亚磷酸酯改性六价钼催化体系催化异戊二烯聚合

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马玉, 薛梅玉, 邹灵丽， 华静*

 （青岛科技大学  橡塑材料与工程教育部重点实验室，山东 青岛 266042）

 摘要： 亚磷酸三壬基苯酯（TNPP）增溶的二氯二氧钼(简称Mo)为主催化剂、间甲酚取代的三异丁基铝(简称Al)为助催化剂，催化异戊二烯（Ip）配位聚合，可制备较高1,2结构和3，4结构含量的聚异戊二烯。研究催化剂用量、溶剂种类、聚合温度等对单体转化率和聚合物特性黏数的影响，并采用凝胶渗透色谱、红外光谱和核磁共振研究产物微观结构。结果表明：该催化体系具有更高的催化活性，其催化效率约为相同条件下MoCl5体系的3倍；TNPP增溶的MoCl2O2催化体系在n(Mo)/n(Ip)=4×10-4，n（Al）/n（Mo）为10时,催化活性较高，单体转化率可达90%；n（Mo）/n（Ip）在4×10-4~10×10-4之间改变时，聚合物特性黏数可以在15~35 dL·g-1之间调节；产物3,4结构和1,2结构摩尔分数之和约为519%。

 关键词： 二氯二氧钼； 聚异戊二烯； 亚磷酸三壬基苯酯； 配位聚合

 中图分类号： O 632.12          文献标志码： A

 Polymerization of Isoprene with Phosphite Modified Molybdenum(Ⅵ)base Catalyst System

 MA Yu, XUE Meiyu， ZOU Lingli, HUA Jing

 (Key Laboratory of ＲubberPlastics,Ministry of Education,Qingdao University of Science and Technology，Qingdao 266042，China)

 Abstract: Polyisoprene containing high 1,2structures content was synthesized with main catalyst MoCl2O2(simplified as Mo) modified by ligand of tri(nonylphenyl) phosphite(simplified as TNPP) and cocatalyst Al(OPhCH3)(iBu)2(simplified as Al). The effects of  n(TNPP)/n（Mo），n(Al)/n（Mo），n（Mo)/n(Ip) and other polymerization conditions on the monomer conversion and product intrinsic viscosity were investigated, and the microstructure of the polymer was characterized. The results showed that the catalyst exhibited higher catalytic activity, the catalytic efficiency of this catalyst system is three times as much as that of MoCl5 base catalyst system. The monomer conversion achieved 90% as the molar ratio of  n(Al)/n(Mo) was 10 and n(Mo)/n(Ip) was 4×10-4. The polymer′s intrinsic viscosity can be ranged from 15 to 35 dL·g-1 when n(Mo)/n(Ip)  changed from 4 × 10-4 to 10 ×10-4, and the molecular weight can be adjusted by changing the dosage of Mo. With MoAlTNPP catalytic system, the sum of structural units content of 1,2and 3,4of isoprene bulk polymerization product reached 519%.

Key words: MoCl2O2; polyisoprene; tri(nonylphenyl) phosphite; coordination polymerization

收稿日期：  20141120

基金项目： 山东省自然科学基金项目（ZR2014BP006）；青岛市科技计划基础研究项目（1314133jch）.

作者简介： 马玉（1990—），女，硕士研究生. *通信联系人.

文章编号： 16726987（2016）02015606； DOI： 10.16351/j.16726987.2016.02.008