二元三氟甲磺酸稀土催化体系合成高顺式-1,4-聚丁二烯橡胶

Synthesis of high cis-1,4-polybutadiene by using binary catalyst system of trifluoromethanesulfonic neodymium

用以Nd（CF3SO3）3·3 TBP（简称Nd,其中TBP为磷酸三丁酯）为主催化剂、Al（i-Bu）2H（简称Al）为助催化剂、己烷（Hex）为溶剂,在少量单体1,3-丁二烯（Bd）存在下配制的催化体系催化Bd聚合,考察了催化剂配制方式、单体加入量、Al/Nd（摩尔比,下同）、催化剂用量、陈化温度、陈化时间等对Bd聚合的影响.结果表明,在催化剂加料顺序为Nd＋ Bd＋ A1＋ Hex,Bd/Nd（摩尔比）为10、Al/Nd为15 ～ 20、Nd/Bd（摩尔比）为8x10-5,50℃陈化1.0h的条件下,聚丁二烯橡胶收率可达75.0％以上,顺式-1,4-结构摩尔分数高达98.0％以上.

With Nd（ CF3SO3 ）3 . 3 TBP（ simplified as Nd, tri-butyl-phosphate abbreviated as TBP） as the catalyst, A1 （i-Bu） 2H （ simplified as A1） as the cocatalyst, in the presence of small amount of monomer 1,3-butadiene （Bd） , polymerization of Bd was catalyzed. The effects of catalyst preparation mode, monomer dosage, A1/Nd （ mole ratio） , the amount of catalyst, aging temperature and aging time on the polymerization of Bd were investigated. Theresults showed that the yield of polybutadiene was over 75.0% and the mole fraction of cis-1,4-unit was more than 98.0% in the cases of adding order of cahalyst Nd ＋ Bd ＋ A1 ＋ Hexane, Bd/Nd （ mole ratio） 10, A1/Nd（mole ratio） 15 - 201 Nd/Bd （mole ratio） 8 xl0-5, aging time 1 h at50 ~C.