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Polymers Revision Notes

Polymers are defined as very large molecules having high molecular mass (103-107 u). These
are formed by joining of repeating structural units, called monomers, on a large scale. The
monomer units, are linked to each other by covalent bonds. The process of formation of
polymer from respective monomers is called polymerisation.

Classification of Polymers
Some of the common classifications of polymers are :
(i) On the Basis of Source
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Natural Polymers These polymers are found in plants and animals, e.g. proteins,
cellulose, starch, resins, rubber etc.
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Semi-synthetic Polymers These polymers are derived from natural polymers by
chemical methods. e.g. cellulose acetate (rayon), cellulose nitrate etc.
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Synthetic Polymers These are man-made polymers. e.g. plastic (polythene), synthetic
fibres, buna-S etc.
(ii) On the Basis of Structure of Polymers,
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Linear Polymers These polymers consist of long and straight chains, e.g. high
density polythene, polyvinyl chloride etc.
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Branched Chain Polymers These polymers consist of linear chains with some
branches, e.g. low density polythene.
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Cross-linked or Network Polymers These polymers contain strong covalent bonds
between various linear polymer chains, e.g. bakelite, melamine etc.
(iii) On the basis of Mode of Polymerisation
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Addition Polymers or Chain Growth Polymers These are formed by the repeated
addition reactions monomer molecules having multiple bonds, e.g. polythene, SBR.
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Condensation Polymers or Step Growth Polymers These are formed by repeated
condensation process with elimination of small molecules like NH3 , H2O etc.
e.g. terylene, nylon-66, nylon-6 etc.
(iv) On the Basis of Monomers
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Homopolymers These are formed by polymerisation of single monomeric species.
e.g. polythene, polypropene etc.
 Copolymers These are formed by polymerisation of two
2. Condensation Polymerisation
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or more different monomer units.

e.g. buna-S, buna-N etc. It is a combination of molecules of same or different
monomers in a controlled stepwise manner with the
NOTE Epoxy resins are used in making adhesives such as araldite etc.
These are copolymer of epichlorohydrin and bisphenol-A. elimination of small molecules such as water, ammonia,
alcohol etc., as by-product.
(v) On the Basis of Molecular Forces
The process is also known as step growth polymerisation
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Elastomers These are rubber-like solids with elastic
properties. They have weak intermolecular forces. e.g. NOTE Other method of polymerisation is copolymerisation. In this
buna-S, buna-N, neoprene etc. method, two or more different monomer units polymerises to
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Fibres These are the thread forming solids and have form a copolymer which contains multiple units of each
strong intermolecular hydrogen bonding. e.g. nylon-6,6, monomer used, in the same polymeric chain.
polyesters (terylene) etc. Examples of Addition Homopolymers
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Thermoplastic Polymers These polymers possess (i) Polymer Polytetrafluoroethene (teflon)
intermolecular forces of attraction, intermediate Monomer Tetrafluoroethene (CF2 == CF2 )
between elastomers and fibres. e.g. polythene,
Uses For making oil seals and gaskets, non-stick surface
polystyrene, polyvinyls etc.
coated utensils.
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Thermosetting Polymers These polymers are cross-linked
(ii) Polymer Polythene (or polyethylene)
or heavily branched molecules e.g. bakelite,
Monomer Ethene (CH2 ==CH2 )
urea-formaldehyde resins etc.
On long exposure to air and sunlight, thermoplastics Uses It is used for making containers, housewares,
become brittle due to the evaporation of plasticiser. bottles,toys, electrical insulation etc.
(iii) Polymer Polyacrylonitrile (PAN)
Monomer Acrylonitrile (CH2 == CHCN)
Polymerisation
Uses Substitute for wool in making commercial fibres
The process or technique through which monomer units
such as orlon or acrilan (or polyproylene).
combine to give a polymer is known as polymerisation. The
polymerisation reaction can’t be controlled easily. (iv) Polymer Polypropene (or polypropylene)
Following are the two principal methods through which Monomer Propene
monomers combine to give polymers. Uses In the manufacture of ropes, toys, pipes, fibres etc.
(v) Polymer Polystyrene
1. Addition Polymerisation Monomer Styrene, (CH2 == CH—C 6H5)
It is the process in which molecules of same or different Uses As an insulator, wrapping material, manufacture
monomers combine together to give a polymer without the of toys, radio and television cabinets, cups for hot
elimination of small molecules. It is also known as chain drinks.
growth polymerisation. (vi) Polymer Polyvinyl chloride (PVC)
This mode of polymerisation is observed in molecules having Monomer Vinyl chloride (CH2 == CH—Cl)
multiple bonds, mainly in CH2 == CHY type molecules
Plasticisers are added to plastics to make them soft and
(where,y may be ¾ H, ¾ X , ¾ CO2 R, ¾ CN etc.) rubber like. e.g. addition of dibutyl phthalate to PVC
The addition or chain growth polymerisation can makes it soft and rubber like.
proceed by the following two mechanisms: Uses In the manufacture of rain coats, hand bags, vinyl
(i) By the formation of free radicals, i.e. free radical flooring, water pipes etc.
polymerisation. (vii) Polymer Natural rubber or polyisoprene
(ii) By the formation of ionic species, i.e. ionic (linear polymer)
polymerisation (cationic or anionic). Monomer Isoprene (2-methyl-1, 3-butadiene)
Cationic addition polymerisation is facilitated in æ ö
ç ÷
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monomers having electron releasing groups such as çCH ==C ¾ CH==CH ÷

