Polymers

Poly means many

Mer means unit
Polymers are macromolecules formed by the combination of many small molecules
called monomers.
The molecular weight of polymer ranges from 500 to 106.
The process of formation of polymer from monomers is called polymerisation.
Degree of polymerization (DP) is the number of repeating units (monomers) present in
the polymer

DP = mol.wt of polymer
mol.wt of monomer
Example:
Polyethylene is made by repeatedly linking ethylene (monomer)

n CH2 = CH2 ( CH2 CH2 ) n

Ethylene
polythene
(monomer)

Dr.VSG & Dr.KY

Page 1

2-8-2014

Functionality
The number of reactive or bonding sites present in the monomer is called its
functionality.
Monomers which possess more than one reactive site alone can undergo
polymerization.

Functionality

Examples

CH4 , CCl4 , C6H6

ROH , RCl , RCOOR, RNH2

Amino Acids , CH2 = CH2 (ethene),

CH2OH CH2OH (glycol)

CH2OH CHOH CH2OH (glycerol)

C6H5OH (phenol)

CH CH (acetylene)

All monomers are molecules but all molecules are not monomers
For example Water is a molecule but does not undergo polymerization (functionality is
0).
On the other hand ethylene molecule polymerises to give polyethylene hence it is a
monomer (functionality 2).
In other words for a molecule to become monomer it should have at least two bonding
sites ie. Its functionality should be at least 2.

Dr.VSG & Dr.KY

Page 2

2-8-2014

Classification
1. Based on Origin

Semi synthetic
Cellulose acetate
Vulcanised rubber

Natural, Synthetic and Semi synthetic

Natural/ Bio polymers : Cellulose, Starch, Proteins, Rubber etc.,
Semi synthetic:Celluloid , Ethyl Cellulose, Cellulose Acetate, Carboxy methyl
cellulose (CMC)
Synthetic (organic) : Polyamides, Poly esters, Poly ethers, PVC, PS PE etc.,
Silicone is an inorganic synthetic polymer

Dr.VSG & Dr.KY

Page 3

2-8-2014

Uses of Synthetic Polymers

No.

Polymer

Uses

Polyethene

plastics, drinking bottles, toys

Polyvinyl
chloride

Polystyrene

Nylon 6

piping, floor tiles, clothing, toys,

wire covering
containers, thermal insulation-ice
buckets
Textile

Nylon 6,6

Sweater

Kevlar

Bullet proof vest

Dacron

Fabric

Terylene

Fiber-optic material

2. Based on Degree of polymerization

Dr.VSG & Dr.KY

Page 4

2-8-2014

3. Based on the Type of Monomer

Homo polymer Prepared by the self polymerization of same type of monomers (A)
- CH2 ( CH2 CH2 ) CH2 CH2 -

(polyethene)

Types: based on the arrangement of monomers

Linear homopolymer: (HDPE)

Branched homo polymer: (LDPE)

A
A

Dr.VSG & Dr.KY

Page 5

2-8-2014

Cross linked polymer (Poly Acetylene)

Dr.VSG & Dr.KY

Page 6

2-8-2014

Heteropolymer / Copolymer:
Prepared by cross polymerization of two or more types of monomers
Example: Nylon 6,6 , Urea formaldehyde , Buna S- rubber ,Buna N
rubber etc.,

Dr.VSG & Dr.KY

Page 7

2-8-2014

Block copolymer

Graft Copolymer
It is a special kind of branched copolymer where the main chain and side chains are made up
of different types of monomers

Dr.VSG & Dr.KY

Page 8

2-8-2014

For example the cationic exchanger of the demineraliser is prepared by

grafting styrene into poly ethylene base polymer and then sulphonating
the resulting graft co polymer.
Scheme of preparing cationic exchanger:

4. Based on main chain (back bone/ skeleton)

i)

Homo chain: made up of single type of atom (ex) PE , Buna Srubber

Dr.VSG & Dr.KY

Page 9

2-8-2014

ii) Hetero chain: made up of different types of atoms (ex) nylons,

polyesters, PVA, PVAc etc.,

5. Based on molecular forces (thermal behaviour)

Thermoplastics / Thermoforming Plastics: Ex. PE, PP, PVC, PS
Thermosetting plastics: Ex. Bakelite, Polyester, Urea- formaldehyde, Epoxy resins

