Kinetics of Polymerization

Yashodha V
 Chain-growth (addition)
polymerization
* The polymerization of unsaturated monomers typically
involves a chain growth polymerization.
* Chain-growth polymerizations require the presence of an
initiating molecule that can be used to attach a monomer
molecule at the beginning of the polymerization.
* Free-radical polymerization has 3 steps:
•Initiation
•Propagation and
•Termination.
 Initiation
* Initiation consists of 2 steps:
* A. Dissociation step: the initiator forms two
radical species. The labile bond can be broken
by heat of irradiation.
* B. Association step: addition of a single
monomer molecule to the initiating radical.
 Propagation
* A process of monomer units addition to the initiated
monomer species. Additional monomers are added
sequentially during subsequent propagation steps.
* Propagation continues until termination process occurs.
 Termination

*Termination occurs when 2 propagating radical

chains of arbitrary degrees of polymerization of
x and y meet their free-radical ends.
*There are 3 mechanisms of termination:
1. Combination
2. Disproportionation
3. Chain transfer
* Combination:
* To give a single terminated chain of degree of
polymerization x + y through the formation of a
covalent bond between the 2 combining radical
chains.

* Example: termination by combination of

styrene polymerization
* Disproportionation:
One terminated chain will have an unsaturated
carbon group while the other terminated end is
fully saturated.

Chain transfer:
To give hydrogen abstraction from an initiator,
monomer, polymer, or solvent molecule.