CHAPTER 21

POLYMERS
FJ/Chemistry Unit, KMPk/Mac 2006 1
21.1 : Introduction
Polymer
- is a macro molecule that is made up of many small repeating units
called monomers linked together by covalent bond.

nA -A-A-A-A-A-A-A-A-n
- monomer
polymer polymer
can be represented by their repeating unit in the long
chain.

nA -A-n
Monomer polymer
- is a basic molecular units that can joined unit)
(repeating to many others to form a
polymer.

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 Homopolymer
- a polymer formed from only one types monomer units.

nA -A-n

- Example :
nCH2 CH2 -CH2CH2-n

ethene polyethene
(ethylene) (polyethylene)

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 Copolymer
- a polymer formed from two or more different monomers.

nA + nB -A-B-n

- Example :

nCH2 CCl2 + nCH2 CHCl -CH2-CCl2-CH2-CHCl-n

1,1-dichloroethene 1-chloroethene Saran®

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21.2 : Structures of Polymers
21.2.1 : Linear Polymers
Linear polymer is a polymer consist of monomers that are
linked in straight and long continuous chain.
Linear or straight-chain polymer can be folded back upon
themselves in a random fashion.
Linear polymer is recycleable because it is soft and can be
reformed when heated.

-A-A-A-A-A-A-A-A-n
monomers link together
in a straight chain
folded linear polymer
in a random fashion
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21.2.2 : Cross-linked Polymers

Cross-linked polymer contains branches that connect linear polymer chain, as shown
in the figures below.

-A-A-A-A-A-A-A-A-A-A-A-A-
X X
-A-A-A-A-A-A-A-A-A-A-A-A-
Cross-linked polymer is harder (rigid) and more elastic polymer compared to linear
polymer.
• Long polymer chain cross-linked by branched
It also cannot be remelted or remolded again.

The equation below shows the chemical reaction for the rubber vulcanization
process.

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In a vulcanization process, long chain of polyisoprene are cross-linked by sulphur
atoms.

CH3 CH3
-CH2C CH-CH2- + -CH2C CH-CH2-

sulphur

CH3 CH3
-CHC CH-CH2-CHC CH-CH2-
After vulcanizationSrubber becomes more
S stable over wide ranges of temperature
and far more durable than natural rubber.
-CHC CH-CH2-CHC CH-CH2-
CH3 CH3

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21.3 : Types of Polymers
21.3.1 : Natural Polymers
Natural polymers are polymers that synthesized in nature
or naturally occurring polymers.

i. Proteins
Protein are the most abundant organic molecules in animals
such as enzymes, hormones, hemoglobin and many other
things.
It is a natural polymer built from amino acids linked by
amide bonds.

H O
HN-C-C
R n
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ii. Carbohydrates
Carbohydrates such as starch is also a polymer.
i. Starch (amylose)

CH2OH CH2OH
O O
H H HH H H
O OH H O OH H O

H OH H OH
ii. Starch (amylopectin) n
- α-(1,4)-glycosidic
contains α-(1,4)-glycosidic linkages linkages.
and α-(1,6)-glycosidic

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iii. Natural Rubber
Natural rubber is a polymer of 2-methyl-1,3-butadiena, also known as
isoprene.

n CH2=C-CH=CH2 -CH2-C=CHCH2-
CH3 CH3 n
Another name for natural rubber is cis-1,4-polyisoprene.
isoprene cis-polyisoprene
All the double bond in natural rubber are cis- configuration.
Natural rubber is soft, not strong or elastic and sticky, that makes it less
useful.
In order to make it more useful rubber has to undergo a vulcanization process.

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21.3.2 : Synthetic Polymers

Synthetic polymers are polymers that are prepared in industries from

monomers that have gone through polymerization process.
Polymerization is a process that combines monomers to form polymers.
Synthetic polymers can be classified base on their method of preparation
( polymerization process ).

21.3.2.1 : Addition Polymerization

Addition polymerization is the addition reaction in which unsaturated

monomers are joined together by covalent bonds to form a polymer
without elimination of a small molecule.
Polymers obtained by addition polymerization are called addition polymers.

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 Therefore, addition polymer always involves the
polymerization of monomers which have double bond within
the monomers.
Peroxide is used as initiator in addition polymerization.

i. Formation of polyethene

n CH2 CH2 ROOR -CH

( 2-CH2-
)n
ethene polyethene

ii. Formation of polyvinyl chloride

n HC CH2 ROOR (
-HC-CH 2-
)n
Cl Cl
chloroethene polychloroethene
(polyvinyl chloride or PVC)
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iii. Formation of polystyrene

n HC CH2 ROOR (
-HC-CH 2-
)n

phenylethene Polyphenylethene
(styrene) (polystyrene)

iv. Formation of polyisopropene

n CH 2 =C-CH=CH 2 -CH 2 -C=CHCH 2-

CH 3 CH 3 n

isoprene polyisoprene
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21.3.2.2 : Condensation Polymerization

Condensation polymerization is a process that combines the monomers

with elimination of a small molecule such as water, methanol, hydrogen
chloride or ammonia to form a polymer.

The polymers obtained from condensation polymerization are called

condensation polymers.

The monomers involves in this polymerization must have at least two

identical or different functional group in the molecule.

When a carboxylic acid with two –COOH group reacts with an amine
with two –NH2 groups, a polyamide is formed.

When a carboxylic acid with two –COOH group reacts with an alcohol
with two –OH groups, a polyester is formed.

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(A). Polyamides
i. Formation of Nylon 6,6
O O
n H2N-(CH2)6-NH2 + n HO-C-(CH2)4-C-OH
hexane-1,6-diamine hexane-1,6-dioic acid

H H O O
(
-N-(CH 2)6-N-C-(CH2)4-C-
)n + n H2O
Nylon
ii. Formation of Nylon 6 6,6

O O
n H2N-(CH2)5-C-OH (
-NH-(CH 2)5-C-
)n + n H2O
6-aminohexanoic Nylon 6 15
iii. Formation of Kevlar

H H O O
n H-N- -N-H + n Cl-C- -C-Cl

1,4-diaminobenzene terephthalic acid

H H O O
(B). Polyester
N- -N-C- -C n + n HCl
The repeating functional groups in this polymer chain are ester.
The most familiar polyester is polyethylene terephthalate known as Dacron and
Terylene. Kevlar

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 The polymer is formed by the reaction of ethylene glycol
with methyl ester or terephtalic acid.
In this process, a molecule of methanol is split out for
each new ester group formed.

i. Formation of Dacron

O O
n CH3O-C- -C-OCH3 + n HO-CH2CH2-OH
1,2-ethanediol
dimethyl terephthalate
(ethylene glycol)

O O
(
-O-CH 2CH2-O-C- -C-
)n + n CH3OH

Dacron or poly(ethylene terephthalate) metanol

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ii. Formation of Terylene

O O
n HO-CH 2CH 2-OH + n HO-C- -C-OH
ethane-1,2-diol benzene-1,4-dicarboxylic acid

O O
(
-O-CH 2CH 2-O-C- -C-
)n + n H 2O
water
Terylene

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21.4 : Uses of Synthetic Polymers

No. Polymer Uses

1 Polyethene plastics, drinking bottles, toys
2 Polyvinyl chloride piping, floor tiles, clothing, toys,
wire covering
3 Polystyrene containers, thermal insulation-ice buckets
4 Nylon 6 Textile
5 Nylon 6,6 Sweater
6 Kevlar Bullet proof vest
7 Dacron Fabric
8 Terylene Fiber-optic material

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