CHAIN TRANSFER ,

INHIBHITORS AND
RETARDERS
OUTLINES
POLYMERIZATION
TYPES OF POLYMERIZATION
CHAIN TRANSFER
INHIBHITORS
RETARDERS
BIBLIOGRAPHY
POLYMERIZATION
It is a process in which large number of low molecular
weight small molecules(monomers) combines
together to form a big molecule or macromolecule
(polymer) of higher molecular weight.
TYPES OF POLYMERIZATION
CHAIN- GROWTH POLYMERIZATION

STEP-GROWTH POLYMERIZATION
 CHAIN POLYMERIZATION
 Characteristics:

Self- addition of monomer molecules, to each other, very

rapidly through a chain reaction

No by-product is formed

Product has same elemental composition as that of monomer

Bifuctionality is provided by double bonds present in monomer

M.W of the polymer= M.W of the monomer

STEP-GROWTH POLYMERIZATION
 Characteristics:

Polymer build up proceeds through a reaction between functional groups of

monomers

Elimination of small molecules takes place as by-product

Product don’t have same elemental compostion of monomer

Reaction takes place in a stepwise manner

M.W of polymer is not equal to M.W of monomers due to elimination of

small molecules
Chain growth polymerization is classified in 3 ways
depending upon mechanism:

Free-radical Polymerization

Ionic polymerization

Co-ordination polymerization
FREE-RADICAL POLYMERIZATION
Initiator:
R-R R* + R*

Initiation:
R* + CH2=CH2 R-CH2-CH*-H

Propagation:
R-CH2-CH*H + CH2=CH2 R-CH2CH-H-CH2-CH*-H or
R CH2 -*CH-H
Termination:
CHAIN-TRANSFER
In case of transfer reaction however, while the growth
of one polymer chain is stopped or arrested, forming a
dead polymer, there is simultaneous generation of new
free-radical capable of initiating fresh polymer chain
growth

Reaction takes place by the abstraction of H-atom or

some other atom from the initiator, monomer or
polymer or from any other species present in system,
including the solvent or any inadvertent impurity.

M* + RH MH + R*
Growing chain is now terminated, but a new free-
radical, R* is formed, which will now initiate the
polymer chain growth afresh, which is will be followed
by chain propagation

NOTE: Chain transfer to initiator is not of great

significance but chain transfer to monomer is more
probable
CHAIN TRANSFER BY SOLVENTS
Chain transfer constant: Ability of different solvents to act
as chain transfer agents, and is defined as:
C= Ktr/ Kp

Chain transfer constant depends on:

(1) Temperature
(2) Nature of growing polymer radical
Solvent & Chain transfer cont.
60 deg C 80 deg C

Benzene 0.18 0.61

Cyclohexane 0.24 0.66

Ethylbenzene 1.25 2.98

Cumene 6.7 10.7

Triphenymethane 8.2 13.1

Butylchloride 35.0

Dichloromethane 1.5

Carbonterrachloride 920 1330

Solvents with very high chain transfer ability are used
for producing low molecular weight liquid polymers.

Generally solvent having chemical structure similar to

that of monomer is selected so that the terminal end
groups formed by solvent molecules do not alter the
chemical structure of polymer formed.

This method of polymerization, utilizing a solvent of

high chain transfer ability & chemical structure similar
to that of monomer to form a liquid polymer is known
as “telomerization” . The solvent used in such case is
known as “telogen”
 CF2-*CFBr + CF3Br CF2CFBr2 + *CF3

*CF3 + NCF2=CFBr F3C + CF2-*CFBr

CF3 CF2-*CFBr + CF3Br

CF3 CF2CFBr2 + *CF3 and so on.

At times, especially in industrial polymerization, specific
chain transfer agents are intentionally added while
carrying out polymerization reaction in order to control
molecular of polymer

A chain transfer agent used for the purpose of controlling

molecular weight is called “Chain Modifier”

Examples: Diisopropyl xanthate disulphide, dodecyl

mercaptan
INHIBITORS
Inhibitors are chemical substances capable of
inhibiting or killing the chain growth by combining
with the active free radical and forming either stable
products or inactive free-radicals

Hydroquinone, nitrobenzene, dinitrobenzene,

diphenyl picryl hydrazide(DPPH) and benzothiazine
are some of inhibitors customarily used in polymer
industry
Structures of DPPH, Nitrobenzene,
Hydroquinone And Dinitrobenzene
Atmospheric Oxygen
Atmospheric oxygen is also a good inhibitor.

P* + O*-O* P-O-O*

P-O-O* + P* P-O-O-P
USES OF INHIBITORS:
Used in preservation of monomers during production
and storage to avoid self-polymerization

Also used in the polymer industry for the purpose of

arresting the polymerization beyond a certain
conversion so as to achieve a uniform product with
controlled molecular weight and avoid cross-linking.
(“Short-Stops”)
RETARDERS
Polymeric retarders are those substances that slows
down the rate of polymerization reaction
They do not inhibit or kill the polymer chain growth
Used in industries to avoid cross-linking and build up
of sudden high molecular weight
Examples: dinitrophenols
Biblography
Polymer Science, V R Gowariker
THANK YOU