Summary

Synthetic polymers can be classified as either chain-growth or step-growth. Chain-growth polymers are prepared by chain-reaction polymerization of vinyl monomers in the presence of a radical, an anion, or a cation initiator. Radical polymerization is sometimes used, but alkenes such as 2-methylpropene that have electron-donating substituents on the double bond polymerize easily by a cationic route through carbocation intermediates. Similarly, monomers such as methyl α-cyanoacrylate that have electron-withdrawing substituents on the double bond polymerize by an anionic, conjugate addition pathway.

Copolymerization of two monomers gives a product with properties different from those of either homopolymer. Graft copolymers and block copolymers are two examples.

Alkene polymerization can be carried out in a controlled manner using a Ziegler–Natta catalyst. Ziegler–Natta polymerization minimizes the amount of chain branching in the polymer and leads to stereoregular chains—either isotactic (substituents on the same side of the chain) or syndiotactic (substituents on alternate sides of the chain), rather than atactic (substituents randomly disposed).

Step-growth polymers, the second major class of polymers, are prepared by reactions between difunctional molecules, with individual bonds in the polymer formed independently of one another. Polycarbonates are formed from a diester and a diol, and polyurethanes are formed from a diisocyanate and a diol.

The chemistry of synthetic polymers is similar to the chemistry of small molecules with the same functional groups, but the physical properties of polymers are greatly affected by size. Polymers can be classified by physical property into four groups: thermoplastics, fibers, elastomers, and thermosetting resins. The properties of each group can be accounted for by the structure, the degree of crystallinity, and the amount of cross-linking they contain.