— CH3 , —C2 H5 etc. Higher the stability of carbocation ç 2 |
2
÷
ç ÷
intermediate, more is the reactivity of monomer towards è CH3 ø
cationic addition polymerisation. Natural rubber can be stretched like a spring and
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Monomers containing electron withdrawing groups readily exhibits elastic properties.
undergo anionic addition polymerisation.
(viii)Polymer Neoprene (synthetic rubber) l
It absorbs a large amount of water and has low tensile
Monomer Chloroprene (2-chloro-1,3-butadiene) strength and elasticity. Due to which, vulcanisation of
æ CH ==C — CH==CH ö
ç
natural rubber is carried out.
2 2 ÷
ç | ÷
ç ÷ Vulcanisation of Rubber
ç Cl ÷
è ø l
To improve the undesired properties of natural raw rubber,
Uses In the manufacture of conveyor belts, gaskets and vulcanisation of rubber is carried out. The process involves
hoses. the heating of raw rubber with sulphur and appropriate
Also, thiokol is a type of synthetic rubber. It is a copolymer additive (ZnO) at a temperature 373-414 K.
of ethylene chloride and sodium tetrasulphide (Na2S4 ). l
Sulphur forms cross links at a reactive sites of double
Examples of Addition Copolymers bonds and makes the rubber stiffened. Rubber made with
(i) Polymer Butadiene-styrene (Buna-S) 1-3% sulphur is soft and stretchy while rubber made with
Monomers 1,3-butadiene (CH2==CH— CH==CH2) and 3-10% S is more rigid (used in making tyre).
styrene (C 6 H5 — CH==CH2 ). Synthetic Rubber
Uses It is quite tough and is a good substitute for natural Synthetic rubber are homopolymers of 1,3-butadiene
rubber. It is used for the manufacture of auto tyres, floor derivatives or copolymers of 1,3-butadiene or its derivatives
tiles, footwear components, cable insulation etc. with another unsaturated monomer.
(ii) Polymer Buna-N Uses Nylon-6 is used for the manufacture of tyre cords,
Monomers 1,3-butadiene (CH2 ==CH ¾ CH==CH2 ) and fabrics and ropes.
acrylonitrile (CH2 ==CHCN).
Uses It is resistant to the action of petrol, lubricating oil
and organic solvents. It is used in making oil seals, tank
Some Other Important Polymers
lining etc. 1. Polythene is a polymer of ethene. Depending upon the
conditions of temperature, pressure and nature of
Examples of Condensation Copolymers catalyst, polythene are of two types:
(i) Polymer Phenol-formaldehyde polymer (bakelite) (i) Low Density Polythene (LDP) is tough, flexible,
Monomers Phenol (C 6H5OH) and formaldehyde (HCHO). transparent, chemically inert as well as poor
Uses It is used for making combs, phonograph records, conductor of electricity. It has moderate tensile
electrical switches and handles of various utensils. strength but good tearing strength.
(ii) Polymer Melamine-formaldehyde polymer It is used in the insulation of electricity carrying
Monomer Formaldehyde (HCHO). wires and manufacture of squeeze bottles, toys and
flexible pipes.
H2N N NH 2
350-570 K
n(CH2 == CH2 ) ¾¾¾¾¾¾¾® ¾ (CH2 ¾ CH2 ¾
)n
N N 1000 to 2000 atm LDP
(Traces of oxygen or
NH 2 a peroxide initiator)
Melamine
(ii) High Density Polyethylene (HDP) has high density
Uses In the manufacture of unbreakable crockery. due to close packing. It is also chemically inert and
(iii) Polymer Urea-formaldehyde resin more tougher and harder.
Monomers Urea (NH2CONH2 ) and formaldehyde (HCHO).
333-343 K
Uses For making unbreakable cups and laminated sheets. n(CH2 ==CH2 ) ¾¾¾¾® ¾ (CH2 ¾ CH2—)n
6-7 atm
Example of Condensation Homopolymers ( Ziegler -Natta
catalyst)
Polymer Nylon-6 (perlon)
Monomer Caprolactam 2. Polyamides are polymers having amide linkages.
H Various types of polyamides are as follows:
O • Nylon-6,6 is obtained by the condensation of adipic
N
6 C1 acid and hexamethylenediamine with the elimination
5 2 of water molecule.
4 3 O O
In this reaction caprolactam is first hydrolysed with water to ½½ ½½
nH2 N(CH2)6NH2 + n HO ¾ C ¾ (CH2)4 ¾ C ¾ OH
form E-amino caproic acid.
Hexamethylenediamine Adipic acid
Natural and Synthetic Rubber H H O O
553 K,
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Natural rubber is considered as a linear polymer of isoprene high pressure ½ ½ ½½ ½½
(2-methyl-1,3-butadiene) and is also called as ¾¾¾¾® ¾( N ¾ (CH2)6 ¾ N ¾ C ¾ (CH2 )4 ¾ C —)n
– nH2O Nylon- 6,6
cis-1,4-polyisoprene.
 It is a linear polymer and has very high tensile strength. It (iii) Terylene (Dacron) is a condensation polymer of ethylene
shows good resistance to abrasion. It is usually fabricated glycol and terephthalic acid. Polymerisation is carried
into sheets. It is used in bristles for brushes and in textile out at 420 to 460 K in the presence of catalytic mixture
industry. of zinc acetate and antimony trioxide.
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Nylon-6 is obtained by heating caprolactum with water O O
at a high temperature.
H HOCH2CH2 — OH + nHO — C — C — OH
Ethylene glycol
N Terephthalic acid
H2C C O O H

