Polyesters

Polyesters are defined as step growth (or condensation) polymers containing ester units as the essential polymer chain forming
linkage. The most important commercial polyester is poly(ethylene terephthalate), often referred to as PET. Polyester fibres or
largely PET fibres dominate the world synthetic fibre industry.
Basic reactions in the synthesis of PET

Poly(ethylene terephthalate) (PET) is formed by step growth reaction of ethylene glycol with either dimethyl terephthalate (DMT)
or purified terephthalic acid (PTA). The chemical structure of monomers and compounds used in PET synthesis is shown below
in table 1.3:
Table 1.3: Chemical Structure of various monomers and compounds used in PET synthesis
Abbreviation
Chemical Chemical Structure
used
Ethylene Glycol EG
Purified Terephalic Acid PTA (TPA)

Dimethyl Terephthalate DMT

Bis(Hydroxyethyl) BHET (also

Terephthalate DTG)
Diethylene Glycol DEG
When DMT is used as the monomer, it is known as the DMT process. This was the first to be commercialized because DMT was
available in required purity, but terephthalic acid was not. Later the purified terephthalic acid became available and PTA process
was introduced. Now both processes are used.

The strategy used to synthesize polymeric chains of PET is very different to that used for nylon 6,6. The ethylene glycol
monomer is not a strong enough base to give rise to a salt with the other monomer, terephthalic acid, therefore the route to exact
stoichiometry is not available for PET synthesis. Therefore, the synthesis is started with an excess of ethylene glycol and later on
removed by evaporation as polymerization proceeds so that ultimately the monomer stoichiometry of 1:1 is achieved.
Synthesis of PET
The synthesis of PET requires two steps. The first step is know as ester interchange (EI) in DMT route or direct esterification
(DE) in PTA route. Both produce a mixture of ethylene glycol esters of terephthalic acids. The second step is polycondensation,
which is common for both routes.
First Step of polymerization

(a) DMT route: Ester Interchange (or transesterification) Reaction

 ----[36]

In the ester interchange (EI) process, excess of ethylene glycol is reacted with dimethyl terephthalate in the presence of
catalysts at temperatures starting from 150°C and slowly increasing to 210°C as shown in reaction [36]. The heat of reaction is
~14 kcal/mol. The reaction is reversible and is driven to completion by distilling off the byproduct methanol. This distillation is
carried out using fractionating column so that a minimum of ethylene glycol is removed. In practice, the ethylene glycol to DMT
ratio of 1.7 - 2 is used so that the temperature at completion does not rise too high.

This pre-polycondensation reaction leads to products which mainly contain bis(hydroxyethyl) terephthalate (BHET). The product
also contains some unreacted ethylene glycol together with linear oligoesters of the general formula as shown in structure [37]:

-------[37]

The average degree of polymerization (n) of oligomers in the reaction mixture depends on the ratio of ethylene glycol to DMT. If
number of moles of EG is twice that of DMT, only BHET is obtained. If it is lower than 2 times the DMT, an higher value of n is
obtained. This mixture is called prepolymer and is used in second step known as polycondensation (discussed later).

The addition of catalyst, most often metallic salts of a weak or volatile acid, such as Pb, Zn, Mn, Ca or Cd acetate, is preferred.
Many of these cationic species are also known to catalyze ester interchange and the thermal degradation reaction that occur at
polycondensation step. Since the thermal degradation reaction becomes more competitive at polycondensation conditions, it
tends to limit the attainable molecular weight and results in a yellow color in the polymer. Therefore, at the end of
transesterification stage, the catalyst must be deactivated by the addition of a sequestering agent such as phosphoric acid and
triphenyl phosphate.
b) TPA Route: Direct Esterification Reaction

In the direct esterification process (DE) as shown in reaction [38], due to the low solubility of terephthalic acid in boiling glycol, it
is necessary to raise the reaction temperature and pressure to 240-260 °C and 4 x 105 Pa, respectively, to obtain an adequate
reaction rate. The reaction is self-catalyzed by the carboxylic acid groups. However, additional catalysts such as stronger acids
and esters of titanic acid are also used. The volatile byproduct of direct esterification is water, which is distilled out of the reactor
to force the reversible reaction towards completion.

Esterification reaction
 -----[38]

One of the side products of this reaction is the formation of diethyl glycol (DEG) as shown in reaction [39].

