Industrial Polymerization Techniques

Industrial Polymerization Techniques Homogeneous (Single phase) Heterogeneous (multi phases)

Bulk Polymerization Bulk Polymerization
Solution Polymerization Solution Polymerization
Emulsion Polymerization
Suspension Polymerization
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Bulk polymerization
Industrial Polymerization Techniques
In bulk polymerization , initial reaction mixture consist entirely
monomer.
Bulk Solution Emulsion Suspension
If the reaction is chain growth type, the mixture may contain
Polymerization Polymerization Polymerization Polymerization
initiator and chain transfer agent as well.
Homogeneous Homogeneous

Heterogeneous Heterogeneous

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Homogeneous Bulk polymerization Homogeneous Bulk polymerization
The system is said to be homogeneous when the polymer after More suitable for step growth polymerization reactions.
forming, remain soluble in the monomer
less heat generation
Features temperature of the system is easy to control

No solvent use
Reaction rate drop significantly with time due to high viscosity. Chain growth reactions can be performed

However reaction has to be stopped before a high degree of

conversion achieved, to prevent over heating.
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Homogeneous Bulk polymerization

Example - stepwise
PET
Nylon 66
Heterogeneous bulk reactions
Example – chain growth
PS
PMMA

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Heterogeneous bulk reactions Heterogeneous bulk reactions

A bulk reaction is said to be heterogeneous if the monomer and the LDPE

polymer are mutually insoluble.
is manufactured in high-pressure reactors operating at 1000 –
LDPE and sometimes PVC are manufactured by this technique. 3000 atm.

The temperature of the reactor is kept 250 ⁰C.

At this pressure and temperature PE partially dissolve in
monomer but the two phases separate at low pressures.

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Heterogeneous bulk reactions

PVC
• Monomer dissolve in polymer
• But 35% difference in densities
Solution reactions
• Mixture exist as two phases.

• Polymerization take place in both phases. Faster in polymer

phase.

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Homogeneous Solution reaction Homogeneous Solution reaction

Both monomers and polymer are dissolved in suitable solvent. Examples:

The solvent has significant impact on degree of polymerization and (1). Polymerization of cis-polybutadine
hence should be carefully chosen. Catalyst – butyl lithium
Solvent - hexane

(2). Polymerization of isobutene

Solvent - methyl chloride

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Homogeneous Solution reaction

Presence of solvent provide better ,

homogenization and mixing
Temperature control Heterogeneous Solution Reactions

However need extra stage in the processing to remove solvent.

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Heterogeneous Solution Reactions Heterogeneous Solution Reactions

Solution systems are heterogeneous when the monomer is soluble Ex: Manufacturing of PP
but the polymer is not. Pressure about 50 atm
Temperature 100 ⁰C
This is the typical feature in most co-ordination polymerization
systems.

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