Anionic synthesis of well‐defined polymer blends by controlled chain‐transfer reactions

Abstract

AbstractThe scope and limitations of controlled chain transfer reactions in living anionic polymerization have been investigated. In contrast to the random nature of normal chain transfer reactions, this procedure first effects controlled living anionic polymerization followed by addition of a stoichiometric amount of suitable chain transfer agent when the monomer has been completely consumed. The resulting anionic species is then used to initiated polymerization of a second monomer charge with the same monomer or with a different monomer. A variety of hydrocarbon acids and amine compounds with pKa values in the range of 30–40 have been evaluated as chain transfer agents in the presence and absence of coordinating ligands. Efficient chain transfer to poly(styryl)lithium has been observed using 1,1‐diphenylpropane. Reinitiation efficiency to both styrene and butadiene monomer was quantitative and controlled blends of different molecular weight polystyrenes or blends of polystyrene with polybutadiene have been prepared. The use of these chain transfer reactions to prepare functionalized polymers has also been investigated.