Chapter 4:

Industrial Polymer
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 Learning
Outcomes:

• Explain the basic steps

in polymerization.
• Elucidate the
production of
polystyrene,
polyvinylchloride,
polyurethane etc.
• State the usage of
polystyrene,
polyvinylchloride,
polyurethane etc.
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 What is Polymer?

• Polymer - a large molecule consisting of (at least

five) repeated chemical units (`mers') joined
together, like beads on a string. Polymers usually
contain many more than five monomers, and
some may contain hundreds or thousands of
monomers in each chain.

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 Types of
Polymers

Natural Synthetic
polymers polymers

Cotton fiber is mostly cellulose, and cellulose is made of

chains of the sugar, glucose linked together a certain way.

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 Starch consisting of a
large number of
glucose units joined by
glycosidic bonds.

DNA (Deoxyribonucleic acid) –

is a polymer, known as a
"polynucleotide” from
“nucleotides” (monomer).

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 What is Polymer?
• Polymer: High molecular weight molecule made up
of a small repeat unit (monomer) – bond together by
covalent bonding.
• Monomer: Low molecular weight compound that
can be connected together to give a polymer.
A is monomer unit
— covalent bonding

• Oligomer: Short polymer chain.

• Copolymer: polymer made up of 2 or more
monomers.
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• Molecular structure of polymer:
– A linear polymer consists of a long
chain of monomers.

– A branched polymer has branches

covalently attached to the main
chain.

– Cross-linked polymers have

monomers of one chain covalently
bonded with monomers of another
chain.
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 Elastomers
• A class of polymers that have some degree of cross
linking and are rubbery. Elastomers possess memory,
that is, they return to their original shape after a
stress is applied

Thermoset
• A network polymer that has undergone a chemical
reaction by the action of heat, catalysts, ultravoilet
light leading to a relatively infusible state.
• Thermo setting plastics harden irreversibly on the
application of heat.
 Thermoplastics

• Thermo plastics are those types, which on heating

soften, and harden on cooling.
• Scraps of this group of plastics can be reconverted.
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Difference between thermoset
and thermoplastic

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 Types of polymer
Homopolymer - consist of monomers of the same type.

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Heteropolymer or copolymer – is a polymer derived
from two (or more) monomeric species (different
repeating units).

In random copolymers
two or more different
repeating units are
distributed randomly.

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 Alternating copolymers are
made of alternating
sequences of the different
monomers.

In block copolymers long

sequences of a monomer are
followed by long sequences
of another monomer. 18
Graft copolymers
consist of a chain
made from one type
of monomers with
branches of another
type of monomer.

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 Polymer Structure and Properties
• The large size of polymer molecules gives them some
unique physical properties compared with small organic
molecules.
• Linear and branched polymers do not form crystalline
solids because their long chains prevent efficient packing in
a crystal lattice. Most polymers have crystalline regions and
amorphous regions.

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 Polymer Structure and Properties

• Crystalline structure – regular chain structure, no

bulky side groups. Eg: nylon, PET
• Amorphous structure – random/ disordered
arrangement. eg: PC, PS

• More crystalline polymer –

stronger and less flexible.
• Both amorphous and
crystalline areas in same
polymer – semi-crystalline.

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 Isomerism/Polymer tacticity
• Polyolefins with side chains have stereocenters on every
other carbon.
CH3
n
CH3 CH3 CH3 CH3 CH3 CH3 CH3

• With so many stereocenters, the stereochemistry can be

complex. Three main stereochemical classifications for
polymers.

✓ Isotactic - All stereocenters have same orientation

✓ Syndiotactic - Alternating stereochemistry
✓ Atactic - Random orientation
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• Tacticity affects the physical properties:
– Atactic polymers will generally be amorphous,
soft, flexible materials.
– Isotactic and syndiotactic polymers will be more
crystalline, thus harder and less flexible.
• Polypropylene (PP) is a good example:
– Atactic PP is a low melting, gooey material.
– Isoatactic PP is high melting (176C), crystalline,
tough material that is industrially useful.
– Syndiotactic PP has similar properties, but is very
clear. It is harder to synthesize.
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 Polymerization Process

▪ Polymerization is a process of reacting monomer

molecules together in a chemical reaction to form
polymer chains or polymeric compound.
▪ There are two basic types of polymerization:
I. chain-growth (or addition) polymerization.
II. step-growth (or condensation) polymerization.

polymer
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monomers
 Chain-growth
Polymerization
• Applies to monomers having double bonds or
ring structure.
• The polymer grows by sequential addition of
monomers to a reactive site.
• Chain growth is linear.
• Steps in chain reaction:
✓ initiation
✓ propagation
✓ termination
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1. Initiation - formation of free radical.
• 2 steps:
– radicals from initiators.

– transfer to monomer.

R—R 2R•
R• +M RM1•
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 • Generation of free radicals from an initiator

• Formation of active centers

Radical 1 predominates
• Attack at the methylene carbon is less sterically-hindered
• Product radical is more stable 29
2. Propagation
• Combining of ‘mers’ to form chain (polymer).

