SOLUTION PROPERTIES AND UNPERTURBED DIMENSIONS OF STEREOIRREGULAR POLY(TERT-BUTYL METHACRYLATES)

A comparative study of the dilute-solution properties of poly(tert-butyl methacrylate) prepared by anionic and free-radical polymerization mechanisms is reported. The latter material has a substantially higher syndiotactic triad content than does the former (59% versus 45%). Significant differences are noted in both thermodynamic (second virial coefficient) and transport (intrinsic viscosity) properties, as well as in the characteristic ratios of these materials. The more highly syndiotactic free-radical polymer is substantially more flexible and exhibits a greater degree of polymer-solvent interaction as compared to the anionically polymerized material.