Free Radical

In this type of polymerization monomer is taken in liquid form
Then the initiator is added which is monomer soluble.

The mixture is then heated to a temperature at which initiator molecules break into free radicals.
These free radicals then react with monomers and start polymerization.
During propagation, monomers combine together and grow into a polymer chain radical.
Polymerization is carried out under continuous agitation to transfer heat and mass properly
To terminate the reaction, chain transfer agent is added.
Finally two polymer chain radicals combine together and form a long neutral polymer chain.
This reaction is purely exothermic and a wide range of molecular masses are
produced.
Advantage of this reaction is the system is very simple, the polymer obtained is
pure and large castings may be prepared directly.
The Disadvantage is heat transfer and mixing become difficult as the viscosity
of reaction increases which leads to broad molecular weight distribution. Due
to highly exothermic nature of the reaction, heat transfer is very difficult. And
this method gives very low molecular weights polymers.
This method is used to synthesize polystyrene, Poly vinyl chloride, polymethyl

methacrylate and low density polyethylene
Solution polymerization is very similar to bulk polymerization except the fact that monomer, initiator, and chain transfer
agent are dissolved in a non-reactive solvent.
So the polymerization step remains the same:

First monomer is taken.
Then the initiator is added and the reaction mixture is heated to initiate the polymerization.
The reaction result in a polymer which is also soluble in the chosen solvent and the heat released by the reaction is
absorbed by the solvent which helps to dissipate the heat
Finally long chain polymers are formed by reacting two polymer chain radicals
To obtain pure polymer excess solvent has to be removed.
Hence, solution polymerization is mainly used for application where the presence of a solvent is desired e.g., varnish
and adhesives
It is not useful for the production of dry polymers because of the difficulty of
complete
solvent removal.
So the advantage of this method is heat transfer is easy due to presence of

solvent.
Solvent also help in reducing viscosity which makes process very simple.
The disadvantage is the process the process of removal of excess solvent
Polymers such as poly(acrylic acid) (PAA) and poly(acrylonitrile) (PAN) are

synthesized
using solution polymerization
Although bulk and solution polymerization are very simple
methods to make polymers but these methods have certain
limitations.
Like we can’t get very high molecular weight polymers ad also
polydispersity is very high.
Bulk polymerization is exothermic and solution polymerization
is not environmentally friendly
Emulsion polymerization is one of the way to overcome the limitations of bulk and
solution polymerization
Water is taken as continuous phase which contains water insoluble or hydrophobic monomer like oil
The emulsifier or surfactant is added to form monomer in water emulsion
If we look in the emulsion we can see that the surfactant surrounds the
monomer droplet and form a micelle structure
This is a schematic of micelle where monomer droplet is surrounded by surfactants
Surfactants have hydrophilic head and hydrophobic tail part. Their hydrophobic tail
is facing monomer and hydrophilic head is in water.
Each monomer droplet contains many monomer molecules

As the initiator enters in droplet through the aqueous phase, it initiates
the polymerization in each micelle
In propagation step the monomers start combining and grow into a chain radical
Once all the monomers convert into polymer chain radical, de-emulsifying agent is
added, which disperse surfactants in water.
The advantage of this method is the rate of polymerization is very high which leads to High
molecular weight polymers.
The continuous water phase is an excellent conductor of heat, so heat is easily controlled.
Polymerization proceeds in micelles so viscosity of the system remains almost the same.
The disadvantage is polymer needs purification, removal of emulsifier and de-emulsifier
And monomers such as vinyl chloride, butadiene, chloroprene, vinyl acetate, and acrylates are
polymerized by this technique, which gives water based paints, adhesive and coating
materials.
Suspension polymerization is similar to bulk polymerization, and it could be considered “bulk
polymerization within a droplet.”
This is one of the most widely used polymerization technique.
It is also called as bead or pearl polymerization.
In this method, initiator is dissolved in hydrophobic monomer.
Then the hydrophobic monomers containing initiator are mechanically suspended in water in
presence of suspending agent.
The polymerization is carried out inside the small droplets of liquid monomer.
Finally the polymer chain radicals undergo termination step and form bead like polymers.
The advantage of this method is no heat, mass, chain transfer problem.
The product obtained is in granular form which is convenient to handle
and isolation is easy.
The disadvantage is only water insoluble monomers are used.

Emulsifier is needed to wash the suspending agent also it requires long
time for high conversion.
Expandable polystyrene beads, PMMA, PVC and PVA beads can be

synthesized using suspension polymerization

Free Radical

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In this type of polymerization monomer is taken in liquid form

Then the initiator is added which is monomer soluble.

This method is used to synthesize polystyrene, Poly vinyl chloride, polymethyl

So the polymerization step remains the same:

So the advantage of this method is heat transfer is easy due to presence of

The disadvantage is the process the process of removal of excess solvent

Polymers such as poly(acrylic acid) (PAA) and poly(acrylonitrile) (PAN) are

Each monomer droplet contains many monomer molecules

The disadvantage is polymer needs purification, removal of emulsifier and de-emulsifier

The disadvantage is only water insoluble monomers are used.

Expandable polystyrene beads, PMMA, PVC and PVA beads can be

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