2 6 .

2 4 | Biomolecules and Polymers

7. CLASSIFICATION OF POLYMERS
(a) On the Basis of Source
(i) Natural polymers: These polymers are found in plants and animals. Examples are proteins, cellulose,
starch, some resin and rubber.
(ii) Semi-synthetic polymers: Cellulose derivatives as cellulose acetate (rayon), cellulose nitrate, etc. are the
usual examples of this sub category.
(iii) Synthetic polymers: A variety of synthetic polymers such as plastic (polythene), synthetic fibers (nylon
6,6) and synthetic rubbers (Buna –S) are examples of manmade polymers extensively used in daily life
as well as in industry.

(b) On the Basis of Structure: There are three different types based on the structure of the polymers.
(i) Linear polymers: These polymers consist of long and straight chains. The examples are high density
polythene, polyvinyl chloride, etc. These are represented as:

(ii) Branched chain polymers: These polymers contain linear chains having some branches, For example,
low density polythene. These are depicted as follows:

(iii) Cross-linked or Network polymers: These are usually formed from bifunctional and trifunctional
monomers and contain strong covalent bonds between various linear polymer chains. For example,
bakelite, melamine, etc. These polymers are depicted as follows:

(c) On the Basis of Synthesis: These are of two types based on synthesis –
(i) Condensation polymerization: In this, the monomer (same or different) units link with each other by
the elimination of a small molecule (for example, water, methyl alcohol) as a byproduct. The polymer
formed is known as condensation polymer. Nylon and terylene are the most common examples.
Since the condensation polymerization proceeds by a stepwise intermolecular condensation, it is also
known as step polymerization and the polymer formed is known as step growth polymer.

n H2N(CH2)6NH2 + n HOOC (CH2)4 COOH → – NH(CH2 )6 NHCO(CH2 )6 CO  – + nH2O

n
Nylon− 6,6

(ii) Addition polymerization: This involves self-addition of several unsaturated molecules of one or two
monomers without loss of any small molecule to form a single giant molecule. The polymer formed is
known as addition polymer. Polythene is the most common example. However, the addition polymers
formed by the polymerization of a single monomeric species is known as homopolymers, for example,
polyethene.

nCH
=2 CH2 → –(CH2 – CH2 ) –Homopolymer
Ethene n
Polyethene

The polymers made by addition polymerization from two different monomers are termed as copolymers,
for example, Buna-S, Buna-N, etc.
 Chem i str y | 26.25

(d) On the Basis of Molecular Forces: A large number of polymer applications in different fields depend on their
unique mechanical properties like tensile strength, elasticity, toughness, etc. These mechanical properties are
governed by intermolecular forces, for example, van der Waals forces and hydrogen bonds.
(i) Elastomer: In these polymers, polymer chains are held together by the weakest intermolecular force.
Weak binding forces permit the polymer to be stretched. A few “crosslinks” are introduced in between
the chains, which help the polymer to retract to its original position after the force is released as in
vulcanized rubber. The examples are Buna-N, neoprene, etc.
(ii) Fibers: In these polymers, polymer chain held together by strong intermolecular forces, like hydrogen
bonding. These strong forces also lead to close packing of chains and thus impart crystalline nature.
Fibers are the thread-forming solids that possess high tensile strength and high modulus. The examples
are polyamides (nylon -6, 6), polyesters (terylene), etc.
(iii) Thermoplastic polymers: These polymers possess intermolecular forces of attraction intermediate
between elastomers and fibers. These are the linear or slightly branched long-chain molecules capable
of repeatedly softening on heating and hardening on cooling. Some common thermoplastics are
polythene, polystyrene, polyvinyls, etc.
(iv) Thermosetting polymers: These polymers are cross linked or heavily branched molecules, which on
heating undergo extensive cross linking in molds and again become infusible. These cannot be reused.
Some common example are bakelite, urea-formaldelyde resins, etc.

