Anionic Chain-Growth Polymerization

Treatment of a cold THF solution of styrene with 0.001 equivalents of n-butyllithium causes an immediate polymerization. This is an example of anionic polymerization, the course of which is described by the following equations. Chain growth may be terminated by water or carbon dioxide, and chain transfer seldom occurs. Only monomers having anion stabilizing substituents, such as phenyl, cyano or carbonyl are good substrates for this polymerization technique. Many of the resulting polymers are largely isotactic in configuration, and have high degrees of crystallinity.

Species that have been used to initiate anionic polymerization include alkali metals, alkali amides, alkyl lithiums and various electron sources. A practical application of anionic polymerization occurs in the use of superglue. This material is methyl 2-cyanoacrylate, CH2=C(CN)CO2CH3. When exposed to water, amines or other nucleophiles, a rapid polymerization of this monomer takes place.

Ring opening polymerization

In this kind of polymerization, molecular rings are opened in the formation of a polymer. Here epsilon-caprolactam, a 6-carbon cyclic monomer, undergoes ring opening to form a Nylon 6 homopolymer, which is somewhat similar to but not the same as Nylon 6,6 alternating copolymer.