异丙氧基钕[Nd(Oi-Pr)_3]/甲基铝氧烷(MAO)催化体系催化月桂烯聚合(英文)  

Polymerization of β-myrcene with isopropoxide neodymium /methylaluminoxane catalyst

作　　者：房梁[1,2] 郭祥峰[1] 胡雁鸣[2] 张学全[2] 

机构地区：[1]齐齐哈尔大学化学与化学工程学院,黑龙江齐齐哈尔161006 [2]中国科学院长春应用化学研究所,长春130022

出　　处：《合成橡胶工业》2016年第2期164-164,共1页China Synthetic Rubber Industry

基　　金：Supported by "973 Program"(2015 CB654702);National Natural Science Foundation of China(51203147;51473156)

摘　　要：以Nd（Oi-Pr）3/MAO为催化体系进行月桂烯聚合。结果表明,该催化体系具有高活性和高顺式-1,4选择性,所得聚合物顺式-1,4-结构摩尔分数可达95.6%。聚合温度的升高可显著提高聚合速率,在0℃下聚合24 h,聚合物收率仅为15.8%;而在70℃下聚合1 h,聚合物收率可达99.0%。随着聚合温度的升高,链转移反应增强,聚合物的相对分子质量下降;同时由于体系中所形成的对式Nd-η^3-烯丁基转变为热力学上更为稳定的同式异构体,使得顺式-1,4-结构含量下降。Regarding the environment impact and depletion of oil reserves, there is growing interest in the development of materials from renew- able sources. β-myrcene（MY） produced by a variety of plants, can be used as conjugated diene monomer for the preparation of bio- sourced elastomers. However, in previous studies, the polymerization of MY with anionic or free radical polymerization afforded polymers with low stereoregularity ; the mole fraction of cis-1,4-unit were in 70% -80%. Recently, considerable progress has been made in the synthesis of highly regulated polyMY. For instance, Nd （ BH4 ） 3 （ tet- rahydrofuran, THF）3/n-BuEtMg afforded polyMY with high mole fraction of c/s-1,4-unit up to 91.0% ; lutetium dialkyl complex bearing bidentate-diimidosulfonate ligand activated by [ Ph3C ] [ B （ C6 F5 ） ] 4 and AI（i-Bu） 3 worked effectively in the polymerization of MY to give isotactic 3,4-polyMY, while these complexes were rath- er difficult to prepare or handle.

关 键 词：钕系催化剂 甲基铝氧烷 月桂烯 配位聚合 

分 类 号：O631.5[理学—高分子化学]