(e) Classification on the Basis of Type of Polymerization: Synthetic polymers have been classified into definite
classes in various manners, for example,
(i) All the synthetic polymers may be classified into two groups based on of the type of the process involved
during their preparation, viz. condensation or addition polymers involving condensation or addition
polymerization processes, respectively, during their synthesis.
(ii) A more rational method of classification is based upon the sequence of synthesis of the polymer (i.e.,
mode of addition of the monomer units to the growing chain).
According to this method, polymers may be of two types, viz. chain growth polymers and step growth polymers.
•• Chain growth polymers (earlier called as addition polymers). These polymers are formed by the
successive addition of monomer units to the growing chain having a reactive intermediate (free
radical, carbocation or carbanion)
The most important free radical initiator is benzoyl peroxide.
• •
heat
E.g. RCO — O — O — OCR  → 2RCOO → 2R + 2CO2
Benzoylperoxide

• • •
heat CH =CH
R + H=
2C CH2  → R – CH2 CH2 
2 2 → R — CH — CH — CH →→ R  –CH – CH  —
2 2 2  2 2
n

Examples of chain growth polymers

Monomer(s) Polymer
Ethylene Polyethylene
Propylene Polypropylene
Tetrafluoroethylene Polytetrafluoroethylene (PTFE) or Teflon
Vinyl chloride Polyvinyl chloride (PVC)
Isoprene Polyisoprene (Natural rubber)
Butadiene Polybutadiene
Butadiene and styrene Buna-S
2 6 . 2 6 | Biomolecules and Polymers

•• Step growth polymers (earlier called as condensation polymers). These polymers are formed through
a series of independent steps (reactions). Each step involves the condensation (bond formation)
between two difunctional units (monomers) leading to the formation of small polymer (say dimer,
trimer, tetramer, etc.)
Step 1. A + B → A–B
Monomer Monomer Dimer
Step 2. A — B + A → A — B —A
Trimer
Step 3. A—B+A—B → A—B—A—B
Dimer Dimer Tetramer
Step 4. A — B — A — B + A — B → A — B — A — B — A — B or (A —B)3
Step 5. (A — B)3 → ( — A — B — )n
Polymer

Examples of step growth polymers

Monomers Polymers
Adipic acid hexamethylene diamine Nylon-66
Terepthalic acid and ethylene glycol Terylene
Phenol and formaldehyde Bakelite

(f) Based on the magnitude of molecular forces the polymers may be classified as:
(i) Elastomers
•• In which the intermolecular forces of attraction are the weakest. They are amorphous and
have high degree of elasticity, for example, Buna-S.
(ii) Fibers
•• In which the intermolecular forces of attraction are the strongest like H bonding or di-
pole-dipole attraction.
•• They have high tensile strength, high melting point and low solubility, for example, polyes-
ters, polyacrylonitriles
(iii) Thermoplastics
•• In which the intermolecular forces of attraction are in between those of elastomers and
fibers
•• They are hard at room temperature, soften on heating without any change in mechanical
properties of plastic, have little or no cross links, for example, polythene, polyacrylonitrile,
Teflon, etc.
•• Semi-fluid substances with low molecular weight that once set into particular mold cannot
be used again and again.
•• This is because of extensive crosslinking between two polymer chains to give a three-dimen-
sional network, for example, bakelite, urea-formaldehyde; melamine formaldehyde etc.
 Chem i str y | 26.27

8. MOLECULAR MASS OF POLYMERS

(a) There are two types of average molecular mass of polymers.

( )
(b) Number average molecular mass Mn : It is determined by methods depending upon the number of molecules
present in the polymer sample, for example, colligative properties like ∆Tf; ∆Tb, Osmotic pressure

=(c) Mn
N1M1 + N2M2 + N3M3
=
∑ N1M1
N1 + N2 + N3 ∑ N1
Where N1,N2, N3 are the number of molecules. M1, M2, M3 are the molecular masses.

Weight Average Molecular Mass: It is determined by using the methods depending upon the masses for the
individual molecules like light scattering, ultracentrifugation, sedimentation, etc.

Mw
=
∑
=
m1M1 ∑ N1M12
; M– is mass of macromolecule
∑ m1 ∑ N1m1
Example in a polymer sample, 30% molecules have molecular mass 20,000; 40% have molecular mass 30,000 and
the rest 30% have 60,000. Calculate the number average and mass average molecular masses.