RM1• +M RM2•
RM2• +M RM3•
Etc.
RMn-1• +M RMn•
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• Rapid sequential addition of monomer to the active
center:

• Head-to-tail addition predominates – less steric

hindrance

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 3. Termination – elimination of free radical
I. by disproportionation:

RMn• + RMn• RMm= + RMn

II. by combination:

RMm• + RMn• RMm—MnR

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 1. Combination

• Head-to-head linkage
• Two initiator fragments Rs (e.g., polystyrene)

2. Disproportionation

• One end saturated and another unsatured

• One R fragment [e.g., poly(methyl methacrylate) (PMMA)]

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Examples of Chain Polymers

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 Step-growth Polymerization

• A.k.a condensation polymerization

• Involves 2 monomers that have different functional
groups. (eg., -COOH, -COOR, -OH, -NH2, -CHO, etc.)
• They also involve the elimination of water or
another small molecule (eg: HCl).
• Monomer A + Monomer B → Polymer + small
molecule (normally water).

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Typical condensation polymers are polyamides,
polyesters, and certain polyurethanes.
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• Monomer containing > 2 functional groups,
will make branched and network polymers

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Example: Phenol-formaldehyde resin

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Differences between chain-growth and
step-growth polymerization.

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 Polymer ID

Society of the Plastic Industry (SPI) – plastic container coding system

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POLYETHYLENE
ETHYLENE DERIVATIVES
 Polyethylene (PE)
• Polyethylene is the most common plastic
(thermoplastic), with the annual production is ca. 80mil
metric ton.
• Its primary use for packaging (plastic bag, plastic films,
geomembranes, containers including bottles, etc.).
• Polyethylene’s dominance can be explained by the fact
that it offers a combination of characteristics that are
ideally suited to the process such as:
• Good flow
• Good thermal stability
• Broad density range
• Excellent chemical resistance
• PE is classified into several different categories based
mostly on its density and branching.
Material Density (kg/m3) /
% crystallinity
Low-density PE 0.920 – 0.929 / 45-53%
Medium-density PE 0.930 – 0.939 / 54-59%
High-density PE 0.940 – 0.965 / 60-75%
• With regard to sold volumes, the most important PE grades
are HDPE, LLDPE and LDPE.

• Linear polyethylene is much stronger than branched

polyethylene, HDPE has higher density levels - it is also
characterized by a linear structure consisting of no branching
- that makes HDPE stronger and more resistant to chemicals.
• But, branched polyethylene is cheaper and easier to make.
 http://upload.wikimedia.org/wikipedia/commons/thumb/a/a0/Resin-identification-code-4-LDPE.svg/80px-Resin-identification-code-4-LDPE.svg.png

Low-Density
Polyethylene (LDPE)
• LDPE has excellent resistance to dilute and
concentrated acids, alcohols, bases and esters.
• LDPE can withstand temperatures of up to 80C – it
has less hardness, stiffness and strength compared to
HDPE, but better ductility.
• Its most common use is in plastic bags and also most
useful and widely used plastic especially in
dispensing bottles or wash bottles.
• Today, it has almost totally been replaced by linear-
low-density polyethylene (LLDPE).
 High-Density
Polyethylene (HDPE)
• HDPE is stronger and stiffer (rigid) than LDPE.
• HDPE can withstand temperatures of up to 120C .
• It is translucent and rigid and is resistant to many
different chemicals.
• The rigid nature of HDPE allows manufacturers to use
it for food product and chemical containers. Other
uses for HDPE include trays, cutting boards, pipe
fittings and tanks.
 Linear-low-density
Polyethylene (LLDPE)
• LLDPE is a substantially linear PE polymer with
significant numbers of short branches, commonly made
by copolymerization of ethylene with longer-chain
olefins (eg: butene, hexene, or octene).
• LLDPE has higher tensile strength and higher impact
and puncture resistance than does LDPE.
• It has good resistance to chemicals and good electrical
properties.
• It is used for plastic bags and sheets (thinner film),
plastic wrap, pouches, toys, covers, lids, pipes,
containers etc.
PE - Polymerization Process
• Polymerization process:
Coordination @ addition
polymerization (most
pervasive technology)., which
means that metal chlorides
or metal oxides are used.

• Catalysts: most common

titanium (III) chloride, the so-
called Ziegler-Natta catalysts
or Phillips catalyst, prepared
by depositing chromium(VI)
oxide on silica.
PE - Polymerization Process
X - radical

polyethylene

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POLYPROPYLENE
PROPYLENE DERIVATIVES
 Polypropylene

• Polypropylene (PP) is a thermoplastic polymer used

in a wide variety of applications including packaging,
textiles (e.g. ropes, thermal underwear and carpets),
stationery, plastic parts and reusable containers of
various types, laboratory equipment, loudspeakers,
automotive components, and polymer banknotes.
• PP was first produced commercially in 1959s
following the discovery of Ziegler-Natta catalysts
based on titanium chlorides and organo-aluminium
compounds.
 Polypropylene
• Polypropylene is a colorless, translucent to
transparent solid with a glossy surface.
• PP has very good resistance to acids, alkalis, and
inorganic chemicals.

