| Abstract: | 13C-NMR has been used to examine a number of dichlorocarbene adducts of cis- and trans-polybutadiene prepared in a two-phase system. Dichlorocarbene was generated by reaction of aqueous or solid NaOH or KOH with CHCl3 in the presence of a phase transfer catalyst. Monomer compositions, comonomer sequence lengths, and stereochemical information were obtained for the resulting polymers. The polymers examined here were stereochemically pure and were treated as simple copolymers. Samples prepared using aqueous NaOH can be described as essentially random copolymers over the entire range of monomer composition. Samples prepared using solid alkali-metal hydroxides contain a higher fraction of blocked units than a polymer of comparable composition prepared using aqueous NaOH. This blockiness can coincide with the presence of two glass transition temperatures and a two-phase morphology as seen by transmission electron microscopy. Fractionation of a substantially blocked sample yielded a chlorine-poor fraction which was a random copolymer and a chlorine-rich fraction which was more blocked than the original unfractionated material. |
