POLYMERIC MATERIALS
Polymer Synthesis: Polymerization
Techniques
Dr. Samrina Sahir
Week 6-7
Polymerization Methods
Homogeneous Polymerization:
In case of homogeneous bulk polymerization, the feed is a liquid monomer. No solvents are
used.
For homogeneous Solution polymerization, the monomer is completely dissolved in a
solvent.
Heterogeneous Polymerization:
In heterogeneous Emulsion polymerization, the monomer molecules are emulsified in
aqueous media in the form of micelles.
For heterogeneous Suspension polymerization, the monomer is suspended in a non aqueous
or other type of media as large droplets.
i .Bulk Polymerization:
In mass polymerization, the whole system remains in a homogeneous phase, because
the monomer is taken in the liquid state, the initiator is dissolved in the monomer
and the chain transfer agent (if used to control the molecular weight) is also
dissolved in the monomer liquid.
The reaction mixture is heated or exposed to a UV radiation source for initiating the
polymerization and is kept on a rotatory shaker for proper mixing the mass and
uniform heat transfer.
This mode of polymerization may be employed to obtain the purest form of polymer
Only the initiator and the chain transfer agent is used therefore, the product formed
has a high degree of purity, i.e., without any contamination of reactant components
Advantages
It is quite simple and requires simple equipment.
Direct utility of the polymer with no isolation/separation requirement.
Polymers are of high purity obtained. Minimum chances of contamination.
No requirement of additives other than the initiators and the chain transfer agent.
Excellent colour and clarity (glass polymers) can be obtained
Large castings may be prepared directly. Casting of objects of various shapes may
be accomplished using the Batch Bulk Polymerization.
Disadvantages
Viscosity of the reaction medium increases and its mixing becomes very difficult.
Diffusibility of the growing polymer chain gets restricted.
Excessive heat due to exothermic reaction may lead to an explosion or
Trommsdorff-Norrish effect (Auto-acceleration).
Non-uniformity in composition: Probability of chain collision becomes less and
termination causes difficulty. Broad molecular weight distribution
Conversion rate is only 80%
Applications
Low molecular weight polymers obtained by this method, are used as adhesives,
plasticizers and lubricants.
Used in casting formulations.
Production of methyl methacrylate (MMA) (suspension also), polyamides,
polycarbonates, polyethylene (low-density), terephthalate, polycaprolactam (nylon
6)
ii .Solution Polymerization:
The whole system is in a homogeneous phase, because the monomer, chain transfer
agent (if used) and initiator are dissolved in an inert suitable solvent, while the
ionic or coordination catalysts can either be dissolved or suspended in the solvent
medium.
The solvent enhances the heat capacity, thereby reducing the viscosity and facilitating
heat transfer. The temperature is easily controlled because of the fact that the
monomers are dissolved in solvent and the upper limit of the whole system depends
upon the boiling point of the solvent.
After the reaction is over the polymer is used as such in the form of polymer
solution or isolated by evaporating the solvent.
Compared to Bulk Polymerization, Solution Polymerization reduces both the reaction
rate and the molecular weight of the compounds. No auto acceleration
ionic or coordination catalyst is used to control the
polymerization process by influencing the mechanism,
reaction rate, and polymer properties.
Ionic Catalysts include cationic (e.g., Lewis acids
like AlCl₃, BF₃) and anionic (e.g., alkali metal
compounds like BuLi, NaNH₂) catalysts.
Commonly used in isobutene and styrene
polymerization.
Coordination Catalysts are transition metal-based catalysts, such as
Ziegler-Natta catalysts (TiCl₄ + AlR₃) or metallocenes (e.g., Cp₂ZrCl₂).
Commonly used for HDPE and isotactic polypropylene
Advantages
Heat removal is accomplished via solvent reflux.
Inert solvent medium helps to control viscosity and promote a uniform heat
transfer. Solvent reduces viscosity, making processing easier.
Heating and stirring are much easier than the bulk polymerization.
Conversion of monomer to polymer is high and typically about 80% - 90%
Disadvantages
The method is costly since it uses costly solvents.
The polymer produced is low average molecular weight (here solvents act as chain
terminators) and is always contaminated with traces of the solvent.
