will be required,
it
seems that polypropylene pipe will be entirely satisfactory. For one thing, the heat resistance of polypropylene
pipe is good enough so that it can be used for hot water as
well as for cold. It can also easily be made strong enough to
withstand normal city water pressures.
Since
a

much

it

this time,

maintenance should be

will not rust or corrode,

less serious

problem. As far as can be determined

polypropylene

is

at

completely free of the pinhoUng

or stress cracking, which has been a serious problem with

polyethylene pipe.
It

must be kept

in

mind

that the

problem

with the resin as with the pipe industry

price competition has caused

it

to

adulterating the product with a large

is

itself.

not so

much

Devotion to

adopt the practice of

amount

of scrap

and

off-grade resin. This has resulted in poor pipe which has given

Applications in the Durable-Goods Industries

199

Figure

7.4..

Polypropylene fittings for polyethylene pipe.

Spencer Chemical Co.)

{Courtesy

polyethylene pipe a bad name. Similar lack of foresight could

damage the polypropylene-pipe industry just as seriously.

The fire underwriters have a logical objection to the use
of any thermoplastic pipe in domestic gas service. Obviously,

would melt through and aUow gas

would be very bad. They do not, how-

in case of fire a pipe that

to feed the flames

ever, object to the use of a thermoplastic pipe in the under-

200

Polypropylene

ground portions of gas lines, and cellulose acetate butyrate

pipe has been used in this manner. Polypropylene pipe should
be cheaper and just as satisfactory in this application.
Polypropylene pipe can be threaded and assembled in
the

same way

however,

this

manner, and
in this

The

as

metal pipe,

does not use

it is

its

unlike

polyethylene

pipe;

strength in the most efficient

doubtful that any great volume will be used

way.
industrial use

of polypropylene pipe for corrosive

5^

and should continue to grow. Apphcations

in domestic service will depend upon the development of
new techniques and methods of installation, as well as revision of building codes. These facts, as well as the interests
of metal-plumbing producers and trade unions in maintaining
the present high-labor-cost methods of installing plumbing
will delay the adoption of polypropylene piping and fittings

2|

for a long time.

service has started

There

>5K

is,

however, increasing discontent with the backward

nature of the housing industry, and this will eventually result

an industrialized house where items such

in

as

plumbing

When

be preassembled by production-line techniques.

happens, polypropylene
for

many

is

the most likely

known

this

candidate

of the components.

POLYPROPYLENE IN AIR CONDITIONING

REFRIGERATION

The growth
of

will

all sorts

AND

of air conditioning and industrial refrigeration

has overtaxed available sources of cooUng water

in almost all parts of the country. This has

to reuse cooling

made

it

necessary

water by dissipating the heat to the atmos-

Some sort of cooling tower is the most economical

method for this purpose. Cooling towers today must take
larger and larger cooling loads, and the economics of their
phere.

Applications in the Durable-Goods Industries

201

operation are constantly being subjected to closer scrutiny.

The cooling process

is

complicated by the variability of

the weather, and the fact that the

Figure 7.5.

warm

water being recircu-

Plastic cooling-tower grid packing. {Courtesy

Fluor

Products Co. )

lated through the system

is

an ideal medium for the develop-

ment of microorganisms, algae, bacteria,

The conventional material for a large

etc.

industrial cooling

tower has been redwood. Being a natural organic material,

it

contributed to the inherent troubles of the cooling tower by

202

Polypropylene

adding nutrients for the microflora of the water, and was

itself

deteriorated by the cooUng-tower environment.

This has led to a continuing search for a superior material

for cooling- tower construction.

of the tower
critical,

is

The problem

of the outside

not too complicated, but the packing

because

this really is

is

very

what determines the perform-

ance of the tower.

The Fluor Products Co. has developed

consists of injection-molded grids,

a packing which
which have shown better

than conventional packings. They are currently

molded of polystyrene, but experimental quantities have
been molded of polypropylene, demonstrating that such
a large and complex molding can be made of polypropylene
without difficulty. Figure 7.5 shows a stack of these grids.
efficiency

be expected that the polypropylene grids will be

where the cooling
water may be contaminated with materials that attack polyIt is to

better than the polystyrene in services

styrene. This

is

where
and eventually

particularly the case of refinery service

traces of aromatic hydrocarbons

may

soften

The polypropylene packing

an advantage in cases where the water entering the
tower approaches the boiling point under some conditions.
destroy the polystyrene packing.
also has

This will warp polystyrene grids but will not affect polypropylene.

As long

as polypropylene

than polystyrene

it

where the service

will

is

more expensive

appreciably

probably be used only in those cases

too severe for polystyrene.

is

POLYPROPYLENE IN TEXTILE MACHINERY

wide variety of
not the major
factor. Typical of these is textile machinery. The high humidity required for successful spinning and weaving is very dePolypropylene

industrial uses

is

also being adopted for a

where

its

chemical resistance

is

Applications in the Durable-Goods Industries

structive

to

metal parts, and

many

203

dyeing and finishing

solutions are corrosive in nature. Polypropylene

is

entirely

unaffected by these adverse conditions. Textile processing

is

dependent upon having smooth hard surfaces in

contact with thread and fabric, so that they do not drag or
snag in any way. The low frictional coefficient and abrasion
also very

Figure

7.6.

Textile machinery parts

made

of polypropylene.

{Courtesy Montecatini)

resistance of polypropylene surfaces make them ideal both

from the operational point of view and for freedom from
maintenance problems. In addition, many complex shapes
can be injection molded at much lower cost than they can be
produced by other means.
Some typical examples of polypropylene textile machinery
parts are shown in Figure 7.6. The items pictured are bobbins, spools, separators, spindles, and containers.

204

Polypropylene

ELECTRICAL USES OF POLYPROPYLENE

The

material used in the electrical insulation of wire gen-

erally represents so small a proportion of the total cost of

an

installation that

its

cost

is

a rather minor factor in selec-

expected to

tion. Electrical installations also are

time without failure, which requires any

new

last a

insulation

long

ma-

go through long testing periods before being approved. These factors have delayed rapid acceptance in this
field, in spite of the fact that polypropylene is for many purterial to

poses the best electrical insulating material available.

Polyethylene

owed

its

original

development entirely to its

Polypropylene shares

exceptional electrical characteristics.

these characteristics,

and

in addition has superior strength^

abrasion resistance, and heat resistance.

Because polypropylene ordinarily retains minute traces of

be needed
for high-frequency applications such as coaxial cable, and
catalyst residues, a specially purified grade will

these grades are not yet available.

For most purposes, howwhich is the principal

ever, the slight increase in loss factor,

penalty of these residues,

is

of

no consequence.

used for two main purposes the transmission of electricity for light and power, and for commuInsulated wire

is

nications.

Light-duty Pevsner Wire

The light-and-power category

is

still

quite varied,

and,

and
heavy duty. Light-duty wiring includes all domestic wiring
and those circuits in commercial and industrial installations
which feed electric light and small loads such as for office
machinery. Such wire is now largely insulated with polyvinyl chloride-based insulations. Voltage used is small, genfor purposes of discussion, can be divided into light

205

Applications in the Durable-Goods Industries

220

erally

60

volts or less,

and the frequency is low, usually

loaded enough to operate very

cps. Circuits are rarely

much above room

temperature. In these applications poly-

propylene would permit very considerable economies. In the

place, the simple substitution of polypropylene for poly-

first

same wall thickness would reduce the

vinyl chloride at the

make

weight of insulating material enough to

The

wall thickness, however,

is

cheaper.

it

not determined by electrical

requirements but by purely mechanical ones.

half mil of

polypropylene would adequately insulate against 220

Two

principal mechanical problems require

The

coatings.
stallations

first is

much

volts.

heavier

abrasion resistance. In the larger in-

such wires are pulled through conduits. This pull-

ing abrades

them heavily

at corners.

Polypropylene insulation has a harder surface

and better abrasion

against the conduit walls, especially

and

resistance,

over metal more

slips

easily than polyvinyl chloride insulation. This should

it

possible to reduce coating thickness

when

make

using poly-

propylene.

The
to cut

tions

other mechanical problem

the tendency of the wire

is

through the insulation at corners and in other situa-

where

it

is

under

strain.

Wire can never be perfectly

centered in the insulation; however, the main problem

when

the wire

is

held firmly against a hard object

pushes through the insulation. This

creep,
is

and softening

is

it

is

that

gradually

a combination of simple

as the temperature rises. Polypropylene

resistant to considerably higher temperatures than polyvinyl

chloride. This factor also permits the use of thinner insulations with polypropylene, without increased danger of failure.

Polypropylene

is

somewhat more

stiff

than polyvinyl chlo-

ride of the type used for insulation. Thus,

if

ness of polypropylene were used, the wire

and

less

the same
would be

thickstiffer

easy to handle; however, thinning the wall would

206

Polypropylene

The thinner wall would have the added

advantage of reducing wire diameter and permitting more
wires to be placed in the same conduit. It is even possible
restore the flexibility.

that the better heat resistance of the polypropylene insulation

would permit heavier loading of the circuits without danger,

and so reduce the amount of wire needed.
These things are all, of course, subject to the strictest regulation, and the changes suggested can be made only after
long and careful testing has shown them to be safe.
Appliance Cord

closely related type of wiring

is

the appliance cord, the

wire used to connect a lamp or appliance to the house wiring.

This

is

now

some rubber

generally insulated with polyvinyl chloride, but

is

Equal durability could be obtained

also used.

with considerably less polypropylene;

would

still

be

stiffer.

in this type of wire,

Since flexibility
it is

is

however,

the

cord

a major requirement

doubtful that present types of poly-

propylene would be suitable.

Heavy light-and-power wiring

ter.

This

main

is

lines.

is

an

entirely different

mat-

the wiring used for heavy machinery and for

These

lines are

not insulated with thermoplastics

but with rubber or neoprene, because they are generally more

highly loaded and operate at higher temperatures.

It is

pos-

sible that the improved thermal resistance of polypropylene

will allow polypropylene-insulated wire to

marginal applications of
thermoplastic will take

it

this type,

but

it is

be used in certain
doubtful that any

over altogether.

Communications Wire
Communications wire

is

the other large use of insulated

two general classes the coaxial

cable used for radar, television, and other high-frequency
work, and telephone and telegraph cable. The situation re-

wire. This also falls into

207

Applications in the Durable-Goods Industries

garding the high-frequency applications has already been

discussed.

Telephone and Telegraph Wire

Thermoplastics are used in two different kinds of applica-

and telegraph

tions in the telephone

ing and primary insulation.

polyethylene.

It

industries

The sheathing used

cable sheath-

is,

at present,

serves as a protection for the cable against

both abrasion and moisture penetration. Because of

this,

and the diameter is

large. Polypropylene would undoubtedly afford the same protection with less material, but, even with reduced wall thickness, it would make a stiff cable which would be very difficult
to handle. It could, of course, be made as flexible as polyethylene, but at this stage of development it appears doubtful
that it would have any advantage over polyethylene in this

wall

thicknesses

rather

are

heavy,

form.

