Polyesters

 Polyesters are among the more versatile synthetic

polymers.
 The common methods of synthesising simple
esters are used to make polyesters.
 These include direct esterification (1),
transesterification (2) and the reaction of alcohols (3)
with acyl chlorides or anhydrides (4).

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Commercially important Polyesters

Poly(ethylene terephthalate)
(PET)

Poly(trimethylene terephthalate)

Poly (ethylene napthalate-2,6-

dicarboxylate) (PEN)

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Commercially important Polyesters

Poly (butylene terephthalate)

(PBT)

Poly (4-hydroxybenzonate)

Polycarbonate

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 Polyethylene Terephthalate (PET)

 Linear polyesters were studied by Carothers during his classical

researches for development of Polyamides.
 But it was Whinfield and Dicson who developed PET at Calico
Printers Association, England I 1941 (As Fibres, Terylene and
Dacron and as Film, Melinex and My lar, with the expiry of the basic
ICI patents on PET there was considerable development in
terephthalate polymers in the early 1970’s.
 More than a dozen companies introduced PBT as an Engineering
Plastics during this time.
 The fiber in the name of Kodel and Film in the name of Kodar was
developed by Kodak.
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 Polyethylene Terephthalate (PET)

 PET was also the basis of glass filled engineering

polymer (Rynite) introduced by DuPont in 1970’s.
Towards the end of 1970’s PET was used for the
manufacture of biaxial oriented bottles .

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 Monomer Ingredients for PET

 The ingredients which are used for PET are ethylene

glycol and dimethyl teraphthalate.

HO – CH2 – CH2 – OH Ethylene glycol

Dimetyl terephthalate

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 Chemistry of Preparation of PET

 The PET polymers is produced by the reaction of ethylene

glycol and Terephthalic acid or Dimethyl terephthalate in the presence
of metal acetate catalyst. This process is called ester exchange
process.

 In this process, a low molecular weight diester, known as the

monomer is first produced by reacting 1 mol. or dimethyle terephthalate
with about 2.1 – 2.2 mol ethylene glycol at 150°C in the presence of
catalysts, such as antimony trioxide and cobaltous acetate.

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 Chemistry of Preparation of PET

 In addition to this diester, di-2-hydroxyethyl terephathalte, some

oligomers of following general structure, are also produced.

HO-(CH2 ) 2 -O[O-C- O -COO-(CH2 ) 2 -O] n-H

When n = 1, 2, 3

 Methanol formed during the condensation is removed using a

distillation column. The monomer is then heated to 270° - 280°C with removal
of volatiles under reduced pressure down to 1 mm Hg. Heat and vacuum are
employed to increase the molecular weight with concurrent removal of volatile
products such as water /alcohol and glycol.

n CH3OOC - O - COO CH3 + n HO - CH2 - CH2 - OH

O O
- [C - O - C - O -CH 2- CH2 - OTRAINING
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-] n + 2nAND
CHPLANNING
3 OH
 Manufacturing of PET

 PET Polymers are manufactured by a stage-wise melt

polymerization process consists of transesterification, pre-
polymerization and finishing polymerization steps.

Continuous melt polycondensation process for PET

manufacture.
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 Manufacturing of PET

 In the transesterification stage dimethyl temphthalate

(DMT) or terephthalic acid (TPA) is converted into bishydroxy
ethyl terephthalate in the presence of metal acetate catalyst.

 Ethylene glycol (EG) DMT, and catalyst are fed at a

molar ratio of 1.7 to 2.0:1 (with TPA this ratio is 1-3 to 1.5:1) and
a temperature of 100-180°C. This stage takes 3-4 hr.
 The reaction byproduct methanol (Water When TPA) is used is
separated from EG vapors in a reflux column.

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 Manufacturing of PET

 After adding stabilizer and additives, the prepolymer is

forced through a superfine fitter to the second (pre-poly
condensation) stage.

