Synthesis of end-functionalized polymers by means of living anionic polymerization. 10. Reactions of living anionic polymers with halopropylstyrenederivatives

Three different omega-alpha-substituted styryl macromonomers with well-cont rolled structures were synthesized by directly terminating either polystyry llithium or polyisoprenyllithium with 4-(3-halopropyl)-alpha-methylstyrenes (2), alpha-(3-halopropyl)styrenes (3), and 1-[4-(3-halopropyl)phenyl]-1-ph enylethylenes (4). With uses of their bromo and iodo derivatives as termina ting agents, the reactions proceeded in a desired manner in THF at -78 degr ees C to afford well-controlled omega-styryl polystyrene and polyisoprene m acromonomers quantitatively. On the other hand, the synthetic utility of ch loride derivatives as terminators was much dependent-on both their polymeri zable styryl groups and living polymers to be reacted. By comparison of the se results with our previous results using 4-(3-halopropyl)styrenes (1), th e scope and limitation of the methodology developed here were discussed fro m a viewpoint of quantitative synthesis of various omega-styryl macromonome rs with well-controlled structures.