Primary insulation of communications wire

divided between vinyl and polyethylene.
polyethylene, which
its

is

is,

at present,

The advantage

gradually replacing the vinyl,

is

of

that

dielectric constant is lower, thus permitting the use of

a thinner insulation.

mined

either

strength.

by

its

The

insulation thickness

electrical resistance or

by

is

its

not deter-

mechanical

thousandth of an inch would give enough

sulation as far as current flow

is

in-

concerned, and primary

is protected by a cable sheath, so it is not subject

any mechanical damage. Insulation is made as thick as it
is simply to hold the wires apart far enough to reduce their
mutual capacitance and prevent "cross talk" in the cable. A
low dielectric constant reduces the distance required for this
purpose, so the insulation can be thinner, and a cable of any
given number of conductors can be smaller.
Polypropylene has a lower dielectric constant than polyethylene, and should have an advantage in this respect. The

insulation
to

208

Polypropylene

advantage

is

a change for

and it may be difficult to justify

purpose alone. The next major change in

small, however,
this

the primary insulation of communications wire will probably

be to the use of foamed insulation. This reduces the dielectric

constant a great deal

more than any

solid insulation.

Polypropylene foam should be a strong competitor in

field,

because of

its

this

superior physical strength. Present tech-

niques do not permit the production of foamed insulation

in the thicknesses required to

much development work

Molded polypropylene
in electrical applications.

is

make

this

an

actuality,

but

going on.

parts also have a great potential

start in this direction

has been

made with a trouble lamp which has a polypropylene handle.

The thermosetting plastics are well entrenched in the electrical field, and for applications where temperatures may be
high, they will certainly retain their places. Polystyrene

is

used for a number of electrical applications where temperature is not a problem, such as switch plates, appUance plugs,
etc.

Polypropylene

much

is

tougher and more heat resistant,

but the difference in price will at

to those applications
quality,

and price

is

first

limit the polypropylene

where a special point

being

is

made

of

of secondary importance.

Polypropylene for Components of

Electronic

Equipment

is an excellent material for coil forms, tube

and many other electronic components. It is comimmune to the effects of dampness which damage
or fiber-based insulation materials, and its heat resist-

Polypropylene
sockets,
pletely
fabric-

ance

is

superior to other thermoplastics.

ing process can

make

and economically.
Figure 7.6,

coil

The

injection-mold-

complex shapes very accurately

form is shown on the far right of

these

209

Applications in the Durable-Goods Industries

I
Electrical Applications of Polypropylene

Film

Both polyethylene and polystyrene found

their

earliest

applications in the electrical field. In this field, superior properties will justfy the relatively

high prices required for the

is no exception
and a considerable amount of polypropylene film has been used, mostly in the form of tapes, for a
variety of electrical applications. These include capacitor dielectrics, cable-barrier tape, layer insulation, and the taping
of coils and foil-wound transformers. The high dielectric
strength of thin films, excellent heat resistance, low dissipation factor, and good winding characteristics have made it

initial

small-scale production. Polypropylene

to this tendency,

quite successful in this field.

The volume involved

in such applications

pared to that in the packaging

field,

but

it

is

small com-

does represent a

growing market for relatively small amounts of the highestquality film.

CONSUMER DURABLES
The consumer durables
people term the American

our possessions that

we

of

life.

They

what

are that part of

expect to last a long time, that

take particular pride in

constitute a great part of

way

we

They are the

and most dynamic industries,

the "big ticket" items.

products of some of our largest

and the envy of the whole world.

The growing importance of plastics

in this field

is

not only

a source of pride for the industry but a real promise of growis already making a contribution
and there is every reason to believe that it
soon be one of the most important plastics for such

ing markets. Polypropylene

in such products,
will

applications.

210

Polypropylene

Polypropylene Applications in Appliance Parts

Despite

its

origin in the metal

appliance industry

is

and mechanical trades the

already a heavy user of plastics, and

growing every day. Impact styrene, vinyls, and

now most heavily used. Polypropylene should add much impetus to this trend, because it will
this

use

is

various copolymers are

provide better parts at lower prices.

Figure

7.7.

Household appliances with polypropylene

parts.

(Courtesy Montecatini)

Typical apphances using polypropylene parts are shown in

Figure 7.7. These are: top

left,

a coffee grinder; center, a

and lower left, a cleaner. All

these have major components made of polypropylene.
The items pictured are European in origin, but similar ones
have been made in this country. For instance, a coffee maker
with a polypropylene pouring lip has been produced. This
replaces a metal lip. The polypropylene lip is more attractive,
immune to tarnish and corrosion, and costs less than the
sterilizer; right,

a hair dryer;

Applications in the Durable-Goods Industries

metal.
coffee

111

The ability to stand repeated contact with boiling

makes polypropylene the best plastic for this use.

Similar considerations resulted in the use of polypropylene

for the silverware container of a

one-piece polypropylene

covered with vinyl

it is

more

scraped
colored

line of dishwashers.

Not only

is this

less expensive;

be cut or

durable, because there

is

no coating

The polypropylene
the way through.

is

corrosion resistant and

to

In addition to the housings which are practical with

plastics,

it

molding replaced a wire basket

plastisol.

off.
all

new

is

possible to

make many

many

of the working parts

themselves out of polypropylene, because of

its

superior

physical properties.

The vacuum-cleaner

polisher and buffer

shown

in Fig-

ure 7.8 has polypropylene-backed brushes as well as housing.

The

great strength of polypropylene

makes

it

possible to use

have heretofore been made of metal,

because the weight of the contents was considered too great
for plastics. The air-conditioner housing shown in Figure 7.9
is a case in point. It can be seen that this is no mere cover,
but the main load-bearing frame of the appliance. Polypropyit

for housings that

lene should permit increased use of plastic housings that are

also load-bearing members. This not only will reduce costs
by decreasing assembly operations, but the reduction in metal
parts will reduce weight and decrease noise.
Other extremely heavy-duty housings being made out of
polypropylene are the hoods for a rotary lawn mower. This
enhances the appearance of the mower, muffles engine noise,
and is extremely resistant to the abrasion, vibration, and
impact experienced in this service. A combination power
mower and outboard motor recently introduced has a poly-

propylene engine shroud. The choice of a thermoplastic for

an application where there are potentially such high temperashows clearly how far superior polypropylene is to other

tures

Polypropylene

212

'

^.__.

Figure

7.8.

Vacuum

m^^M

cleaner-polisher-buffer showing polypropylene

parts.

(Courtesy Montecatini)

Applications in the Durable-Goods Industries

213

thermoplastics. Polypropylene, in this instance, was chosen

for

its

heat resistance, appearance, rigidity, and ease of mold-

ing, after careful consideration of cast

styrene,

aluminum, high-impact

and hnear polyethylene.

Figure 7.9.

Air-conditioner housing of polypropylene. {Courtesy

Montecatini)

Polypropylene has proved to be an excellent material for

fans, both of the propeller type and the squirrel-cage blower.

The

entire blade

one time.
it

assembly can be made in one piece and

Its light

can reach

full

at

weight reduces the inertia of the fan; thus

speed more rapidly, has

less

bearing load.

214
and

Polypropylene
is

much

less

dangerous

the blades. Housing and

made

fingers accidentally get into

if

as well as the blades, can be

grill,

of polypropylene. These fans are quieter than metal

fans, because the polypropylene parts

have less tendency to

and the light weight of the

vibrate in audible frequencies,

rotating parts

makes imbalance

tion-molding method makes

of

problem. The injec-

less of a

economical to produce blades

it

complex shapes conforming

to the best

aerodynamic prin-

ciples, thus increasing efiiciency.

Humidifiers and medicinal vaporizers are another type of

appliance for which polypropylene
corrosion

make metal very poor

plastics are, at best,

being used. Rust and

is

for this service,

marginal where vaporization

plished by boiling water.

Water can be boiled

and other
is accom-

in a polypro-

pylene container without any danger of distortion, discoloration, or

embrittlement with age.

Polypropylene has shown

itself

to

be particularly well

adapted to use in automatic dishwashers; almost every major

dishwasher brand has at least one polypropylene part, and

some have many. The reasons

for this are the resistance of

polypropylene to chemical attack, especially by the strong

detergents used in dishwashing; the good finish obtainable;

high resistance to abrasion; and good impact strength.

Typical polypropylene parts include a molded distributor

arm

in the water-distribution system, the impeller in the

main

water pump, trim rings and grommets, detergent cups, and

rails.

dispensing unit for a floor waxer has also been

out of polypropylene.
tion

and for

its

It

was chosen

for

its

resistance to the solvents used in the wax. It

is quite permeable to
one of the solvents involved, but this is no
this application. Many of the weaknesses of poly-

should be noted that polypropylene

turpentine,

obstacle to

made

ease of fabrica-

propylene turn out not to cause practical problems.

215

Applications in the Durable-Goods Industries

Polypropylene Film for Magnetic Tape

increasing use of magnetic tape for sound recording

The
and

its

potential for television-signal recording will undoubt-

edly create a great market for superior tape material.

Oriented polyester film

this

purpose

mand

now

is

probably the best material for

available, but

its

high price creates a de-

for a less expensive substitute.

Ordinary unoriented polypropylene film

is

much

too exten-

sible for this purpose, permitting signal distortion at slight

differences in tension.
ciently

its

extensibility

ideal tape material

By orienting polypropylene film suffican be greatly decreased. Probably the

would be oriented lengthwise

to obtain

the highest possible strength in this direction. Although such

material

is

not yet in commercial production

it

appears to

be technically feasible and should compete very favorably

in this market.

Polypropylene as Photographic-Film Support

Polypropylene film has a great potential as a photographicfilm support.

Its

stiffness

and strength

characteristics

are

considerably better than those of the cellulose acetate base

now commonly
more

used, and

has the advantage of being

much

and processing chemicals. Polyshould resist the drying and embrittle-

propylene movie film

ment

it

resistant to moisture

that

now

limits the life of

such

film.

In addition,

it

should be appreciably cheaper.

As

with so

many

appUcations, good physical properties

and low cost are not going

to convert the long-established

photographic film industry overnight.

Polypropylene has several drawbacks as a film base, the

most serious of which

adhere to

it.

long, because

is

that photographic emulsion will not

is

not likely to prove an obstacle for very

many

techniques for improving adhesion are

This

216

Polypropylene

known. Work is in progress on this problem, and Montecatini

has obtained a patent on an adhesive layer composed of

amorphous polypropylene which is partially sulfonated or

They claim that this material gives excellent adhesion between gelatin emulsions and isotactic polypropylene film. Abrasion tests are cited to show that the
chlorosulfonated.

gelatin

is

well bonded.

The

existence of a patent does not

necessarily prove that the process will be competitive with

it does mean that promising
seems quite probable that polypro-

presently available methods, but

work has been done.

It

pylene will be a major factor in photographic film in the

future.

Automotive Uses for Polypropylene

In spite of the gradual increase in the use of plastics in
automobiles, this industry has been slow to adopt plastics

on any

large scale.

the greatest

is

There are many reasons for this. One of

and reliability

that the standards of durability

in the automotive field are extremely high. Until recently,

only steel parts could meet these standards. Very few plastics
are able to withstand the severe service requirements.

The automotive

industry in America has, for years, been

extremely conservative. For

this

all its

emphasis on modernity,

has generally been only in matters of

style.

The main

working parts of an automobile have changed very little in

20 years or more, and the materials of construction are likewise unchanged.
To a great extent the American automobile industry
considers itself not as a purveyor of transportation, but rather
as a seller of elegance and prestige. These are, by their
nature, traditional and opposed to changes made in the interests of economy and efiiciency. The success of the small

European car

in recent years has

shown

that the

American

people are tired of spending a large part of their income

Applications in the Durable-Goods Industries

111

merely on a symbol of conspicuous consumption. A lot of

them want economical transportation. Although the "compact
car"

is a start in this direction, Detroit is poorly equipped

compete with low European wages in producing them.
To make a real transportation bargain under American conditions, radical changes are needed. Costs must be cut, especially labor costs, and the clearest road open to the kinds of

to

Figure 7.10.

