A proposal on the steric course of propagation in the homogeneous cationic polymerization of vinyl and related monomers

A stereochemical scheme of propagation was proposed for polymerizations of vinyl and related monomers by Friedel‐Crafts catalysts. For the cationic propagation proceeding via the simple carbonium ion pair, the following two factors were considered to be of primary importance in determining the steric course of propagation: (1) the conformation of the last two units of the propagating polymer segment and the direction of approach of the incoming monomer; (2) the tightness of the growing ion pair. Thus, the front‐side (less hindered site) attack to the carbonium ion gives rise to a syndiotactic placement and the back‐side attack an isotactic placement. The present model can satisfactorily explain the effects of substituents, catalysts, polymerization media, and polymerization temperature on the steric structure of polymers in cationic polymerization of vinyl ethers. Extension of the scheme to polymerization of the β‐substituted vinyl ethers in nonpolar solvents predicts formation of the diisotactic structures consistent with the experimental result. The influences of the polymerization condition on the steric structure of polymer were studied for cationic polymerizations of α‐methylstyrene at low temperatures. Highly syndiotactic polymers were obtained for homogeneous reactions in toluene‐rich media. The isotactic unit increased by increasing the content of methylcyclohexane in the solvent mixture. The effect of catalysts, though insignificant in toluene‐rich media, was clearly noted in methylcyclohexane‐rich media, less active catalysts (e.g., SnCl4) yielding higher amounts of the isotactic unit than more active catalysts (e.g., AlCl3). These results can be readily accommodated in the present model.