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由丁二烯出发,在高的顺式聚合物收率下,钕系催化剂和阳离子催化剂可原位合成环化聚丁二烯(CPB)。由新癸酸钕、氢化二异丁基铝[Al(i-Bu)2H]和一氯二异丁基铝组成的均相催化剂在甲苯溶液中、聚合温度为50℃的条件下聚合丁二烯,当聚合物收率达到80%后,加入叔丁基氯(RCl),可原位引发聚丁二烯的阳离子环化反应。考察了聚合时间、丁二烯质量浓度和RCl/Al(i-Bu)2H(摩尔比)对原位环化反应的影响。结果表明,环化反应可在丁二烯质量浓度为0.05g/mL时进行;调节丁二烯质量浓度,可获得数均相对分子质量为4500～12000的CPB;调节RCl/Al(i-Bu)2H,可获得环化度为17%～55%的CPB。
Starting from butadiene, neodymium-based catalysts and cationic catalysts can synthesize cyclized polybutadiene (CPB) in situ at high cis-polymer yields. A homogeneous catalyst composed of neodymium neodecanoate, diisobutylaluminum hydride [Al (i-Bu) 2H] and diisobutyl aluminum chloride was polymerized in a toluene solution at a polymerization temperature of 50 ° C. to synthesize a Ene, when the yield of polymer reaches 80%, adding tert-butyl chloride (RCl) can initiate the cationic cyclization of polybutadiene in situ. The effects of polymerization time, mass concentration of butadiene and RCl / Al (i-Bu) 2H (molar ratio) on in-situ cyclization reaction were investigated. The results showed that the cyclization reaction can be carried out when the mass concentration of butadiene is 0.05g / mL. The mass concentration of butadiene can be adjusted to obtain CPB with the number average molecular weight of 4500-12000. The concentration of RCl / Al (i-Bu ) 2H, CPB with a degree of cyclization of 17% -55% can be obtained.