POLYMER

PROCESS
ENGINEERI
NG

POLYETHYLENE TEREPHTHALATE
Table of Contents

1 Introduction
2 Synthesis
3 Structure
4 Properties
Physical Properties
Mechanical Properties
Optical Properties
Thermal Properties
Electrical Properties
Chemical Properties
5 Rheology

 Factors affecting Rheology

6 Conclusion

INTRODUCTION:
Polyethylene
terephthalate
is
a thermoplastic polymer resin of the polyester family and
is used in synthetic fibers, beverage, food and other
liquid containers;
thermoforming
applications;
and
engineering resins often in combination with glass fiber.
Depending on its processing and thermal history,
polyethylene terephthalate may exist both as an
amorphous and as a semi-crystalline polymer. The semicrystalline material might appear transparent (particle
size < 500 nm) or opaque and white (particle size up to a
few microns) depending on its crystal structure and
particle size. Its monomer (bis--hydroxyterephthalate)
can
be
synthesized
by
the esterificationreaction
between terephthalic acid and ethylene glycol with water
as
a
byproduct,
or
by transesterification reaction
between ethylene
glycol anddimethyl
terephthalate with methanol as
a
byproduct.
Polymerization is through a polycondensation reaction of
the monomers with water as the byproduct.
PET consists of polymerized units of the monomer
ethylene terephthalate, with repeating C 10H8O4 units. PET

is commonly recycled, and has the number "1" as

its recycling symbol.

SYNTHESIS:
Polyethylene terephthalate is produced from ethylene
glycol and dimethyl
terephthalate (C6H4(CO2CH3)2)
or terephthalic acid.
The former is a transesterification reaction, whereas the
latter is an esterification reaction.
Dimethyl terephthalate process
In dimethyl terephthalate process, this compound and
excess ethylene glycol are reacted in the melt at 150200
C with a basic catalyst. Methanol (CH3OH) is removed by
distillation to drive the reaction forward. Excess ethylene
glycol is distilled off at higher temperature with the aid of
vacuum. The second transesterification step proceeds at
270280 C, with continuous distillation of ethylene glycol
as well.
The reactions are idealized as follows:
First step
C6H4(CO2CH3)2 +
2
HOCH2CH2OH
C6H4(CO2CH2CH2OH)2 + 2 CH3OH
Second step
n C6H4(CO2CH2CH2OH)2
[(CO)C6H4(CO2CH2CH2O)]n + n HOCH2CH2OH

Terephthalic acid process

In the terephthalic acid process, esterification of
ethylene glycol and terephthalic acid is conducted
directly at moderate pressure (2.75.5 bar) and high
temperature (220260 C). Water is eliminated in the
reaction, and it is also continuously removed by
distillation:
n C6H4(CO2H)2 + n HOCH2CH2OH
[(CO)C6H4(CO2CH2CH2O)]n + 2n H2O

STRUCTURE:

Polyethylene terephthalate (PET) is a semi crystalline

polymer possessing excellent chemical resistance, melt
mobility and spinnability. The polymer is composed of
repeating units as shown in the above figure. Each unit
having a physical length of about 1.09 nm and a
molecular weight of ~200. When it is produced from the
reaction of terephthalic acid and ethylene glycol, it is
capped on the left by H- and the right by OH.
Polymerization is thus accompanied by the production of
water which is removed under elevated temperature and

vacuum. Accordingly the presence of water in the molten

state will rapidly depolymerize the structure so that
thorough drying of the polymer prior to melt spinning of
fibers is necessary.
The aromatic ring coupled with short aliphatic chain
makes the polymer a stiff molecule as compared to other
aliphatic polymers such as polyolefin or polyamide. The
lack of segmental mobility in the polymer chains results
in relatively high thermal stability. A textile grade polymer
will have an average number of 100 repeat units per
molecule so that the extended length of the typical
polymer chain is about 100nm with a molecular weight
about 20,000. Higher levels of polymerization produces
higher strength fibers but the melt viscosity and stability
of the melt to even tiny amounts of moisture causes
hydrolytic degradation. The measurement of average
degree of polymerization is done either by molten
viscosity (by measuring the pressure drop through a
calibrated orifice) or the viscosity of the diluted polymer
in an appropriate solvent.

