chemistry

POLYMERS
Sakshi Vora

IIT - Roorkee

10th, 12th CBSE State Topper

7+ Years of Teaching Experience

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Polymers
➔ POLYMERS: A very large molecule that is made up of many small
repeating molecular units.
➔ MONOMERS: These small molecular units from which the polymer is
formed
➔ POLYMERIZATION: The chemical reaction that joins the monomers
together
TYPES OF POLYMERS
Homopolymers
➔ Polymers which are formed by only one type of monomer
Copolymers
➔ Polymers, which are formed by more than one type of monomers
Classification of polymers
BASED ON SOURCE
Classification based upon Source
➔ Natural Polymers:
Polymers which are obtained from animals and plants are known as
natural polymers..
Classification based upon Source
➔ Semisynthetic Polymers:
➢ Polymers which are prepared from natural polymers
➢ Most of the semisynthetic polymers are prepared from cellulose.
Cellulose acetate, cellulose, nitrate, cellulose xanthate and Rayon.
Classification based upon Source

➔ Synthetic Polymers:
Man-made polymers, i.e. polymers prepared in laboratory
Example are : PVC, polyethylene, polystyrene, nylon-6, nylon-66, nylon-
610, terylene, synthetic rubbers etc.,
BASED ON SHAPE
Classification based upon Shape
➔ Linear Polymers:
Polymer whose structure is linear
The various linear polymeric chains are stacked over one another to
give a well packed structure.

The structure is close packed in nature, due to which they have high
densities, high melting point and high tensile (pulling) strength.
Classification based upon Shape
➔ Branched chain Polymers:
➢ The monomeric units constitute a branched chain.
➢ Due to the presence of branches, these polymers do not pack well.
➢ Have lower melting points, low densities and tensile strength
➢ Examples are amylopectin, glycogen, low density polyethylene and all
vulcanised rubbers.
Classification based upon Shape
➔ Cross-linked or Three Dimensional network Polymers:
➢ In these polymers the initially formed linear polymeric chains are joined
together to form a three dimensional network structure.
➢ These polymers are hard, rigid and brittle.
due to branched packing
BASED ON SYNTHESIS
Classification based upon Synthesis
➔ Condensation Polymerisation:
➢ They are formed due to condensation reactions.
➢ Condensation polymerisation is also known as step growth polymerisation.
➢ For condensation polymerisation, monomers should have at least two
functional groups.
so that chain can be formed

amide bond
Condensation Polymers
➔ Condensation Polymerisation:

ester bond
Condensation Polymers
➔ Condensation Polymer:
➢ Condensation polymers do not contain all atoms initially present in the
monomers.
➢ Examples are : Urea-formaldehyde resin, phenol-formaldehyde resin.
Addition Polymers
➔ Addition Polymer:
➢ Polymers which are formed by addition reaction
Addition Polymers
➔ Addition Polymer:
➔ Polystyrene, Polytetrafluoroethylene, polyacrylonitrile
Classification based upon Synthesis
➔ Addition Polymer:
Classification based upon Synthesis
➔ Addition Polymer:
Addition polymerization
Radical Polymerization
➔ Radical Polymerisation
Radical Polymerisation takes place in the presence of radical initiators.

peroxide bonds are unstable due to electron repulsion,

hence bond breaks to form radical
Addition Polymerisation
Radical Polymerisation
➔ Chain Initiation Step :

➔ Chain propagation Step :

Radical Polymerisation
➔ Chain Terminating Step :
1,4 POLYMERIZATION
1,4- polymerisation.