-----[39]

The catalytic action of acid groups and the high temperature employed during the esterification increases the formation of DEG.
DEG formation can be reduced by reducing the EG/TPA ratio during the start of the reaction and by addition of chemicals which
reduce or prevent DEG formation. Therefore an EG/TPA ratio of 1.1 to 1.3 is used and consequently, the initial reaction product
is a mixture of linear oligomers of a somewhat higher degree of polymerization (n) than that from ester interchange reaction
discussed above.

A very small amount of a strong base, such as sodium hydroxide or an organic quaternary hydroxide is added as effective
catalysts to reduce DEG formation. The formation of DEG during pre-polycondensation step results in decrease of the melting
point of the polymer obtained from TPA route, and therefore, its melting point is generally lower than that obtained by DMT route.
After esterification is complete, a phosphite or phosphate ester may be added to inactivate the basic additive and stabilize the
polymer.

TPA route has several economical advantages over DMT route, which are given below:

• The yield by weight of polymer obtained from the monomer is higher in PTA route, because, DMT is a diester with two
methanol molecules which needs to be removed during ester interchange reaction.

• EG/PTA ratio is much lower in PTA route than EG/DMT ratio used in DMT route, therefore lower amount of EG needs to
be removed during the polycondensation step (i.e. 2nd step) to achieve same molecular weight.

• The cost of PTA is lower than that of DMT

• Methanol obtained from ester interchange reaction, needs to be collected, purified by distillation and sold as a
byproduct, which makes DMT route more expensive.

Therefore, the PTA- based production saves 8% of total capital investment and 15 % of feedstock cost.

Second step of polymerization

Melt polycondensation (PC) reaction
The product from first step is subjected to a further reaction stage known as polycondensation (PC) which produces
poly(ethylene terephthalate) of fibre-forming molecular weight. This reaction takes place in melt phase and the byproduct, EG is
removed from melt using high vacuum. Reaction [40] shows stoichiometric equation for the synthesis of PET. High viscosity PET
grades for bottles or technical yarns are typically produced by further polycondensation in an additional solid state process (SSP)
under vacuum or in an inert gas atmosphere.

At this stage of polymer synthesis, the BHET molecules or its short oligomers undergo ester interchange reactions (i.e.
transesterification reaction) at their reactive ends to join up into longer chains (in presence of suitable catalyst). One mole of
glycol is eliminated in each reaction step.

----[40]

As the polycondensation reaction is reversible, and the whole process is in complex equilibrium of forward and backward
reactions. Therefore, it is important to remove the glycol produced from the system as quickly as possible. As the glycol is
removed by high vacuum; the reaction is forced to move towards higher and higher molecular weight. With increase in molecular
weight, the melt becomes increasingly viscous; the melt viscosity of the fibre grade PET polymer at 285°C is of the order of 3000
poise under the shear conditions of roughly 1000 s-1. It is difficult to continue to drive the reaction forward as the viscosity
becomes very high and it becomes difficult to turn the reactant mixture. This prevents EG from evaporating further and makes
difficult for any two reactive ends of polymer chains to find each other for further reaction. This stage of the reaction is called
diffusion controlled.

The polymerization may be carried out in a semibatch reactor or a continuous reactor.

Usually, the molecular weight in a semi-batch reactor can be controlled by comparing the power input of the agitator motor.
Power required by the stirrer motor to keep the stirring going is proportional to the viscosity of the polymer. A reaction may be
stopped once a predetermined power value drawn by the stirrer motor is reached, indicating that the targeted viscosity has
reached.
In this step, a further catalyst (explained later) is added to the mixture of linear oligomers, free glycol is distilled out, and the
temperature is raised until it reaches 280-290°C. The pressure is reduced as rapidly as possible without causing carry-over due
to foaming, and polymerization is carried out at a pressure below 25 Pa (0.2 mm Hg) until the required molecular weight is
attained. In the melt phase, a molecular weight (number average) of typically between 16000 and 19000, which is equivalent to
Intrinsic viscosity (IV) of 0.58-0.68, is reached.

What are the Catalysts used for polycondensation

Polycondensation reaction also requires a catalyst, popular catalyst for transesterification reaction at this stage is antimony
trioxide, Sb O , although antimony pentaoxide and germanium dioxide have also been used. The proposed catalysis mechanism
2 3
of titanium compounds is illustrated in reaction [41].