PROPERTIES:
PHYSICAL PROPERTIES:
Physical Properties

Density ( g.cm-3 )

1.3-1.4

Flammability

Self
Extinguishing

Limiting oxygen index ( % )

21

Refractive index

1.58-1.64

Resistance to Ultra-violet

Good

Water absorption - equilibrium ( % )

<0.7

Water absorption - over 24 hours ( % ) 0.1

PET in its natural state is a colorless, semi-crystalline
resin. Based on how it is processed, PET can be semi-rigid
to rigid, and it is very lightweight. It makes a good gas
and fair moisture barrier, as well as a good barrier
to alcohol (requires
additional
"barrier"
treatment)
and solvents. It is strong and impact-resistant.

MECHANICAL PROPERTIES:
The mechanical properties of a polymer include its
strength, elongation, modulus, impact strength, and
toughness. It has high strength, toughness, shatter

resistance, good barrier properties, low weight and easy

recyclability
Mechanical Properties
Coefficient of friction

0.2-0.4

Hardness Rockwell

M94-101

Izod impact strength ( J.m-1 )

13-35

Poissons ratio

0.370.44(oriented)

Tensile modulus ( GPa )

2-4

Tensile strength ( MPa )

80, for biax film

190-260

CHEMICAL PROPERTIES:
Chemical properties involve the reactivity of polymer with
acids, alkalis, alcohols and many other chemicals. PET
has good resistance against most of the chemicals.
Because of this property it is used to store many
chemicals.
Chemical Resistance

Acids concentrated

Good

Acids dilute

Good

Alcohols

Good

Alkalis

Poor

Aromatic hydrocarbons

Fair

Greases and Oils

Good

Halogens

Good

Ketones

Good

THERMAL PROPERTIES:
Thermal properties are the properties exhibited by the
substance when it is subjected to heat. These include the
heat distortion temperature, glass transition temperature,
thermal conductivity, etc.
Thermal Properties
Coefficient of thermal expansion ( x10 - 20-80

K-1 )

Heat-deflection temperature - 0.45MPa

115
( C )
Heat-deflection temperature - 1.8MPa
80
( C )
Lower working temperature ( C )

-40 to -60

Specific heat ( J.K-1.kg-1 )

1200 1350

Thermal conductivity ( W.m-1.K-1 )

0.15-0.4 @ 23

Upper working temperature ( C )

115-170

ELECTRICAL PROPERTIES:
Electrical Properties
Dielectric constant @1MHz

3.0

Dielectric strength ( kV.mm-1 )

17

Dissipation factor @ 1kHz

0.002

Surface resistivity ( Ohm/sq )

1013

Volume resistivity ( Ohm.cm )

>1014

OPTICAL PROPERTIES:
The
optical
properties of
thermally
crystallized
polyethylene terephthalate (PET) were investigated using
the methods of small-angle light scattering, density, and
haze measurements. The results indicate that the haze in
crystallized PET results from scattering due to crystalline
aggregates called spherulites. The formation of
spherulites can lead to high levels of haze even at very
low levels of crystallinity. A detailed analysis of polarized
light-scattering patterns was employed in order to define
the various structural parameters responsible for haze.
The relationships between haze, crystallinity, spherulite
size, and volume fraction of spherulites were developed
for PET.

RHEOLOGICAL PROPERTIES:
Steady-state
flow
properties
of
poly(ethylene
terephthalate) melts as a function of Temperature (T),

shear rate (), and inherent viscosity (I.V.) were

determined. An Instron capillary rheometer was used to
obtain data on wall shear stress (W) vs. for
poly(ethylene terephthalate) (PET) at temperatures of
265 to 295C. The polymer samples investigated covered
an inherent viscosity range of 0.35 to 0.82, corresponding
to a weight-average molecular weight range of 23,000 to
70,000. Capillaries used in this investigation covered the
range of 10 to 67.5 in length/diameter (L/D) values. Endeffect corrections (n) estimated by Bagley's method were
small with n < 1 over the entire shear rate range covered
(5024,000 sec.1). Flow curves showed (1) that over the
shear rate range of about 50 to 1000 sec. 1, the flow
behavior of PET was nearly Newtonian, i.e., log-log plots
of W vs. were linear with slopes of about 1, and (2)
that over the shear rate range of 1000 to 24,000 sec. 1,
the flow behavior of the polymer was slightly
pseudoplastic. Using Mendelson's shear rate-temperature
superposition scheme with an additional shifting to a
single reference I.V. level, we were able to shift all the
data to a single master curve of log (aTb
),
where aT and b
are the shift factors for temperature
and molecular weight, respectively.

CONCLUSION:
Polyethylene terephthalate is one of the widely used
polymer in todays world. It is used in food packing
industry extensively. It is also recyclable. This is a very
important polymer which we use it in our everyday life.