30 × 20000 + 40 × 30,000 + 30 × 60,000 600000 + 1200000 + 1800000 3600000

Mn = = Mn = 36000
30 + 40 + 30 100 100

30(20000)2 + 40(30,000)2 + 30(60,000)2

Mw = 43,333
30 × 20000 + 40 × 30,000 + 30 × 60,000

9. VARIOUS TYPES OF POLYMERS

Table 26.7: Types of polymers

Name of the polymer Structure of Natural of polymer Properties Uses

along with abbreviation monomer
A. Addition Polymers
I. Polyolefins
1. Polymers or polythome CH2 = CH2 (a) Low-density Transparent, Packing material
polyethylene (LDPE) in an moderate tensile (plastic films, bags etc.)
CH2 CH2 addition or chain-growth strength, high insulation for electrical
homopolymer. It is a toughness. wires and cables.
highly branched polymer
Translucent, Manufacture buckets,
and is obtained by free-
chemical tubs, pipes, bottles and
radical polymerization
inert, growth toys.
(b) High-density toughness and
polyethylene (HDPE) is tensile strength.
obtained by coordination
polymerization. It is a
linear addition or chain-
growth homopolymer.
2. Polypropylene or CH3CH=CH2 Addition homopolymer Harder and Packing of textile and
Polypropene linear can be obtained by foods, for making liners
stronger than
free-radical or Ziegler- of bags, heat shrinkable
polythene
—CH–CH2— Natta polymerization. wraps, carpet fibers,
CH3 ropes, automotive
— molding, stronger pipes
and bottles.
2 6 . 2 8 | Biomolecules and Polymers

Name of the polymer Structure of Natural of polymer Properties Uses

along with abbreviation monomer
3. Polystyrene or Styron C6H5CH=CH2 Addition homopolymer, Transparent Plastic toys, household
linear chain wares, radio and
CH CH2 television bodies,
n refrigerator linings etc.
II Polydienes
1. Neoprene Cl Addition homopolymer Rubber like, Hoses, shoe heels,
CH2 CH C CH2 inferior to natural stoppers etc.
CH2 CH C CH2 rubber but
Cl Chloroprene or 2- superior in its
n
Chloro-1, 3-butadiene. stability to serial
oxidation and its
resistance to oils,
gasoline, etc.
III. Polyacrylates
1. Poly (methyl Cl Addition homopolymer Hard, transparent, Lenses, light covers,
methacrylate) Plexigas, CH2 C COOCH3 excellent light light shades, signboards,
Lucise, Acrylite Perspex transmission transparent domes,
(PMMA) Methyl methacrylate properties, skylights, aircraft
optical clarity windows, dentures and
better than glass. plastic jewelry.
2. Poly (ethyl acrylate) CH2=CHCOOC2H5 Addition homopolymer. Tough, rubber like —
product.
CH2 CH
COOH n

3. Polyacrylonitrile (PAN) CH2 = CH–CN Addition homopolymer. Hard and has Manufacture of fibers,
Acrylonitrile high melting orlon, acrilon used for
CH2 CH
material. making clothes, carpets,
CN n blankets.

IV. Polyhalolefines
1. Polyvinyl chloride (PVC) CH2=CH–Cl Homopolymer, chain Pliable (easily (i) When plasticized
Vinyl chloride growth molded) with high-boiling esters
used in rain coats, hand
CH2 CH
bags, shower curtains,
Cl n upholstery fabrics, shoe
soles, vinyl flooring

(ii) Good electrical

insulators for wires and
cables

(iii) Making hose pipes.

