Polymers
• A polymer is a very large molecule, having a high
molecular weight formed by the combination of
small units (monomers) by polymerization rection,
such as carbohydrates, proteins, nucleic acids (
Biological macromolecules), silk, rubber, cotton and
synthetic polymers – polythene, PVC, Nylon 66,
bakelite, polyurthane etc. They are typically
composed of thousands of atoms or more.
Addition polymerization
Addition polymerization : A chain reaction which adds new monomer
units to the growing polymer molecule one at a time through double or
triple bonds in the monomer. This process takes place in three distinct
steps:
• 1.Chain initiation —usually by means of an initiator which starts the
polymerization process. The reactive initiation molecule can be a
radical (free radical polymerization), cation (cationic polymerization),
anion (anionic polymerization), and/or organometallic complex
(coordination polymerization).
• 2.Chain propagation —a monomer adds onto chain and each new
monomer unit creates an active site for the next attachment.
• 3.Chain termination —the radical, cation, or anion is “neutralized”
stopping the chain propagation.
• Classes of Addition polymerization
Radical polymerization, Ionic polymerization (Cation
&Anionic) , Coordination polymerization
Ring-opening polymerization
Radical polymerization is a chain polymerization in which the
kinetic-chain carriers are radicals. Usually, the growing chain
end bears an unpaired electron. Free radicals can be initiated
by many methods such as heating, redox reactions, ultraviolet
radiation, high energy irradiation, electrolysis, sonication, and
plasma. Free radical polymerization is very important
in polymer chemistry. It is one of the most developed method
in chain-growth polymerization. Currently, most polymers in
our daily life are synthesized by free radical polymerization,
such as polyethylene, polystyrene, polyvinyl chloride,
Macromolecules
Head to head
• Cationic polymerization occur in alkene monomer
with electron donation groups eg isobutene,
or
• In presence of catalyst –BF3, AlCl3
• Anionic polymerization occur in alkene monomer
with electron withdrawing groups eg styrene,
methyl acrylate, aldehydes, epoxides acrylonitriles
or
• in presence of organoalkali compound like n-
butyllithium
Cationic polymerization
• Cationic polymerization is a type of
polymerization in which a cation transfers charge
to a monomer which then becomes reactive. This
reactive monomer goes on to react similarly with
other monomers to form a polymer.
• If the alkene is present at high concentration, the
alkene can act as a nucleophile toward the
carbocation, forming a dimeric species containing
a new carbon-carbon bond and also a new
carbocation center. This process is illustrated
below for the case of isobutene. When this second
(dimer) carbocation reacts with another molecule
of isobutene, still another C-C bond is formed,
giving a trimeric species. This can continue until a
large number (n) of isobutene molecules is
incorporated into the final product, which is called
a polymer, specifically polyisobutene.
Chain Initiation
Chain Propagation
Chain Termination
Polyisobutene
(butyl rubber)
This kind of polymerization is called cationic
polymerization, because it involves a chain process which
is propagated by carbocation intermediates.
• Cationic polymerization of simple alkenes is
especially efficient for alkenes which form relatively stable
carbocations (note the tertiary carbocation intermediate)
and which have one double bond terminus of the alkene
unsubstituted, so as to minimize steric effects in the TS for
the addition reaction.
• Thus, isobutene is especially amenable to cationic
polymerization, but other alkenes with electron donating
groups (oxygen and nitrogen-based functionalities) are
also efficiently polymerized.
Anionic Polymerization
In contrast to cationic polymerization, anionic
polymerization is relatively efficient when the
intermediate anionic species is relatively
stabilized. Since alkyl groups are donor groups,
simple alkenes are not polymerized efficiently by
the anionic method.
An example of an alkene which is readily
polymerized by anionic polymerization is methyl
acrylate, an alkene which has a strongly electron
withdrawing ester function.
Chain Initiation
Anion
Chain Propagation
Chain Termination
The polymerization process terminates when all the monomers are consumed.
Chain termination
The termination in anionic polymerization is not a
spontaneous process. The polymerization process
continue till the monomers are consumed.
Termination can be accomplished by transfer of
negative charge to a species that is not directly
involved in the reaction like carbon dioxide, water,
etc.
Questions
Q. Explain the Cationic polymerization reaction with a
suitable example.
Q. Explain polymerization mechanism of Vinyl group with
electron donating groups.
Q. Explain the mechanism of polymerization of vinyl group
in the presence of BF3 or AlCl3.
Q. Explain the cationic polymerization reaction with H+ or C+ or
carbonium ion as an chain initiator.
Q. How does the termination reaction occur in free radical
polymerization reaction.
