Synthesis of End-Functionalized Polymers by Means of Living Anionic Polymerization. 10. Reactions of Living Anionic Polymers with Halopropylstyrene Derivatives

Abstract

Three different ω−α-substituted styryl macromonomers with well-controlled structures were synthesized by directly terminating either polystyryllithium or polyisoprenyllithium with 4-(3-halopropyl)-α-methylstyrenes (2), α-(3-halopropyl)styrenes (3), and 1-[4-(3-halopropyl)phenyl]-1-phenylethylenes (4). With uses of their bromo and iodo derivatives as terminating agents, the reactions proceeded in a desired manner in THF at −78 °C to afford well-controlled ω-styryl polystyrene and polyisoprene macromonomers quantitatively. On the other hand, the synthetic utility of chloride derivatives as terminators was much dependent on both their polymerizable styryl groups and living polymers to be reacted. By comparison of these results with our previous results using 4-(3-halopropyl)styrenes (1), the scope and limitation of the methodology developed here were discussed from a viewpoint of quantitative synthesis of various ω-styryl macromonomers with well-controlled structures.