 The poly condensation reaction is performed under

vacuum (15-25 torr) and elevated temperature. (280 – 300°C).

 The resulting EG is removed by a vacuum pump while the

prepolycondensation product – a low molecular weight (DP= 30)
relatively non-viscosity material (40 poise) is pumped to the
finishing poly condensation stage after a residence time of about 2
hrs.
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 Manufacturing of PET

 The finishing polymerization stage, which is operated at 0.5 – 1

torr, requires special wiped film or extruder type reactor in order to handle
the high viscosity of the polymer ((DP = 100), few thousand poise).

 Many manufacturer have devised their own proprietary agitation

systems to minimize the build-up of the solidifying polymer layers.

 The EG vapours contaminated with oligomers are drawn off

through a special condensing system and sent to a recovery unit

 The polymers melt can be sent to a direct spinning plant or

transformed into pellets.

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 Relations of Structure and Properties of
PET

 There are various classes of linear polyesters.

 The concentration of ester groups has predominant effect on the
properties of linear polyesters.
 For the aromatic classes of linear polyester, decreasing the
concentration of ester groups apparently leads to a reduction in melting
point.
 However, in such aromatic linear polyester the decrease in
concentration of ester group is accompanied by the p-phenylene group
concentration.
 It is found from aliphatic polyester that the ester group concentration
has little effect on the melting point.
 In fact a decrease in ester group concentration leads to a slight increase
in the melting point.
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 Relations of Structure and Properties of
PET

 It is found that in an ester group the in chain ether link –C-O-C-

increase the chain flexibility compared with a polyethylene chain to
decrease the heat of fusion.
 At the same time there will be some increase in inter chain attraction via
the carbonyl group which will decrease the entropy of fusion.
 Since these two effects almost cancel each other out there is almost no
change in ester group concentration.
 With all linear series of polyester as the no. of methylene groups in the
repeating unit increases so the polymer becomes more like a linear
polyethylene (polymethylene).

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 Relations of Structure and Properties of
PET

 It is also observed that Tm (melting point) of a polymer with an odd no.

of methylene groups in the aliphatic portion of the repeat unit is lower than
for the polymer with one more but an even no. of methylene groups.
 Generally, the highest melting points are obtained where the in-chain
aromatic ring is of the p-phenylene type.
 The materials have a disadvantage of sensitivity to water and alkaline
solution.
 These materials are crystalline and only proton donors that are capable
of inter action with the ester groups are effective solvents.

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 Characteristics of PET (For
Identification)

 The PET is a semicrystalline material, normally

amorphous with low crystallinity and high transparency.

 It is identified by sweet smell, when burns, orange flame,

soot forming and melt drips.

 It is scratch resistant

 Melting point is 220°C

 It is having short and long term thermal limit temperature

respectively 135°C and 100°C

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 Characteristics of PET

 Outstanding chemical resistance to organic and inorganic

liquids
 Water repellent
 Sterilizable by ethylene oxide and X-rays
 Inherent good electrical property
 Ability to orient
 Good tensile strength
 Superior strength and stiffness
 Excellent dimensional stability
 Excellent melt strength with slower crystallization rate
 Good impact strength even at low temperature
 High tear strength
 Heat resistant
 Flame retardant
 Outstanding clarity
 High gloss
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 Properties of PET
Properties Units Values
Specific gravity ---- 1.40
Tensile strength MPa 51
Tensile modulus MPa 175
Flexural modulus Mpa 204
Elongation at break % 7
Impact strength izod, Notched, kg.cm/cm 9.25
Hardness R 105
Deflection temperature under load 0
C 205-210
(1.82 Mpa)
Vicat softening point °C 75
Coefficient of linear expansion mm/mm/ 0C
6.0 x 10-5
Water absorption, 24hrs % < 0.1
Refractive index 1.62
Dielectric strength KV/mm 26
Dielectric constant 10-6 Hz 3.3
Power factor 0.03
Volume resistivity Ohm.m 1013
Melting point 0
C 265
Glass transition temperature °C 67

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 Properties of PET

Mechanical Properties
PET exhibits a high modulus up to 75°C, when it is
crystalline and 40°C, when it is amorphous even when
they are mechanically stressed for a long period.

