POLYMERIZATION TECHNIQUES

Polymerization techniques

Homogenous system Heterogeneous system

• Bulk polymerization • Suspension polymerization
• Solution polymerization • Emulsion polymerization
 Homogenous Polymerization

In a homogenous polymerization process, all

reactants including monomers, initiators, and
solvents, are mutually soluble and compatible
with the resulting polymer.
BULK POLYMERIZATION
 Bulk Polymerization

 Bulk polymerization: polymerization of the undiluted

monomer.
 Carried out by adding a soluble initiator to pure monomer
(in liquid state).
 The mixture is constantly stirred and heated to
polymerization temperature.
 Once the reaction starts, heating is stopped as the
reaction is exothermic.
 The heat generated is dissipated by circulating water
jacket.
 Bulk Polymerization

 Viscosity increases dramatically during conversion.

 The method is used for the polymerization of liquid state
monomers.
Bulk Polymerization

Chain-growth polymerization
 Monomer, initiator are miscible.
 Generally exothermic
 The higher the conversion, the
higher the viscosity.
 Bulk Polymerization

 Applications: in synthesizing
- Polystyrene
- Polyvinyl chloride
- Polymethyl methacrylate
- Low density polyethylene
 The products might be
- a melt in the case of polystyrene
- a solid in the case of acrylic polymers
 Bulk Polymerization

Step-growth polymerization
 Reactants are usually of low activity.
 Not very exothermic.
 High temperatures are required.
 Bulk Polymerization

 Viscosity increases dramatically during conversion.

Problems with the removal of volatile byproducts (in
step-growth polymerization).
 Applications: in synthesizing
- Polyurethanes
- Polyesters
 The products might be
- a solution of polymer in monomer, in the case of
certain alkyd type polyesters.
 Bulk Polymerization

The process is carried out in 2 stages.

 Stage 1: Prepolymerization or polymerization initiation
stage in a short period (5-10mins)
 Low degree of polymerization and low viscosity
 Stage 2: Polymerization stage, which is often carried out
in a mold resulting solid polymer in a relatively long
period.
 Bulk Polymerization

Advantages
• The system is simple and
requires thermal control
• The polymer is obtained
pure.
• Easy to obtain polymer.
• Polymerization yield is
rather high.
• Molecular weight
distribution can be
controlled by using chain
transfer agent.
Disadvantages
• Heat transfer and mixing
become difficult as the
viscosity of reaction mass
increases.
• Highly exothermic.
• The polymerization is
obtained with a broad
molecular weight distribution
due to the high viscosity and
lack of good heat transfer.
• Very low molecular weights
SOLUTION POLYMERIZATION
 Solution Polymerization

 Some disadvantages of bulk polymerization

are eliminated in solution polymerization.
 Monomer along with initiator dissolved in
solvent.
 The temperature and mixing can be controlled
easier.
 The viscosity of solution does not significantly
increase.
Solution Polymerization

Chain-growth polymerization
 Monomer, initiator, catalyst are
soluble in the solvent.
 Generally exothermic
 The higher the conversion, the
higher the viscosity.
 Solution Polymerization

 If obtained polymer is in the form of polymer solution, it

can be used for surface coating, adhesives.
 Applications: in synthesizing
- Polyacrylonitrile
- Polyvinyl chloride
- Polyacrylic acid
- Polyacrylamide
- Polyvinyl alcohol
- PMMA
- Polybutadiene
- High density polyethylene
 Solution Polymerization

Advantages
• The solvent acts as a diluent & helps in facilitating
continuous transfer of heat of polymerization
 easy to control temperature.
• The solvent allows easy stirring as it decreases the
viscosity of reaction mixture.
• Solvent also facilitates the ease of removal of polymer
from the reactor.
 Solution Polymerization

Disadvantages
• To get pure polymer, it is essential to separate & recover
the solvent.
• The method is costly since it uses costly solvents.
• Polymers of high molecular weight polymers cannot be
formed as the solvent molecules may act as chain
terminators.
• Smaller yield of polymer per reactor volume.
• The purity of product is also not as high as that of bulk
polymerization.
 Solution Polymerization

Disadvantages
• It is necessary to select an inert solvent to eliminate the
possibility of chain transfer to the solvent.
• The solvent frequently presents hazards of toxicity, fire,
explosion, corrosion, and odor problems not associated
with the product itself.
• Removal of last traces of solvent is difficult.
SUSPENSION POLYMERIZATION
 Suspension Polymerization

 Liquid or dissolved monomer suspended in liquid phase

like water.

