Synthetic Polyesters

Polyesters are polymers in which the monomeric units are joined by ester groups:

monomeric unit

O
||
C
ester
group

monomeric unit

Polyesters are formed in condensation polymerisation reactions between adicarboxylic

acid and a diol:
dicarboxylic acid

diol

polyester

water

Polyesters formed from a diol and a dicarboxylic acid are linear, that is, consist mainly
of straight chains with few branches.

Polyesters can be drawn out into fibres or stretched into films.

The C=O bond in the ester link is polar,

C+=O-

Dipole-dipole interactions act between the polymer chains,

C+=O-

......

C+=O-

The polar C=O bond provides an active site for chemical reaction: polyesters readily
hydrolyse in strongly alkaline conditions.

Examples of polyesters:
poly(ethylene adipate)
poly(ethylene terephthalate), PET
poly(trimethylene terephthalate), PTT
poly(butylene terephthalate), PBT

Poly(ethylene adipate)
In the 1920s, W.H. Carothers, working for Du Pont, discovered that diols (alcohols with 2 OH
functional groups) and dicarboxylic acids (carboxylic acids with 2 COOH functional groups)
could be mixed to make polyester polymers#.
He produced polyethylene adipate by heating ethylene glycol (1,2-ethanediol) with adipic acid
(hexanedioc acid).
Monomer name

Monomer structural formula

Monomer's functional groups

trivial: adipic acid

IUPAC: hexanedioc acid

HOOC-CH2-CH2-CH2-CH2-COOH

two carboxylic acid, COOH, functional groups

trivial: ethylene glycol

IUPAC: 1,2-ethanediol

HO-CH2-CH2-OH

two hydroxyl, OH, functional groups

Each time an OH functional group reacts with a COOH functional group, an ester link, -O-CO- ,
is formed between the two molecules and a molecule of water is eliminated.
This is an example of a condensation polymerisation reaction, the monomeric units join
together by eliminating the small water molecule.
ethylene glycol
+
(1,2-ethanediol)
H
H
|
|
HO - C - C - OH
|
|
H
H

adipic acid
(hexanedioc acid)
O
H
||
|
HO - C - C |
H

H
H
H
O
|
|
|
||
C - C - C - C - OH
|
|
|
H
H
H

polyethylene adipate
H
H
O
H
H
H
H
O
|
|
||
|
|
|
|
||
-(- O - C - C - O - C - C - C - C - C - C -)n |
|
|
|
|
|
H
H
H
H
H
H

+ water

H-O-H

In order to drive the reaction forward to maximise the production of the polyethylene adipate
polymer, Carothers's team developed a "molecular still" in which water was removed as a
vapour and then condensed on a "cold finger". By Le Chatelier's principle, removing water
shifts the equilibrium position to the right to compensate for the loss of the water so that
more polymer and more water is produced.
Unfortunately, polyethylene adipate has poor resistance to heat, melting during the hot
ironing process so when Carothers discovered nylon, Du Pont devoted itself to developing
nylon rather than polyesters.
Poly(ethylene terephthalate)

British Chemists Whinfield and Dickson finally patented PET or PETE (polyethylene
terephthalate) in 1941.
Polyethylene terephthalate (PET) forms the basis of synthetic fibres such as
dacron(manufactured by Du Pont), terylene (manufactured by ICI##) and 'polyester'.
These polyester fibres were very popular in the 1970s, but were declining in popularity until
1989 with the development of microfibres which are polyester fibres with the look and feel of
silk.
Because polyethylene terephthalate is strong and has good resistance to impact, it is used to
make containers like drink bottles.
When formed into films such as biaxially-oriented polyethylene terephthalate (BoPET),
polyethylene terephthalate is the basis for Mylar which is used in shiny, colourful, expensive,
helium balloons and space blankets.
Polyethylene terephthalate films can also be shaped into packaging materials like trays and
blister packs.
Polyethylene terephthalate can be prepared in the laboratory by heating terephthalic acid
(1,4-benzenedicarboxylic acid) with ethylene glycol (1,2-ethanediol) in the presence of an acid
catalyst.*
Monomer name
trivial: terephthalic acid
IUPAC: 1,4-benzenedicarboxylic acid
trivial: ethylene glycol
IUPAC: 1,2-ethanediol

Monomer structural formula Monomer's functional groups

HOOC

COOH

HO-CH2-CH2-OH

two carboxylic acid, COOH, functional groups

two hydroxyl, OH, functional groups

The reaction is a condensation polymerisation reaction in which water, H2O, is eliminated.

