用溶液型磷酸酯钕催化合成高顺式丁戊橡胶  

Synthesis of high cis-1,4-butadiene-isoprene rubber catalyzed by solubilized neodymium phosphate ester catalyst

作　　者：兰莹 张华强 董静 张松波 刘丕博 胡雁鸣 周光远 LAN Ying;ZHANG Hua-qiang;DONG Jing;ZHANG Song-bo;LIU Pi-bo;HU Yan-ming;ZHOU Guang-yuan(Division of Energy Materials,Dalian Institute of Chemical Physics of the Chinese Academy of Sciences,Dalian 116023,China;Lanzhou Petrochemical Research Center,Petrochemical Research Institute,PetroChina,Lanzhou 730060,China)

机构地区：[1]中国科学院大连化学物理研究所能源材料研究部,辽宁大连116023 [2]中国石油石油化工研究院兰州化工研究中心,兰州730060

出　　处：《合成橡胶工业》2024年第5期373-377,共5页China Synthetic Rubber Industry

基　　金：国家重点研发计划项目(2022 YFB 3704704)。

摘　　要：使用溶液型磷酸二(2-乙基己基)酯钕为主催化剂、烷基铝为助催化剂、氯化铝为第3组分,构建了均相磷酸酯稀土催化体系并用于催化丁二烯和异戊二烯进行共聚合,研究了烷基铝和氯化铝的组成及用量、催化剂用量和单体投料配比对共聚物性能的影响。结果表明,该催化体系可以高效催化丁二烯和异戊二烯的共聚合反应,所得聚合物为具有立构规整性、窄分子量分布的高顺式无规丁戊橡胶;当烷基铝为二异丁基氢化铝时,催化体系表现出可逆配位链转移聚合特征,每一个钕原子可产生高达10.3条聚合物分子链。A homogeneous phosphate ester rare earth catalytic system was constructed with solubilized neodymium di(2-ethylhexyl)phosphate eater as the main catalyst,alkyl aluminum and aluminum chloride as co-catalyst and the third component,respectively.The copolymerization of butadiene and isoprene was catalyzed by this catalytic system.The effects of the composition and dosage of alkyl aluminum and aluminum chloride,catalyst dosage,and monomer feeding ratio on the properties of the copolymer were studied.The results showed that the catalytic system could efficiently catalyze the copolymerization of butadiene and isoprene,and the resulting polymer was a random butadiene-isoprene rubber with high cis-1,4-unit stereoregularity and narrow molecular weight distribution.When diisobutylaluminum hydride was chosen as the alkyl aluminum,the catalytic system exhibited reversible coordination chain transfer polymerization characteristics with 10.3 polymer molecular chains gene-rated per neodymium atom.

关 键 词：丁戊橡胶 磷酸酯钕 顺式-1 4-结构含量 可逆配位链转移 丁二烯 异戊二烯 分子量及其分布 

分 类 号：TQ333.99[化学工程—橡胶工业]