高乙烯基高相对分子质量环保型充油星形溶聚丁苯橡胶的合成

Synthesis of environmental friendly oil extending star-shaped solution polymerized styrene-butadiene rubber with high vinyl and high relative molecular mass

以环己烷/己烷为溶剂,正丁基锂为引发剂,乙基四氢糠基醚（ETE）为结构调节剂,采用间歇聚合工艺对丁二烯与苯乙烯进行负离子共聚合反应合成溶聚丁苯橡胶（SSBR）,考察了引发温度、ETE用量对单体转化率及乙烯基含量的影响,研究了偶联剂种类对SSBR性能的影响以及偶联的最佳条件.结果表明,采用ETE调节体系、甲基三氯硅烷偶联体系,填充牌号为VIVATEC 500的环保型填充油37.5份,当聚合引发温度为35～45℃、ETE质量分数为350×10-6时,可以得到数均分子量约为29.00×104左右、乙烯基质量分数为60％以上的充油星形SSBR,其力学性能和动态力学性能较好.随着偶联温度的升高和偶联时间的延长,偶联效率提高,当偶联温度达到55℃以上、偶联时间为15 min时,偶联效率超过50％.

Solution polymerized styrene-butadiene rubber（SSBR） was synthesized by batch anionic copolymerization,using cyclohexane/hexane as solvent,n-BuLi as initiator,ethyl tetrahydrofurfuryl ether（ETE） as modifier,butadiene and styrene as monomer,the effects of initiation temperature and ETE dosage on monomer conversion and vinyl content of SSBR were investigated,and the effect of coupling agent kind on properties of SSBR and the optimum coupling conditions were studied.The results showed that the number-average molecular weight of the oil extending star-shaped SSBR was about 29.00 × 104 and the mass fraction of vinyl was above 60％,and the mechanical and dynamic mechanical properties of synthesized SSBR were better in the presence of ETE modifier and CH3SiCl3 coupling agent at initiation temperature 35-45 ℃,mass fraction of ETE 350 × 10-6,environmental friendly extending oil VIVATEC 500 37.5 phr.With increasing coupling temperature and time,the coupling efficiency increased and reached above 50％ at 55 ℃ for 15 min.