Techniques of Polymerisation

Techniques of Polymerisation
4 general types techniques:
(1) Bulk
(2) Solution
(3) Suspension
(4) Emulsion

2 useful distinctions:
- between batch and continuous
- between single-phase and multi-phase
Techniques of Polymerisation
SINGLE – PHASE (homogenous reactions)

(1) Bulk / Melt polymerisation

(2) Solution polymerisation

MULTI – PHASE (heterogeneous reactions)

(1) Suspension
(2) Emulsion
Bulk Polymerisation

Simplest technique

Laboratory preparation of vinyl polymer

(polyethylene, PS, PMMA)

Most difficult to control

(FRP reaction = exothermic)

System with monomer, monomer-soluble initiator,

catalyst, & chain transfer agents

Use to control molecular weight

Bulk Polymerisation

POLYMER
+
MONOMER
Unreacted
+ MONOMER
INITIATOR
Unreacted
+ INITIATOR

IMPORTANT

POLYMER & INITIATOR MUST BE SOLUBLE

IN monomer
Bulk Polymerisation

[Advantage] High yield, high purity, easy

polymer recovery

[Disadvantage]
•Monomer-polymer solution may increase
viscosity – high conversion & high viscosity
•Auto-acceleration – hard to control rate

Major commercial uses of bulk vinyl polymerisation

adhesives, platicizer, lubricant
Bulk Polymerisation
[STEP polymerisation]
•most of the polymers
•NYLON 66

[CHAIN-GROWTH polymerisation]
•Clear products
•PE/PS/PMMA/PC
Solution Polymerisation

POLYMER
+
MONOMER Unreacted
+ MONOMER
INITIATOR
Unreacted
+ + INITIATOR
SOLVENT +
SOLVENT
Solution Polymerisation

Simplest technique in formulation & equipment

Polymerisation done in solvent

(organic solvent or water)

monomer & polymer both soluble in solvents

(eg. PS in toluene)

monomer soluble in solvents but polymer is

insoluble (eg. acrylonitrile in chloroform)
Solution Polymerisation
ADVANTAGES Better heat control

DISADVANTAGES

• PURITY
• Removal of solvents from polymer (need
distillation thus increase cost)
• Chain-transfer reaction by solvent

ApplicationS

Application that uses solvent directly

(adhesives or solvent-based paint)
Solution Polymerisation

Type of Reaction
Component
1 2 3 4

Monomer &
Soluble Soluble Soluble Soluble
solvent

Initiator Soluble Insoluble Insoluble Soluble

Polymer Soluble Soluble Insoluble Insoluble

Solution Polymerisation

Type of Reaction
Component
1 2 3 4

Monomer &
Soluble Soluble Soluble Soluble
solvent

Initiator Soluble Insoluble Insoluble Soluble

Polymer Soluble Soluble Insoluble Insoluble

SOLID :
Cr-SiO2-AlO3 catalyst
Suspension Polymerisation
Suspension Polymerisation

Also known as PEARL polymerisation, BEAD

polymerisation & GRANULAR polymerisation

A process uses mechanical agitation – to

mix monomer in liquid phase (eg. water or
organic solvent)

Product = a slurry of suspended polymer

particles (granular polymer: PS, PVC, PMMA)

Monomers suitable = sparingly soluble in

water & that can be polymerised by FRP
Emulsion Polymerisation

Monomers are dispersed as fine droplets into

water (dispersion medium) using surfactants/
soap/detergent (emulsifying agent) then FRP

Polymer product slurry = “latex”

Initiator radical (water soluble, redox type)

& generated in aq. phase & diffuse into soap
micelles swollen with monomer molecules
 Emulsion Polymerisation

Widely used in manufacturing water-based (latex) paints

or adhesives
Example: styrene-butadiene copolymer
Emulsion Polymerisation

As the monomer is used, more monomer

migrates into micelle = reaction continue

Initiator radical (water soluble, redox type)

& generated in aq. phase & diffuse into soap
micelles swollen with monomer molecules

Termination occur by radical combination

(a new radical diffuses into the micelle)