Selective Living Anionic Polymerization of a Novel Bifunctional Monomer 4-(Vinylphenyl)-1-butene and the Preparation of Uniform Size Functional Polymers and Amphiphilic Block Copolymers

Abstract

A novel bifunctional monomer, namely, 4-(vinylphenyl)-1-butene (VSt), was prepared by the coupling reaction between vinylbenzyl chloride and allylmagnesium chloride with a high yield (93%) and monomer purity. This monomer contains both a styrene type and a 1-butene type CC double bond. The former double bond can be selectively polymerized by anionic polymerization to generate a polymer with a polystyrene [poly(St)] backbone and functional butenyl side chains. The effects of the initiator, temperature, and solvent were investigated, and the optimum conditions for the selective living anionic polymerization of this monomer were determined. Using n-BuLi as initiator, in a mixture of toluene and tetrahydrofuran (5:1−2:1), at −40 °C, VSt could undergo anionic polymerization in a living manner without cross-linking and any other side reactions. The polymer thus obtained possesses a controlled molecular weight and a very narrow molecular weight distribution (Mw/Mn = 1.03−1.05). The quantitative presence of the u...