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采用多级串联连续溶液聚合工艺,以n-BuLi为引发剂,四氢呋喃(THF)为结构调节剂,环己烷为溶剂,研究了不同平均停留时间、不同n-BuLi浓度以及聚合温度等反应条件对丁二烯(Bd)-苯乙烯(St)连续溶液共聚合反应动力学的影响。结果表明:在THF/[n-BuLi](摩尔比)为30、Bd/St(质量比)为7/3、聚合温度为80℃的条件下,多级串联连续溶液共聚合反应过程中Bd和St共聚合反应速率对[n-BuLi]呈近一次方关系,对单体浓度呈一次方关系;Bd的反应活化能为40.15kJ/mol,St的反应活化能为36.75kJ/mol。在上述同样的条件下而聚合温度为50~90℃时,Bd和St共聚合反应的竞聚率随温度的增加逐渐趋同。
Using n-BuLi as initiator, tetrahydrofuran (THF) as structural modifier and cyclohexane as solvent, the reaction conditions of different average residence time, different n-BuLi concentration and polymerization temperature were studied by using multi-stage serial continuous solution polymerization process. On the kinetics of continuous solution copolymerization of butadiene (Bd) -styrene (St). The results show that the Bd value of Bd in the process of copolymerization of multi-stage serial continuous solution under the condition of THF / [n-BuLi] (molar ratio) 30, Bd / St (mass ratio) 7/3 and polymerization temperature 80 ℃ The copolymerization rate of St and St was nearly one-way relationship [n-BuLi], and the concentration of monomer was a linear relationship. The activation energy of Bd was 40.15kJ / mol and the activation energy of St was 36.75kJ / mol. Under the same conditions as above, when the polymerization temperature was 50 ~ 90 ℃, the reactivity ratio of Bd and St copolymerization gradually converged with the increase of temperature.