Template polymerization by free radical mechanisms

A polymerization in which propagation can proceed along macromolecular templates, is termed template polymerization. As compared to the blank (i.e. conventional) polymerization such a propagation, made possible through cooperative interaction, affects the kinetics of the reaction and the structural features of the formed (daughter) polymer. This is called template effect. Template systems can be classified according to the degree of monomer adsorption on the template which is characterized by the Langmuir equilibrium constant KM. In type I systems where KM = ∞ propagation proceeds exclusively by addition of adsorbed monomer arrays; in type II systems with KM = 0 propagation proceeds exclusively by addition of monomer molecules from solution. Such extreme cases are rare, however. Since most template systems have finite values between very large and very small, a generalized kinetic model for free‐radical template polymerizations has been developed from the type II model. Examples are given to illustrate the application of the generalized model. Some attention is paid to the structural features (average molecular weight and tacticity) of the daughter polymers, as well as to template copolymerization.