Motorcycle shock absorber with polypropylene

{Courtesy Montecatini)

parts.

cuts required is to make many of the assemblies

now made
out of numerous metal parts, by means of several operations

on one part

from

one

plastic

part

molded

in

single

European motorcar makers have been quicker

to

adopt

operation.

plastics for functional parts

turers.

than have our

own manufac-

The shock absorbers shown in Figure 7.10 are a case

They are made almost entirely of polypropylene,

in point.

except for the internal steel rod and spring.

Many

other func-

undoubtedly be made of polypropylene before

long. Fiat has a polypropylene fan under development.
tional parts will

218

Polypropylene

The actual motor parts are probably out of reach of polypropylene for reasons of high temperature; and parts in direct
contact with gasoHne, such as fuel lines, pumps, carburetors,
etc.,

made

are better

out of nylon because polypropylene

too readily permeated and softened by gasoline. This

is
is,

however, not as serious a limitation as might be thought.

Body and running gear are the largest part of a car. Direct
load-bearing
that

is

members

will

be

steel for

a long time yet, but

about the only limitation. Various

cellulose acetate butyrate,

plastics, especially

have been used for items in the

car interior, such as steering wheels,

arm

rests,

etc.

The

between polypropylene and

butyrate has been pointed out before. Lighter weight and
similarity in physical properties

lower cost should put polypropylene into these applications.

Polypropylene dashboards have already appeared in Eu-

much

rope and are

better than metal ones, safer for the

passengers in case of accidents, and not prone to rattles and

vibrations.
is

molded

The
in

real

economy

will

come when

one piece, including

all

the entire dash

instrument dials and

the necessary fasteners so that instruments and controls can

be assembled very rapidly and economically. Quite possibly,

can be molded in, thus eliminating the present tangle underneath the dashboard. This archaic and wasteful construction is long overdue for a sweeping redesign,
electrical wiring

and the availabiHty of polypropylene may stimulate the

change.

Automobile air-conditioner ducts, and other parts of the

air-conditioning equipment, have already been

made

of plas-

and are also suitable polypropylene applications. Knobs,

handles, push buttons, switches, window moldings, parts of
seat frames, door liners, and many such items are within the
range of present technology and should improve durability as
well as economy. The strength-weight ratio of polypropylene
is favorable enough to make it possible, when suitable fabritics

Applications in the Durable-Goods Industries

cation techniques are developed, to consider

major parts such

its

219

use even on

body panels.

as

Other applications now under active development include

electrical

lamp

connectors, terminal blocks,

fuse blocks,

horns,

sockets, reflectors, dome-light lenses, etc.

It is

conservatively estimated that 1962 will see 2 to 3 lb

of polypropylene in a new car, which would put 15 to 20

million

pounds

into automotive uses.

Polypropylene Furniture

Many

people see a great future in polypropylene in the

furniture field,

and

this

viewpoint

is

being strengthened by

the appearance of several highly successful items.

One

of the

was in self-stacking utility

shelves. More recently, a bookcase has been introduced. The
combination of good appearance, durability, and low cost
will inevitably bring about an increase in such items. Most
furniture is rather large for injection molding, and this will

first

furniture-like

keep

initial

introduction to relatively small pieces, or to ones

that can be built

pected that
is

applications

up

this will

in sections. It cannot, however,

constantly improving, so that a piece that

jection

molding today

manner

be ex-

always be a handicap, because technology

may be

very

is

large for in-

commonly handled

in

few years.
In addition to the molded pieces mentioned above, polypropylene is appearing as webbing, woven from monofilament. This webbing forms the back and seating of metal
outdoor furniture. Polypropylene monofilaments have weather
this

in a

They also show

summer sun,
frames. The excel-

resistance superior to competitive filaments.

very low residual shrinkage on exposure to hot

thus preventing tightening and warpage of
lent resilience of polypropylene

monofilament and

its

resist-

ance to cold flow keeps polypropylene webbing from deteriorating with time.

220

Polypropylene
very ingenious polypropylene assembly clip for holding

webbing to the frame has been devised. This clip is

molded directly to the end of the piece of webbing, giving
uniform load over the entire width, and eliminating the stress
concentration which causes premature failure when other
methods of fastening are used.

the

8.

APPLICATIONS OF POLYPROPYLENE
IN THE SOFT-GOODS INDUSTRIES

Soft goods include

all

the

many

things

we

use every day

we use up
Although the requirements for many of these
applications are quite severe and entail very special properties, they are rarely as extreme as in the hard-goods field.

that are not expected to last long

and wear

It is

the things

out.

for this reason that polypropylene has not yet penetrated

this field as far as

it

has the hard-goods area. There are

many

other materials that serve reasonably well and, at present, are

cheaper.

It also

more salesmanship

takes

to sell

200 miUion

consumers on the idea of using a new material than it does

to sell the relatively few engineers and executives who can
put the material into a hard-goods item.
This chapter

starts

with a discussion of

fibers.

Many

people

expect this to be the largest single application for polypropylene, yet, except for a rather small

the material

is

practically

amount of coarse fiber,

the American market.

unknown on

POLYPROPYLENE FIBERS
In marked contrast to the rapid growth of the plastics
industry, the textile-industry growth has not even kept

up with

consumption in the
United States has averaged 6 billion pounds a year since
World War II, with rather wide fluctuations but no net

the population

increase.

Textile-fiber

growth.
221

222

Polypropylene

The composition of this total has seen a gradual change,

however, with various synthetic fibers taking an increasing
share of the market, and the natural fibers declining. Despite
the trend toward synthetics, their performance has not been
spectacular. Nylon was the first true synthetic, and its performance has been the best by far. Nylon consumption for
1960 will probably approach 400 million pounds, as compared with about 30 million in 1945. The acrylics may hit
180 million in 1960 after 10 years of intensive effort, and the
polyesters will have achieved markets of only 80 million in
about the same length of time. This is in marked contrast to

the billion-pound total polyethylene achieved in a similar

time. Obviously, markets are not lying

product in
It is

around waiting for a

this industry.

estimated that the development of a

textile fiber costs

new

synthetic

over 10 million dollars, and the promotion

budget needed to make a market for

it is

greater than that.

American Viscose stated that

"in five years we will all be making polypropylene fiber."
While firms other than Montecatini and the Industrial

In spite of

this,

an

official of

Rayon Corp. have been very

quiet about their plans, there is

doubt that practically every firm involved in the synthetic-fiber business is taking a very close look at polypro-

little

With the synthetic-fiber industry operating well

below capacity, none of the producers are eager to launch
a new product and add more capacity unless it is absolutely

pylene

fiber.

essential.

very brief glance at the polypropylene-fiber picture

shows that it
ducers to be

is

going to be essential for synthetic-fiber pro-

in the polypropylene field also. Polypropylene

any synthetic in the market and it has

low specific gravity,
so that the area of goods of any given thickness produced by

fiber

is

as strong as

good abrasion

resistance. It has a very

223

Applications in the Soft-Goods Industries

a

pound

of polypropylene

synthetic or natural fiber.

fiber

is

greater than that from any other

domestic price for polypropylene

yet to be established, but, considering probable

facturing costs,

rayon

is

it

be

will eventually

in the general

manu-

range of

well below the cost of the other true synthetics.

Polypropylene fibers demonstrated by Montecatini show

which makes them very easy to spin

and weave. This is in marked contrast to other synthetics,
which were very troublesome in this respect until special
means of destaticizing them were found. Polypropylene
fabrics are also quite free from the "pilling" that has been
a serious drawback of most synthetics.
The low moisture absorption of the fabric makes it drip
dry readily, and properly designed fabrics will satisfactorily
"wash and wear" without ironing. Like all thermoplastic
fibers, care must be taken not to apply too much heat in
ironing or the fiber will melt; however, Americans are conditioned to this idea by now, and it should cause no trouble.
Polypropylene-fiber cloth can be machine-washed without
damage. Perhaps the most remarkable fact about polypronegligible static effects,

pylene fiber

is its

versatility.

Coarse Polypropylene Fiber for Heavy-Duty Use

Polypropylene monofilament has already achieved a substantial

market

production in

this country. It is the

after the injection-molding industry.

Figure 8.1 shows

some typical polypropylene monofilament.

the markets pioneered

second largest

It is

taking over

by polyethylene monofilament, which

are mainly in the cordage field. It

is

the best available cordage

mooring lines. Being completely immune to rot

and weakening by salt water, a polypropylene rope w^ill outlast a manila fine by a wide margin. Its light weight not only

for marine

facilitates

handling but enables

it

to float

if

accidentally lost

224

Polypropylene

Figure

overboard.

FolypTopylene monofilament (Courtesy Spencer

Chemical Co.)

8.1.

It also dries

water, and retains

its

out rapidly, since

it

does not absorb

excellent handling properties even

when

wet. These advantages are, of course, shared by polyethylene,

but the superior strength and abrasion resistance

make

poly-

propylene the fiber of choice in heavy-duty applications. In

tanker service

it

resistance to oil

has the additional advantage of superior

and grease.

225

Applications in the Soft-Goods Industries

compete favorably with nylon

which makes it
unsuitable for mooring service, has not been such a serious
obstacle in towing work; however, the less extensible polypropylene line has stretch enough to cushion sudden
In towline applications

The

line.

stresses,

but

lene line

it

will

great extensibility of nylon line,

gives better control of the tow. Polypropy-

still

as

is

strong as nylon, considerably lighter,

and

appreciably cheaper.

Table 8.1 compares polypropylene rope with manila and

polyester types.

Ropes were chosen

Table

8.1.

Comparison of Ropes
Breaking

Inches
around

Fiber type

Manila

same

that have about the

strength (lb)

Weight per
ft

(lb)

Cost per
ft

(dollars)

12

105,000

4.36

2.57

Polyester

103,000

2.07

7.90

Polypropylene

81/2

106,000

1.70

3.91

breaking strength. Although the polyester rope has a slightly

smaller diameter,

it is

much

heavier than the polypropylene

rope and a great deal more expensive. The manila rope

much

is

and heavier, which, for many applications, will

outweigh its relatively small cost advantage. This shows
larger

clearly

why

polypropylene

recent development

is

polypropylene cordage. This

Somewhat higher

penetrating this field so rapidly.

the introduction of multifilament

is

is

rope

made up

of fibers as fine

can be obtained in these

very fine fibers, but the main advantage is that the cordage
is much more flexible and easily handled. Polypropylene has
as silk.

tenacities

revolutionized the material base for heavy cordage, and

may

revolutionize the entire technique of manufacturing

it

it

as

well.

Polypropylene monofilament also has applications in chemresistant filter cloths and other heavy-duty fabric
which needs strength and chemical resistance.
ically

226

Polypropylene
highly probable that polypropylene monofilament will

It is

be a strong competitor for

many

of the uses

now

served by

saran and vinyl monofilament, such as automobile seat covers,

insect screens, lawn-furniture covers,

webbing,

etc. Its

much

furniture upholstery,

fighter weight should

to

compete with these cheaper

its

physical properties are far superior.

resins

on a

make

it

possible

price basis,

and

Wool-like Polypropylene Fabrics

In

April,

1957,

Milan

Montecatini

exhibited

polypropylene

These consisted of pure polypropylene, and polypropylene-wool blends; they were indistinguishable in texture, hand, and appearance from pure natural
woolens. Figure 8.2 shows wool-like polypropylene fabrics.
The blanket in the upper left is pure polypropylene, and so
are the hound's-tooth check below it and the modified plaid
at the upper right. The glen plaid in the center is a polypropylene-wool blend.
Everyone who has had an opportunity to handle these

fabrics at the

fabrics

is

Fair.

impressed by their very "natural" feel and texture.

