Free Radical Polymerization

CHAIN POLYMERIZATION
Free Radical Polymerization
• Free radical are independently-existing species that have
unpaired electron. Normally they are highly reactive with
short life time.
• Free radical polymerization’s are chain polymerization’s in
which each polymer molecules grows by addition of
monomer to a terminal free-radical reactive site known as
active center.
• After each addition the free radical is transferred to the
chain end.
• Chain polymerization is characterized by three distinct
stages, Initiation, propagation and termination
Example

• The formation of polyvinyl monomer.

• CH2 = CHX
 INITIATION
• This stage is a two steps stage
• 1. The formation of free radicals from an initiator.
• 2. The addition of one of these free radicals to a
monomer molecules.
• Free radical can be formed by two principal
• 1. Homolytic scission (homolysis) or breakage of a
single bond.
• 2. Single electron transferred to or from an ion or
molecule (redox reactions)
• Homolytic can be achieved by heat (thermolysis)
or by light such as U.V. (photolysis).
Example

O O O
 -C-0-0-C- 2 -C-O

Benzoly peroxide Benzolyooxy radicals

 (CH3)2 C-N = N- C (CH3)2 2(CH3)2C + N2

 CN CN CN
Azobisisobutyronitril 2-Cyanopropyl radicals

• Sometimes the radicals undergo further breakdown (-

scissions) such as
 O O
 -C-0 +C=O

(CH3)2 - C-O CH3 + (CH3)2-C = 0
 CH3 Methyl acetone
 radical
 PHOTOLYSIS

• Photolysis is the second principle of free

radical formation.
• The advantage of this method is that the
formation of free radicals begins at the
instant of exposure and cases as soon as the
light source is removed.
 REDOX REACTION
• Redox reaction defined as the generation of free radicals
by electron transfer and it is use when polymerization
performed at low temperature.
• Example
 CH3 CH3
 -C-0-0H + Fe2+` -C-O + OH + Fe3+
 CH3 CH3
 Cumyl Ferrous Cumyloyloxy
 hydroperoxide ion radical

 O O O O O O
O-S-O-O-S-O + HO-S-O 0-S-O + O-S-O + OH-S-O
 O O O O
Presulphate Bisulphate Sulphate Sulphate Bisulphate
 ion ion ion radical radical
• An active center is created when a free radical (Ro) which
is generated from an initiator attacks the -bond of the
monomer molecules.

R + CH2 = CH R-CH2-CH or R-CH - CH2

X X X
This is more This is more
likely stable

Sometime free radical react with each other such as:

O O O
2 -C-0 -C-O- +C=O

OR

2
 PROPAGATION
• The addition of monomer molecules to the active center to grow the
polymer chain.
• There are two modes of chain propagation
1. Head to Tail
R-CH2-CH + CH2=CH R-CH2-CH-CH2-CH
X X X X
2. Head to Head
R-CH2-CH + CH2=CH R-CH2-CH-CH-CH2
X X X X
Again mode (1) are more dominant.
Therefore polymer structure are like
-----CH2-CH-CH2-CH-CH2-CH-CH2-CH------
X X X X
Time of addition for each monomer is of the order of a millisecond.
Thus several thousands of additions can take place in a few seconds.
 TERMINATION
• The last stage of chain reaction in which the growth of
the polymer chain terminated (or stopped).
• There are two mechanisms of termination
• 1. Combination
• Coupling together of two growing chains to form a single
polymer molecules. polystyrene
 --CH2-CH + CH - CH2--- ---- CH2-CH- CH-CH2---
 X X X X
 2. Disproportionation
 when a hydrogen atom move from one growing chain to
another
 H H
--CH2-CH + C - C--- ----CH2-CH2 + CH=CH2---
 X X H X X
 Saturated end Unsaturated end
 group polymer group polymer
 Thank You

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