When the polymerisation takes place at C1 and C4 of butadiene, an

unbranched polymer is formed.
1,4- polymerisation.
ZIEGLER NATTA CATALYST
Ziegler-Natta Polymerisation :
➔ Addition polymerisation which takes place in the presence of Ziegler-
Natta catalyst [(C2H5)3Al and TiCl4]
➔ Ziegler- Natta polymerisation always gives linear, stereoregular only cis or only
trans (not both)
polymers.
➔ High density polyethylene is prepared using a Ziegler-Natta catalyst.
BASED ON INTERMOLECULAR FORCES
ELASTOMERS
Elastomers :
➔ An elastomer is a plastic that stretches and then reverts back to its
original shape.
➔ Very weak Van Der Waal forces are present in between polymeric
chains.
➔ When elastomers are stretched, the random chains stretch out, but there
are insufficient Vander Waal forces to maintain them in that
configuration and position.
➔ When the stretching force is removed, they go back to their random
shape.
➔ Examples are vulcanized rubbers.
FIBRES
Fibres :
➔ Fibres are linear polymers in which the individual chains of a polymer are
held together by hydrogen bonds and / or dipole-dipole attraction.
➔ In the fibres, the polymeric chains are highly ordered with respect to one
another.
➔ Due to strong intermolecular forces of attraction and highly ordered
geometry, fibres have high tensile strength and least elasticity.
➔ They have crystalline character and have high melting points and low
solubility.
➔ Examples are cellulose, nylon, terylene, wool, silk etc.
THERMOPLASTIC POLYMERS
Thermoplastic Polymers
➔ Have both ordered crystalline regions and amorphous/non crystalline
regions (the regions of the polymer in which the chains are randomly
oriented).
➔ The intermolecular forces of attraction are in between elastomers and
fibres. high VW low VW
➔ Thermoplastic polymers are hard at room temperature. but when they
are heated, the individual chains can slip past one another and the
polymer become soft and viscus, this soft and viscous material become
rigid on cooling.
Thermoplastic Polymers
➔ The process of heating softening and cooling can he repeated as many
times as desired without any change in chemical composition and
mechanical properties of the plastic.
➔ As a result, these plastics can be moulded into toys, buckets, telephone
and television cases.
➔ Some common examples are : polyethene polypropylene, polystyrene,
polyvinyl chloride. teflon etc.
THERMOSETTING POLYMERS
Thermosetting Polymers
➔ Polymers which become hard on heating are called thermosetting
polymers.
➔ They can be heated only once when it permanently sets into a solid,
which cannot be remelted by heating.
➔ Thermosetting polymers are cross- linked polymers.
Thermosetting Polymers
➔ Cross-linking reduces the mobility of the polymer chains, causing them
to be relatively brittle materials.
➔ The hardening on heating is due to the extensive cross-linking between
different polymer chains to give a three dimensional network solid.
➔ Examples are : phenol formaldehyde resin, urea-formaldehyde resin,
melamine - formaldehyde resin.
 DIFFERENCE B/W
THERMOSETTING & THERMOPLASTIC
Difference between thermoplastic & thermosetting polymers
NATURAL Rubber
Natural rubber
➔ Natural rubber is a polymer of 2-methyl-1.3-butadiene (isoprene)
➔ It has low elasticity and low tensile strength. .
➔ All the double bonds in rubber are cis, hence natural rubber is cis-
polyisoprene.
Natural rubber
Natural rubber
➔ Gutta-percha is a naturally occurring isomer of rubber in which all the
double bonds are trans. Thus, gutta-percha is trans-polyisoprene.

➔ It is harder and more brittle than rubber. It is the filling material that
dentists use in root canal treatment.
Vulcanization of rubber
➔ In order to give strength and elasticity to natural rubber, it is
vulcanized. becomes cross linked structure
➔ Heating of rubber with sulphur or sulphur containing compound at 150°
C for few hours is known as vulcanisation.
Vulcanization of rubber
➔ The essential feature of the vulcanisation is the formation of cross-
linking between the polymeric chains.
➔ This cross-linking gives mechanical strength to the rubber.
➔ Natural rubber is used for making shoes, waterproof coats and golf
balls.
➔ Vulcanised rubber is used for manufacture of rubber bands, gloves
tubing and car tyres.
synthetic Rubber
SYNTHETIC RUBBER OR
POLYMERISATION OF DIENES

➢ Polymers of 1,3 - butadienes are called synthetic rubbers

➢ They are more flexible, tougher and more durable than natural rubber.
Homopolymers
➔ Monomer of this class is 2-substituted - 1,3-butadienes.