There appears

to

be no reason to expect any consumer

resistance to these materials.

Even

at current prices for poly-

propylene fibers (and they can be expected to decrease as

competition develops), wool-like polypropylene fabrics can be

made less expensively than an equivalent quality of woolens.

The care of these fabrics should be a good deal simpler
than the care of woolens, since they are essentially shrinkproof and unaffected by water, completely inedible to moths,

and immune to mold. They should be extremely durable

because of the high tenacity and abrasion resistance of the
fiber,

and

their heat-insulating value

is

excellent.

As technology and public acceptance

lene should make serious inroads into
appHcations.

develop, polypropythe traditional

wool

Applications in the Soft-Goods Industries

Figure

8.2.

Polypropylene

fiber fabrics.

Montecatini has since extended

its

227

(Courtesy Montecatini)

line of textile materials

wide variety of fibers, and in the form of staple, multifilament, and monofilament yarns suitable for every textileto a

manufacturing operation.

228

Polypropylene

Silk-like

The

Polypropylene Fibers
multifilament yarns

produce fabrics
silk.

Although

are

very

similar

to

silk

and

v/ith the traditional finishes typical of fine

this

market

is

rather limited and has been the

traditional target of synthetics,

it

still

should be taken into

account. Since polypropylene can be expected, before long,

to

compete in the price range of viscose rayon,

readily take

it

should

over a considerable amount of this market.

Rayon, of course, has serious weaknesses, such as its poor

wet strength and general moisture susceptibility. The other
man-made fibers that compete in this field are more expensive
and have properties that do not appear to be superior to those
of polypropylene fiber and this also would seem to be a
fertile field for

polypropylene

fiber.

Polypropylene Fibers Resembling Cotton and Linen

The latest development in polypropylene fibers was introduced by Montecatini in 1959. This consists of polypropylene fabrics, and blends of polypropylene and viscose, that
closely resemble cotton and linen. The synthetics have heretofore kept away from this market, in spite of the fact that
cotton is still the most widely used fiber. This is because price
competition from cotton has made it unattractive. The
ultimate cost of polypropylene fiber should be low enough to
make it possible to compete in this field, and considerable
penetration of the market should be possible even at a considerably higher price.

strength

The polypropylene

and better abrasion

much more

resistance,

fiber has greater

and

it

should be

durable than cotton. Unlike other synthetics, the

polypropylene fibers have no tendency to develop

static

charges.

Montecatini has exhibited

all

of these fabrics in bright, gay

colors. Figure 8.3 shows some examples. The

floral print in

Applications in the Soft-Goods Industries

Figure

8.3.

229

Polypropylene fiber fabrics. (Courtesy Montecatini)

the upper left corner and the period print at the lower right
are

made of 65 per cent polypropylene and 35 per

The floral design at the lower left is 100 per

viscose.

cent
cent

polypropylene.

These fabrics have the cool,

crisp,

hand

characteristics of

230

Polypropylene

cotton and linen and should be well adapted to a wide variety

From the samples

shown, they should make excellent summer clothing for
women and shirts for men, as well as curtains, draperies, and
of characteristic cotton and linen uses.

other uses in the home.

By

use of the proper manufacturing techniques

that polypropylene will be able to

it

appears

compete in any

textile

market.

As with

other synthetic fibers, there are problems con-

nected with the dyeing of polypropylene

fiber,

and Monte-

has been quite successful in solving them. They are

catini

no

essentially

different

from the problems successfully solved

with other synthetics. Polypropylene, being a pure hydro-

carbon

resin,

for dyeing.

does not offer dyes the active

One

sites

of the methods for solving this

monomer

merize a small percentage of

is

necessary
to copoly-

containing an active

grouping with the base monomer. Montecatini has patent

coverage on a number of such combinations. This produces a
polymer that offers the necessary reactive sites for satisfactory dyeing.
fiber

is

It is

probable that

this is the

way polypropylene

rendered dyeable, although other techniques are also

available.

Some

organizations with experience in the dyeing field are

actively investigating,

and soon many others

be offering dyed polypropylene

At

this

time the Industrial

will follow

and

fibers.

Rayon Corp.

is

the only

Amer-

ican firm that has definitely announced plans to produce

polypropylene
trial

fiber.

Since this

applications, they

may

company
feel

specializes in indus-

that they have

sufficient

markets available without a complete answer to the dyeing

problem.

The

technological problems involved and the traditionally

conservative nature of the textile market will prevent very

rapid growth of this market. Fifteen million pounds in 1963

Applications in the Soft-Goods Industries

231

appears to be a reasonable estimate, and it should ultimately

grow to be the largest-volume synthetic fiber, with 500 million
pounds a year or more before the end of the 60's, and the

bilhon-pound goal not impossible.

NONWOVEN

NETTING

Polypropylene has recently been

made

available in the

form of netting which is made from sheeting in the same way

that expanded metal grids are made. Staggered rows of slits
are made in the sheeting, and then, under carefully regulated
conditions of temperature and tension, the sheet is stretched
sideways to expand the slits into diamond-shaped holes.
This material has a wide variety of uses. The fact that it
cannot rust or corrode makes

it

valuable for flooring chicken

or turkey coops, and for decorative fencing around shrubbery

or flower beds.

which the metal

filters,

It is
is

also useful for

used

many

applications for

decorative grids and grids to support

for instance.

Attractive all-through color should be an advantage in the

decorative applications, and as a

filter

support

its

corrosion

resistance should be of importance. It should be a useful

material for the fabrication of wastebaskets, fruit or vegetable

and containers of all sorts. When made from thin sheetwebbing is quite flexible and has possibilities for
conveyor belts, hammocks, and outdoor furniture.

bins,

ing, this

POLYPROPYLENE SHOE PARTS

Plastics

have been associated with the heels of women's

The thin black nitrate

women's shoes dates back to
collar, and survived that piece of

shoes since the start of the industry.

cover on the

wooden

heels of

the days of the celluloid

232

Polypropylene

flammable finery by many years. Up to the time of World

War II, there were many shoe heels covered this way.
The tide had, however, begun to change before that, and
as long as 25 years ago the first injection-molded cellulose
acetate women's shoe heels had their first vogue. Almost
every

other

and impact

plastic

styrene.

has had its turn butyrate, acrylic,

Even nylon had a short-lived promotion.

In recent years shoe designers constantly have gone to

thinner and higher heels on women's shoes. In part, this has
been a response to the design freedom given them by the
availability of molded heels. It would have been ridiculous
to make such heels of wood.
The extremes of style, however, have gone beyond what
even the strongest plastic can stand, so that the modern
women's shoe heel is a steel spike, gracefully contoured, and
fastened to the shoe by means of a plastic.

In the last few years, polypropylene has had good accept-

ance in women's shoe heels in Europe, and

market

likely that the

will

it

appears very

go in the same direction in

this

country.

Although

it

seems very simple, the shoe heel really presents

problems, not the least of which

many remarkably complex

on treating it as if it
wood. They nail it to the shoe and also nail
a lift to the bottom of it. They even insist on using a
curious blunt-pointed nail that was very reliable on wooden
is

that the shoe manufacturers insist

were

still

made

of

heels.
It

give

should not be a great surprise, therefore, that plastics

them some

trouble; the nails are hard to drive in, the

plastic distorts near the nail,

and the heels loosen with time.

Polypropylene shows very good properties in

all

these re-

makes

its

resistance

spects. Its resilience

to creep helps

it

for easy nailing,

and

grip the nail for a long time.

In spite of the availability of all-through color in plastics.


233

Applications in the Soft-Goods Industries

the shoe manufacturers

Uke

tradition even older than the

entrenched that

it is

to

paint the heels. This

wooden

heel,

and

unlikely to be changed soon.

is

is

so firmly

The

solvents

used in the stains and lacquers tend to attack, craze, and

weaken most

plastics quite seriously.

Polypropylene

is

ex-

tremely resistant to such attack.

A shoe heel also is by no means an easy object to mold.

A very thin covering over the spike at the bottom spreads out
quickly to a thick mass at the top, which tapers off to a very

around the top. These rapid changes in cross secand the presence of the steel insert, create problems
with flow marks, sink marks, splitting around the insert, and
others. The combination of free flow and good physical
properties makes polypropylene one of the easiest plastics
thin edge
tion,

mold in this application. Since the steel insert in modern

makes the strength of the plastic secondary to other
properties, polypropylene makes extremely strong heels.
to

heels

It

now

tually

appears very likely that polypropylene will even-

take a good proportion of the women's

shoe-heel

Although the shoe industry is still dominated to a

surprising extent by the handcraft technology it has inherited
from the use of natural materials, it has been quick to adopt
the new synthetics. There is no shoe part that has not, at
some time or under some circumstances, been made out of
plastic. The plastic parts generally are better looking and
business.

more durable than

Some shoe

leather.

parts are conventionally

made

of polyethylene

and toe boxes, for instance.

In almost every instance a somewhat thinner polypropylene
piece would be better and cheaper.
Styrene copolymers are not likely to be displaced by polypropylene as soles, and styrene copolymer and vinyl "uppers"
also give such good service that they are probably not very
counters, insoles, dutchmen,

vulnerable.

234

Polypropylene

What

is

vulnerable, however,

antiquated industry.

It is

is

this

entire

musty and

inconceivable that people will long

continue to nail and glue shoes together out of dozens of bits

and pieces as they now do.

A few crude attempts at making a shoe by more modern
methods have been made, and the products have found a
limited market. A real program for producing footgear from
a plastic material, however, starting with fundamentals and
not just adapting current practice,
this

happens, and

of flexibility

is still

in the future.

When

be long delayed, the combination

in thin sections and stiffness in heavy ones,
it

will not

resilience, resistance to long-time creep, abrasion resistance,

and easy fabrication should make polypropylene a strong

contender as the material for the job.

HOUSEWARES APPLICATIONS OF POLYPROPYLENE

<;
(I)

"I

Housewares are one of the largest traditional applications

makes it possible to predict with confidence
not only what will be done with polypropylene in this area,
but also how much of it is likely to be consumed for this
for plastics. This

purpose.

Polypropylene has already established a certain position in

this field. It is difficult to estimate just

how

the injection-

molding poundage reported is split into the various uses, but

it is probable, judging from advertising and items exhibited
at various

shows, that the largest single item

is

for house-

wares.

In 1959, 170,000,000 lbs of polyethylene and about three

times that

much polystyrene was

injection molded.

The

largest

polyethylene item in this total was housewares. Polystyrene

housewares totaled about 50,000,000 pounds.

In the past few years plastics, especially polyethylene and
polystyrene, have taken a very large percentage of the house-

235

Applications in the Soft-Goods Industries

wares business away from the traditional metals,

ceramics. Polypropylene has already
tinue the trend.

indication of

shown

that

glass,
it

and

will con-

A few items already in production give a good

what

is

to

come.

Drinking Glasses
Plastic drinking "glasses" are already quite familiar.