Polymer will also have to be isolated from the solution either by precipitation or by
evaporation of the solvent.
Environmental pollution due to solvent release.
Purity of product is also not as high as that of bulk polymerization
The requirements for the selection of the solvent are:
Both the initiator and monomer be soluble in it.
Have acceptable chain-transfer characteristics.
Suitable melting and boiling points for the conditions of the
polymerization and any subsequent solvent-removal step.
➤ Examples of suitable organic solvents include aliphatic and
aromatic hydrocarbons, esters, ethers, and alcohols.
Applications
Production of polyacrylonitrile by free-radical polymerization and also
polyisobutylene by cationic polymerization.
Exclusively used in the production of block co-polymers.
In the solution form, it can be directly used as adhesives and coatings.
Polyethylene (high density), polybutadiene, polypropylene, butyl rubber,
polystyrene, polyisoprene and polyformaldehyde are produced this way.
Polymerization Methods
An emulsion is a mixture of two or more liquids that are
normally immiscible (unmixable or unblendable) owing to
iii .Emulsion Polymerization: liquid-liquid phase separation.
This is the most widely used method of polymerization.
This process overcomes the difficulty of heat control and low degree of
polymerization.
The organic reaction mass is emulsified with soap in a continuous aqueous phase.
The dispersed particles are smaller in size than in Suspension Polymerization ( ≤ 0.1
μm) . In addition, due to stabilizing action of soap, the emulsion obtained is stable
and agitation may not be necessary.
In some methods, a water – soluble initiator may be used.
The main product of Emulsion Polymerization is latex, which forms the basis of the
popular latex paints. By coagulating the latex with ionic salts and acids, solid rubber
may also be obtained.
A micelle forming emulsifier is used.
Initiator is water soluble.
The formed latex particles are much smaller than suspension particles
(0.05-2 µm).
Kinetics differ considerable from other techniques.
Polymer is formed within the micelles and not in the monomer
droplets.
Components of Emulsion Polymerization
Monomer
Polymer
Monomer
Droplet
500-2000 A
Monomer Micelle 20 -30 A
Radical.
Water soluble initiator
Monomer Droplet
10,000 A (1 )
Advantages:
1. Efficient heat transfer: Good heat control over the entire polymerization process.
The heat control occurs by transfer to the aqueous phase, and this enables little change in
the viscosity of the emulsion medium.
2. Low tendency to agglomerate. Emulsified polymer may be stabilized and used directly
The reaction mass is emulsified with soap in a continuous aqueous medium. Soap has a
stabilizing action, and hence, the emulsion obtained is stable and no agitation is
necessary. Due to this, extra cost incurred in employing agitators is avoided.
3. High molecular weights: Overcomes the difficulty of low degree of polymerization, as
encountered in Solution and Bulk Polymerization. Since the degree of polymerization
directly depends upon the droplet sizes, and in this process, spherical monomer particles
(micelles) in the range of 1 – 10 μ, are yielded ; hence, the degree of polymerization is
sufficiently higher than in the other two processes.
Disadvantages:
1. It blocks the emulsifiers used in the process.
2. Polymer surface contaminated by surface active agents.
3. Coagulation introduces salts
POLYMERS PRODUCED USING EMULSION PROCESSES
Polymer Applications
Styrene-Butadiene Rubber Tires, Belting, Flooring,
(SBR) Molded goods, Shoe soles, Electrical
insulation
Butadiene-Acrylonitrile (nitrile Fuel tanks, Gasoline hoses, Adhesives,
rubber) Impregnated paper, leather and textiles
Acrylonitrile-Butadiene-Styrene Engineering plastics, household appliances,
(ABS) Automobile parts, Luggage
Polyacrylates Water based latex paints
a suspension is a heterogeneous mixture of a fluid that
contains solid particles sufficiently large for sedimentation.
iv .Suspension Polymerization:
To control the enormous amount of heat release in Bulk Polymerization, Suspension
Polymerization method was developed.