➔ Chloroprene undergoes free radical polymerisation to form neoprene

(polychloroprene.)
Homopolymers

➔ Neoprene is more resistant to action of oils, gasoline and other

hydrocarbons. It is also resistant to sunlight, oxygen. ozone and heat.
➔ It is non - inflammable is used for making automobile and refrigerator
parts, hoses for petrol and oil containers, insulation of electric wires and
conveyor belts.
Copolymers
BUNA S & BUNA N
Buna-S (SBR : Styrene-butadiene rubber)
Buna-S rubber is a copolymer of three moles of butadiene and one mole of
styrene.
It is extremely resistant to wear and tear and therefore used in the
manufacture of tyres and other mechanical rubber goods.

inner C
Buna-N
➢ Buna-N : It is obtained by co-polymerisation of butadiene and
acrylonitrile
outer C

It is very rigid and is very resistant to action of petrol, lubricating oil and
many organic solvents. It is mainly used for making fuel tanks.
Nylon
Nylon
➢ Nylon is used for all synthetic fibres forming polyamides, i.e.,having a
protein like structure.
➢ A number is usually suffixed with the name 'nylon' which refers to the
number of carbon atoms present in the monomers. NYLON - 66
➢ First number indicates the number of C atoms in amine, 2nd number
indicates the number of C atoms in acid part
x: no of C atoms in the amine part
y: no of C atoms in the carboxylic
acid part
Nylon

It is obtained by the condensation polymerisation of hexamethylenediamine

and adipic acid
NYON-6
➢ It is prepared by prolonged heating of caprolactum at 260-270°C.
➢ Since, caprolactum is more easily available, it is used for
polymerization, with is carried out in the presence of H,O that first
hydrolyses the lactam to amino acid.
➢ Subsequently, the amino acid can react with the lactam and the process
goes on and onto form the polyamide polymer.
NYON-6
polyethene
Low Density Polyethylene (LDPE)
It is manufactured by heating ethylene at 200OC under a
pressure of 1500 atmospheres and in the presence of traces of oxygen. This
polymerisation is a free radical polymerisation.
Low Density Polyethylene (LDPE)

➢ The polyethylene produced has a branched structure.

➢ Due to this, polyethylene has a low density (0.92) and low melting point
➢ It is a transparent polymer of moderate tensile strength and high
toughness. It is widely used as a packing material and as insulation for
electrical wires and cables.
High Density Polyethylene (HDPE) :
➔ It is prepared by the use of Ziegler - Natta catalyst at 160°C under
pressure of 6 to 7 atmosphere. since catalyst is used, high pressure and temp not req
➔ The polymer is linear chain. hence it has high density (0.97) and has high
melting point (130°C).
➔ It is a translucent polymer. It has greater toughness, hardness and
tensile strength than low density polyethylene.
➔ It is used in the manufacture of containers ( buckets, tubes), house
wares, bottles and toys.
Melamine formaldehyde resin
Melamine - formaldehyde resin
➔ This resin is formed by condensation polymerisation of melamine and
formaldehyde.

➔ It is quite hard polymer and is used widely for making plastic crockery
under the name melamine. The articles made from this polymer do not
break even when dropped from considerable height.
bakelite
Bakelite
➔ Phenol-formaldehyde resins are obtained by the reaction of phenol and
formaldehyde in the presence of either an acid or a basic catalyst.
➔ The reaction starts with the initial formation of ortho and para-
hydroxymethyl phenol derivatives, which further react with phenol to
form compounds where rings are joined to each other with -CH2 groups.
Bakelite
Bakelite
polyesters
Polyesters
aka terylene
➔ Dacron is a common polyester, prepared using ethylene glycol and
terephthalic acid.

terepthalic acid
Polyesters

➔ The terylene fibre (Dacron) is crease resistant and has low moisture
absorption. It has high tensile strength. It is mainly used in making
wash and wear garments, in blending with wood to provide better
crease and wrinkle resistance.
Biodegradable polymers
NON BIODEGRADABLE POLYMERS
Non - biodegradability is due the carbon-carbon bonds of addition polymers
which are inert to enzyme catalysed reaction. These polymers create
pollution problem.
BIODEGRADABLE POLYMERS
➢ Biodegradable polymers are the polymers that can be broken into small
segments by enzyme catalysed reactions
➢ In biodegradable polymers, bonds that can be broken by the enzymes
(hydrolysable esters) are inserted into the polymers.
 Poly- hydroxybutyrate-CO-β-Hydroxyvalerate (PHBV)

It is a copolymer of 3- hydroxybutanoic acid and 3 hydroxypentanoic acid,

in which the monomer units are connected by ester linkages.

