Kinetic and thermodynamic factors in polymer chemistry

Many polymer structures cannot be established unambiguously by the traditional methods used by organic chemists, and often it is necessary to postulate the likely manner in which the molecules are distributed and/or the detailed chemical structure of the repeat units. In many cases, polymer scientists have predicted structures based on thermodynamic factors. This approach has been fairly successful in the past, but it is now apparent that unqualified application of considerations based on thermodynamic stability can be misleading in certain cases. Specific examples of this are discussed with reference to the placement of monomers in vinyl polymerization and to the repeat units in cyclopolymerization; other examples are mentioned briefly.