醚/酯复合内给电子体Ziegler-Natta催化剂对丁烯-1聚合的影响  

Diether/Diester Internal Electron Donor in Ziegler-Natta Catalysts for Butene-1 Polymerization

作　　者：任合刚[1] 王曦[1] 王路海[1,2] 张宁宁[1] 刘盘阁[1] 姬荣琴[1] 闫卫东[1] 

机构地区：[1]河北工业大学化工学院,高分子科学与工程研究所,天津300130 [2]中国石油大庆化工研究中心,黑龙江大庆163714

出　　处：《高分子材料科学与工程》2009年第3期13-16,共4页Polymer Materials Science & Engineering

基　　金：中国石油科技创新基金研究项目(2008D5006-05-02)

摘　　要：制备了5种含有不同内给电子体(乙二醇二甲醚,邻苯二甲酸二丁酯和三种二者不同比例复合内给电子体)的Mg-Cl2负载型丁烯-1聚合Ziegler-Natta(Z-N)催化剂,研究了复合和单一给电子体催化剂的相关性能。结果表明,复合内给电子体催化剂的活性有很大提高,对聚丁烯-1等规度影响较小;加入外给电子体后明显提高了聚合产物的等规度(由55.9%增加到84.5%),而且环己基甲基二甲氧基硅烷(CHMMS)更有利于等规度的提高;Al(i-Bu)3有利于聚丁烯-1等规度的提高,而AlEt3有利于催化活性的提高;复合内给电子体催化剂使聚丁烯-1的分子质量增大。Five MgCla-supported Ziegler-Natta catalysts containing different internal donors were prepared for butane-1 polymerization. The internal donors are ethylene glycol dimethyl ether（EGDE）, dibutyl phthalate（DBP） and three mixes with different proportion of EGDE and DBP. Moreover, the performance of different external donors and alkylaluminiums as cocatalysts for butene-1 polymerization was also investigated. The results indicate that the addition of mixed ether-ester as internal donor to catalysts used in butane-1 polymerization leads to a significant increase in activity; isotactic index of polymers is improved by conducting external donor in the polymerization system （I. I. from 55.9% to 84.5%）. The polymerizations were carried out activated with AlEt3 and Al（i-Bu）3 respectively. It is found that Al（i-Bu）3 is of benefit to isospecificity of Z-N catalysts, whereas A1Et3 is of benefit to the catalytic activity. The polybutene-1 prepared by TiCl4/MgCl2/EGDE/DBP posses higher molecular weight than that by TiCl4/MgCl2/EGDE.

关 键 词：Zieglex-Natta催化剂 丁烯-1聚合 给电子体 乙二醇二甲醚 邻苯二甲酸二丁酯 

分 类 号：TQ314.242[化学工程—高聚物工业]