Chain growth polymerization

Unsaturated monomer molecules add onto an active site of a growing polymer

chain.

Growth of the polymer occurs only at an end of the chain.

Addition of each monomer unit regenerates the active site.

Polyethylene, polypropylene, and polyvinyl chloride (PVC) are made by chain-

growth polymerization.

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 Chain growth polymerization

-is basically a three-stage process, involving:

• initiation of active molecules
• propagation,
• termination of the active chain ends.

active center :
Free radical in radical polymerization,
Carbocation in cationic polymerization,
Carboanion in anionic polymerization.

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 Free-Radical Chain-Growth Polymerization

Initiation is the mechanism which starts the polymerization process.

Vinyl monomers -variety of activating methods.

Styrene:
by heating
by ultraviolet light

Usually an activating agent (initiator) is used.

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 Free-Radical Chain-Growth Polymerization

INITIATOR:
unstable chemical which produces active particles that attack the monomer.

Benzoyl peroxide - splits up when heated.

A free radical:
with an unpaired electron.
very reactive and attack monomer molecules when it is in polymerization vessel.

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 Free-Radical Chain-Growth Polymerization
INITIATION:

as benzoyl peroxide is added to styrene, it splits to make free radicals

product is still a radical - attacking further monomer molecules.

the attack will lead to a larger molecule (macroradical) -free radical will be
preserved.

The reactions are referred to as free radical polymerization.

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 Free-Radical Chain-Growth Polymerization
INITIATION:
consequence of the general bond dissociation energy:
C-H > C-C > C-N > O-O

Peroxides such as benzoyl peroxide require temperatures in the range of

60–140°C

Dinitrile or azo compounds such as 2,2′-azo-bis-isobutyronitrile, AIBN, require

temperatures of about 70–80°C

formation of a stable N2 molecule is the thermodynamic driving force allowing

dissociation to occur at typically lower temperatures.
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 Free-Radical Chain-Growth Polymerization
INITIATION:

Light in the ultraviolet and visible range can disrupt selected bonds forming free radicals.

The advantages of the photochemical initiations:

polymerization can be carried out at room temperature.
polymerization can be carried out in thin layers (polishing of furniture).

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 Free-Radical Chain-Growth Polymerization

Propagation.

Small number of chains have been started, propagation involves successive

addition of monomer units to achieve chain growth.

At each step the free radical is regenerated as it reacts with the double bond .

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 Free-Radical Chain-Growth Polymerization

Termination:
-combination,
-disproportionation.

Combination increases molecular mass.

Disproportionation has no effect on molecular mass.

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 Free-Radical Chain-Growth Polymerization

Method of termination is also chain transfer.

Macroradical abstracts a hydrogen atom from a neighbouring molecule.

In the case of transfer to a polymer it may result in branching.

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 Free-Radical Chain-Growth Polymerization

Method of termination is also chain transfer to:

monomer,
initiator,
solvent,
other additives present in the polymerization system

A·, may or may not initiate the growth of another polymer chain.

If A・ is unreactive toward the monomer, the entire reaction could be inhibited.

During transfer the overall number of growing radicals remains unchanged.

Reduction of the average polymer chain length.

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 Cationic Chain-Growth Polymerization

Carbon–carbon double bond can be polymerized either by free radical or ionic methods

Initiator performs either homolytic or heterolytic bond breakage.

All three types of initiation do not work for all monomers.

In cationic chain polymerization, the propagating species are carbocations.

Initiation - an electrophile to a monomer:

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 Cationic Chain-Growth Polymerization

Initiators:
H2SO4 and H3PO4,
Lewis acids such as: AlCl3, BF3, TiCl4, SnCl4.

Lewis acids with water form the electrophilic species

Initiator - coinitiator

Some organic initiators can easily form cations:

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 Cationic Chain-Growth Polymerization

(1) initiation,
(2) propagation
(3) termination.

Feasibility of polymerization depends on the ease of cation formation

from monomer.

The addition of the electrophile (carbocation) to monomer and with formation more
stable intermediate.

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 Cationic Chain-Growth Polymerization

Rate of initiation is proportional to the concentration of the monomer

and the concentration of the catalyst–cocatalyst complex.

isobutylene

Propagation

The rate is fastest in solvents with high dielectric constants-

separation of the carbocation -counter ion pairs.

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 Cationic Chain-Growth Polymerization

Termination occurs:
by rearrangement of the ion pair (1)

through transfer to a monomer (2)

Unlike in free-radical polymerization, the catalyst is not attached to the resulting polymer
molecule

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 Anionic Chain-Growth Polymerization

propagating chain is a carbanion

nucleophilic addition of initiator to monomer:

(1) initiation,
(2) propagation,
(3) termination

Base as an initiator:
NaNH2, hydroxides, amines,
organometallic compounds such as C4H9Li and C6H5–MgBr.

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 Anionic Chain-Growth Polymerization

Initiation proceeds by metal alkyl:

Alkyl lithium is the most useful initiator for 1,3-butadiene and isoprene
commercially.

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 Anionic Chain-Growth Polymerization

Many anionic polymers, such as styrene, 1,3-butadiene, have no termination reaction.

Living polymers:

The growing species remain active in the absence of monomers.

They resume their growth activity with a fresh monomer supply.

Opportunity for the preparation of block copolymers.

AAAABBBBAAAA (e.g., styrene–isoprene copolymer)

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 Anionic Chain-Growth Polymerization

Many anionic polymers have no termination reaction.

By adding proton donor (water or alcohol) to the living polymers, the living chain
can be terminated.

The hydroxide ion is not sufficiently nucleophilic to reinitiate polymerization.

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 Anionic Chain-Growth Polymerization

Living polymers do not live forever.

The concentration of carbanion centers decreases with time.

Polystyrene carbanions are the most stable:

for weeks in hydrocarbon solvents.

Stability is enhanced by storage below 0 °C.

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 Anionic Chain-Growth Polymerization

in an inert atmosphere
with purified reagents,
and cleaned glassware.

Oxygen and carbon dioxide:

peroxy and carboxyl anions:

They are not reactive enough to continue propagation.

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