Living free radical polymerization process

摘要

A new class of "living" free radical initiators that are based on alkylperoxydiarylborane and its derivatives and that may be represented by the general formula. R-[O-O-B-phi1(-phi2)]n wherein n is from 1 to 4, R is a hydrogen or a linear, branched or cyclic alkyl radical having a molecular weight from 1 to about 500, and phi1 and phi2, independently, are selected from aryl radicals, based on phenyl or substituted phenyl groups, with the proviso that phi1 and phi2 can be the chemically bridged to each other with a linking group or with a direct chemical bond between the two aryl groups to form a cyclic ring structure that includes a boron atom are disclosed. At ambient temperature the R-[O-O-B-phi1(-phi2)]n species spontaneously homolyzes to form an alkoxyl radical R-[O*]n, which is active in initiating "living" polymerization of radical polymerizable monomers, and a "dormant" diarylborinate radical *O-B-phi1(-phi2), which is too stable to initiate polymerization due to the back-donating of electron density to the empty p-orbital of boron, but which may form a reversible bond with the radical at the growing polymer chain end to prevent undesirable side reactions. The "living" radical polymerization is characterized by a linear increase of polymer molecular weight with monomer conversion, a narrow molecular weight distribution, and the formation of block copolymers by sequential monomer addition.