Many

have been made of polystyrene, and more recently more of

polyethylene. The former were too brittle and cracked
quickly in service, in addition to distorting when used for hot
liquids or washed in hot water. The polyethylene types were
too

soft,

squeezing out of shape in the hand, readily bitten

by children, and so low in abrasion resistance as to present

a poor appearance quite quickly. Polypropylene has taken
over several drinking-glass applications because

it

is

almost

and nearly as tough as polyethylene. In addition, it has ample heat resistance for any
temperature likely to be used, and is very abrasion-resistant.
In addition to glasses of normal design, polypropylene is
being used in some ingenious double-walled glasses designed
to keep hot drinks hot and cold drinks cold. Since this glass
is made of two molded pieces that must fit into each other
as

hard and

stiff

as polystyrene,

accurately, the ability of polypropylene to

parts

is

make

reproducible

valuable.

Dinnerware

One

field that

has seen

little

penetration by plastics, and

none by thermoplastics is that of dinnerware.

amounts of "picnic" plates and cups
have been made of polystyrene, but this was insignificant. The only real penetration of plastics in this field was
with melamine, a thermosetting resin that must be compression-molded. Both the melamine resin and the method of
molding are comparatively expensive. The great durability

practically
It is

true that limited

236

Polypropylene

of this dinnerware has brought

by

institutional users

it

many

where breakage

item. It has also achieved

some

markets, especially

is

an important cost

success as a second or "every-

day" table setting in the home. Good "china" has such a

strong place in the tradition of the American people that it

Figure

8.4.

Polypropylene picnic

setting.

(Courtesy Spencer

Chemical Co.)

seems unlikely that any

substitute,

no matter how great

practical superiority, will soon replace

Polypropylene

The

its

entirely.

already

been

relatively inexpensive resin,

made

dinnerware,

quite well received.

it

however,

has

economical injection molding, makes it possible

produce inexpensive items. The strength and abrasion
resistance of polypropylene should make it as durable as
melamine. In addition, polypropylene is enough stronger
and tougher than melamine to permit production of thinnerwalled and more graceful pieces. Melamine, because of its
strength limitation and the difficulty of making complex

by
to

fast-cycle,

237

Applications in the Soft-Goods Industries

shapes by compression molding, was limited to rather thick

and

designs,

stolid

reminiscent of cheap stoneware rather

than elegant china. Polypropylene

tions. It

is

free

from such

limita-

cannot be made quite as thin as the most delicate

porcelain

because

teacup

it

is

little

too

flexible,

but

moderate thicknesses. The freeflowing properties of polypropylene make the molding of the
most complex shapes quite easy. Polypropylene should continue its growth in this field. Figure 8.4 shows a complete
adequately

it is

stiff

at very

picnic setting of polypropylene.

Kitchenware
Polypropylene

is

falling heir to the

carried polyethylene into so

ent,

upgrading trend that

many kitchenware

items.

At

pres-

only a few are produced in polypropylene, but these are

generally by firms emphasizing quality.

ware item

is

better,

if

Almost any kitchenlittle more

perhaps at present prices a

expensive, in polypropylene. Mixing bowls, pitchers, dishpans, measuring spoons, funnels, pails, water bottles, colanders,

and many other such items are natural applications for

polypropylene, some having been marketed and

many more

being in the process of development.

Polypropylene also makes excellent handles of

all sorts

and spoon handles, and handles for strainers,

ladles, and can openers, for instance. The kitchenware
handles can be washed in an automatic dishwasher without
knife, fork,

fear of softening or distorting them.

line

of polypropylene-handled paintbrushes has

also

been introduced. These handles are attractive and will retain

their original appearance indefinitely, because the color is all
the way through
not a coating. They will not scratch or mar
easily, and they are not attacked by any materials with which

they will

come

in contact.

Their thermoplastic nature makes

it

possible to fasten

238

Polypropylene

handles very solidly to the

article, either

by molding them

in

place or by softening them for insertion in the piece. This

makes for economical mounting without need of extra parts,

and in a single quick operation. Although the polypropylene
handle will cost more than a painted wooden one, the rapid
assembly

may

Figure

save a good part of the extra cost.

A polypropylene basin, which can be sterilized.

8.5.

{Courtesy Nalge Co.)

At
ings,

to

present,

it

appears that some of the very largest mold-

such as garbage cans, laundry baskets,

make

as large as baby's bathtubs have

in

etc.,

are difficult

in presently available polypropylene, although items

been made of polypropylene

Europe. As molding and resin technology advance, these

also should be likely polypropylene applications.

Figure 8.5 shows a polypropylene basin suitable for

steri-

hzation.

SANITARY PRODUCTS
Hospital and sickroom equipment that must be steriHzable

been beyond the capabilities of thermonylon has made a little headway

but polypropylene should be much more successof the excellent qualities of nylon sanitary ware,

has, until recently,

plastic materials. Recently,

in this field,
ful.

In spite

Applications in the Soft-Goods Industries

Figure

it

is

8.6.

239

Polypropylene sanitary ware. (Courtesy Montecatini)

just too expensive.

Polypropylene

articles

can be pro-

duced much more economically.

For most purposes the polypropylene article will be just
as good as the nylon. For some purposes the superior mois-

240

Polypropylene

makes

ture resistance of the polypropylene

even

it

better.

withstand sterilization at any ordinarily used steam

pressure, being entirely free of the hydrolysis that deteriorates
It will

nylon on repeated steam

sterilization.

enamel, or dent like aluminum.

to clean,

One

and can be made

of the

made out

not chip like

It will

lightweight and easy

in attractive colors.

oldest plastic

handle, has been

It is

the

applications,

toothbrush

of a wide variety of plastics during

the development of the industry.

It

seems quite

likely that

polypropylene will be able to take a large share of

business. Figure 8.6

this

shows some sanitary items and some

made of polypropylene.
A related item made in this country is a carafe and tumbler
set for hospital use. The carafe has a disposable plastic-film
toothbrushes

liner

which assures clean water

sterilization.

When

at all times

without daily

the patient leaves the hospital, carafe and

tumbler must, of course, be sterilized by autoclaving.

POLYPROPYLENE LABORATORY WARE

One
was

of the

first

American applications

of polypropylene

in laboratory ware. Previous experience with polyethylene

shown that there were many applicawhere the plastic is better than glass. The superior heat
resistance and strength of polypropylene obviously extend
laboratory ware had
tions

this

range of usefulness considerably.

The

first

uses were those where glass

is

unsuitable, such

as procedures using hydrofluoric acid or other fluorides that

attack glassware.

Many

procedures that can be carried out

perfectly wefl in glass, however, are preferably

propylene, simply because

it

is

less

fragile.

done

in poly-

Polypropylene

beakers are not recommended for heating over direct flame

or even a hot plate, because their thermal conductivity

low that the outside

will overheat;

is

so

however, hot water can

241

Applications in the Soft-Goods Industries

be poured into polypropylene beakers, and exothermic reactions resulting in boiling-water temperatures

can be safely

carried out in them.

Most

pieces of laboratory apparatus never are subjected to

flame temperatures, but often experience rough handling.

Funnels are a typical example. Polypropylene funnels are

made

in a large variety of sizes

and shapes, including analyt-

WW ^
^
i

Figure

8.7.

ical funnels

Polypropylene laboratory funnels in several

(Courtesy Nalge Co.)

sizes.

designed specifically for use with the most pop-

ular standard sizes of

filter

paper. These funnels are less

expensive than glass ones and will not break

dropped. Their heat resistance

is

quite

if

accidentally

adequate for the

filtration of boiling solutions.

Graduated cylinders are

also available with dimensions in

accordance with federal specifications. In addition to unbreakabihty, these cyUnders have the advantage that the
liquid level can be read

more

easily

than in

glass,

because

water solutions in polypropylene have practically no meniscus; the water level

laboratory ware are

is

perfectly

shown

flat.

Typical examples of

in Figures 8.7

and

8.8.

In addition to beakers in the familiar glassware shapes.

242

Polypropylene

heavy-handled beakers are available in polypropylene which

are graduated both in EngUsh and metric units for approximate measurement of liquid volume. These are especially

recommended

and photographic

for handling acids, alkalies,

chemicals.

Figure

8.8.

A polypropylene graduate with graduations molded in.

(Courtesy Nalge Co.)

POLYPROPYLENE TOYS

The toy

industry was one of the

first

to use plastics in

volume. The celluloid doll was a standard

article for

many

and polystyrene is used in large volumes for toys.

Recent years have seen a steady upgrading in toys, using
more durable and more expensive resins to replace polystyyears,

243

Applications in the Soft-Goods Industries

rene.

Polyethylene,

cellulosics

styrene

vinyls,

have benefited from

copolymers,

and even

The low cost and

polypropylene make for a

this trend.

excellent physical properties of

natural continuation of the trend.

The current explosive growth of blow molding is opening

up tremendous toy markets for polypropylene. The strength
and resihence of polypropylene make it possible to blow
lightweight thin-walled toys of low cost and excellent durability. Dolls, animals, rocket models, and many other complex hollow toys will be made in this way. For the present,
polypropylene is limited mostly to the high-quality segment
of the market, but once its good performance is recognized it
should penetrate widely.

Formed polypropylene

sheet

toy wagons, automobiles,

etc.,

is

excellent for the bodies of

and for parts of

tricycles,

bicycles, etc.

The

great

volume

The high

in plastic toys

is

in injection-molded

molds tends

to retard changes
Using polystyrene or polyethylene molds with
polypropylene increases the cost of the article, because no
advantage can be gained from the superior strength of the

articles.

cost of

in this field.

To achieve the full advantages, molds will

have to be designed especially for polypropylene. This is
being done, and a gradual increase in injection-molded polypropylene toys can be expected. This will, however, probably
not be any great volume when compared with many of the
polypropylene.

other applications mentioned.

toy volume, the model

Some

kits, is

of the largest polystyrene-

almost completely closed to

polypropylene because the basic appeal of these

kits is

home

assembly. This can be done very easily with polystyrene, but

a convenient and effective cement for polypropylene

available at present. Similarly,

volume

is

in the inflatables,

propylene competition.

some

is

not

of the largest vinyl-toy

which are not susceptible

to poly-

244

The

Polypropylene

immediate volume for polypropylene in the

toy field appears to be for dolls and doll parts. Blow-molded
polypropylene doll parts have had good success recently, and
it

largest

appears that the combination of low cost and excellent

serviceability will enable polypropylene to replace

the slush-molded vinyl plastisol

Polypropylene
its

is

now

also going into

high strength and resilience

much

of

going into this business.

some

make

applications where

it

superior to other

molded yoke for a pull toy

which is press-fitted to a wooden handle. With other plastics,
there were problems with breakage, and the handle loosened
materials.

typical

example

is

because of cold flow. Polypropylene obviated

This easy adaptability to snap-and-press

advantage in

fits

this trouble.
is

one great

this field.

INTEGRAL-HINGE APPLICATIONS

may be used for a variety of applifrom luggage to notebooks, it seems worth while to
make special mention of the one-piece molding with a narrow
Since hinged articles

cations,

thin section that acts

as

a hinge.

These designs were originally developed for polyethylene

and enjoyed a fair degree of popularity. The flex resistance
of polyethylene is, however, quite variable, and many such
hinged parts did not stand up too well, although some were
very good. Polypropylene seems much better adapted to this
application; the flex

life

of the hinge

is

very good, and,

because of the greater strength of the material,

it

has more

tear resistance as well.