enzymes can hydrolyze

hence, biodegradable
butyrate: butanoic acid valerate: pentanoic acid
NYLON-2-NYLON-6
It is in alternating polyamide copolymer of glycine and aminocaproic acid
and is biodegradable.
MOLECULAR MASS OF POLYMER
MOLECULAR MASS OF POLYMER
Normally, a polymer contains chains of varying lengths and therefore, its
molecular mass is always expressed as an average.
In contrast, natural polymers such as protein contains chain of identical
length and hence, have definite molecular mass.
MOLECULAR MASS OF POLYMER
The molecular mass of a polymer is expressed as

● Number average molecular mass (Mn)

Where Ni is the number of molecules of molecular mass Mi

COMMON POLYMERS
Common Polymers
Common Polymers
Common Polymers
Common Polymers
Common Polymers
Common Polymers

pthalic acid
ethylene
glycol
Common Polymers
Common Polymers

urea
Practise questions
Which one of the following polymers is not obtained by
condensation polymerisation?

A. Nylon 6,6 [JEE Main 2020]

B. Buna - N
C. Bakelite
D. Nylon 6
Which of the following is a thermosetting polymer
A. Bakelite
B. Buns-N
[JEE Main 2019]
C. Nylon 6
D. PVC
The correct name of the following polymer is

[JEE Main 2019]

A. Polyisobutane
B. Polytert-butylene
C. Polyisoprene
D. polyisobutylene
Which of the following is a condensation polymer?

A. Buna - S
B. Neoprene [JEE Main 2019]
C. Teflon
D. Nylon 6, 6
The structure of Nylon-6 is

A.
[JEE Main 2019]

B.

C.

D.
Which of the following polymers is synthesized using a free
radical polymerisation technique ?

A. Terylene
[JEE Main 2016]
B. Melamine polymer
C. Nylon 6, 6
D. Teflon
Which polymer has ‘chiral’ moment(s)?

A. Neoprene
B. Buna-N
[JEE Main 2020]
C. Nylon 6, 6
D. PHBV
Preparation of Bakelite proceeds via reaction

A. Electrophilic addition and dehydration

B. Condensation and elimination
[JEE Main 2020]
C. Electrophilic substitution and dehydration
D. Nucleophilic addition and dehydration
Which of the following compounds is a constituent of the polymer

[JEE Main 2019]

A. N-Methyl urea
B. Formaldehyde
C. Methylamine
D. Ammonia
Poly-β -hydroxybutyrate-co-β-hydroxyvalerate (PHBV) is a
copolymer of _________.

A. 3-Hydroxybutanoic acid and 4-Hydroxypentanoic acid

B. 2-Hydroxybutanoic acid and 3-Hydroxypentanoic acid
C. 3-Hydroxybutanoic acid and 2-Hydroxypentanoic acid
D. 3-Hydroxybutanoic acid and 3-Hydroxypentanoic acid

[JEE Main 2019]

The two monomers for the synthesis of Nylon 6,6 are

A. HOOC(CH2)4COOH, H2N(CH2)6NH2
B. HOOC(CH2)6COOH, H2N(CH2)6NH2 [JEE Main 2019]
C. HOOC(CH2)4COOH, H2N(CH2)4NH2
D. HOOC(CH2)6COOH, H2N(CH2)4NH2
The polymer obtained from the following reactions is

A. B.

C. D.

[JEE Main 2019]

The homopolymer formed from 4-hydroxy-butanoic acids is -

A.

B.

C.
[JEE Main 2019]

D.
Major product of the following reaction is -

[JEE Main 2019]

A.

B.

C.

D.
The formation of which of the following polymers involves
hydrolysis reaction?

A. Nylon 6
B. Bakelite
C. Nylon 6, 6
D. Terylene [JEE Main 2017]
Which of the following is a biodegradable polymer ?

A.

B.

[JEE Main 2017]

C.

D.
Which of the following statements about low density polythene is
FALSE?

A. Its synthesis requires dioxygen or a peroxide initiator as a catalyst.

B. It is used in the manufacture of buckets, dust-bins etc.
C. Its synthesis requires high pressure.
D. It is a poor conductor of electricity. [JEE Main 2016]
On complete hydrogenation, natural rubber produces

A. ethylene-propylene copolymer
B. vulcanised rubber
C. polypropylene
D. polybutylene
[JEE Adv. 2016]
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