----[41]

The primary step in catalysis is the coordination of metal ion to the ester carbonyl bond to increase its polarity to facilitate
nucleophilic attack. In the early stages of polycondensation, when the hydroxyl group concentration is high, the antimony
catalysts coordinate with hydroxyl groups, and therefore, the catalytic activity of antimony is lower in the initial stages of
polycondensation. As the EG is evaporated, the effectiveness of antimony catalysts improves towards the later part of the
polycondensation reaction.
Antimony trioxide has a tendency to produce a gray-green tinge in the polymer due to a reduction of a small proportion of
catalyst to antimony metal. Therefore, germanium dioxide is used where particularly white fibre is required, although its cost is
high, and therefore, precludes general use.
How to obtain high molecular weight?

(a) Reactor design

As stated above, the rate of attainment of high molecular weight is diffusion-controlled rather than chemically controlled. It is
useful to minimize the diffusion path by maximizing the surface to volume ratio and the rate of generation of free surface. This
helps in escape of EG under vacuum and high temperature. This may be facilitated by feeding the melt into rotating disc ring
reactors that have multiple discs that create thin and renewable film of the polymer melt, thus significantly increasing the
available surface area, and decreasing the diffusion path for condensate (EG) removal.
However, concurrently with polycondensation, a thermal degradation reaction also takes place, which leads to chain scission
and a drop in molecular weight. This thermal degradation reaction, which is discussed more fully along with side reactions, is the
major cause of the presence of carboxyl end-groups in the polymer and the fibre.
(b) Chain extenders

The later stages of the polycondensation can be chemically modified to overcome the limitation imposed by the diffusion rate of
EG. At an intermediate stage in the polycondensation, 0.5-2% of a diphenyl ester, preferably phenyl carbonate or diphenyl
terephthalate is introduced into the reaction mixture. These molecules act as chain extenders and react rapidly to couple
polymer chains with evolution of phenol. It has been reported that PET formation proceeds at two to three times faster and the
product colour is improved when TPA is added as a chain extender. The amount of TPA to be added depends on the DP of the
polymer at the time of addition.
The equilibrium in this reaction is much more favorable to the formation of polymer and free phenol than it is in usual reaction
which forms polymer and free EG. This helps in greatly accelerating the polymerization reactions and substantially reducing the
reaction times. A further result is that polymers of lower carboxyl end-group content and higher molecular weight can be
obtained. This modification is now little used because it is less advantageous in a continuous polymerization reactor.

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Side Reactions in melt PET polymerization and their influence on PET

properties
In order to meet the stringent product specifications it is required that the molecular weight and side product concentration is
strictly controlled in the polymer. The important side products, which critically control the product quality, are acetaldehyde,
diethylene glycol, acid end groups, vinyl end groups and cyclic oligomers. The rate of formation of these side products depends
on the operating conditions and also on the type and concentration of the catalysts used in PET manufacture .

In addition, PET may undergo degradation reactions. The catalysts used in the transesterification and polycondensation stages
are also known to catalyze the degradation reactions.
(i) Formation of Diethylene Glycol (DEG) and Dioxane

DEG (Diethylene glycol) is the most important side product in PET synthesis. DEG and dioxane can be regarded as
condensation products of EG formed according to the following stoichiometric as shown in reactions [42-44].

----[42]

------[43]

------[44]

Reaction for the formation of DEG and DIOXANE

PET made by direct esterification of TPA generally contains more DEG than PET made by transesterification of DMT. Alkaline
compounds of alkali metals, alkaline earth metals, amines or ammonium compounds of the fourth group are effective catalysts
for reducing DEG formation. It is reported that most of the DEG (70%) is formed during the preheating and low vacuum stage of
polycondensation. Only about 20% is formed during the transesterification stage and about 10% is formed in the final stages of
polycondensation.

Dioxane, which is formed from DEG, has a high vapour pressure (i.e. is quite volatile) and is removed from the process as
column top product. However, DEG is less volatile (boiling point 215°C) and, since it is a diol, it gets incorporated into the PET
chain as comonomer. This alters the crystallization behaviour of PET.

