POLYMERIZATION TECHNIQUES

Different Polymerization technique are:

1. Bulk polymerization
2. Solution polymerization
3. Emulsion polymerization
4. Suspension polymerization

BULK POLYMERIZATION
Bulk polymerization is the conversion of monomer into a

polymer without the aid of a solvent. Both addition and

condensation can be carried out in a bulk
polymerization reactor.
Polymerization is carried out in pre- and postpolymerization stages for controlling heat of
polymerization.
Advantage

There is no problem of getting solvent out of the finished

product

Disadvantage

As the viscosity increases with polymerization, mixing

become difficult

SOLUTION
POLYMERIZATION
If the temperatures required to melt the monomer are too

high, or if bulk polymerization would be so exothermic as to

be hazardous, solution polymerization is used.

Monomer is dissolved in suitable solvent, then initiator is

added to start polymerization. When reaction is over,

polymer is obtained by precipitation.

The presence of inert solvent medium helps to control

viscosity increase & promote a proper heat transfer.

Disadvantage -

It is difficult to get high molecular weight product

The polymer formed will also have to be isolated from
the solution

Used as in case of adhesives & coating

E.g. Polymerization of Polyacrylonitrile & polyisobutylene

SUSPENSION
POLYMERIZATION
Also known as bead/pearl polymerization
If the monomer is insoluble in water, bulk polymerization

can be carried out in suspended droplets which are kept in

suspension by mechanical agitation.

The water phase act as an efficient heat transfer medium,

so the process is also economical as compared to solution

polymerization.

In this system, the monomer must be either 1) insoluble in

water or 2) only slightly soluble in water, so that when it

polymerizes it becomes insoluble in water. so removal is
quite simple

The disadvantage is that few monomers are water soluble

so they cannot be polymerized by this method.

Eg. Polymerization of Polystyrene

EMULSION
POLYMERIZATION
The monomers are dispersed in aqueous

medium as a uniform emulsion which are

stabilized by surfactants or protective
colloids.
At critical micelle concentration (CMC),

polymerization takes place and micelles

get swelled with the growing polymer.
Eg. Polymerization of Polyvinyl chloride

Examples of few
polymers

Polyethylene (-CH2-CH2-)n
Prepared by the process of addition

polymerization of ethylene.
Two Types:

Low density polyethylene (LDPE)

Prepared by heating very pure ethylene at

190-210 0C under a pressure of about 10005000 atmospheres in the presence of traces of

oxygen (free radical initiator).
Polymer produced consists of highly branched
chain molecules.

Due to branching, density of polymer is

low.
Chemically inert, tough but flexible.

High-density polythene (HDPE)

Prepared by heating ethylene in a

hydrocarbon solvent at 60-70 0C under a

pressure 6-7 atmosphere in the presence of
catalyst such as triethylaluminium and
titanium tetrachloride.
Polymer produced is linear and density is high.
Chemically inert but more tougher and
harder .

USES
In making moulded parts/toys and fibers
Its fibers are used in making ropes(extremely

strong by weight)
Carpets
Furniture upholstery, Blankets, Hand bags,
etc.
Insulator for wires/cables
Buckets, milk bottles, ink tubes for pens etc.
Washing machine parts
Sterilizable hospital equipment

Poly propylene(

Prepared by passing polypropylene through n-

hexane containing Zeigler-Natta catalyst at

1000C under 10 atm. Pressure.
Stereo regular ( isotactic)
Highly crystalline polymer (M.P 160-170 0C)
Better hardness than PE
Strength
Stiff than PE
More resistant than PE

USES
In disposable syringes
In making accelerators pedals
Boxes, Chairs, etc.

Poly vinyl chloride (PVC)

It is a thermoplastic and made by addition

polymerization.
It is of two types

1. Rigid PVC
2. Plasticized PVC
n CH2=CHCl

[ -CH2-C(Cl)H-]n

RIGID PVC
Prepared by heating vinyl chloride(in the form

of emulsion of it in water) in the presence of

small amount of benzoyl peroxide or H2O2 as
catalyst under pressure in an autoclave.
nCH2=CHCl

H2O2

[ -CH2-C(Cl)H-]n

Cl atoms present in alternate C-atom

increases hardness.
Polar polymer
Colourless and odourless

PLASTICIZED PVC
Prepared by adding plasticizers such as

dioctyl phthalate, dibutyl phthalate etc. to

rigid PVC.
Good insulators for direct current
Flexible
Resistant to water, atmospheric oxygen

and chemicals
It is harmless if taken orally

USES
For making
Window frames
Chewing gums
Doors
Bottles
Helmets
Hand bags
Electrical insulation of domestic as
well as industrial wires and cables

Polystyrene (PS)

It is prepared by free radical addition

polymerization of styrene in the presence of

benzoyl peroxide as catalyst.
It is an amorphous and non-polar polymer
Good optical properties (transparent so it can
absorb all wavelengths).

