Classification of Polymer

Polymer contains repeating units
Macromolecules
contain
no
repeating
units,
examples are DNA, proteins, etc

A polymer is a macromolecule...but
a macromolecule may not be a polymer
Many + Parts
The repeating structural units are derived from some simple
and reactive molecules known as monomers and are linked to

each other by covalent bonds
The word, polymer, implies that polymers are constructed from
pieces (monomers) that can be easily connected into long chains

(polymer)
This process of formation of polymers from respective
monomers is called polymerization

The transformation of ethene to polythene and interaction of
hexamethylene diamine and adipic acid leading to the formation

of Nylon 6, 6 are examples of two different types of
polymerisation reactions
The functionality of a monomer is the number of sites it
has for bonding to other monomers under the given conditions

of the polymerization reaction
Thus, a bifunctional monomer, i.e., monomer with functionality
two, can link to two other molecules under suitable conditions

A polyfunctional monomer is one that can react with more than
two molecules under the conditions of the polymerization

reactions
The number of repeating units (n) in the chain so formed is called
the degree of polymerization (DP = n)

Polymers with a high degree of polymerization are called
high polymers and those with low degree of polymerization are

called oligopolymers (short chain polymers or oligomers)
Polymers
do
not
exhibit
strength
for
<
30
and
that the optimum strength of most of the polymers is obtained at n

around 600
The useful range of n is from 200 to 2000
The following are some of the common classifications of
polymers:
[1] by Source
[2] by Backbone of the chain
[3] by Structure
[4] by Compostion
[5] by Mode of Polymerization
[6] by Molecular force
Classification Based on Source:

[1] Natural Polymers: These polymers are found in plants and
animals. Examples are proteins, cellulose, starch, resins and rubber

[2] Semi-synthetic Polymers: Cellulose derivatives as cellulose
acetate (rayon) and cellulose nitrate, etc. are the usual examples of
this sub category
[3] Synthetic Polymers: A variety of synthetic polymers as plastic
(polythene), synthetic fibres (nylon 6,6) and synthetic rubbers

(Buna - S) are examples of man-made polymers
Classification Based on Backbone of the polymer chain:

Organic and Inorganic Polymers: A polymer whose backbone chain
is essentially made of carbon atoms is termed as organic polymer

The atoms attached to the side valencies of the backbone carbon
atoms are, however, usually those of hydrogen, oxygen, nitrogen, etc.

The majority of synthetic polymers are organic
On the other hand, generally chain backbone contains no carbon
atom is called inorganic polymers

Glass and silicone rubber are examples of it
Classification Based on Structure of Polymers:

[1] Linear Polymers: These polymers consist of long and straight chains.
The examples are high density polythene, PVC, etc. Linear polymers are
commonly relatively soft, often rubbery substances, and often likely to
soften (or melt) on heating and to dissolve in certain solvent
[2] Branched Polymers: These polymers contain linear chains having some
branches, e.g., low density polythene

[3] Cross-linked Polymers: These are usually formed from bi-functional
and tri-functional monomers and contain strong covalent bonds between

various linear polymer chains, e.g. vulcanized rubber, urea-formaldehyde
resins, etc. Cross linked polymers are hard and do not melt, soften or
dissolve in most cases
Classification Based on Composition of Polymers:

[1] Homopolymer: A polymer resulting from the polymerization of a single
monomer; a polymer consisting substantially of a single type of repeating unit

[2] Copolymer: When two different types of monomers are joined in the same
polymer chain, the polymer is called a copolymer

Copolymerization: A heteropolymer or copolymer is a polymer derived from
two (or more) monomeric species, as opposed to a homopolymer where only

one monomer is used
Copolymerization refers to methods used to chemically synthesize a copolymer.
Commercially relevant copolymers include ABS plastic, SBR, Nitrile rubber,

styrene-acrylonitrile, styrene-isoprene-styrene (SIS) and ethylene-vinyl acetate
In an alternating copolymer, the two monomers are arranged in an
alternating fashion
In a random copolymer, the two monomers may following any
order
In a block copolymer, all of one type of monomers are grouped
together, and all of the other are grouped together

In graft copolymer, a block copolymer can be thought of as two
homopolymers joined together at the ends: branched copolymers

with one kind of monomers in their main chain and another kind of
monomers in their side chains
Classification Based on Mode of Polymerisation:

Two sub groups; (a) Addition and (b) Condensation Polymers.
Addition Polymers: The addition polymers are formed by the
repeated addition of monomer molecules possessing double or triple

bonds, e.g., the formation of polythene from ethene and polypropene
from propene
However, the addition polymers formed by the polymerisation of a
single
monomeric
species
are
known
as
homopolymer,
e.g., polythene
The polymers made by addition polymerisation from two different
monomers are termed as copolymers, e.g., Buna-S, Buna-N, etc
Condensation Polymers: The condensation polymers are formed by
repeated condensation reaction between two different bi-functional or

tri-functional monomeric units
In these polymerisation reactions, the elimination of small molecules such
as water, alcohol, hydrogen chloride, etc. take place

The examples are terylene (dacron), nylon 6, 6, nylon 6, etc
For e.g., nylon 6, 6 is formed by the condensation of hexamethylene
diamine with adipic acid

It is also possible, with three functional groups (or two different
monomers at least one of which is tri-functional), to have long linkage

sequences in two (or three) dimensions and such polymers are
distinguished as cross linked polymers
Classification Based on Molecular Forces:

