Abstract: | The use of living linking reactions of poly(styryl)lithium with 1,3-bis(1-phenylvinyl)benzene followed by crossover reactions with styrene or butadiene monomers has been used to prepare four-armed heteroarm, star-branched polymers. Bimodal molecular weight distributions have been observed for crossover reactions with both styrene and butadiene. Addition of THF (THF]/Li]=14–32) for crossover to styrene and lithium sec-butoxide for crossover to butadiene produces monomodal molecular weight distributions. Symmetrical, four-armed star polystyrenes have been synthesized; properties have been compared with a corresponding polymer prepared via a silicon tetrachloride linking reaction. Heteroarm, star-branched polymers with two polystyrene arms and two polybutadiene arms with high 1,4-microstructure have been prepared. |