Polymerisation
420-460 K
533-543 K
H2C CH2 —C—(CH2)5—N—
H2O n
H2C CH2 Nylon-6
Caprolactam
It is used for the manufacture of tyre cords, fabrics and
ropes.
æ O O
æ
ç ç
3. Polyesters are the polymers which contain an ester linkage. ç O— CH CH O — C ç
ç 2 2 Cç
The examples are as follows:
ç ç
(i) Polymethylmethacrylate (PMMA) is prepared by the è èn
polymerisation of methylmethacrylate in the presence of Terylene or dacron
suitable organic peroxide.
• Terylene is highly resistant to the action of chemicals
æ CH3 æ and biological agents. Its fibres are quite strong and
ç ç Organic peroxide
durable. It can also be blended with wool or cotton to
n çCH 2 == CH 2 ¾ COOCH 3 ç obtain fabrics of desired composition.
ç ç
è Methylmethacrylate è æ CH3 æ • It is used in the manufacture of a variety of clothes
ç ç such as terycot, terywool and terysilk as a result of
ç CH2 — C ————
— ç blending with other yarns. It is also used for preparing
ç ç magnetic recording tapes, conveyer belts, aprons for
è COOCH3è n
PMMA
industrial workers etc.
4. Bakelite is a condensation polymer. The reaction starts
The polymer is known by several commercial names with the initial formation of o- and p-hydroxy
such as lucite, acrylite, plexiglass and perspex. methylphenol derivatives which further reacts with
It is a hard and transparent polymer and is quite phenol to form compounds having rings joined to each
resistant to the effect of light, heat and ageing. It is used, other through —CH2 groups. The initial product formed
in the manufacture of unbreakable lights, protective is novolac which on heating with formaldehyde
coatings and in making windows for aircrafts. undergoes cross-linking to form infusible mass called
(ii) Glyptal is a polyester having cross-links. It is a bakelite. It is used in making combs,switches and
thermosetting plastic. It is obtained by condensation of handles.
ethylene glycol or glycerol and phthalic acid. OH OH OH
HOOC COOH CH2 CH2
H2C
CH2

n ( HO— CH2— CH2 — OH ) + n

–nH2O
Heat

Ethylene glycol
Phthalic acid CH2 CH2

æ O O æ
ç ç
ç O— CH — CH — O — C C ç CH2
ç 2 2
ç H2C CH2 CH2
ç ç OH OH OH
ç çn
è è
Glyptal NOTE Biodegradable polymers can be degraded by environmental
processes like degradation by bacterial enzymes. e.g.
When its solution in a suitable solvent is evaporated, it poly-b-hydroxy butyrate-co-b-hydroxy valerate (PHBV),
leaves a tough but non-flexible film. Therefore, it is used nylon-2-nylon-6.
in the manufacture of paints and lacquers.