Each carboxyl, COOH, functional group can react with a hydroxyl, OH, functional group to

produce water and an ester, -COO-, link between the two molecules.
To start the polymerisation, 1 molecule of terephthalic acid reacts with 1 molecule of ethylene
glycol to produce 1 molecule of the ester and 1 molecule of water:

1HOOC

COOH

1HO-CH2-CH2-OH

HOOC

COO-CH2-CH2-OH

+ 1H2O

The ester molecule has a carboxylic acid, COOH, functional group at one end and a hydroxyl,
OH, functional group at the other end so it can react with both the ethylene glycol monomer
and the terephthalic acid monomer.
If the ester molecule reacts with the 1 terephthalic acid monomer, a new ester link is formed
and a molecule of water is eliminated:

1HOOC

COO-CH2-CH2-OH

1HOOC

COOH

HOOC

COO-CH2-CH2-OOC
+ 1H2O

COOH

The new ester molecule has carboxyl, COOH, functional groups at both ends, so it can react
with ethylene glycol to produce another ester link and molecule of water:
In this way long chains of alternating ethylene glycol and terephthalic acid monomeric units
are built up to form the polyester polymer.
Each time a molecule of dicarboxylic acid reacts with a molecule of diol, 1 water molecule is
eliminated:
Number of
dicarboxylic acid
monomers

Number of
diol
monomers

Number of
ester links
formed

Number of
water molecules
eliminated

1
2
3
4

1
2
3
4

1
3
5
7

1
3
5
7

If n is the number of dicarboxylic acid monomers and also the number the diol monomers,
then
number of ester links formed = (2 x n) -1
Since 1 water molecule is elimated every time 1 ester link is formed, the number of water
molecules eliminated during the polymerisation reaction is equal to the number of ester links
formed:
number of water molecules formed = (2 x n) -1
Therefore we can write a general equation for the polymerisation of polyethylene
terephthalate as:
n terephthalic acid
nHOOC

COOH

n dicarboxylic acid

n ethylene glycol

nHO-CH2-CH2-OH

n diol

polyethylene terephthalate (PET)

-(-OC

COO-CH2-CH2-O-)n-

polyester

(2n-1) water

(2n-1)H2O

(2n-1) water

Oxygen is more electronegative than carbon. So the oxygen atom in each ester link is slightly
negatively charged, O-, while the carbon atom of the ester link is slightly positively charged,
C+. The C+ on one polymer chain is attracted to the O- on another polymer chain, so the
chains are held together by dipole-dipole interactions.
H
|

one polymer chain

H
|

O||

-(- O - C - C - O - C+
|
H

-(-

C+ -)n -

.
.

|
H
H
|

one polymer chain

O||

C
|
H

.
.

H
|
-

dipole-dipole interactions

O||

O||

C+

C+

-)n

|
H

The dipole-dipole interactions and the regularity of the stacking of the benzene rings results in
a highly crystalline polymer with a melting point of about 240oC.
Polyethylene terephthalate (PET) is a thermoplastic material which means that when it is
heated it becomes soft and can be molded into a new shape, making it suitable for recycling.
After materials have been collected for recycling, the polyethylene terephthalate (PET)
materials must be separated from the other materials.
The polyethylene terephthalate (PET) materials are then ground into smaller particles known
as flakes.
The flakes undergo further purification to remove any remaining foreign material. This can be
achieved by washing and air classification, as well as by water baths which can separate
particles that float from particles that sink.
The purified polyethylene terephthalate (PET) is then rinsed to remove any foreign materials
including detergent and disinfectant residues, and then dried.
The polyethylene terephthalate (PET) is heated to melt it, and the molten PET material passes
through a series of screens to form pellets (any non-molten material, non-PET material, will
not pass through the screens).
After cooling, the recycled polyethylene terephthalate (PET) pellets are ready to be used to
make new polyethylene terephthalate (PET) objects.
Recycled polyethylene terephthalate (PET) can used to make polyester carpet fibres, polyester
fabric for T-shirts and underwear, shoes, luggage, upholstery, automotive parts, sheets, films
and new PET containers.
Poly(trimethylene terephthalate)
Poly(trimethylene terephthalate) or PTT is produced by Du Pont as Sorona and by Shell as
Corterra.
Poly(trimethylene terephthalate) is produced by reacting terephthalic acid with 1,3propanediol.
Monomer name
trivial: terephthalic acid
IUPAC: 1,4-benzenedicarboxylic acid
IUPAC: 1,3-propanediol

