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Dr.

Sunita Nair / CSE B & BME

AUG 2015

Introduction to Polymer
Polymer is derived from Greek word (Poly = many &
mers = Units)
Polymers are macromolecules formed by the
combination of large number small molecules known as
monomers.
Therefore a monomer is a micromolucule composed of a
single unit
Like H2O, CO2, H2O2 etc.
Whereas polymer is a macromolecule composed of large
number of repeating units called monomer.
n CH2 = CH2 ( CH2 CH2 ) n
ethylene (monomer)
polythene or
polyetylene

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H H
n C=C
H
Styrene
(monomer)

H H
C C
H

n
Polystyrene
(Polymer)

POLYMERISATION
Definition: Polymerisation is a chemical process in which a
number of monomers are linked together to form a polymer.
Polymerisation proceeds by the chemical combination of two
or more identical or different monomers with or with out the
elimination of small molecule like H2O, MeOH etc..

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Functionality
Functionality of a monomer is no. of reactive sites or
bonding sites or functional group present in the
repeating units.
For a substance to act as a monomer, it must have at
least one double bond.
Polymerisation proceeds with breaking of these double
bonds.
Functionality is also given by the no. of functional groups
a molecule has.
Example: In case of ethylene, a double bond is broken
during homolytic cleavage in presence of uv light or heat
and each carbon atom gets converted to free radical.

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In ethylene now we have two reactive sites can undergo


polymerisation.
All monomers are molecules but all molecules are
not monomers
All macromolecules need not be polymers.
Carbon dioxide is a molecule but does not undergo
polymerization. On the other hand ethylene
molecule, which is a monomer, polymerizes to give
polyethylene.
In other words for a molecule to become monomer it
should have at least two bonding sites.

Homolytic cleavage

CH2=CH 2

CH

n CH
2

hv

CH2 + CH2
CH
2

CH2
..

CH2

CH2
CH2

CH2
PE

CH2

CH2

Therefore ethylene is considered as bifunctional monomer.


Depending upon the presence of no. of bonding site present in the
monomers , they are classified as
Functionality
Bonding Sites
Example
Monofunctional
One
CH3OH, CH3COOH
Bifunctional
Two
(CH2)4(COOH)2 & (CH2)6(NH2)2
Trifunctionl
Three
(CH2 OH)2CHOH, Phenol
Tetrafunctional
Four
Acetylene,
Non functional
Zero
Methane
REFER CLASS NOTES FOR MORE EXAMPLES
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When bi-functional (BF) monomers undergo polymerisation then


linear polymers are formed.
When bi-functional monomers mixed with trifunctional (TF) & if the
ratio of bi-functional monomer is > than tri-functional monomers,
then branched chain polymers are formed.

During mixed polymerisation , when the ratio of trifunctional


monomer is > than bi-functional ,then cross linked polymer could be
formed.
When the tri-functional monomer undergoes polymerisation then
cross linked or three dimensional net work polymers are formed.

Dr. Sunita Nair

Classification
1)

Based on origin:
The polymers obtained from nature (plants and
animals) are called natural polymers. These polymers
are very essential for life.
i) Natural : Known as Biopolymer: Examples are
Cellulose( polymer of glucose), protein, starch, fibres,
silk, wool etc
ii) Synthetic : Examples are polypropylene, polystyrene,
polyethylene etc
iii) Semi synthetic : These polymers are mostly derived
from naturally occurring polymers by chemical
modifications. Examples are Cellulosics such as
cellulose acetate, cellulose nitrate ( gun cotton),
Rayon etc.

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2) Based on Degree of Polymerisation (DP)


The number of repeating (monomers) units present in
polymer chain is known as DP.
i) Low DP: Known as Oligomers
( Molecular weight 500 to 5000)
ii) High DP : High Polymers
( Molecular weight 104to106)

3) Based on Structure
i)
Linear Polymers : HDPE, Nylon, Polyester
ii)
Branched Polymers : LDPE, glycogen
iii)
Cross linked or three dimensional Polymers :Bakelite, urea
formaldehyde
4) Based on monomers
A polymer may consists of identical (Homopolymer) or different
monomers (Hetero polymer)
a)
Homopolymer
Polymer consists of identical monomer
- CH2 (CH2 CH2 ) CH2 CH2 - (polythene)
Other Examples are PS, PVC, PTFE,
Based on type of arrangements of identical monomers