The quantity of DEG in PET molecules influences many important properties of the polymer; e.g., density, thermal, oxidative and
hydrolytic degradation, light-stability, and thermal transitions. Incorporation of DEG is known to increase the dyeability, though
the dye take-up of PET is not uniform. DEG content in the polymer decreases the melting point and thermal stability of the
polymer. The melting point of the polymer is depressed by approximately 2.5-5°C for each 1% of DEG incorporated in the
polymer chain. It is therefore important to control DEG formation in PET manufacture.

(ii) Thermal degradation of Repeat units

Thermal degradation of PET polymer chains is a major problem at temperatures above the melting point and occurs during the
melt polycondensation because of high temperature and residence time required for obtaining high molecular weight. The major
consequences of these on the PET quality are: drop in intrinsic viscosity, formation of carboxyl end groups and acetaldehyde,
and yellowing of polymer.
 --------[45]

Mechanism of Thermal Degradation of PET

The mechanism of thermal degradation of PET is shown in reaction [45] .Carboxyl end groups reduce the hydrolytic and thermal
stability, and in standard PET grades, their concentration should not exceed 25 mmol/kg. Acetaldehyde migrates into the
contents of food packaging, so causing flavour problem of the products. For bottle-grade PET, often acetaldehyde content below
1 ppm is specified. By-products of thermal degradation are light gases, being mainly CO, CO , ethene, methane, and benzene,
2

together with PTA, BHET and short-chain oligomers.

The thermal degradation of PET is strongly influenced by metal catalysts. The acetates of Na and Mg have little activity, whereas
the acetates of Co, Cu and Zn accelerate the thermal degradation, with Zn being the most active.
The addition of stabilizers such as triarylphosphites or triarylphosphates blocking the metal ions has been recommended for
providing control of thermal degradation reactions.
(iii) Thermo-oxidative degradation
Presence of oxygen and traces of water/moisture, during the synthesis and processing stage of PET results in thermo-oxidative
degradation and hydrolysis take place, which cause a drop in molecular weight. Therefore, it is very critical to maintain moisture
free inert atmosphere during synthesis and processing by application of high vacuum.
iv) Formation of oligomers

During the process of melt polycondensation of PET, about 2-3 % of short chain oligomers are also formed as shown in
structure [47]. Oligomers can occur as linear or cyclic molecules; however the cyclic trimer has been postulated to be
predominant (60 to 80% of the total amount of cyclic oligomers). The structure of cyclic Trimer as shown below in [48].

---[47]

Cyclic dimers
It has been shown that during thermal processing, 98% of trimer primarily migrates to surface and cause serious problems in
spinning, dyeing, and subsequent processing steps. It exudes to the hot polymeric surface and coats spinneret plate on the melt
spinning unit leading to frequent filament breakages. During dyeing process it causes the coating of dyeing equipment and
interferes with the process.

-----[48]

Cyclic Trimer
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Solid state polymerization of polyamides and polyesters

After polymerization in the melt phase, the molecular weight of polyester can be further increased by polycondensation of PET
chips in the solid state and this process is called solid state polymerization (SSP). This process enables higher molecular
weights to be reached which are either technically or commercially not feasible in the melt phase. Solid state polymerization in
the form of chips or powder, pre-extrusion SSP is a common approach in the production of high molecular weight polymers for
molded products.
How solid state polymerization helps?
Polycondensation reaction is exothermic, therefore, it can also be driven forward to give polymer with higher molecular weight if
the reaction is carried out at a lower temperature. At lower temperatures of polycondensation, equilibrium shifts forward to higher
completion enabling formation of higher molecular weight of the product. Since temperatures can not be lowered in melt
polymerization, the best solution is to carry out the reaction in solid state, wherein temperatures lower than melting point of the
polymer can be used. At these temperatures, the kinetics of the reaction is slow and it takes a long time to complete the reaction.

The molecular weight can be increased up to 27000 (IV, 0.90) for bottle grade and as high as 38000 (IV, 1.20) for technical
applications such as tyre cord, seal belts and air bags.

What is the process of solid state polymerization?

The first step before carrying out the solid state polymerization is precrystallization of chips. The water quenched polymer chips
obtained from melt polycondensation stage are almost wholly amorphous. Therefore, the chips are first intensely dried and
annealed at a gradually increasing temperature up to the point of maximum crystallization rate to impart high level of crystallinity.
This raises the glass transition temperature of the chips and prevents their sticking to each other during solid state
polymerization.