The
mechanical
properties
of
polymersare
governed
by
intermolecular forces, e.g., van der Waals forces and hydrogen bonds,
present in the polymer, these forces also bind the polymer chains
Under this category, the polymers are classified into the following
groups on the basis of magnitude of intermolecular forces present in

them, they are
(i) Elastomers
(ii) Fibers
(iii) Liquid resins
(iv) Plastics [(a) Thermoplastic and (b) thermosetting plastic].
Elastomers: These are rubber like solids with elastic properties

In these elastomeric polymers, the polymer chains are random coiled
structure, they are held together by the weakest intermolecular

forces , so they are highly amorphous polymers
These 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 vulcanised rubber
The examples are buna-S, buna-N, neoprene, etc
Fibers: If drawn into long filament like material whose length is at
least 100 times its diameter, polymers are said to have been
converted into fibre
Polymeric chains are straight chain polymers, they are held together
by the strong intermolecular forces like hydrogen bonding,

these strong forces also lead to close packing of chains and thus
impart crystalline nature
Fibres are the thread forming solids which possess high tensile
strength and high modulus

Examples are polyamides (nylon 6, 6), polyesters (terylene), etc.
Liquid Resins: Polymers used as adhesives, potting compound sealants,
etc. in a liquid form are described liquid resins, examples are epoxy
adhesives and polysulphide sealants.
Plastics: A polymer is shaped into hard and tough utility articles by the
application of heat and pressure; it is used as a plastic

The intermolecular force between polymeric chains are intermediate
between elastomers and fibers, so they are partially crystalline

Typical examples are polystyrene, PVC and polymethyl methacrylate.
They are two types

(a)Thermoplastic and
(b)Thermosetting plastic.
Thermoplastic Polymers: Some polymers soften on heating and
can be converted into any shape that they can retain on cooling
The process of heating, reshaping and retaining the same on cooling
can be repeated several times, such polymers, that soften on heating

and stiffen on cooling, are termed thermoplastics
These are the linear or slightly branched long chain molecules
capable of repeatedly softening on heating and hardening on cooling

These
polymers possess intermolecular forces of attraction
intermediate between elastomers and fibres

Polyethylene, PVC, nylon and sealing wax are examples of
thermoplastic polymers.
Thermosetting Polymers: Some polymers, on the other hand,
undergo some chemical change on heating and convert themselves

into an infusible mass
They are like the yolk of egg, which on heating sets into a mass, and,
once set, cannot be reshaped. Such polymers, that become infusible

and insoluble mass on heating, are called thermosetting polymers.
These polymers are cross linked or heavily branched molecules,
which on heating undergo extensive cross linking in moulds and

again become infusible
These cannot be reused. Some common examples are bakelite,
urea-formaldelyde resins, etc.

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Polymer contains repeating units

examples are DNA, proteins, etc

a macromolecule may not be a polymer

and reactive molecules known as monomers and are linked to

pieces (monomers) that can be easily connected into long chains

monomers is called polymerization

hexamethylene diamine and adipic acid leading to the formation

The functionality of a monomer is the number of sites it

has for bonding to other monomers under the given conditions

two, can link to two other molecules under suitable conditions

two molecules under the conditions of the polymerization

The number of repeating units (n) in the chain so formed is called

the degree of polymerization (DP = n)

high polymers and those with low degree of polymerization are

that the optimum strength of most of the polymers is obtained at n

The following are some of the common classifications of

Classification Based on Source:

animals. Examples are proteins, cellulose, starch, resins and rubber

(polythene), synthetic fibres (nylon 6,6) and synthetic rubbers

Classification Based on Backbone of the polymer chain:

is essentially made of carbon atoms is termed as organic polymer

atoms are, however, usually those of hydrogen, oxygen, nitrogen, etc.

atom is called inorganic polymers

Classification Based on Structure of Polymers:

branches, e.g., low density polythene

and tri-functional monomers and contain strong covalent bonds between

Classification Based on Composition of Polymers:

monomer; a polymer consisting substantially of a single type of repeating unit

polymer chain, the polymer is called a copolymer

two (or more) monomeric species, as opposed to a homopolymer where only

Commercially relevant copolymers include ABS plastic, SBR, Nitrile rubber,

In an alternating copolymer, the two monomers are arranged in an

together, and all of the other are grouped together

homopolymers joined together at the ends: branched copolymers

Classification Based on Mode of Polymerisation:

repeated addition of monomer molecules possessing double or triple

monomers are termed as copolymers, e.g., Buna-S, Buna-N, etc

Condensation Polymers: The condensation polymers are formed by

repeated condensation reaction between two different bi-functional or

as water, alcohol, hydrogen chloride, etc. take place

diamine with adipic acid

monomers at least one of which is tri-functional), to have long linkage

Classification Based on Molecular Forces:

groups on the basis of magnitude of intermolecular forces present in

Elastomers: These are rubber like solids with elastic properties

structure, they are held together by the weakest intermolecular

Fibers: If drawn into long filament like material whose length is at

by the strong intermolecular forces like hydrogen bonding,

strength and high modulus

Liquid Resins: Polymers used as adhesives, potting compound sealants,

application of heat and pressure; it is used as a plastic

between elastomers and fibers, so they are partially crystalline

They are two types

Thermoplastic Polymers: Some polymers soften on heating and

can be repeated several times, such polymers, that soften on heating

capable of repeatedly softening on heating and hardening on cooling

polymers possess intermolecular forces of attraction

intermediate between elastomers and fibres

Thermosetting Polymers: Some polymers, on the other hand,