Living anionic polymerization of divinylbenzene derivatives

Abstract

This paper deals with our recent work on selective living anionic polymerization of divinylbenzene derivatives. We first successfully demonstrated that one of the two vinyl groups of p-divinylbenzene (p-DVB) exclusively undergoes selective vinyl polymerization in a living manner in THF at -78°C with oligo(α-methylstyryl)lithium in the presence of a 10-fold excess of tert-BuOK. Indeed, we found that the obtained polymer has a predictable molecular weight and a narrow molecular weight distribution (Mw/Mn ∼ 1.05). Herein, we discuss that the polymerization factors, such as counter cation, added salt and polymerization temperature, strongly affected the polymerization behavior of p-DVO. The precise synthesis of architectural polymers, such as diblock copolymer, triblock terpolymer, tetrablock quarterpolymer, and star-branched polymer containing poly-(p-divinylbenzene) segments, is also described.