NEET Revision Notes

Chemistry
Polymers

Introduction:
Polymer is defined as a veritably large patch having high molecular mass
(103  107 u) .
● Polymers are macromolecules, which are formed by joining or repeating
structural units on a large scale.
● This process of conformation of polymer from separate monomers is called
polymerisation.
● The metamorphosis of ethene to polythene and commerce of
hexamethylene diamine and adipic acid leading to the conformation of
Nylon 6, 6 are illustration of two different types of polymerization
response.

Classification of polymers
S.N Basis of
Nature of polymers Common example
o classification
Natural polymers Cotton, silk
1 Source of polymer Semisynthetic polymers Cellulose rayon
Synthetic polymers Polythene
Linear polymer
High density polythene
Structure of Branched chain
2 Low density polythene
polymers Cross linked or network
Bakelite melamine
polymer
Terylene
Mode of Condensation polymer
3 Polypropylene,
polymerisation Addition Polymers
polythene.
Buna-N
Elastomers
Polyamides such as
Fibres
Nylon-6,6
4 Molecular force Thermos plastic Polymers
Polythene, Polystyrene
Thermosetting polymers
Bakelite, Urea-HCHO
cannot be remoulded
resins

Class XII Chemistry www.vedantu.com 1

 Cationic polymerization Polystyrene; Polyvinyl
polymers ethers
5 Polarity
Anionic Polymerization Buna type synthetic
Polymers rubbers
Polyethylene, PVC
Thermoplastic polymers Nyon
6 Heat treatment
Thermosetting Polymer Bakelite,
Polysiloxanes
Organic and
Organic Polymers Leather; Cellulose
7 inorganic
Inorganic Polymers Glass, Silicone rubber
substance

Classification based on growth polymerisation

The addition and condensation polymers are nowadays also referred to as chain
growth polymers and step growth polymers depending on the type of
polymerization mechanism they undergo during their formation.

Types of Polymerisation Reaction

Addition polymerisation or chain growth polymerisation:
● In this type of polymerisation, the molecules of the same monomer or
different monomers add together on a large scale form a polymer.
● The monomers used are unsaturated compounds, e.g., alkenes, alkadienyls
and their derivation.
● This mode of polymerisation leading to an increase in chain length or chain
growth can take place through the formation of either free radicals or ionic
species.

A. Cationic Addition Polymerization

When the initiator is cationic in nature, in addition to the double bond, it would
generate a cationic intermediate for propagation of the chain process and is
termed as cationic addition polymerization.
● The process is initiated by a Lewis acid.
● The important chain initiators used for the cationic polymerisation are
BF3 , AlCl3 .
● Cation polymerization is facilitated in monomers containing electron-
releasing group.

Class XII Chemistry www.vedantu.com 2

 ● Isobutylene undergoes cationic polymerization easily as it has two
electrons releasing the - CH3 group that will stabilize the intermediate
cation.
The reaction proceeds through 3 steps:
● Chain initiation step:
H 2O  AlCl3  H   [ AlCl3 (OH )  ]
● Chain propagation:
CH 3  C  HR  CH 2  CHR  CH 3  CHR  CH 2  C  HR
● Chain termination step:
(AlCl3 (OH) - )
CH3 - CHR - CH2 - C + HR + n(CH2 = CHR)  CH3 -CHR-{CH2 - CHR}n - CH = CHR + H +

B. Anionic Addition Polymerization

An anion initiator will similar generate carbanionic intermediate and the resulting
polymerization is categorized as anionic addition polymerization. Here, the active
centre of the propagating species is negatively charged.
● It occurs fluently with monomers containing electron withdrawing groups
similar as phenyl, nitrile etc., which are suitable to stabilized the
propagation species.
● Inauguration can be brought about by reagents similar as n-butyl lithium
or potassium amide.
The steps with the vinyl derivative can be written as follows:
● Chain initiation
Na  NH 3  Na  NH 2 
NH 2  M  NH 2 M 
● Chain propagation
NH 2 M   (n  1) M  NH 2 M n 
NH 2 M n  NH 3  NH 2 M n H  NH 2