• Except for hydrocarbons and

chlorinated compounds, PP
has a good resistance to
organics.
Polypropylene Uses
 Polypropylene tacticity
• Polypropylene can exist in the three stereoisomeric forms:

▪ Isotactic PP – is high
melting (176C),
crystalline, tough
material that is
industrially useful.
▪ Syndiotactic PP – has
similar properties but is
very clear. It is harder to
synthesize.
▪ Atactic PP – is a low
melting, gooey material.
 Polyvinylcholride (PVC)
• Polymerization of PVC:

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PVC Uses

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 Polystyrene (PS)
Polymerization of PS:

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PS Uses

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 Melamine

• Melamine is the organic compound with the formula

C3H6N6. This white solid is a trimer of cyanamide,
with a 1,3,5-triazine skeleton.
• It contains 67% nitrogen by mass.
• It is widely used in
production of certain
plastics, e.g. Formica.

Formica laminates 64
• In one large scale application, melamine is combined
with formaldehyde and other agents to
produce melamine resins - a synthetic polymer that is
fire resistant and heat tolerant.
• The resin is a versatile material that has a highly stable
structure.
• Such resins are characteristically durable thermosetting
plastic used in high pressure decorative laminates such
as Formica, melamine dinnerware, laminate flooring,
kitchenware, fire retardant fabrics and commercial
filters.

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 MF Resin
• Melamine formaldehyde aka melamine resin - resins
are primarily made up of melamine and
formaldehyde with formaldehyde acting as the
crosslinker.
• It is made from melamine and formaldehyde by
condensation of the two monomers.
• Its good fire retardant properties are due to the
release of nitrogen gas when burned or charred
(burnt).

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The melamine reacts with formaldehyde under slightly alkaline
conditions to form mixturers of various methylolmelamines:

Further heating causes condensation of the methylolmelamines:

MF resin str.
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Melamine Uses

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 Melamine Issues
• The 2008 Chinese milk scandal was a
widespread food safety incident in China. The
scandal involved milk and infant formula along with
other food materials and components
being adulterated with melamine. Of an estimated
300,000 victims in China, six babies died from kidney
stones and other kidney damage and an estimated
54,000 babies were hospitalized.

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 Melamine Issues
• Melamine tableware - FDA's Safety and Risk
Assessment of Melamine states that this type of
plastic tableware is safe for use. The study concludes
that the chemicals in melamine will not migrate, or
transfer, into food product as long your food is not
heated to 160 F ( ~71C) or higher.

• Melamine dinnerware is not a

great candidate for the
microwave.

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 Polyurethane (PU)
• Polyurethanes are made by the exothermic reactions
between alcohols with two or more reactive hydroxyl
(-OH) groups per molecule (diols, triols, polyols) and
isocyanates that have more than one reactive
isocyanate group (-NCO) per molecule (diisocyanates,
polyisocyanates).
• For example a diisocyanate reacts with a diol:

“Urethane linkage”

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 Polyurethane (PU)
• PU is polymer material that is popular
in many application for its:
− Toughness
− Abrasion resistance
− Cut and tear resistance
− Ease of processing
− Versatility

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PU Uses

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 Polyethylene terephthalate
(PET or PETE)
• PET - is the most common thermoplatic polymer of the
polyester family and is used in fibres for clothing,
containers for liquid and foods, thermoforming for
manufacturing, and in combination with glass fibre for
engineering resins.

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 Polyethylene terephthalate
(PET or PETE)
• PET is produced by the polymerization of ethylene
glycol and terephthalic acid.

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PET @ PETE Uses

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 Plastic vs. Environmental
Issues
1. Nonrenewable resources
– Polymers are made from monomers - majority of
these monomers are derived from petrochemicals.
2. Limited biodegradability
– most polymers are not "natural" but rather
synthetic, so they are generally not biodegradable.
– plastic in some way is good (i.e.,
durable, long lasting) but when
thrown away, they create
significant problems by piling up
in landfills. 79
3. Incidental Pollution
– The manufacture of plastics often involves the use
of toxic or environmentally harmful chemicals - for
example, the manufacture of polystyrene foam
involved the application of chlorofluorocarbons
(CFC), which are powerful ozone-depleting
compounds.
– Phthalates, commonly added to some polymers to
improve tensile properties, have been flagged as
hormone disrupters in humans.

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4. Physical effects
– Plastics which are dispersed into the natural
environment can cause many problems for wildlife
who interact with them – example; clogged digestive
systems in the animals and in some cases illness due
to toxic chemicals leached out of the plastics.
– Garbage container (i.e., empty plastics or container)
that hold water, becomes a breeding place for
mosquitoes – spread diseases.
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 Ways to dispose synthetic polymer properly:

• Pyrolisis - burn without oxygen

• Incineration - gas is filtered
• Invent a biodegradable synthetic polymer

Practicing good habit in disposing synthetic polymer:

• Separate the synthetic polymers

from other wastes.
• Recycle
• Reuse

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