Polymer chain-length dependence of bimolecular reaction and polymerization

This article deals with polymer effects on both activation- and diffusion-controlled bimolecular reactions. The reaction rate constants for the former reactions are independent of the chain length of reactants, and those for the latter reactions decrease with increasing degree of polymerization of reactants. Quantitative studies on the chain length dependence of the diffusion-controlled reactions are mentioned with the historical development. Termination reaction in radical polymerization is a typical example of the radical polymerization is a typical example of the diffusion-controlled reaction. The effect of chain-length of the termination rate constant on radical polymerization kinetics is shown both computationally and experimentally. At last, several examples of polymer effect on stereoregularity of polymers obtained by radical polymerizations are given.