USES
For making
Disposable drinking cups
Audio casettes
Containers for talcum powder
Combs
Brush handles

Poly methyl methacrylate or

Lucite or plexiglass (PMMA)
Is obtained by the polymerization of

methyl methacryalate (ester of methyl

acrylic acid) in presence of acetyl peroxide
or hydrogen peroxide as catalyst.
It is colorless, transparent and amorphous
thermoplastic with high optical
transparency.
It is hard and non-flexible
Polar so do not have electrical insulation

Preparation

Uses
Lenses
Light fitting for street lamps
Automobile rear lamp housing
Jwellery
Wind screens
T.V screens
Guards
Wash basins

Poly acrylonitrile (orlon,

PAN)
I t is obtained by the polymerization of

acrylonitrile in the presence of a peroxide

Preparation:
nCH2=CHCN

FeSO4 + H2O2

[CH2-

C(CN)H-]
Properties:
It is a high melting and hard solid.
Dissolve in solvents like dimethylformamide
so used as fibres which are resistant to water,

Uses
As a substituent for wool for making fibres like

acrilan. Thus it is used for making warm

clothes, carpets , blankets etc.
This polymer form water resistant and quick
drying fiber.

Polyethylene
terephthalate (PET)
It is also called terylene or Decron.
Preparation;

It is prepared by heating dimethyl

terephathalate and ethylene glycol in basic
medium
n H3C-O-CO-C6H4-CO-O-CH3 + nHO-(CH2)2-OH

[-CO-C6H4-CO-O-(CH3)2-O-]n

Properties
It readily crystallize because of symmetrical

structure and numerous polar groups.

This fiber has outstanding grease resistance,
low moisture absorption and more durable.
Good resistance to hydrocarbon solvents and
moisture
Good mechanical properties like high
modulus, tensile strength and impact strength
which are retained up to 150-1750C.

Uses
Used for making transparency of

overhead projector.
Bottles are used for cold-drinks, fruit
juice concentrate and sauces.
Wide necked jars for coffee.
Terylene fibers are
also used for
blending with wool.

Polyurethane:
Addition polymer containing urethane linkage
[-NH-(C=O)-O-]

diphenylmethane-4,4diisocyanate

ethylene glycol

Properties
Because of their saturated character,

they are highly resistant to oxidation.

Low melting point and high degree of
flexibility.
Resistant to water, oil and corrosive
chemical.

USES
Used in tyres.
In light weight water repellent garments

like swim suits.

Used in floor coating of gymnasium, dance
floors etc.
Making car and furniture cushions and are
good leather substitute.

Phenolic resins or
Phenoplasts
They are the condensation polymerisation

products of phenolic derivatives(like phenol,

resorcinol) with aldehydes (like
formaldehyde).
Most important member of this class is
Bakelite
It is prepared by condensing phenol with
formaldehyde in presence of acidic/alkaline
catalyst
The initial reaction results in the formation of
o- and P-hydroxy methyl phenol, which reacts

Prepartion

During moulding hexamethylene tetra amine

is added , this provides formaldehyde, which

converts the soluble , fusible navolac in to a
hard infusible and insoluble solid of cross
linked structure
Properties:
Rigid
Hard
Scratch resistant
Infusible
Water resistant
Insoluble solid

Resistant to non oxidising acids, salts and

many organic solvents but are attached by

alkaliesbecause of the presence of free
hydroxy group in their structure
They posses excellent insulating character

Uses
For making electrical insulating partslike

switches, plugs, switch boars, heater handles

etc
For making moulded articles like telephone
parts, cabinets of radio and television
As adhesives for grinding wheels used in
propeller shafts for paper industry for rolling
mills

Polyamides
Long chain of condensation polymers consist

of amide linkage formed by condensation of

amino group and carboxylic group with the
elimination of water
nHOOC-(CH2)4-COOH+n H2N-(CH2)6-NH2---->[OC-( CH2)4-CO-NH-(CH2)6-NH-] n+2nH2O
These polymer are designated by two numbers,
the first represents the number of C atom in
diamine and second is the number of carbon
atom in dicarboxylic acid.

Properties
Linear structure
Molecular chains are held by

hydrogen bonds.
High strength, High M.P., toughness,
elasticity.
Sterillisable
Good hydrocarbon resistance and
moisture resistance.

Uses
Polyamides are commonly used in textiles,

automotives, carpet and sportswear due to

their extreme durability and strength.
Moulding having application in medicine
and pharmacy because of sterilisability.
In gears, bearing, making tyre cords,
hair comber etc.

Vulcanization
In order to give strength and elasticity,

natural rubber is vulcanized.

Vulcanisation is a process of treating natural
rubber with sulphur or some compounds of S
under heat as to modify its properties.
It provides broader useful range (-40 to
1000C) than raw rubber(10 to 600C)
Sulphur form cross linked network to polymer
that give mechanical strength.