| Grafts comprising a polychloroprene backbone carrying poly(isobutyl vinyl ether), polyisobutylene, and poly(isobutylene-b-(alpha)-methylstyrene) were synthesized using select cationic coinitiators. The discovery that allylic chlorines in conjunction with silver hexafluorophosphate initiate isobutyl vinyl ether polymerization was exploited to synthesize poly(chloroprene-g-isobutyl vinyl ether). Selective solvent extraction of the graft coupled with H('1)NMR, DSC, and thermal dehydrochlorination indicate the presence of poly(isobutyl vinyl ether) branches. Thermal dehydrochlorination indicates the absence of active chlorine in the graft copolymer.;This graft in conjunction with diethylaluminum-chloride has been used to initiate (alpha)-methylstyrene polymerization and led to the synthesis of a new graft-block: poly{chloroprene-g-(isobutylene-b-(alpha)-methylstyrene)}.;Application of principles similar to those used for the synthesis of poly(chloroprene-g-isobutyl vinyl ether) was employed for the synthesis of grafts comprising a polychloroprene backbone carrying polyisobutylene branches with tertiary chlorine endgroups using the polychloroprene/BCl(,3)/isobutylene system. The latter endgroup arises from the chlorination of the growing polyisobutylene cation by the BCl(,4)('-) counteranion. Selective solvent extraction coupled with H('1)NMR, GPC, molecular weight determination, thermal dehydrochlorination, and exhaustive controlled oxidation of the backbone coupled with surviving polyisobutylene branch analysis indicate the presence of poly(chloroprene-g-isobutylene). Thermal dehydrochlorination confirmed the presence of tertiary chlorine endgroup. |