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i) Linear homopolymer
M

ii) Branched homopolymer


M

M
M
M

iii) Cross linked homo chain polymer


M

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b) Hetero polymer / Copolymer


Polymer is made up of different types of monomers

M1

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M2

M1

M2

M1

Nylon 6:6
Nylon 6:6 is prepared by the condensation polymerisation between
hexamethylene diamine and adipic acid.
H
n

C N
H H 6H

Hexamethylene diamine

OH H

OH

H 4H

condensation
polymerisation

2n-1 H2O

Adipic acid

C
H

H
N
6H

Nylon 6:6

C
O

H 4O

OH
n

Based on arrangements
i) Linear heteropolymer
M1

M2

M1

M2

M1

M2

M1

ii) Branched heteropolymer


M1

M2

M1
M2
M1

iii) Cross linked hetero polymer


M1

M2

M1

M2

M1

M1

M2

M1

M2

M1

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iv) Graft hetero polymer


Back bone of the polymer is made up of one kind of monomers
& branches made up of another type
M1

M1

M1

M1

M2

M2

M2

M2

M1

v) Block hetero polymer


A

A A

B B

Blocks of monomers arranging in orderly or disorderly


form in a polymer
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BLOCK POLYMER

GRAFT POLYMER

RANDOM POLYMER

5) Based on main chain of the polymer


i) Homochain polymer
Main chain is made up of same atoms
-C-C-C-C-C-CExample : Polyethylene, polystyrene etc
ii) Heterochain polymer
Main chain is made up of different atoms
-C-C-C-O-C-C-O-CExample : Polyamides, Nylon6, Nylon 6:6 etc.

6) Based On Geometry ( Tacticity)


The orientation of monomeric unit with respect to main chain can
either be an orderly or random manner. This is called as tacticity.
If monomeric units are arranged in some regular order,then the
polymer is termed as Stereo Specific Polymer (SSP)

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i) Isotactic;
In this functional groups ( monomeric unit) are arranged in the same side
of the main chain

R R R R R R R
C C C C C C C
H H H H H H H

ii) Syndiotactic
In this functional groups ( monomeric unit) are arranged in the
same side of the main chain
R H R H R H R
C C C C C C C
H R HR H R H

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iii) Atactic
In this functional group ( monomeric unit) are arranged at random
around the main chain.
R R H R R R
H C C C
C C C
H H R H H H

7) Based on Thermal properties (or Molecular forces)


Thermoplastics:
Plastics that soften when heated and become firm again when cooled. This is
the more popular type of plastic because the heating and cooling may be
repeated.
Ex : Poly ethylene, polypropylene, PVC, PTFE

Dr. Sunita Nair

Thermosetting plastics:
Plastics that soften when heated and can be molded,
but harden permanently. They will decompose when
reheated.
Ex. Bakelite, urea formaldehyde, polyesters etc.

8)Based on synthesis
i) Addition Polymers: Involves addition of monomers to
one another to form a long polymer chain without
forming any by product.
Example: PE,PP, PVC, TEFLON.
ii) Condensation polymers
Involves addition of identical or different monomers to
one another to form a long polymer chain with the
elimination of by product.
Example: Bakelite, Nylon 6, Nylon11,Nylon6:6 etc.

Nylon 6:6
Nylon 6:6 is prepared by the condensation polymerisation between
hexamethylene diamine and adipic acid.
H
n

C N
H H 6H

Hexamethylene diamine

OH H

OH

H 4H

condensation
polymerisation

(2n -1)H2O

Adipic acid

C
H

H
N
6H

Nylon 6:6

C
O

H 4O

OH
n

9) Based on nature of polymer


i) Organic: PP, PVC, PS
ii) Inorganic: Silicones, polysilanes,
polyphosphazene

10) Based on application


Plastics : PVC, PP
Elastomers: Rubber
Fibers: Nylon, terylene, Dacron
Resin : epoxy resin sealing agents, polysulphide

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(11) Based on degradability of Polymers


(i) Bio- degradable polymers
Natural Bio- degradable polymers
Synthetic Bio- degradable
Ex. Collagen
Polymers.
Ex: Aliphatic polyesters,
polyanhidride, Polyphosphazene

(ii) Non-Bio- degradable polymers


Hydrophobic Polymers
Ex: HPMC (hydroxypropyl
methyl cellulose)

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Hydrophilic polymers
Ex. Ethyl cellulose,
silicones

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