The
it

greater stiffness of the polypropylene molding

makes

possible to produce a precision-fitted piece of excellent

appearance, which will retain that appearance owing to

good abrasion

resistance.

its

Thus hinged polypropylene cases

Applications in the Soft-Goods Industries

for high-value

appUcations, where a long

appearance retention

is

essential,

life

245

with good

should be in demand.

Several firms are working on luggage of this design.

It

could greatly simplify luggage manufacture and produce a

superior piece at low cost.

Up

to this time, relatively small cases, such as spectacle

cases and fishing-tackle boxes have been

made

in this

way.

luggage-type record-carrying case with an integral hinge

has also appeared.

FUTURE DEVELOPMENTS

9.

There are many kinds of future developments coming in

The commercial development, as more and

polypropylene.

more producers put

in plants, and various phases of the

market are tested, is one kind. The technical developments,
as the tremendous versatility of the material is exploited to
make a wider range of products, v^ill be equally important.

New

ideas in processing technology, as applications of poly-

propylene multiply, constitute a third class and applications a

fourth.

We

will start

with the commercial phase.

COMMERCIAL DEVELOPMENT
Development
It

of the Industry

seems very

development of the polysee a marked departure from the

likely that the

propylene industry will

pattern that has been characteristic of the plastics industry

during the past three decades. The traditional pattern of a

large chemical

methods and

company making

selling this

resin

by mass-production

raw material

to a host of small

molders, extruders, and fabricators

finished or

which they market in a Umited

has already shown its inadequacy in the

semifinished products from

geographical area,

who make

it,

case of polyethylene.

had grown in size and comwhere the limited financial and technical
resources of the film-extrusion industry could no longer keep

The

polyethylene-film market

plexity to the point

246

Future Developments

up with

it.

The

247

material manufacturers found themselves sup-

staffs and great development laborawhich had no other purpose than furnishing technical support for their customers. The processor was no longer
able to afford the technical staff essential for him to remain

porting large technical

tories

in business.

In addition, resin suppliers, by credit arrangements and

otherwise, found themselves supplying a large part of the

financing of the industry as well. This

meant

that they

were

bearing most of the expenses of the film industry without

having any control over

it,

or making any profit from

it,

except in their sales.

This resulted in a sweeping wave of integrations in which

the resin producers, for
film industry.

Most

all

practical purposes, took over the

of the few surviving film extruders were

who

absorbed by other large corporations

ability,

integrate

backward and

start

prob-

will, in all

making

resin,

as has

happened with other plastics. At least one large molder has

already done this with polystyrene, and the vinyl industry has
seen similar developments.

Except for the injection-molding phase, the polypropylene

industry will be integrated from the start. Montecatini
setting the pattern,

film will

and AviSun

is

following

it.

The

fiber

be made by the same firm that makes the

Blow molding may develop along

similar

lines.

At

is

and

resin.

least

temporarily, the injection-molding portion of the business

resist this tendency to some extent. The
tremendous variety of the molders products makes a national
market of the kind needed by the large corporation very

has been able to

difficult to achieve.

The molding

greater ability to solve

its

own

industry has also

shown a

technical problems than have

the other parts of the plastics industry.

Integration in this industry has been in the other direction.

Large consumers of molded parts have set up their own mold-

248

Polypropylene

The vacuum-forming industry is similarly characby captive shops operated by the consuming in-

ing shops.
terized
dustries.

Increasingly, the traditional

is

custom molder and extruder

being confined to small markets for specialty products, and

the large

volume

is all

taken by integrated organizations.

Probably very few independent film producers will be

willing to undertake the cost of developing polypropylenefilm technology or markets, in the face of the large integrated

production

who

now

in near prospect. It

from

try will benefit

it,

is

doubtful that the few

unless they have great financial

resources.

The

be completely integrated, except

monofilament production which is affili-

fiber industry will

perhaps for a

little

ated with the consuming industries.

Any

estimate of the polypropylene market that

fails

to

take into account this basic change in the character of the

plastics industry will

be in serious error. This was, perhaps,

the basic error in linear-polyethylene market estimates. It

much

not so

was

that the markets did not exist, but that the

consuming industries lacked the technical and financial resources to develop them at anything like the speed necessary
to use the resin production capacity.

There

make
will

is

little

sign that the polypropylene industry will

a similar mistake. Facilities for processing the resin

be

and the

built at the

same time

as the production facilities

resin will be sold as fiber, film, or other finished

or semifinished goods. The customers for these products will

who will use them in large volume

own manufacturing operations. This new industry

be other large corporations

in their

pattern will enable polypropylene to achieve the fantastic

growth predicted for

The small

it.

plastic processor

who

has

filled

thousands of

garages, lofts, and defunct textile plants in the past decades

249

Future Developments
has served his purpose in

lifting plastics

from a

business to a great mass-production industry.

go the way of the family farm or the village

tiny special

He must now

gristmill.

Companies Entering Polypropylene Field

The
is

list

of companies entering the polypropylene picture

impressive. In addition to those listed in the historical

section as having

announced plans

to construct plants, the

way

or another that they are

following have indicated in one

going to manufacture polypropylene:

I. duPont de Nemours & Co.
Union Carbide Plastics Co.

E.

U.S. Industrial Chemicals Div. of National Distillers

Phillips

Petroleum Corp.

Monsanto Chemical Co.

Grace Chemical Co.

Many

others are

known

to

be

active,

but their intentions are

not yet clear.

The Rexall Company has recently announced that it will

produce polypropylene. This company has for several years
been acquiring plastics-consuming companies, and now owns
important film and bottle-blowing operations. This

is

an

example of the integrating trend where a large consumer

starts to make resin. RexaU has not made any specific statement regarding the timing or the size of its projected production operations except that they will be substantial.
Fibers.

The polypropylene fiber field is beginning to show

more companies announce their plans.

signs of developing as

Reeves Brothers, long active in the monofilament

field,

started production in August, 1959, of low-denier polypro-

pylene

fiber.

This material

had some success

is

trade

marked "Reevon" and has

in rugs, upholstery fabric

and padding, and

250

Polypropylene

batting for pillows, comforters, and cushions. It is available

from 3 denier up as staple and multifilament yarn.
AviSun Corporation has announced the name "Olane" for
its new polypropylene fiber. Production from a pilot plant
at

New

Castle, Delaware,

Beaunit Mills will

is

start

expected "early in 1960."

making polypropylene

fiber

in

February, 1961. They have bought machinery expected to

give an annual capacity of 12 million

pounds of

staple fiber

a year.

Beaunit will buy polymer to

who can

supply

it,

make

the fiber from anyone

thus breaking the pattern of close tie-ins

between polymer producer and fiber producer that has been

characteristic of developments so far.
The United States Rubber Company has started to market
polypropylene fiber. Although no announcement of production facilities has been made, it seems evident that, if the
marketing program is successful, they will manufacture both
fiber

and

resin.

Capacity Prospects

The development of polypropylene will not be held back

by lack of work or money. Capacities, even of those already
announced, are not always known, and the timing of new
capacity can only be estimated. There could, however, easily
be over 500 million pounds of polypropylene a year available
by the end of 1963.
Such a capacity expansion would dwarf that of linear polyethylene, which shot up to about 300 million pounds in the
first two years but has grown little since.
It is almost inconceivable that a market of this magnitude
could be developed in the next four years. Linear polyethylene
had the fastest initial growth of any plastic in history and
took four or five years to reach the 1959 sales of 83 million
pounds. Despite optimistic predictions of accelerated growth,

Future Developments
it

251

seems unlikely that markets for the 300-milHon-pound

capacity will be reached in less than four or five years more.

It

only the change in the industry pattern and the

is

difference in the approach to the marketing

problem indicated

by the polypropylene producers that give any hope that polypropylene will be able to achieve the goals set for

it.

Market Prospects
It is

customary to estimate markets by estimating the rate

economy, and of the particular industry,

and then applying suitable factors to present production. This
is evidently useless at this stage, since no reasonable base
has been established, and, in order to come anywhere near
the expectations held for it, polypropylene must grow as no
plastic has ever before grown in history. Hercules Powder
of growth of the

reported capacity operation for the last quarter of 1959. This

had been described as a 20-million-pound plant when

was constructed, but it is beUeved to be considerably larger.
Montecatini has also been selling a small amount of material
in this country, and AviSun went into production in August,
plant
it

1959.

It

is

doubtful, however, that a total of

10 million

pounds of polypropylene was sold in 1959.

The annual rate at the end of that year may have been up
to 30 million pounds a year. If this is true, it represents a
phenomenal growth and acceptance of a new material, particularly as this includes only monofilament and molding
material. Film and true fiber markets have not yet been
touched.

Some people

in the industry

are confidently predicting

billion-pound sales sometime in the

likely that the

mid

60's. It

seems quite

production capacity will be available. Whether

the sales will or not

lene sales have

is

grown

another matter.
at

It is

true that polyethy-

an annual rate of about 200 million

pounds a year since 1955, and

at

such a rate for polypropy-

252

Polypropylene

would reach 1 billion in 1965, but this was only done

had established a solid technological base
through years of experience, and the production capacity of
the consuming industries has been under constant strain to
lene

it

after polyethylene

achieve these totals.

The big difference is that the polypropylene industry shows

no intention of waiting for the consuming industry to build
up the capacity to consume the resin. The resin producers
themselves are building the consuming plants. The only problem will be marketing the goods.
All things considered, the billion-pound goal

and polypropylene

servative,

eventually; however,
its

it

will

is

probably exceed

very conthis goal

appears more likely that the time for

will be late 60's rather than middle.

market timetable might as follows

achievement

A possible

1960
1961

100,000,000 lb

1963
1968

1,000,000,000 lb

30,000,000 lb

250,000,000 lb

This would be an unprecedented rate of growth, but the

power of the organizations behind the development of poly-

propylene

is

such that

it

may be

possible.

Price Prospects

The

intention of polypropylene producers to go after

markets

is

shown by

in the initial stages of

their willingness to reduce prices

market development. At

mass
even

present, poly-

propylene has a premium of 7 cents over linear polyethylene,

but this cannot be expected to
acute.
is

last

when competition becomes

reasonable estimate of price for the near future

that producers will try to maintain the present IVz-CQni

between high-pressure and linear polyethylene,

and perhaps about the same premium for polypropylene over
differential

the linear polyethylene.

253

Future Developments

As noted

before, this resin price

is

really of little

impor-

tance as such, as the greatest part of the polypropylene resin

produced

probably never change hands as

will

The important

resin.

facts are that polypropylene film will

be

cheaper than cellophane and that polypropylene fiber will be

cheaper than any other synthetic. Montecatini has already put
a 60-cent lb price on

advantage, puts
price

it

its

fiber

which, considering the weight

in a class with viscose rayon.

may be much

The

ultimate

lower.

TECHNICAL DEVELOPMENTS

The

prospects for technical developments in polypropylene

are perhaps the

most

of the material in this

interesting of

all.

Actually, a good deal

book has described future

possibilities

rather than present actualities.

There are two broad classes of technical developments to

developments in the resin, or resin technology, and developments in processing or application tech-

be considered

nology.

Developments in Resin Technology

Present polypropylene applications are
the largely isotactic, hard,

stiff

the market. Polypropylene

is

simply in degree of

all

concerned with

was the first one on

tremendous variation

resin that

capable of

tacticity. It

seems certain that products

and tried in certain
polypropylene might be de-

of lower tacticity will be developed

markets. For instance, a flexible

veloped to compete for

many markets

held by vinyls and

rubbers.