Thermal Properties
PET has excellent dimensional stability.

Electrical Properties
PET has high dielectric strength and high volume
resistivity. The dielectric properties are adequate for
many electronics applications.

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 Properties of PET

Water Absorption
PET is hygroscopic and in its melt states the resin
hydrolyses.

Optical Properties

The light transmission of PET differs greatly according

to chemical composition.

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 Properties of PET

Permeability to water vapour and Gases

 PET is less permeable than PVC-U.

 The permeability of film is 40µm/1.58 mil.
 The permeability to water vapour is higher than that of
the polyolefins but lower than that of PC, PA, POM. PET
films are largely odor-proof which leads to their frequent
use in packaging materials in combination with PE films

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 Properties of PET

Chemical Properties

 PET is resistant to weak acids and alkaline solutions,

oils, fats, aliphatic and aromatic hyrocarbons, carbon
tetrachloride.
 It is not resistant to strong acids and alkaline solutions,
phenol, long exposure to hot water.
 The crystalline polyalkyle terephthalates are
susceptible to hydrolysis which precludes their use in
aqueous solution temperatures above 70°C for in steam.
 PET does not show any pronounced tendency to stress
cracking.

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 Properties of PET

Weathering Resistance

The relatively high resistance to weathering can be

increased by the use of carbon black to protect against
UV.
Resistance to High energy Radiation

PET is relatively resistant to high energy radiation. It is

degraded more strongly only at absorbed energies of
more than 100 KJ/ Kg. After 7 to 8 MJ/Kg it decomposes
into powder.

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 Properties of PET

Flammability
PET burns with a sooty orange-yellow flame, it drips and
smells sweetly aromatic. Flame retardant grades donot
drip and meet the requirements of UL 94 V-0.

Toxicity
PET is suitable for applications involving contact with
food stuffs and is physiologically inert.

Sterilization
PET can be sterilized in an ethylene oxide atmosphere
or by irradiation.

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 Additives of PET

1. Functional additives

2. Fillers

3. Reinforcements

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 Functional Additives

1. Anti-oxidants
2. UV absorbers
3. Flame retardants

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 Fillers and Reinforcements

1. Mica - Fillers
2. Thermoplastics glass fiber - Reinforcements

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 Grades of PET

The PET is available in the following grades.

Injection moulding grade

Extrusion grade

Stretch blow moulding grade

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 Processing considerations of PET

PET can be processed by the following techniques :

 Injection moulding

 Stretch blow moulding

 Thermoforming

 Extrusion

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 Processing considerations of PET
 PET resins are primarily for injection moulding.

 PET is hygroscopic and in its melt state the resin hydrolyzes.

 PET resin supplied in moisture porof containers can have a

moisture content upto 0.04%, but hydrolysis can occur at a moisture level
above 0.02%.

 Therefore, even virgin PET directly from suppliers containers, as

well as regrind, should be dried to level of less than 0.02% and maintained
at that level.

 Dehumidifier hopper is recommended with injection moulded PET.

 Drying time values from 4 hrs. for wet resin to 2 hrs. for virgin resin
at 135°C.

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 Processing considerations of PET

 The moulding must be carried out with dried material and

because of the free flowing nature of the melt, restricted nozzles
should be used and a back flow valve fitted to screw injection
moulding machine.

 Cylinder temperature are about 260 – 290°C.and mould

temperature as high as 140°C to promote a controlled crystallization.

 A significant degree of crystallinity occurs in the mould.

Therefore, mould temperature should be selected carefully in order to
enhance crystalline formation.

