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POLYMERS
 Inroduction
Polymers (Greek Poly= many; mers= units or parts)
are “Macromolecules” (giant molecules of high molecular
masses)built -up by the linking together of a large number of
small molecules (called monomers)
Ex: Polythene is a polymer formed by linking together of a large
number of ethene (C2H4)molecules.
• Thus, small molecules which
combine with each other to form
polymer molecules , are termed
monomers, the ‘repeat unit’ in a
polymer is called mer.
Applications of polymers
 What is polymerization?
In polymer chemistry, p
olymerization is a
process of reacting mo
nomer molecules togeth
er in a chemical
reaction to form polyme
r chains or three-dimen
sional network.
 What is degree of polymerization?

The number of repeating units(n) in a polymer , is know

n as the “degree of polymerization”(DP)
There may be hundreds or thousands or ten
thousands monomer molecules linked together in a
polymer molecule.
( Most of the polymers, usually fall into the
5,000-2,00,000)
 Homo polymer
A polymer may consist of identical monomers called
homo polymers.

.........-M-M-M-M-M-M-M-M-…………..
 Copolymer
A polymer may consist of monomers of different
chemical structures called
copolymers.

……..-M1-M2-M1-M2-M1-M2-M1-M2-……
 Homo chain polymer
If the main chain is made up of same
species of atoms , the polymer is
called homo chain polymer.
……….-C-C-C-C-C-C-C-………….
 Hetero chain polymer
If the main chain is made up of
different atoms then it is called
hetero chain polymer.
…….-C-C-O-C-C-O-C-C-O-C-C-O-……….
 What do you mean by
tacticity of polymers?
The orientation of monomeric units in a
polymer molecule can take place in orderly or
disorderly fashion with respect to the main
chain.
The difference in configuration (tacticity)
does affect their physical properties.
 Isotactic polymer
The head to tail configuration in which the
functional groups are all on the same side of the chain, is c
alled isotactic polymer.
 Atactic polymer
If the arrangement of functional groups are at rando
m around the main chain, it is called atactic polymer.
 Syndio tactic polymer
If the arrangement of side groups is in
alternating fashion, it is called
syndiotactic polymer
 Plastics
Plastics are a wide range of synthetic or semi-synthetic materials that
use polymers as a main ingredient. Their plasticity makes it possible fo
r plastics to be moulded, extruded or pressed into solid objects of
various shapes. This adaptability, plus a wide range of other properties
,
such as being lightweight, durable, flexible, and inexpensive to produc
e, has led to its widespread use. Plastics typically are made through h
uman industrial systems.
Most modern plastics are derived from fossil fuel-based chemicals like
natural gas or petroleum; however, recent industrial methods use varia
nts made from renewable materials, such as corn or cotton derivatives
 Types of polymerization
1. addition polymerization
2. condensation polymerization
3. copolymerization polymerization
 Addition polymerization
What is addition polymerization?
Addition or chain polymerization is a reaction
that yields a product, which is an exact multiple
of original monomeric molecule.
Such a monomeric molecule usually contains one or more
double bonds.
The addition polymerization reaction must be instigated
by
the application of heat, light, pressure or a catalyst for
breaking down the double covalent bonds of monomers.
 Example
Polyethylene :
(ii) Polypropylene:
(iii) Polyvinyl chloride(PVC):
Polyvinyl acetate (PVA):

H H Polymerization
n C C H
* CH2 C *
OCOCH3
H n
Vinyl acetate OCOCH3
PVA
 Condensation polymerization
What is condensation polymerization?
Condensation or step polymerization may be
defined as a reaction occurring between
simple polar group containing monomers with the formation of po
lymer and
elimination of small molecule like water, HCl etc.
Condensation reaction
 Example
Preparation of nylon 6:6
Chain and condensation polymerization
Addition Polymerization Condensation Polymerization
1. Only growth reaction adds repeating 1. Any two molecular species present
can react.
units one at a time.
2. Monomers disappears early in the
2. Number of units increases steadily reaction.
through out the reaction.
3. Longer reaction times have little effect on 3. To obtain high molecular weight,
molecular weight, but gives higher yields. longer reaction time is essentials.
4. The reaction mixture contains only
monomers, high polymers and about 10-8 4. All types of molecular species are
present at any stage.
part of growing chains.
 Copolymerization
What is copolymerization polymerization?
Copolymerization is the joint polymerization
of two or more monomer species. High
molecular weight compounds obtained by
copolymerization , are called copolymers.
Example
 Breaking of polymers

What is hydrolysis reaction?

Hydro = water; lysis = loosening

Hydrolysis is cleavage of polymeric

chain by the addition of water.
Hydrolysis
 Classifications of Polymers
Classification on the basis of source:
• Natural polymers: Natural polymers are found in
nature in animals and plants.
Example: starch(a polymer ofα-D-glucose),cellulose
( a polymer of β-D glucose), proteins( polypeptides
and polyamide), natural rubber ( a polymer of cis
isoprene)
• Synthetic polymers: (manmade polymers)
Example: polyethylene(PE), polypropylene(PP),
polyvinyl chloride(PVC), nylon, terylene, Bakelite.
 Classifications of Polymers
Classification on the basis of structure:
• Linear polymers: polymers in which monomeric
units are joined in the form of long straight chains.
Example: HDPE( high density polythene), nylons,
polyester .
These polymers possess high m.p., density, tensile
strength, due to close packing of polymer chains.
E. Representation of polymer types

(a) linear (b) branch

(c) network
Branched chains polymers: Branched chain polymers
are mainly linear in nature , but also possess some
branches along the main chain.
Examples: low density polythene(LDPE),glycogen etc..