Polypropylenes of practically 100 per cent isotactic

polymer have also been produced. When these are made in
high molecular weights, they produce materials much stiff er
and stronger than any that have been described here. Process-

254

Polypropylene

ing problems will prevent their wide

high-value

applications

the

acceptance, but for

can be

processing, difficulties

overcome.
This

is

particularly true because the typical polypropylene

processor will not be the small firm limited both in finances

and technical resources that has processed other

plastic

material, but will generally be one quite adequately financed

and having the support of large corporation laboratory and

staffs. A processing problem that would be difficult or even impossible with conventional equipment used
in the traditional manner may be easily solved by firms of
engineering

this caliber.

Stereoblock Polymers. The stereoblock polymers mentioned in the section on polypropylene chemistry will certainly

be produced commercially, and

if

they live up to their

promise of giving resins that behave lik6 a vulcanized elastomer, without the need for the time-consuming vulcanizing

could easily lead to a revolution in

step, this

Copolymers. In addition

to these variations

this field.

which

polypropylene as such, there will be great strides

polymerization.

The

made

in co-

stereospecific catalysts are well suited to

forming a variety of copolymers.

have been made experimentally, and

many

relate to

great

it is

number

of these

highly probable that

technically valuable ones will be found. Readily dye-

able polypropylene

comonomer

may be produced by

the inclusion of a

that has a strong affinity for dyestuffs in the poly-

merization. Polypropylene film that

is

printable and glueable

be made of a copolymer. Some other physicalproperty variation may be more readily made by copolymerization; permeability is an example. Specific resistance to
specific permeants may be made possible by certain copoly-

may

also

merizations.

improved thermal and light

improved low-temperature performance, and a host

Increased heat resistance,

stability,

255

Future Developments

of other developments can also be expected from copolymers.

Montecatini is already producing copolymers of ethylene

and propylene which can be vulcanized to give an excellent
elastomer. This is competitive with natural and synthetic

rubber in

many

fields.

The precise direction

monomers cannot be

industry as regards basic

at this time.

monomer

It is,

base

may

and the materials

however, very clear

of the rubber
clearly defined

that,

whatever the

be, stereospecific catalysts will

will

have

their valuable properties

of the control of molecular configuration

first

be used,
by virtue

demonstrated

with polypropylene.

High-pressure Polypropylene. There have been recent rumors that a high-pressure process, similar to that used to

make

polyethylene, is being developed for polypropylene.

There are serious theoretical problems in such a process.
Almost certainly a simple free-radical catalyst, such as is
used for polyethylene, would produce an atactic polypropylene with few useful properties. Metallic catalysts, however,
such as are used in the solvent polymerization of polypropylene, have been used in high-pressure reactors with some
success, and these might produce polypropylene with useful
properties. This would retain the high-capacity advantage of
the high-pressure reactor, but would still require the removal
of catalyst residues. This might be considerably
in the bulk resin produced
it is

difiicult

in the finely divided resin

produced by present processes.

many

possible technological changes

This
"^--that

more

by the high-pressure reactor than

is

only one of

could change the entire polypropylene picture in the

next few years.

Other Ordered Polymers. Since we are studying the

great sterically ordered plastic,

cluding in our
that

may be

considerations

expected.

we

first

are perhaps justified in in-

other plastics

of

The rubbers produced from

this

type

sterically

ordered diene polymers have already been mentioned.

Mono-

256

Polypropylene
than propylene can be polymerized into steriordered polymers of valuable properties. Somewhat

olefins higher

cally

surprisingly,

polymers of higher melting point and greater

produced from some of the higher mono-

tenacity can be

The monomers involved are not present in refinery

same extent as propylene, and pyrolytic
reactions producing them from saturated hydrocarbons are
rather more difficult; however, their production should not be
costly compared to the cost of many commonly used plastic
olefins.

gases to quite the

monomers.
is already being produced in pilot-plant quanby Montecatini in Ferrara, Italy. Its usefulness for many
of the applications mentioned in this book for polypropylene
has been demonstrated. Petro-Tex Chemical is building a
pilot plant in Houston, Texas, to produce this polymer, and
many others are also interested. PetroTTex has been studying this polymer since 1955, and they feel that it has great
possibilities in pipe and film. Especially for the latter use,
superior tear strength recommends it over polypropylene.
Many of the traditional monomers such as styrene and the

Polybutene-1

tities

acrylates also give sterically ordered polymers of vastly dif-

ferent properties

mers. Certainly

from those of

many

their ordinary

random

poly-

valuable products will be developed

from this tremendous range of possibilities.

Polymer Blends. There has also been an increasing
in simple blends of polymers.

The

interest

success of blends of linear

and high-pressure polyethylene has aroused great interest in

very simple way of obtaining variations in polymer properties. Polypropylene is closely enough related to polyethylene
so that blends of the two can easily be made. Although many
of these blends exhibit properties that are only an average of
the two materials, or worse, there are some blends that appear
to have valuable special properties.
this

Blends of polypropylene with elastomers such as butyl

257

Future Developments

rubber give considerable promise as a means of improving

the low-temperature brittleness of polypropylene.

As was

the

case with polyethylene and polystyrene, this sort of blend

will

probably be only a temporary measure until the time

when

more

sophisticated answer can be found in copolymer-

ization or in other

means of

controlling the structure of the

molecule.

The use

of reinforcing

dimensional

stability of

development;

also,

fillers

to

enhance the strength and

polypropylene

a highly probable

is

polypropylene foams are very promising

and, as yet, completely unexploited.

It is

possible to

foam

polypropylene by any of the techniques used for other thermoplastics,

and

its

strength, light weight,

should give these foams wide

probable that

It is

all

and abrasion resistance

utility.

these avenues toward fitting poly-

propylene more exactly to specific applications will be explored in the near future, as well as

perhaps

many more, some

now unknown.

DEVELOPMENTS

IN

PROCESSING TECHNOLOGY

Two
lighted
first is

developments in processing technology which high1959 have great implications for polypropylene. The
the growth surge in blow molding. This process, which

for years took

some

three per cent of the nation's poly-

ethylene, matching the growth rate of this skyrocketing

terial

was no mean

feat,

ated expansion that

has suddenly taken

may make

it

off

on an

ma-

acceler-

a real rival of injection

an excellent blow-molding material

and should profit from this development.
The other feature of 1959 was the replacement of metal

molding. Polypropylene

is

detergent cans by containers of linear polyethylene. Poly-

propylene apppears to have superior properties for

cation,

and

will certainly offer stiff competition.

this appli-

Many

other

258

Polypropylene

applications

now

being served by metal cans will be vulner-

able to competition

from polypropylene containers

technology develops.

The

much

have been

may be more

as this

all-plastic aerosol containers

which

discussed as a possible nylon application

nearly economically feasible using polypro-

pylene.

Biaxially Oriented Pipe

very interesting technical development being exploited

Germany is a
The great gain
in

process for making biaxially oriented pipe.

in

biaxial orientation

strength that polypropylene

means

gets

from

that this process should broaden

polypropylene applications, not only in strong lightweight

pipe but also as a source of strong cylinders for a variety of
purposes, such as can bodies.

recent announcement of the Kordite

Company may

well

be the beginning of an entirely new development in polypropylene

film.

They

are offering 0.5-mil biaxially oriented

polypropylene film that

plastic resin

is

coated on both sides with a thermo-

which heat-seals

of the polypropylene. This

temperatures of 250
the seal can be

This makes

it

to

at well

makes

it

below the melting point

possible to heat-seal at

350F, and, even more important,

made without

melting the body of the resin.

possible to use this resin

on machinery which

has sliding-type sealer bars without the film sticking to the

bar and tearing. Many overwrap machines designed for use

on cellophane and coated papers use such heater bars, and
their use on ordinary polypropylene film requires expensive
conversion of the equipment. The coated polypropylene film

should be usable without any such conversion.

The

film

is,

at present,

being offered at prices slightly

below those of the premium grades of cellophane with which

it competes, and officials of the Kordite Company have predicted that it will eventually be the cheapest available film.

259

Future Developments
It is

quite possible that this

and similar developments

will

greatly facilitate the conversion of the packaging industry to

polypropylene.

Cold Stamping
Another processing development that has seen only small
may well assume major dimen-

use with previous plastics but

sions with polypropylene

temperatures well below

is

cold stamping. Polypropylene, at

softening point, can be formed and

its

stamped in ways entirely analagous to sheet-metal forming

and stamping. This process has the advantage that, when
properly performed, it orients the polypropylene and increases
its strength. Since the part is entirely rigid as soon as it is
formed, no cooling is required, and cycles can be much
shorter

makes

than

with

traditional

to large-scale

methods.

hot-forming

the process very inexpensive

This

and especially suitable

mass production.

Polypropylene Paper

There are also some

entirely

new

fields

that

may be

important in polypropylene. For instance, Montecatini has

a patent on a process for

making paperlike polypropylene

which can be written and printed on just like paper.

Paper made from synthetic fibers has been known for years,
and polypropylene fibers, being highly oriented, will fibrillate
under beating as well as any other synthetic. Such paper may
well have considerable specialty uses.
The material made by the Montecatini process mentioned,
however, is not a true paper in this sense, but a film made
with the use of solvents, which is very different from film
drawn from hot melt. Such film will, of course, be more ex-

film,

pensive than paper, but there are

paper where price

is

many

applications

for

unimportant. For instance, present evi-

dence leads us to believe

that, in the

absence of direct sun-

260
light,

Polypropylene
polypropylene

is

much more

durable than paper, neither

drying out and becoming brittle nor being attacked by dampness and microorganisms. It could well

become

the writing

base for valuable documents whose long preservation

essary. It

is

also possible that

its

is

nec-

wear resistance would be

enough better to justify its use on library or schoolbooks that

have a very heavy use.
Polypropylene is also entering into technology in forms
that are far

from those mentioned here.

Polypropylene Waxes
Low-molecular-weight isotactic polypropylene waxes have
a great deal of promise.

They have high melting

points, great

low melt viscosity. Possible applications are polishing waxes and modifiers for other plastics,
coatings, etc. These waxes may be polymerized directly under
some conditions but are more conveniently made by thermal
surface hardness, and a

cracking of high polymers.

Atactic polypropylene also has possibilities, one patented

use being as a thickener for

oils

and greases.

It

may

also

enter the adhesives field, especially for adhesives suitable for

bonding polypropylene.

PROGRESS

The tendency toward

IN APPLICATION

integrated operations which will con-

centrate polypropylene processing into large organizations

will affect the pattern of

growth in applications. Whereas the

customer for a small independent plastics processor

was a retail or wholesale marketing group dealing with an
end user, the large integrated processor will naturally look for

logical

other equally large corporations as customers.

In addition to the packaging previously mentioned, these

customers will have need for component parts for their prod-

Future Developments

261

Examples of industries are machinery, appliance, autoetc. These fields have already begun to use some
plastic parts but are still largely oriented toward the metal
trades from which they originated. To a great extent they
have been discouraged from considering plastic parts because
the independent plastic processor did not have the financial
resources to furnish the volume of parts required, or the technical resources to make them with the necessary control and
precision. This situation is rapidly changing, and these industries will soon either have suitably financed and technically competent suppliers, or they themselves will build
ucts.

motive,

processing

facilities.

The economic

lever that will accomplish these changes

that business will

the 60's.

become

The consumer

better bargain.

is

increasingly competitive through

will increasingly expect,

With metals and

and

traditional metals

get,

trades

facing mounting costs, the only recourse will be an increasing use of plastics.