The SSP is performed at temperatures between 220 and 235°C for PET, which lie above the glass transition temperature and
below the crystalline melting point of PET. Under these conditions, polymer chain end groups are mobilized sufficiently to
undergo polycondensation. The annealed chips are heated in a stream of hot inert gas or by agitating in a vacuum drier to
remove small traces of EG and other volatile by-products. As the reaction is carried out in the solid phase, volatile by-products
can diffuse easily to the surface of each polymer chip and are instantly carried away by the gas flow or high vacuum.

The main advantages of increasing molecular weight in solid state compared to melt phase are:

• Problems associated with stirring of viscous melt are eliminated.

• Degradation and side reactions are limited in the solid state due to lower processing temperature used. Solid state
polycondensation process favours polymerization process compared to depolymerization.

• Best means of achieving PET with acceptable level of acetaldehyde.

The rate of the solid state polycondensation process depends on particle size, initial molecular weight, crystallinity of PET chips
and end group concentration. The pellet size has generally been used to identify the rate controlling mechanism of overall
reaction rate. When the reaction rate is chemically controlled, then the pellet size has no effect on the reaction rate. On the other
hand, if reaction rate is diffusion controlled, i.e. limited by the diffusion of byproducts from inside of the pellet chips to the pellet
surface, then the reaction rate can be increased by decreasing the pellet size, due to decrease in the length of diffusion path.

It has also been shown that the higher starting molecular weights enable higher molecular weights to be achieved. this has been
attributed to the tendency of the lower starting molecular weights to lead to higher crystallinity build-up during SSP.
Crystallization reduces the SSP reaction rate by reducing chain mobility and by increasing the diffusion path length of the
by-products. The crystallinity of polymer should be between 33 and 58% and should not exceed 80%.The reaction rate is very
sensitive to the ratio of hydroxyl to carboxyl end groups. At low carboxyl concentrations, the transesterification reaction will be
favoured, while at high carboxyl concentrations the esterification route will be preferred. The optimum ratio of hydroxyl end
groups to carboxylic end groups has been experimentally found to be two.

Can solid state polymerization be used for polyamides?

Similar to PET, nylons can also be subjected to solid state polymerization to achieve high molecular weight for tyre cord and
other industrial grade polymers. The principle remains the same as described above, except that the temperature of
polymerization is much lower at 180-210°C and the reaction is carried out in a rotating vacuum vessel (similar to tumble dryer)
under nitrogen blanket. It takes about 48 h to achieve the desirable molecular weight, which is about 2 times the fibre grade
molecular weight.
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Modified polyesters
In spite of outstanding properties, such as chemical resistance, easy care properties, resistance to moth, mildew and
microorganisms, the PET fibres have some shortcomings, for example:

• Hydrophobic nature

• Ease of soiling

• Static charge build up

 • Pilling tendency

• Lack of dye receptor sites

These drawbacks can be overcome by changing processing conditions or molecular weight, introducing additives or fillers to
polymer matrix, or by copolymerization with new monomers. Incorporation of third/or fourth component or nano materials into
PET backbone during polymerization changes some of the fundamental properties of the polymer. Production of PET
copolymers for textile applications is certainly not new and a brief summary is given in Table 1.4 below.
Table 1.4: Various approaches for modification of Polyester.
Type of
Approach By using
Modified PET
Deep dyeable By Reducing T using a
g Segments of polyethylene oxide (PEO) in
PET flexible comonomer PET backbone
Carrier free By adding additives that polyethylene glycol ( PEG), adipic acid to
dyeable PET reduce the T g form block copolymers
Cationic dyeable By introducing sulphonic
5-sulpho-isophthalic acid as comonomer
PET acid groups
By copolymerizing with
Biodegradable Tetra methylene succinate or ethylene
polyethers or aliphatic
PET succinate copolymers
polyesters
By introducing
Flame retardant
phosphorus containing phosphate esters for copolymerization
PET
groups
By block
Antistatic and copolymerization with introduction of polyethylene oxide by block
antisoiling PET hydrophilic, humectant copolymerization
polymer
High Replacement of some
Dimethyl-2,6-naphthalenedicarboxylate for
performance phenylene units by more
copolymerization
PET rigid aromatic units

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