Classification of Polymerization Reactions and Kinetic Considerations

Historically polymers have been divided into two broad classes condensation polymers and addition polymers (Flory, 1953a Carothers, 1929,1931). Flory (1953b) has defined these as follows  

Condensation polymers, in which the molecular formula of the structural unit (or units) lacks certain atoms present in the monomer from which it is formed, or to which it maybe degraded by chemical means, and addition polymers, in which the molecular formula of the structural unit (or units) is identical with that of the monomer from which the 

an example of a condensation polymer would be a polyester, formed by the condensation reaction between a glycol and a dicarboxylic acid (with the evolution of water), whereas an addition polymer is exemplified by polystyrene, formed by the self-addition of styrene monomers. 

Although these earlier definitions were based on the chain structure of the polymers, they were closely related, as just described, to the mode of formation as well. It soon became apparent that such a classification has serious shortcomings, as so-called polycondensates could result from addition polymerization reactions. For example, although Nylon 6 can be prepared by the polycondensation reaction of e-aminocaproic acid (Braun et al., 1984), it is now synthesized by the ring-opening addition polymerization of e-caprolactam (Sandler and Karo, 1992), and this process has a profound effect on the 

Because it is the extraordinarily large size of the macromolecules which leads to their unusual properties, it would be most sensible to classify polymerization reactions in accordance with the way in which they affect the molecular size and size distribution of the final product, i.e., in terms of the mechanism of polymerization. On this basis, there appear to be only two basic processes whereby macromolecules are synthesized (Zhang et al., 2012 Penczek and Premia, 2012 Moore, 1978 Saunders and Dobinson, 1976 Odian, 2004b Penczek, 2002 Jenkins et al., 1996) (1) step-growth polymerization (polycondensation and polyaddition) and (2) chain-growth (chain) polymerization. 

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