The reaction mass is dispersed as minute droplets of size 0.01 – 1 mm in diameter in a
continuous aqueous phase. Each of these droplets act as tiny bulk reactors. Heat transfer
occurs from the droplets to the water having large heat capacity and low viscosity. Cooling
jackets are used to facilitate heat removal. Agitators are used along with suspending agents in
the aqueous phase to maintain a specific droplet size and dispersion.
On a commercial scale, Suspension Polymerization is carried out in jacketed, stainless steel or
glass – lined stirred tanks, which may have a capacity of 20,000 gal or 75.5 m3.
Suspension Polymerization produces small, uniform polymer spheres. These are used
directly, or may be extruded and chopped to form larger, molded pellets.
Water insoluble monomers are dispersed in water.
Initiator dissolved in monomer.
Stabilization of droplets/polymer particles with non-micelle forming
emulsifiers like polyvinylalcohol or Na-carboxymethylcellulose.
Equivalent to bulk polymerization, small droplets dispersed in water.
Product can easily be separated, particles 0.01-1mm.
Pore sizes can be controlled by adding a combination of solvent (swelling
agent) and non-solvent.
Viscosity does not change much.
Advantages:
Aqueous (hydrocarbon) media provides good heat transfer
Good particle size control through agitation and dispersion agents
Control of porosity with proper additives and process conditions
Product easy to recover and transfer
Disadvantages:
Suspending Agents contaminate product
Removal of residual monomer necessary
Emulsion Suspension
An emulsion is a mixture of two or more liquids that are a suspension is a heterogeneous mixture of a fluid
normally immiscible (unmixable or unblendable) owing to that contains solid particles sufficiently large for
liquid-liquid phase separation. (milk: fat dispersed in water) sedimentation (mud in water)
Initiator is water soluble Initiator is monomer soluble
Emulsifying agent or surfactant is added to stabilize the Suspending agent is added to stabilize the suspension
emulsion
Polymerization usually occurs in an emulsion, does not It requires mechanical agitation
require mechanical agitation
The final product is a mixture of two immiscible liquids one The final product is solid polymer which can be easily
of which is dispersed as minute globules into other (latex), separated
so separation is a difficult process thus used as it is.
High molecular weight polymer can be obtained quickly Takes time for high conversion (low degree of
(high degree of polymerization) polymerization)
Particle size of emulsion is Particle size will be 0
Polymer obtained is impure and hence purification is Polymer obtained is more pure as compared to
needed. De-emulsifier is needed emulsion polymerization
Overview of Polymerization processes
Method Advantages Disadvantages
Bulk (Neat) Simple equipment Heat buildup
Rapid reaction Gel effect
Pure polymer isolated Branched or crosslinked product
Solution Good mixing Lower mol. Wt.
Ready for application Low Rpoly (rate of polymerization)
Solvent Recovery
Suspension Low viscosity Removal of additives
(Pearl) Direct bead formation
Emulsion High Rpoly Removal of additives
Low Temperatures Coagulation needed
High Mol. Wt. Latex stability
High surface area latex
Suspension Polymerization of Styrene
Monomer Phase
16.6 Kg. Styrene (primary monomer)
(0.5 kg Methacrylic Acid) (comonomer to impart specific properties)
0.012 kg AIBN (Azobisisobutyronitrile) (A free-radical initiator to start the
polymerization process)
Temp 0.006 kg Benzoyl Peroxide (Another radical initiator to sustain polymerization)
0.015 kg tert-Butyl Perbenzoate (A higher-temperature initiator used later in the process
for further polymerization.)
Aqueous Phase:
16.6 Kg of H2O (The continuous phase to disperse the monomer phase)
0.24 kg Ca3PO4 (Acts as a stabilizer to prevent coalescence of monomer droplets)
0.14 kg Na+ Naphthalene sulfonate (A surfactant to maintain the suspension.)
0.077 kg. 15% Sodium Polyacrylate (Another dispersant to stabilize the monomer
droplets.)
Polymerization Time. Hours
Polymerization techniques
Sometimes for one monomer several techniques of polymerizing are
available. Choice of a specific technique depends on a number of factors:
Kinetic / mechanistic factors related to chain length, chain
composition
Technological factors e.g. heat removal, reaction rate,
viscosity of the reaction mixture, morphology of the product
Economic factors; production costs, environmental aspects,
purification steps etc.