Polymerization Mechanisms

polymerization processes are classified as step-reaction (condensation) or chain-reaction

(addition) polymerization. In this lecture 4 , we will discuss the different types of polymers based
on the different polymerization mechanisms.

In chain polymerization, a simple, low-molecular-weight molecule possessing a

double bond is treated so that the double bond opens up and the resulting free
valences join with those of other molecules to form a polymer chain.
No side products are formed
The composition of the polymer or repeating unit of the polymer (-CH2–CHCl-) is
identical to that of the monomer (CH2=CHCl)
 The polymer grows at a very fast rate
 It is characterized by a very high molecular weight most of the time

 chain initiation,
 chain propagation, and
 chain termination, and may be
 Chain transfer, (it may be regarded as a combination of chain termination and chain
initiation.).

 a free radical,
 a cation, or
 an anion.

 free-radical polymerization,
 cationic polymerization, or
 Anionic polymerization.
Chain-reaction polymerization, an important industrial method of polymer preparation, involves the
addition of unsaturated molecules to a rapidly growing chain. The most common unsaturated compounds
that undergo chain-reaction polymerization are olefins, as exemplified by the following reaction of a
generalized vinyl monomer .The growing polymer in chain-reaction polymerization is a free radical, and
polymerization proceeds via chain mechanism. Chain-reaction polymerization is induced by the addition
of free-radical-forming reagents or by ionic initiators. Like all chain reactions, it involves three fundamental
steps: initiation, propagation, and termination. In addition, a fourth step called chain transfer may be
involved.

Initiation involves the gain of an active site by the monomer. This may occur spontaneously by the
absorption of heat, light (ultraviolet), or high-energy irradiation. The active species produced by
these processes are referred to as initiators, Free radicals can be generated by a number of ways
Thermal or photochemical decomposition of organic peroxides, hydroperoxides, or azo or
diazo compounds. But most frequently, “initiation free radical polymerization is brought about by the
addition of small quantities of compounds called initiators”. Typical initiators include peroxides, azo
compounds, Lewis acids, and organometallic reagents. An initiator is usually a weak organic compound
that can be decomposed thermally or by irradiation to produce free radicals, which molecules are
containing atoms with unpaired electrons.
Initiation: Start of a polymerization.
Other methods of generation of free radicals include dissociation of covalent bonds by high-
energy irradiation and oxidation–reduction (redox) reactions.
The initiation step in free-radical polymerization in the presence of thermal initiators is a two-
step process: first is the hemolysis of the relatively weak covalent bond in the initiator,
appointed here by I:I.

Second, in the presence of a vinyl monomer, the free radical thus generated adds to one of the
electrons of one of the bonds constituting the double bonds in the monomer. The remaining
electron now becomes the new free radicals:
 Or

Propagation: Continuous successive chain extension in a chain reaction.

 The free radical generated in the initiation step adds monomers in very rapid
succession. Again, this consists of an attack of the free radical on one of the carbon
atoms in the double bond. One of the electrons from the double bond pairs up with
the free-radical electron forming a bond between the initiator fragment and the
attacked carbon atom. The remaining electron shifts to the “unattacked” carbon
atom of the double bond, which consequently becomes the free radical. In this way
the active center is transferred uniquely to the newly added monomer.
 Two configurations are possible Trans or Cis.

 Three possible ways for the propagation step to occur: head to- tail , head-to-head),
and tail-to tail.

 Steps can occur by either of two mechanisms: combination (coupling)

or disproportionation. This process of propagation continues until another process
intervenes and destroys the reactive center, resulting in the termination of the
 polymer growth. There may be several termination reactions depending on the type
of the reactive center and the reaction conditions.
 Combination or coupling — joining of two active species.

 Disproportionation — Process by which termination occurs as a result of chain

transfer between two macro radicals yielding dead polymers. This involves
hydrogen transfer with the formation of two polymer molecules, one with a
saturated end and the other with an unsaturated terminal olefin and each with an
initiator fragment.
Dead polymer: Polymer in which chain growth has been terminated.

 For example, two growing radicals may combine to annihilate each other’s growth
activity and form an inactive polymer molecule; this is called termination by
combination or coupling: The termination reactions that are more important in
polymer production are combination (or coupling) and disproportionation. In
termination by combination, two growing polymer chains react with the mutual
destruction of growth activity, while in disproportionation a labile atom (usually
hydrogen) is transferred from one polymer radical to another.
  Chain transfer is a polymerization reaction by which the activity of a
growing polymer chain is transferred to another molecule.
 "Chain transfer" is the name for chemical reactions where a radical group is
transferred from the propagating chain to another species in the reaction mixture
such as initiator, monomer, other polymer chains, and solvent. In chain transfer the
radical is not terminated and will proceed to initiate either another polymer chain
or a branch on an existing polymer chain.

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

The species, TA, could be a monomer, polymer, solvent molecule, or other molecules
added into the reaction mixture. Two types We discuss the next lecture, transfer to
monomer and transfer to solvent
 H.W
Q1) Give at least three example (with the name and structure) of initiation used in radical
chain polymerization?
Q2) Termination of chain growth can occur by coupling/disproportionation, explain the
mechanism for polystyrene in this stage?
Q3) What does chain transfer mean?
Q4) What are the three main stages of chain growth polymerization?
Q5) What are the steps to initiate free radical polymerization?