Thermoplastics (TP)

Thermosettes (TS)

They are formed by addition

polymerization

They are formed by condensation

polymerization

They are linear / branched long chain

polymers

They consist of three dimensional network

structure joined by strong covalent bonds

On cooling they get hardened

On heating they get hardened

They are soluble in organic solvents

Insoluble in organic solvents

Softens on heating , because Vander

Waals forces existing between the
individual chains can break easily by heat
and pressure

They do not soften on heating because the

covalent bonds retain their strength on
heating

Dr.VSG & Dr.KY

Page 10

2-8-2014

They can be remoulded any number of

times

Once set, they cannot be remoulded

They are soft, weak and less brittle

They are hard, strong and more brittle

5. Based On Application
(a)Resins: Half polymerized polymers are called resins
They are used as ion exchangers and in the preparation of adhesives
(b) Fibres: Usually polymers with high tensile strength will be drawn into wires.
Examples: PET, nylons etc.,
(c) Elastomers (Ex) rubbers
(d) Plastics ; TP and TS
6. Method of synthesis
Addition polymer: Polymers prepared by addition reaction
Ex.: PE,PVC,PVA , PS, Buna S-rubber etc.,
Condensation polymer: Polymers prepared by condensation reaction.
Ex.: Poly amides, Poly Esters, Poly Ethers, PET, Bakelite, PC, Poly Urethane etc.

Addition Polymerization / Polymers

Condensation polymerization /
Polymers

Monomers add on to give polymers

without forming by products

Monomers condense to give

polymers and by products like H2O, HCl,
MeOH etc. are formed.

Monomers must have atleast one double

bond

Monomers must have atleast two identical

or different functional groups

It is a chain forming reaction

It is a step wise reaction

The polymer product is formed at once

The polymer product is formed stepwise

steadily

Dr.VSG & Dr.KY

Page 11

2-8-2014

Molecular weight of the polymer is an

integral multiple of the molecular weight of
the monomers

Molecular weight of the polymer is less

than the integral multiple of the monomers

Mostly Thermoplastics are obtained

Mostly Thermoset resins are obtained

Thermosetting
Epoxy
Rigid
Urea-formaldehyde
Hard rubber
Highly loaded or highly
Flexible vulcanized rubbers
Rubbery Vulcanized rubbers

Thermoplastic
PS
PVC Unplasticised
PP
PE, Acetate copolymers,
PVC Plasticised
TPE Thermoplastic elastomer

7. Based on Tacticity

Tacticity is the orderly arrangement of groups around polymer main chain

Ex: Poly Styrene
If all of the phenyl groups are on the same side of the chain, the polymer is
isotactic.
If the phenyl groups come on alternating sides of the chain, the polymer is
syndiotactic.
If the phenyl groups are on both sides and right and left following no particular
order, in a random fashion, then the polymer is atactic.

Dr.VSG & Dr.KY

Page 12

2-8-2014

Extra information
Biopolymers (Natural Polymers)
All organic polymers are threads made using repeating units, the monomers, that are
either similar or different.
(i)

.The similarly beaded "homo polymers" are made by linking together many of
the same monomers.

Starch or cellulose are homo polymers

ii). The differently beaded "hetero polymers" are made of different monomers.
"Hetero" is a prefix that implies that components are different.
DNA, RNA are both heteropolymers.

Dr.VSG & Dr.KY

Page 13

2-8-2014

Hetero polymer

Inorganic Synthetic Polymers

Dr.VSG & Dr.KY

Page 14

2-8-2014

Plastics Application Summary

Material Types

Industry Types

Acrylic

Medical equipment

Polycarbonate

CD, Bullet Proof Helmet

PVC

Defence, Medical

Polypropylene

Aerospace, syringe

SBR

Elastomer

PEEK

Engineering

(Poly Ether Ether Ketone)

PVDC

Food Processing

(Poly VinyliDene Chloride)

PTFE

Design houses

(Teflon)

Kevlar

Dr.VSG & Dr.KY

Strong Fibre

Page 15

2-8-2014