Monomer structural formula

HOOC
COOH
HO-CH2-CH2-CH2-OH

Monomer's functional groups

two carboxylic acid, COOH, functional groups
two hydroxyl, OH, functional groups

The reaction is a condensation polymerisation reaction in which a molecule of water is

eliminated each time a hydroxyl, OH, group reacts with a carboxyl, COOH, group to form an
ester, O-CO-, link:
n terephthalic acid
nHOOC

COOH

n dicarboxylic acid

n 1,3-propanediol

nHO-CH2CH2CH2-OH

n diol

polytrimethylene terephthalate (PTT)

-(-OC

COO-CH2CH2CH2-O-)npolyester

+ (2n-1) water
+

(2n-1)H2O

+ (2n-1) water

The carbon of the ester link has a slightly positive charge, C+, and the oxygen atom has a
slightly negative charge, O-, because oxygen is more electronegative than carbon. Therefore
dipole-dipole interactions between the polymer chains hold them together.
Polytrimethylene terephthalate has 1 extra non-polar methylene (CH2) group in the chain than
polyethylene terephthalate, and this makes polytrimethylene terephathalate material softer,
easier to stretch and more easily coloured.
Polytrimethylene terephthalate can be used as a carpet fibre because it has good wear and
stain resistance.
Poly(butylene terephthalate)
Polybutylene terephthalate or PBT can be prepared by reacting 1,4-butanediol with
terephthalic acid (1,4-bezenedicarboxylic acid).
Monomer name

Monomer structural formula Monomer's functional groups

trivial: terephthalic acid

IUPAC: 1,4-benzenedicarboxylic acid

HOOC

IUPAC: 1,4-butanediol

COOH

HO-CH2-CH2-CH2-CH2-OH

two carboxylic acid, COOH, functional groups

two hydroxyl, OH, functional groups

The reaction is a condensation polymerisation reaction in which a molecule of water is

eliminated each time a hydroxyl, OH, group reacts with a carboxyl, COOH, group to form an
ester, O-CO-, link:
n terephthalic acid
nHOOC

COOH

n dicarboxylic acid

n 1,4-butanediol

+ nHO-CH2CH2CH2CH2-OH
+

n diol

polybutylene terephthalate (PBT)

-(-OC

COO-CH2CH2CH2CH2-O-)npolyester

+ (2n-1) water
+

(2n-1)H2O

+ (2n-1) water

Like polyethylene terephthalate (PET), polybutylene terephthalate (PBT) has polar C=O bonds
with the carbon being slightly positive, C+, and the oxygen atom being slightly negative, O-,
so that dipole-dipole interactions between the polybutylene terephthalate chains hold them
together.
The melting point of polybutylene terephthalate, 170oC, is less than that of polyethylene
terephthalate, 240oC.
The additional non-polar CH2 groups in the polybutylene terephthalate chains reduces the
melting point.
Polybutylene terephthalate has low moisture absorption, good fatigue resistance, good solvent
resistance, good self-lubrication, and maintains its physical properties well when heated.
Hydrolysis of Polyesters
Simple esters can be hydrolysed by reaction with dilute acids or alkalis.

Polyesters react with water so slowly that this reaction can be ignored. For this reason
polyesters can be used to make water bottles.
Polyesters react only very slowly with dilute acids. For this reason polyesters can be used to
make soft drink bottles since soft drinks are acidic.
Polyesters react readily with strong alkalis. The ester links are broken and the products of the
reaction are the diol and the salt of the carboxylic acid.

-(-OC

COO-CH2-CH2-OOC

COO-CH2-CH2-O-)n-

NaOH
Na+-OOC

COO-Na+

(salt of carboxylic acid)

HO-CH2-CH2-OH
(diol)

Na+-OOC

COO-Na+

(salt of carboxylic acid)

HO-CH2-CH2-OH
(diol)

Perhaps we should say rediscovered since it is believed that polyesters had been made earlier by Gay-Lussac and
Thophile-Jules Pelouze in 1833 and Jns Jakob Berzelius in 1847.
#

##

Imperial Chemical Industries

Polyethylene terephthalate is prepared commercially by converting terephthalic acid to the dimethyl ester first. The
dimethyl ester is much more easily purified by distillation or crystallisation than the acid. The dimethyl ester reacts
with the ethylene glycol in an ester interchange reaction to form polyethylene terephthalate.
*