These polymers possess low m.p., density and tensile

strength compared to linear polymers, due to poor
packing of polymer chains in presence of branches.
Three -dimensional network polymers:

This polymers contain monomer molecules

connected to each other by only covalent bonds.
They are giant molecules in which movement of
individual monomeric units is prevented by strong
cross links.
Due to presence of strong cross links, they are hard,
rigid, brittle, and do not melt, but burn on strong
heating.
Examples : Bakelite, Urea -formaldehyde resins
 POLYESTER RESIN
Polyethylene terephthalate(PET)

HOOC COOH
2 CH3OH
H3COOC COOCH3

Terephthalic acid Dimethyl terephalate

H3COOC COOCH3
+ n HO (CH2)2 OH

Ethylene glycol
Dimethyl terephalate

O O

* C C O (CH2)2 O *

PET
Phenol (excess) + Formaldehyde

ACID catalyst

NOVOLACS

Heat & Curing agents

Bakelite
 Phenolic resins
Step-1

OH OH
OH
CH2OH
+ HCHO +

CH2OH
Phenol
Mono methyl phenol
Step2

OH OH
OH H OH
CH2OH H CH2OH 2
-H2O C CH2OH
+

dihydroxy diphenyl methane

Further Condensation

OH OH OH
CH2

NOVOLAC
Novlac
• Step 3
OH OH OH OH

CH2 CH2 CH2 CH2

OH OH OH OH

Bakelite
 Uses Of Bakelite
• Bakelite due to its high resistance to electricity and heat is used
in automotive components and industrial applications.
• Due to its excellent insulating properties it is used for making
switches and other electrical appliances.
• It is also used to make various kitchenware products like frying
pans etc.
Urea-formaldehyde resins(UF)
 Monomethylol urea
Urea

Dimethylol urea

Dimethylene urea MonomethyleneUrea

Cross linked polymer Partially cross linked polymer Linear polumer

Fully cross linked UF polymer
 Uses Of Urea Fromaldehyde resines
• Urea-formaldehyde is pervasive. Examples include decorative
laminates, textiles, paper, foundry sand molds, wrinkle-
resistant fabrics, cotton blends, rayon, corduroy, etc. It is also
used as wood glue. UF was commonly used when producing
electrical appliances casing (e.g. desk lamps).
Classification on the basis of their methods
of synthesis:
Addition polymers: Addition polymers are obtained by
addition polymerization method, which involves the
repeated addition of monomers (unsaturated derivatives of
ethane) to yield long chains.
Example: polyethylene, polypropylene, polyvinyl chloride
Condensation polymers: Condensation polymers are
obtained by a series of condensation reactions, generally
involving two monomers.
The condensation reactions, usually, result in the loss of
small molecules (like H2O, HCl, NH3).
Examples: nylon-6, Bakelite, polyester
Classification on the basis growth
polymer chains:

Chain growth polymers: They are formed by the

successive addition of monomer units to the
growing chain carrying a reactive intermediate.
Ex: polythene, polystyrene, polypropylene,
polyvinylchloride etc.
Chain growth polymers
Step growth polymer : They are formed through a
series of independent reactions involving bond
formation (condensation) between two different
monomers with loss of small molecule like H2O,HCl etc.

A-X + B-Y A-B + XY

A-B + A-B A-B-A-B or (A-B)2

(A-B)2 + (A-B)2 (A-B)4 (A-B)n

Condensation polymer
Classification based on molecular forces:
On the basis of the magnitude of intermolecular forces
present in polymers, they are classified into four
categories:

1. Thermoplastic polymer
2. Thermosetting polymer
3. Elastomer
4. Fibres
Thermoplastic polymers: These are linear,
long chain polymers, which can be softened on heating
and hardened on cooling reversibly, i.e. their hardness is
temporary property, subject to change with rise or fall of
temperature.
Thus, they can be processed again and again.

Example: polythene (PE), polypropylene (PP), nylons etc.

Thermosetting polymers: Thermosetting polymers are
those polymers, which during moulding get hardened
and once they have solidified, they cannot be
softened, i.e., they are permanent setting polymers.
Such polymers during moulding acquire three-
dimensional cross linked structure, with predominantly
strong covalent bonds.
Thus, a thermosetting polymer once moulded cannot be
reprocessed.

Example: Polyester, Bakelite, epoxy-resin etc.

Elastomer(Or synthetic rubber):

Elastomer is any rubber like elastic polymer, which

can be stretched to at least thrice its length, but it
returns to its original shape and dimensions as soon
as stretching force is released.
Thus, elasticity of an elastomer is caused by the
lengthening and shortening of their polymeric chain
springs.
Fibres: Fibres are those polymers whose chains are held by strong inte
rmolecular forces like hydrogen
bonding. They are crystalline in nature and of high
tensile strength, due to strong intermolecular forces.
Example: nylon, polyester.