C. Free radical addition mechanism

Here the chain initiator (catalyst) may be benzol peroxide, acetyl peroxide is tert-
butyl peroxide, acetyl peroxide is tert-butyl peroxide.
The main steps are involved:
● Chain initiating step
● Chain propagation step

Class XII Chemistry www.vedantu.com 3

 ● Chain terminating step

Condensation Polymerization and step growth polymerisation:

When both the reactants are bifunctional, they undergo a series of condensation
reaction in a controlled stepwise manner with the elimination of small molecule
like H 2O , alcohol to form polymers, and the process is called condensation
polymerization.
● This process is also called step-growth polymerization’.
● Condensation polymerisation takes place between molecules having
polyfunctional groups.
Polyamides: Polymers enjoying amide liaison are important synthetic fibres.
They are made by condensation of diamines with dicarboxylic acid and also from
amino acids or caprolactams the cyclic amides.
Polyesters: Dacron is the best known of the polyesters and is manufactured from
ethylene glycol and terephthalic acid.
● The reaction is carried out at 420 to 460K in the presence of catalyst
mixture of zinc acetate and antimony trioxide.

Image: Terylene
● The Terylene fibre (Dacron) is grease resistant and has low moisture
absorption.
● It has high tensile strength.
● It is mainly used in making wash and wear garments, in blending with wool
to provide better grease and winkle resistance.

Phenol-formaldehyde polymer (Bakelite and related polymer)

● Phenol is condensed with formaldehyde in the presence of either an acid or
a base.
● The reaction starts with the initial formation of O and/or P-hydroxymethyl
phenol derivatives, which further react with phenol to form compounds
where rings are joined to each other with - CH 2 groups.
● The initial product could be a linear product Novolin used in paints.

Class XII Chemistry www.vedantu.com 4

Image: Novolac
On further heating with formaldehyde, novolac undergoes cross-linking to
crystallize an infusible common sense called Bakelite.

Image: Bakelite
● This polymer called Bakelite is hard, scratch and water resistant.
● It possesses excellent electrical insulating character and hence, it finds
major use in making electrical goods.
Copolymerization: If a mixture of more than one monomeric species is allowed
to polymerise, a co-polymer is formed and it contains multiple units of each
monomer used in the same polymeric chain. The co-polymer can be made not
only by chain growth polymerisation, but by step growth polymerisation also.
Co-polymers are further classified into four categories depending on the nature
of the different monomers in the chain.
Random copolymers are formed by the random arrangement of monomer units
in the polymer chain.

Class XII Chemistry www.vedantu.com 5

Alternating copolymer chains contain the monomer units in alternate.

Natural Rubber
● It is a natural polymer and possesses remarkable elasticity.
● Latex is a conflation of poly hydrocarbon driblets in a waterless result (oil
in water emulsion). It consists of negatively charged particles of rubber.
The latex contains about 35% rubber. The rubber present in the latex is
coagulated by the addition of CH3COOH or HCOOH .
● This solid is crude rubber: This is refined by
a. Break down i.e., masticating the raw rubber and
b. Compounding i.e., the addition of necessary agents to the rubber

Structure of Rubber:
● The empirical formula of Natural rubber is C5H8 .
● Natural rubber may be considered as a linear 1, 4- addition polymer of
isoprene.
● The residual double bonds are located between C2 and C3 of isoprene
units in the polyme the position of double bonds is detected by ozonolysis.
All these double bonds have cis configuration and thus, rubber is cis 1, 4 -
polyisoprene.