The
in the

building industry faces a similar challenge and will go

same

direction.

Up

to the present time, the progress of

plastics in the building industry

has been hampered by the

and the marginal

properties of most of them. Polypropylene has the combination of excellent physical properties with low cost that is
needed in this industry.
Plastics have also been hampered by the opposition of
the craftsman in the building trades to new materials whose
relatively high cost of plastic materials

is to reduce labor costs. As long as conperformed mainly by small contractors operating

in local areas and using on-the-job production methods, polypropylene can be used in building merely in the small special

primary advantage
struction

is

items such as are

The

now

being served by other plastics.

building industry

is

of development very long.

not going to remain at

The

this stage

prefabricated house, which

262

Polypropylene

was an

few years ago, now repand a constantly growing pro-

interesting curiosity only a

resents a substantial industry,

new houses being

portion of the

With the increase

tory methods, the path is open
prefabricated.

of

built

are

more or

mass production and

less

fac-

for greatly increased use of

plastics.

The

great traditional obstacle to the use of plastics in

building,

and for that matter

building practices,

is

to

any change or advance

the presence of building codes in

in

many

communities that require the use of certain specific tradiAlthough it would be foolish to expect this
obstacle to evaporate quickly, more and more communities
tional materials.

are showing a willingness to consider updating of building

codes to permit the use of modern materials.

There has also been an increasing trend toward the conand unification of building codes which decreases
the number of authorities that have to be convinced of the
solidation

value of a change. In addition, the authorities in charge of

more likely to be trained engineers

proposed changes objectively, rather than
the local craftsmen or small contractors who dominate code
authorities at the local level and consider building codes
mainly as a means for protecting their traditional ways of
the consolidated codes are

who

will

making a
troduce

look

living.

new

few

at

This will

make

it

increasingly easier to in-

materials into the building trades.

have been mentioned so

difficult to assess, but which

specific applications that

recently that their significance

is

appear to be potentially important, are discussed in the

fol-

lowing pages.

Thermoplastic Recording Tape

The use

of polypropylene film as a base for magnetic-

recording tape has already been mentioned.

newly de-

veloped tape-recording process has recently been announced

Future Developments

may broaden

that

263

market considerably. This

this

called

is

thermoplastic tape recording. In this process an electrical

signal

which

used to modulate the discharge from an electron gun

is
is

is

captured by the

static stresses in the material.

enough

The discharge of
up electro-

directed at a thermoplastic tape.

the electron gun

plastic, setting

The

plastic

is

then softened

to permit these electrostatic stresses to

deform the

surface into a series of fine ripples. These ripples can be

reconverted into electrical impulses by an optical system which

uses the ripples as a diffraction grating to modify a light

beam

sent through the tape. In its present form the heating

by radio-frequency heaters, so the low dielectric loss factor
of polypropylene makes it unsuitable for recording. The great
potential market here, however, is not in the recording tape
but in the fact that a metaUic master can be made from these
tapes, and used to produce a large number of reproductions
in a manner analogous to the production of phonograph records. For this purpose polypropylene tape would be entirely
satisfactory. The thermoplastic tape can store a good deal
more information on a given area than can magnetic tape,
and should be cheaper. Both audio and video signals can be
is

stored. This system brings the

home video player much

nearer.

Polypropylene Fiber as Tire-Cord Material

Preliminary testing

is

in progress to determine

propylene will join in the fierce fight

now

if

poly-

going on between

rayon and nylon for the automobile-tire business.

The high strength and resilience of polypropylene fiber

make it very attractive for this application, and its potentially

low cost makes

it

able to enter this strongly cost-com-

petitive situation with reasonable profit expectations.

The main drawback

tion
is

is

its

of polypropylene fiber in this applica-

comparatively low softening point. Heat build-up

quite severe in automobile tires,

and there

is

some question

264

Polypropylene

about the ability of the polypropylene fiber to stand up. It is,

however, quite probable th^t the heat resistance of polypropylene fiber can be improved beyond its present temperature
range, and

make

not possible

known

to

it is

it

satisfactory for this appHcation. If this

is

quite likely that other isotactic polymers,

have superior heat

resistance, will

be developed

for this purpose.

No mention whatsoever has been made of the many "blue

sky" possibilities open to polypropylene. This is because they
would take a book in themselves. We are entering a syntheticremake the whole structure and
industrial and mechanical revolutions were only new ways of handling and using materials
that have been known for centuries.
materials revolution that will

operation of our society.

The

The

primitiveness of our culture, from a raw-materials

point of view,

is

quite

The primary metals

amazing

if

one stops to analyze

iron, copper, lead, zinc, etc.

long

it.

pre-

ceded industrialization. Of the mass-produced metals, only

aluminum is modern. Our home-building materials, wood and
brick,

are the

most primitive

possible, going

beginning of civilization, and the

crete. Fabrics are

together, the

We

way

still

Romans

largely plant

they were at the

are currently seeing the

and animal

dawn

end of

back

could

to the

make con-

hairs twisted

of civilization.
this

dependence on

primitive materials. In the next few decades the synthetics

will take

over and transform

it

has been transformed in

is

one of the

first

life

all

of the great

this transformation.

and technology more than

history before. Polypropylene

new

materials that will

make

INDEX

Abrasion resistance, 10,

Aerosol containers, 187
Air knife. 111, 116
Apparent density, 12
Appliance parts, 210
Atactic polymer, 66
Automotive parts, 216

Containers, molded, 189

Cooling towers, 210
Copolymers, 254
Corrosive chemical uses, 192

14, 16

Creep, 26
Crystallinity,

75

Crystallite size, 91

AviSun Corp., 7

Crystal structure, 71

Biaxial orientation, 53, 58,

122,

Deflection temperature, 14, 16

Deformation under load, 10

258

Blow molding, 155

Density, 13, 16

Bottles, 184

Dielectric constant, 11, 15, 17, 60

Boxes, 190

Dielectric strength, 10, 15, 60

Brittle point, 53

Dinnerware, 235
Diolefin polymers, 84

Building industry, 261

Bulk resistivity, 12
Burning rate, 13
Burst strength, 62

Dissipation factor, 11, 15

Capacity prospects, 250

Eastman Chemical Products Co.,

Dow

Chemical Co., 7

Drinking glasses, 235

Carbon dioxide permeability, 58

Catalysts, 81,97

Closures, 188

modulus, 13, 16
204
Electronic components, 208

Coating, 128

Elongation, 10, 13, 16, 19

Cold stamping, 259

"Engel" process, 161

Environment, effect of, 3
"Escon" resin, 13
Expansion coefficient, 10,

Elastic

Chill roll casting, 110

Electrical uses,

Coloring, 104

Communications wire, 206

Companies entering field, 249
Compressive strength,

16

12, 14, 16

265

12, 14,

266

Index

Extractables, 80

Isotactic index, 46, 76

Izod impact, 10, 12, 16, 25, 51

Extraction, 100

Extrusion, 107, 120, 124

Kitchenware, 237

Extrusion coating, 128

Extrusion die design, 108, 114

Laboratory ware, 240

Light stabilizers, 41

Ferro Corporation, 105

Fibers, 4, 221, 226
Film,

6, 54,

163

Film extrusion, 109

Film insulation, 209
Firestone Chemicals Co.,

Flame

Linear polyethylene,

spraying, 161

Machining, 160
Magnetic tape, 215

Market prospects, 251

Flexural strength, 20
vs.

temperature, 138

Fluidization on heating, 147

Fluidized powder, 161

Furniture, 219

Melt index, 13, 16

Melting point, 10, 14

Modulus of

Gas permeability, 58

Hardness, 10, 12, 13, 16, 20, 48

distortion temperature, 10,

Heat

Mold
Mold

design, 145

shrinkage, 10, 13, 17, 143

59

Hercules Powder Co., 10

High pressure process, 255
Hot gas welding, 159
Housewares, 234

Industrial

Montecatini,

4, 6,

12

"Moplen," 12

44

scalability, 57,

Immersion,

variables, 149

Multifilament yarn, 132

21

resistance,

effect of,

Rayon

32

Corp., 8

Industry development, 246

Natta, Professor, 2,

Nonwoven

netting,

3,

Injection molding, 134

Integral hinges, 244

88

83

231

Optical activity, 74

Ordered dienes,

58
Overwrap packages, 167
Oxidation, 42, 86
Oxidation stabilizers, 43
Oriented

Oxygen

film,

transmission, 58

In phase modulus, 29

Intrinsic viscosity,

16

Molecular weight, 87
Monofilament extrusion, 129
Monofilament uses, 223

Gels in film, 118

16,

elasticity, 13,

Moldability area, 144

Molding

Heat
Heat

22

Loss factor, 27

Flexural modulus, 11, 13, 49

Flow

1, 5,

Liners for tanks, 195

Packaging, 163

baked goods, 168

confectionery, 178

267

Index
dairy products, 179

Resin developments, 253

dried products, 166

Resistivity, 11, 17

fresh produce, 172

Rockwell hardness,
Rope, 225

frozen foods, 174

12, 20,

48

meat and poultry, 177

paper, 183

180

textile products,

tobacco, 182

Shear

rate,

Paper, 259

Shoe

parts,

Silk like fibers,

hexane. 38

hydrogen peroxide, 39

methyl-ethyl ketone, 35
silicone oil, 36

Specific heat vs. temperature, 127

volume,

12, 18

Spencer Chemical Co.,

Spherical venturi, 105

7,

16

Stabilizers, light, 41

215

film,

197, 258

Pipe extrusion, 125

Polybutadiene. 85

Standard Oil of New Jersey, 7, 13

Stereoblock polymers, 72, 254
Stereo-chemical fundamentals, 66
Stiffness, 10. 12, 14, 16, 19

Polymer blends, 256

Stress cracking, 10. 13, 17

Polymerization, 96

Sulfochlorination, 87

"Poly-Pro," 16

Surface

Powder, 161

resistivity,

60

Syndiotactic polymer, 70

factor, 12, 17

wire;

Specific

Spherulites, 92

water, 34

Power
Power

'"^

Specific heat, 12, 16

isopropyl alcohol, 37

methyl alcohol, 36

Photographic

228

Skin packaging, 154, 190

Specific gravity, 10, 12

"Clorox," 40

6,

231

to

chloroform. 37

Pipe,

shear stress, 140

Shear strength, 50
Sheet extrusion, 124

Permeability. 77
resistance

Sanitary products, 238

Synthetic rubber,

204

3,

84

Pressure forming, 153

Price prospects, 252

Tacticity, 65

Processing conditions, film, 122

Production, 94

Tanks, 194
Tensile modulus,

"Pro-Fax," 10

Tensile strength, 10, 13, 16, 18

10, 16

Propane propylene separation, 94

Textile machinery, 203

Puckering of

Thermal conductivity, 12, 14

Thermal expansion, 10, 16
Thermoforming, 151

film.

117

Recording tape, 262

Relative

volatility,

pylene, 95

propane-pro-

Tire cord, 263

Torsion modulus, 23

268

Index

Trays, 190

Water absorption, 10,

Water bath extrusion,
Waxes, 260

Vacuum

Weld

Toys, 243

Valve

13
1

19

values, 160
Wool-like fabrics, 226

forming, 151

gating, 141

Valves, 196

Vicat softening point, 12, 14, 52

Yarn, 132

Viscosity, intrinsic, 88

Volume

resistivity, 11, 14, 17,

60

Yield

stress, 10, 13, 16,

47

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