Polymers

You may think of polymers as being a relatively

modern invention however naturally occurring
polymers have been used for thousands of years
– wood, rubber, cotton, wool, leather, silk,.. etc
• Artificial polymers are, indeed, relatively
recent and mostly date from after WWII
in many cases, the artificial material is both
better and cheaper than the natural alternative
A polymer is a large molecule of high molecular mass
made by linking together repeating units of small
molecules called monomers
• Polymerization: process of joining small monomers to form a
polymer.

• Degree of polymerization(n): the number of monomeric units

which combine to form a polymer.
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Classification on the basis of:
•Buna S/ Styrene Butadiene rubber/ SBR/GR-S Rubber

CH2 CH2 CH CH CH2 CH CH2

CH CH CH2 + n CH
n CH2
1,3-butadiene
n

Buna S
Styrene

Uses: For making automobile tyres, rubber soles, belts etc.

•Buna N/ Nitrile Butadiene rubber/ NBR/ GR-A Rubber

CH2 CH CH CH2 CH CH2
CH2 CH CH CH2 + n CH2 CH CN
Vinyl cyanide CN
1,3-butadiene Acrylonitrile n

Buna N

Uses: Aeronautical applications, footwear, sponges, floor mats

etc.
 Classification on basis of Method of
Synthesis/Polymerization
Addition or chain growth Polymerization
Condensation or step growth Polymerization

1.Addition or chain growth Polymerization: done by addition of

monomer units having multiple bonds and without the elimination of
any molecule. e.g. Polyethene , polypropylene
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2) Condensation or step growth
polymerization

Monomers containing some active functional groups react together

with the elimination of simple molecules like NH3, H2O, CO2 etc.

nH2N(CH2)6NH2 + nHOOC(CH2)4COOH  (-HN(CH2)6NHCO(CH2)4CO-)n + nH2O

hexamethylene adipic acid nylon-66
diamine
 Polyamide
•Nylon66: O O
-H2O
C OH
n H2N (CH2)6 NH2 + n HO C (CH2)4
Adipic acid
Hexamethylendiamine

H H O O

N (CH2)6 N C (CH2)4 C
n

Nylon 66

Uses: for making bristles for brushes, blended with wools for making
socks and sweaters etc.
O
•Nylon 6
-H2O
HN (CH2)5 C
n H2N (CH2)5 COOH
n

Amino caproic acid Nylon 6

Uses: tyre cords, fabrics and ropes.

.
•Nylon 6,10

O O
-H2O
n HO C (CH2)8 C OH
n H2N (CH2)6 NH2
Sebacic acid
Hexamethylendiamine

H H O O

N (CH2)6 N C (CH2)8 C
n

Nylon 6,10
 Polyesters
•Terylene/Dacron:
-H2O
n HO CH2 CH2 OH +n HOOC COOH

Ethylene glycol Terephthalic acid

O O

O CH2 CH2 O C C
n

Terylene/ Dacron
Uses: for making cloths by mixing with cotton, magnetic
recording tapes.
•Glyptal: O O
HOOC COOH
n HO CH2 CH2 OH +
-H2O O C C
n O CH2 CH2
Ethylene glycol
n

Phthalic acid Glyptal

Uses: in manufacturing paints and lacquers, building materials

such as asbestos, cement etc.
 Uses of PET
Poly(ethyleneterephthalate)
• polyester fabrics are used in apparel and
home furnishings such as bed sheets, beds,
table sheets, curtains and drape
• used in tyre reinforcements, ropes, fabrics for
conveyor belts, safety belts, coated fabrics
and plastic reinforcements with high energy
absorption
• Polyester fibers are also used to stuff pillows,
comforters and cushion padding
Classification on basis of intermolecular
forces or end use
Classification on basis of elemental
composition
 Classification on basis of
configuration/stereochemistry
• Tacticity: It is relative stereochemistry of adjacent chiral
centres within a macromolecule (polymer).
• If the monomer unit has a chiral center than different
stereochemistry is obtained. Polymerization of such a
monomer yield different stereoisomers.
• e.g. polymerization of propene.
• three types of stereochemistry is possible
• Isotactic: If similar groups are all on the same side of the
chiral centre i.e. if stereochemistry at all the chiral centre is
same within a macromolecules.
CH3 CH3 CH3 CH3 CH3 CH3 CH3

C CH2 C CH2 C CH2 C CH2 C CH2 C CH2 C CH2

H H H H H H H
Isotactic
• Syndiotactic: If stereochemistry at alaternating chiral cnetre
is same within a macromolecules.
CH3 H CH3 H CH3 H CH3

C CH2 C CH2 C CH2 C CH2 C CH2 C CH2 C CH2

H H CH3 H CH3 H
CH3

• Atactic: If the stereochemistry at chiral centre is random.

within a macromolecules.

CH3 H CH3 CH3 H CH3 H

C CH2 C CH2 C CH2 C CH2 C CH2 C CH2 C CH2

H CH3 H H CH3 H CH3

Atactic
 Copolymerization
• It is process of formation of polymer from
different types of monomer units.
• E.g. Buna N, Buna S
Thermopalstic on heating becomes Soft on further
heating beyond melting point it melt & flow Such
properties called plastic deformation.
Significance of Plastic deformation: used in molding
operation.
Thermosetting polymers do not exhibits plastic
deformation, because they undergoes cross linking
during molding to form 3-D structural material.
All monomer units are held together by strong
covalent bond throughout the structure.
On heating, degradation of polymer occurs instead of
plastic deformation due to breaking of covalent bond
Chemical structure of basic
polymers
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•Natural Rubber

CH2 C CH CH2
n CH C CH CH2
2

CH3
CH3 n

Polyisoprene
Isoprene

•Synthetic Rubber/Neoprene

CH2 C CH CH2
n CH2 C CH CH2

Cl Cl
n

Chloroprene Neoprene

Uses: For making stoppers, shoe heals, containers for

storing petrol, oil and other solvents.
 •Polystyrene/Styron
Monomer: Styrene

CH CH2 CH CH2

n
Styrene
Polystyrene

Uses: for making hot drink cups, combs, radios and television
bodies, tiles to be used in covering ceilings and floors.
• Polyacrylonitrile (PAN)/ orlon

CN CH2 CH
n CH2 CH

Vinyl cyanide CN
Acrylonitrile n
Polyacrylonitrile/ Orlon

Uses: for making blankets, sweaters, synthetic carpets etc.

 Properties and uses of polymer
• Good fiber-forming material and is converted into commercial
fibres.
• Have high stretch, high crease and wrinkle resistance.
• Highly resistant to mineral and organic acid, but is less
resistant to alkalies.
• Used for making synthetic fibres like terylene, dacron etc.
• For blending with wool to provise better crease and wrinkle
resistance.
• A glass reinforcing material in safety helmets, aircraft battery
boxes, etc.
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• LDPE/low density polyethylene: It is formed from
ethylene monomer under high temperature and pressure
conditions. It is highly branched polymer. Due to branching
the polyethylene chains do not packed closely.. Therefore, it
has low density. It is used for making thin plastic film bags,
insulating wires and cables etc.

• HDPE/High density polyethylene: It is formed from

ethylene monomer in the presence of triethylaluminium
((C2H5)3Al) and Titanium tetrachloride (TiCl4) catalyst
(Ziegler Natta Catalyst) at low temperature and pressure. It
consists of linear chains. Therefore, the polyethylene chains
are closely packed. Hence it has high density. It is used for
making containers, pipes etc.