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以双卤代烷烃取代型双锂齐聚物为引发剂、环己烷为溶剂,丁二烯(B)、苯乙烯(S)单体采用1次加入的方法,合成了对称型双端过渡态丁二烯/苯乙烯嵌段共聚物S-(S/B)-B-(B/S)-S,并对双锂体系丁二烯、苯乙烯共聚合反应过程进行了研究,将丁二烯、苯乙烯共聚合反应动力学数据进行分段处理,求得不同引发温度、不同单体配比、不同极性添加剂用量[二乙二醇二甲醚(2G)/Li]下丁二烯聚合段、苯乙烯聚合段假一级表观增长反应速度常数kp_1、kp_2;求得不同2G/Li下丁二烯、苯乙烯共聚合反应的表观竞聚率,随着2G/Li的增大,丁二烯的表观竞聚率减小,苯乙烯的表观竞聚率增大,表明随着2G/Li的增大,丁二烯、苯乙烯逐渐向无规共聚合方向发展。
The double-ended transitional state was synthesized by using double-halogenated alkylidene bis-lithium oligomer as initiator and cyclohexane as solvent, butadiene (B) and styrene (S) Butadiene / styrene block copolymer S- (S / B) -B- (B / S) -S. The copolymerization of butadiene and styrene in bis-lithium system was studied. Ethylene and styrene copolymerization kinetic data were subdivided to obtain different starting temperature, different monomer ratio, different polar additive content [diethylene glycol dimethyl ether (2G) / Li] butadiene In the polymerization zone, the pseudo-first-order apparent growth rate constant kp_1, kp_2 of the polymerization stage of styrene was calculated. The apparent reactivity ratio of butadiene and styrene copolymerization at different 2G / Li was obtained. With the increase of 2G / Li The apparent reactivity ratio of large and butadiene decreases, while the apparent reactivity rate of styrene increases, indicating that the butadiene and styrene gradually evolve to random copolymerization with the increase of 2G / Li.