 Initiators used are monomer soluble e.g. dibenzoyl

peroxide

 The size of monomer droplets is 50-200 mm in diameter.

 The dispersion is maintained by continuous stirring and

the droplets are prevented to coalesce by adding small
quantity of stabilizers.
Suspension Polymerization
 Suspension Polymerization

 Polymerization temperatures are limited by the boiling

point of water, so the temperatures are usually in the
range 70 - 90℃.
 The stabilizers used are PVA, gelatin, cellulose, kaolin,
magnesium silicate, aluminum hydroxide,
calcium/magnesium phosphate,…
 Stabilizers are usually at levels of 3-5 wt% to monomer.
 Suspension Polymerization

 Each droplet is tiny bulk reactor.

 The polymerization takes place inside the droplet &

product formed being insoluble in water.

 The product separated out in the form of spherical pearls

or beads of polymer (10-1000 mm).
 Suspension Polymerization

 The products are small uniform spheres. They can be

used directly for some applications as precursors of ion
exchange resins.

 The products can be extruded & chopped to form larger,

easily moulded pallets.

 They can be dissolved in a suitable medium for use as

adhesives & coatings.

 Suspension polymerization is suitable for free-radical

polymerization and step-growth polymerization.
 Suspension Polymerization

 Applications: in synthesizing
- Polyvinyl chloride
- Polyvinyl acetate
- Polystyrene
- Polymethylmethacrylate
 Suspension Polymerization

Advantages
• The process is comparatively cheap as it involves only
water instead of solvents.
• Viscosity increase is negligible.
• Agitation and temperature control is easy.
• Product isolation is easy since the product is insoluble in
water.
• Polymer produced may be used directly as polymeric
suspension.
• Good heat transfer.
• The purity of obtained polymer is high.
 Suspension Polymerization

Advantages
• Suitable for preparing high molecular weight products.
• At high conversions, auto-acceleration can occur but is
much better controlled than in bulk polymerization due to
the greatly improved heat dissipation.
 Suspension Polymerization

Disadvantages
• This method only can be applied for water-insoluble
monomers.
• It is difficult to control polymer size.
• Suspension polymerization is strongly affected by mixing.
• Large volume of reactor is taken up by water.
• The method can’t be used for elastomers due to the
tendency for agglomeration of polymer particles.
• Need extra process in washing out suspending
agent/contaminants and drying the polymer beads.
• Polymer beads may stick together and may be
contaminated with suspending agent.
EMULSION POLYMERIZATION
Emulsion Polymerization
 Emulsion Polymerization

 The reaction components differ from those used in

suspension polymerization only in that the initiator must
not be soluble in monomer but soluble only in the
aqueous dispersion medium.
 The most common type of emulsion polymerization is an
oil-in-water emulsion, in which droplets of monomer (the
oil) are emulsified (with surfactants) in a continuous
phase of water.
 Water-soluble polymers, such as certain polyvinyl
alcohols or hydroxyethyl celluloses, can also be used to
act as emulsifiers/stabilizers.
 Emulsion Polymerization

 Applications: in synthesizing
- Polyvinyl chloride
- Polystyrene
- Polymethylmethacrylate
- Polyvinyl fluoride
 Emulsion Polymerization

Advantages
• High molecular weight polymers.
• Fast polymerization rates.
• Allows removal of heat from the system.
• Viscosity remains close to that of water and is not
dependent on molecular weight.
• The final product can be used as such does not need to
be altered or processed.
 Emulsion Polymerization

Disadvantages
• Surfactants are difficult to remove.
• Water removal to isolate polymer is an energy-intensive
process.
• Designed to operate at high conversion of monomer to
polymer.
Glass Transition Temperature