SELECTIVE VINYL CATIONIC POLYMERIZATION OF MONOMERS WITH 2 CATIONICALLY POLYMERIZABLE GROUPS .4. NEW INITIATING SYSTEMS FOR SELECTIVE AND LIVING POLYMERIZATION OF PARA-ISOPROPENYLPHENYL GLYCIDYL ETHER

A variety of cationic initiators were employed for p-isopropenylphenyl glycidyl ether (IPGE), an alpha-methylstyrene derivative with an epoxy pendant, and optimum initiators and reaction conditions were evaluated in terms of its selective vinyl polymerization and living polymerization. Despite the coexistence of two cationically polymerizable groups in IPGE, binary initiating systems (HI, CF3COOH, or CH3CH(OiBu)-OCOCH3, each coupled with ZnI2) and sulfonic acids (CF3SO3H and CH3SO3H) selectively polymerized the vinyl group of IPGE in CH2Cl2 at - 78-degrees-C to produce soluble polymers with epoxy pendant groups in high yield. Metal halides (BF3OEt2 and AlEtCl2) polymerized both the vinyl and epoxy groups of IPGE to give crosslinked insoluble polymers. In contrast, under these conditions, the HI/ZnI2 system also led to a long-lived polymer, the molecular weight of which increased upon addition of a fresh feed of monomer to a completely polymerized reaction mixture, whereas the use of other initiators resulted in nonliving polymers. At higher temperatures (-40 and -15-degrees-C), soluble poly(IPGE) was also obtained with HI/ZnI2, but the polymer yield decreased with raising temperature, because of the occurrence of termination reaction.