 Mould temperature also influence cycle time and products

quality, particularly warpage shrinkage, surface gloss depth or colour
and chemical resistance.

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 Processing considerations of PET

 Although resin grades from the same supplier show the

same melt temperature, PET from different suppliers shows
different melt temperature ranging from 260 – 290°C .The
recommended typical injection moulding cylinder temperature
also differ between suppliers.

 An interesting feature of PET is that according to the

moulding conditions two quite dissimilar products one
amorphous, the other transparent, may be obtained, this beings
a consequence of having a Tg of about 80°C.

 Because of the low melt viscosity injection moulding

screw for PET should be fitted with back flow valves and the
barrel nozzles should have shut-off-valves.
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 Surface Finishing of PET

 The high chemical resistance of the polyalkylene terephthalates

necessitates the use of special purpose lacquers to ensure good
adhesion.
 The same applies to hot embossing (temperature range of the
die 140 - 200°C).
 PET can be polished easily. Metallization can be only be
carried out by high vacuum deposition.
 Where high gloss surfaces are required on filled and reinforced
product, an intermediate lacquer must be used.

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 Machineability of PET

 Cutting
Cutting can be possible in PET with suitable equipments in a specified
speed.

 Joining

Welding
Moldings and semi-finished products can be welded and bonded.
Unreinforced moldings can be joined by hot gas and heated tool welding. With
increasing glass fiber and the flame retardant content, the welded joints
decrease in strength. Friction and ultrasonic welding are efficient joining
methods.
The conditions for heated tool welding are
Heated tool temperature - 260°C
Contact pressure at start of heating - 0.5 bar
Contact pressure at start of welding - 0.5 bar
Heating up time (according to wall thickness) - 10 to 30 s
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 Applications of PET
 Appliances

 Automotive

 Electrical/Electronics

 Films

 Furniture

 Packaging

 Miscellaneous
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 Applications of PET

Appliances :
Oven and appliance handles, coil forms for
microwave oven transformers, small appliance
structural framers, panels, chassis and housing and
instrument covers.

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 Applications of PET

Automotive:
Structural parts such as luggage racks and grills,
fuctional housing such as windshield, wiper motor
housing , fuel filters, blade supports and bells, sensor,
lamp sockets, relays, switches and solenoids

Grill opening retainer Door module

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 Applications of PET

Electrical/Electronics:
Lamps sockets , coil forms for audio/video
transformers, terminal blocks, electrical. Electronic
connectors and thrust washers.

Electricals Connectors
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 Applications of PET

Films:
X-ray films, photographic films, magnetic
tapes and printing sheets.

Food packaging
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 Applications of PET

Furniture:

Pedestal bases, sent pans, chair arms and

castes.

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 Applications of PET

Packaging :
Carbonated soft drink containers, distilled
spirits, toiletries, food products, mustard, pickle foods,
peanut butter, spices, edible oil cocktail mixer and
syrups.

Containers
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 Applications of PET

Miscellaneous:
General purpose pumps housing , mirror
housings three dimensional circuit boards and
structural components in office automation
equipment, computer housing and structural
components, containers, trays, blisters and drinking
cups.

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 Applications of PET

Automobile engine cover Heat shield

Gear box Door washers

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 Blends of PET

PET/PC

 Partially miscible blends (miscibility is controlled by the

level of transesterification) with co-continuous morphology
show improved processability, chemical resistance,
crystallinity, elongation, low temperature impact and tensile
strength.

 Blends also show decreased shrinkage and high heat

deflection temperature.

 These blends are especially interesting for reinforced

products because the warpage is significantly decreased.
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 Blends of PET

PET/Elastomers

 These blends are formulated for extrusion, injection,

compression, blow and transfer molding.
 The blends contain up to 35 wt. of glass fiber.
 They show good processability rigidity impact and tensile
strength as well as excellent weatherability.

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List of Manufacturers/Suppliers of PET

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