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Polymerization Mechanism
Polymer Classification
Carothers
Addition polymers
Condensation polymers
Further
Ring opening polymers
Polymerization mechanism
Step-reaction (condensation) polymerization
Chain-reaction (addition) polymerization
Ionic polymerization
Copolymerization
Persulfate ion initiator (e.g., from K2S2O8) reacts with a reducing agent such as a bisulfite ion
(e.g., from NaHSO3) to produce radicals for redox initiation
I I 2 I
M +I MI
tail-to-tail
-hydroxycproic acid
polycaprolactone
ester linkagae
poly(ethylene terephthalate) is formed from the condensation of a dicarboxylic acid and a diol
Step-growth
polymerization
Polyaddition: monomers react without the elimination of a
small molecule
Chain Polymerization
Step-growth polymerization
Cationic Polymerization
Monomers with electron-donating groups like isobutylene form stable positive charges and
are readily converted to polymers by cationic catalysts
Any strong Lewis acid like boron trifluoride (BF3) or FriedelCrafts catalysts such as AlCl3
can readily initiate cationic polymerization in the presence of a cocatalyst like water, which
serves as a Lewis base or source of protons
During initiation, a proton adds to the monomer to form a carbonium ion, which forms an
association with the counterion
Ionic polymerization
The reaction produces a carbanion at the head end to which is associated the positively
charged lithium counterion.
Propagation occurs by the successive insertion of monomer molecules by anionic attack of
the carbanion.
No chain transfer or branching occurs in anionic polymerization, particularly if reactions are
carried out at low temperatures.
Termination of the growth activity of the polymer chain takes place either by the deliberate
or accidental introduction into the system of oxygen, carbon dioxide, methanol, water, or
other molecules that are capable of reacting with the active chain ends.
In some systems, termination can be avoided if the starting reagents are pure and
the polymerization reactor is purged of all oxygen and traces of water
When fresh monomer is added, polymerization resumes referred to as living
polymers because of the absence of termination.
Polymers produced by living polymerization are characterized by very narrow
molecular weight distribution (Poisson distribution).