Synthesis of end-functionalized polymer by means of anionic living polymerization .6. Synthesis of well-defined polystyrenes and polyisoprenes with 4-vinylphenyl end group

In order to synthesize end-functionalized polymers with 4-vinylphenyl group (so-called omega-styryl macromonomers), anionic living polymers of styrene and isoprene were allowed to react with five 4-(omega-haloalkyl)styrene derivatives in THF at -78 degrees C. 4-Vinylphenyl-terminated polymers of well-controlled molecular weights and narrow molecular weight distributions (M(W)/M(n) < 1.05) as well as with nearly quantitative end functionalities were obtained in 100% yields by the reactions with 4-(2-bromoethyl)styrene, 4-(3-bromopropyl)styrene, 4-(3-iodopropyl)styrene, and 4-(4-bromobutyl)styrene. On the other hand, the reactions of anionic living polymers with 4-(3-chloropropyl)styrene were complicated by competitive side reactions of anion attack on the vinyl groups of terminating agent and the macromonomer produced.