Vulcanization of Rubber
Natural rubber becomes soft at high temperatures (>335K) and brittle at low
temperatures (< 283 K) and shows high water absorption capacity. It is soluble in
nonpolar solvents and is non-resistant to attack by oxidising agents.
● Addition of sulphur to hot rubber causes changes that improve its physical
properties. This process is called Vulcanization.
● It was performed by heating a mixture of raw rubber and sulphur at 373 to
415 K.
● This process is slow and additives such as zinc oxide, zinc stearate etc., are
used to accelerate the rate of vulcanization.
● The Vulcanized rubber has excellent elasticity, low water- absorption
tendency, resistant to oxidation and organic solvents.

Synthetic Rubber:

Class XII Chemistry www.vedantu.com 6

 ● The Polymers derived from butadiene derivatives and contain carbon-
carbon double bonds so that they can also be vulcanized.
● Synthetic rubbers are either homopolymers of buta -l, 3 - diene derivatives
or copolymers, of which one of the monomers is buta -1, 3 - diene.
Commonly used synthetic rubbers are Buna-S, Buna-N, Neoprene and
Butyl rubber.

Difference between Natural and synthetic polymers:

S.N Synthetic
Distinguishing property Natural Polymers
o Polymers
Prepared in the
Source of their preparation Obtained in natural lab, nylon,
1
and common example wool, silk, jute, etc terrene, Dacron
etc.
Can be of uniform
2 Length of polymer chain Not of uniform length
length
Affinity for sulphur and vat Posses very high Possess low
3
dyes affinity affinity
4 Fixing quality Low High

Determination of Molecular Mass of Polymers

The Molecular mass of a polymers can be expressed in two ways:
a. Number average molecular mass ( Mn )
If N1, N2 , N3 ,...... are the number of molecules with molecular masses
M1, M 2 , M 3 ,...... respectively, the number average molecular mass is
n
N M
N1M1  N 2 M 2  .......  Ni M i i 1 i i
Mn   n
N1  N 2  N3  ........  N I
 Ni
i 1
M n is determined by
● End group analysis method
● Colligative properties like osmotic pressure
M n is related to osmatic pressure by the equation

Class XII Chemistry www.vedantu.com 7

   1 C 
●    RT . or Mn    RT
 C 0 Mn   0
C is concentration of polymer solution in gm/litre is osmatic pressure in cms
  
●   value is calculated from the graph plotted between on y axis and
 c 0 c
C on X-axis by extrapolated technique, the graph is straight line with an
RT
intercept is on y axis
Mn
b. Weight average molecular mass (M w ) .
When the total of groups of molecules, having different molecular are multiplied
with their all the, molecules, the result obtained is called the or weight average
molecular
n
 Ni M i2
N1M12  N 2 M 22  .......  Ni M ii i 1
Mw   n
N1M1  N 2 M1  ........  Ni M i
 Ni M i
i 1
N1, N2 , N3 ,...... are number of molecules
M1, M 2 , M 3 ,...... are molecular masses
Weight average molecular weight is determined by
● Light scattering
● Ultra-Centrifugal method
● Viscosity measurements

PDI: The ratio of weight average molecular mass to the number average
molecular rms is called Poly dispersity index (PDI).
M
PDI  w
Mn
● The value of PDI for polymers in between 1 and 1.5.
● For natural polymers, PDI is usually unit (natural polymers and mono
dispersed) ( M w  M n ) .
● For synthetic polymer, PDI is greater than one ( M w  M n ) .
● M n is measured on the basis of the colligative properties.
● The mass average molecular mass M w is measured with the help of ultra-
centrifugations, sedimentation etc.

Class XII Chemistry www.vedantu.com 8

Biodegradable polymers:
● These are polymers which are degraded by microorganisms with in a
suitable period so that the polymers and their degraded products do not
cause any serious effects on the environment. Biopolymers degrade
mainly by enzymatic hydrolysis and oxidation.
● These synthetic polymers mostly have functional groups which are
normally present in biopolymers and lipids.

Class XII Chemistry www.vedantu.com 9