2.Polytetrafluoro ethylene F2C = CF2 Chain growth, Flexible and (i) For making nonstick
of Teflon (PTFE) Tetrafluoroethylene homopolymer inert to solvents, utensils coating
boiling acids,
F F (ii) Making baskets,
even aquaregia,
C CH pump packings, valves,
stable up to
seals, nonlubricated
F F 598 K.
n bearings.
Condensation Polymers
I. Polyesters
 Chem i str y | 26.29

Name of the polymer Structure of Natural of polymer Properties Uses

along with abbreviation monomer
1. Terylene or Dacron HO–CH2–CH2–OH Copolymer, linear, step- For making paints
growth. and lacquers.
Ethylene glycol or
O Ethane-1, 2-diol and Thermoplastic, dissolves
O O O in suitable solvents
HO C C OH and its solutions, on
evaporation leaves a
Terephthalic acid tough but non-flexible
or Benzene-1, a film.
O 4-dicarboxylic acid
O

2. Glyptal or Alkydresin HO–CH2–CH2–OH Copolymer, linear, step- For making paints

growth. and lacquers.
Ethylene glycol and
O
Thermoplastic, dissolves
HOOC HOOC
CH2 in suitable solvents
O O and its solutions, on
Phthalic acid or evaporation leaves a
Benzene-1, tough but non-flexible
a film.
2-dicarboxylic acid
O O
CH2
O

II. Polyamides
Nylon-6,6 O O Copolymer, step, growth, High tensile (i) Textile fabrics, carpets,
NH2 HO C (CH2)4 C OH linear strength, abrasion bristles for brushes
resistant,
Adipic acid and (ii) Substitute for metals
somewhat elastic.
in bearings and gears.
H2N—(CH2)4—NH2
(iii) Crinked nylon is
Hexamethylene used for making elastic
O
diamine hosiery.
OH
2. Nylon-610 H2N(CH2)6NH2 Copolymer, step- growth, For making (i) Textile fabrics, carpets,
linear points and bristles for brushes
H H O O Hexamethylene
lacquers.
diamine (ii) Substitute for metals
[ N (CH2)6 N N (CH2)8 C [
in bearings and gears.
and
(iii) Crimped nylon is
HOOC(CH2)8
used for making elastic
COOH hosiery.
Sebacic acid
3. Nylon-6 or Parlon H Homopolymer, step Mountaineering ropes,
O N growth, linear tire cords and fabrics
(CH2)5 C O
N
H E-Caprolactam
III Formaldehyde resins
2 6 . 3 0 | Biomolecules and Polymers

Name of the polymer Structure of Natural of polymer Properties Uses

along with abbreviation monomer
1. Phenol-formaldehyde Phenol and Copolymer, step (i) Bakelite with low
resin or Bakelite formaldehyde growth, highly branched degree of polymerization
thermosetting polymer is used as binding glue
for wooden planks and in
varnishes and lacquers

(ii) Bakelite with high

degree of polymerization
is used for making combs
and micatable tops,
fountain pen barrels,
electrical goods (switches
and plugs), gramophone
records etc.

MASTERJEE CONCEPTS

•• Polymers are product of large number of small molecules, called monomers, chemically bonded to
each other.
•• The individual large polymer molecules are known as macromolecules.
•• Polymers are characterized by the average molecular mass of the chains and the number of repeating
units in such polymers is known as the degree of polymerization.
•• The physical properties of a polymer are determined by such factors as the flexibility of macromolecules,
the sizes and types of group attached to the polymer chains and the magnitude of intermolecular
forces.
•• Polymers may be linear, branched or cross linked.
•• Copolymers are produced from two monomers combined randomly or in a specific manner
•• To participate in polymerization, a molecule must be able to react at both ends.
•• The principal types of polymerization reaction are chain reaction polymerization (initiation
propagation and termination), which is undergone by monomers such as vinyl bromide and step
reaction polymerization, which involves reactions between functional group on different monomer
molecules like adipic acid and hexamethylene diamine to give nylon 66.

Neeraj Toshniwal (JEE 2009, AIR 21)

Illustration 9: Write the structures of the monomers of the following polymers:  (JEE MAIN)

(a) ( CH2CH2—O—CH2CH2 )n (b) [ = CH(CH2)4CH = N(CH2)6N = ]n

Sol: (a) CH2—CH2 (b) HO — CH —(CH2)4—CH2 — OH and H2N—(CH2)6—NH2

Hexane-1, 6 diol Hexamethylenediamine
O
(Monomer) (Monomer)
Ethylene oxide
(Monomer)