中华医学超声杂志

应用化学 ›› 2010, Vol. 27 ›› Issue (06): 626-631.DOI: 10.3724/SP.J.1095.2010.90592

• 研究论文 • 上一篇    下一篇

TiCl4/XROH/MgCl2/Et3Al催化剂合成宽分子量分布乙烯/1-己烯共聚物

孔媛1,汪红丽1,义建军2,张明革2,黄启谷1*,杨万泰1   

  1. (1.北京化工大学化工资源有效利用国家重点实验室，碳纤维及功能高分子教育部重点实验室 北京100029；
    2.中国石油石油化工研究院合成树脂重点实验室 北京)
  • 收稿日期:2009-09-03 修回日期:2009-11-30 出版日期:2010-06-10 发布日期:2010-06-10
  • 通讯作者: 黄启谷，博士，教授; E-mail:huangqg@mail.buct.edu.cn; 研究方向：聚烯烃催化剂及高性能聚烯烃的设计与合成
  • 基金资助:
    国家自然科学基金（20574003）中石油风险创新基金(07-06D01-04-04-06)北京市教委重点学科共建项目（XK100100540，XK100100640）及“长江学者和创新团队发展计划教育部创新团队”( IRT0706)资助项目

Ethylene/1-Hexene Copolymer with Broadened Molecular Mass Distribution Obtained by Catalysis of  TiCl4/XROH/MgCl2/Et3Al

KONG Yuan1, WANG Hong-Li1, YI Jian-Jun2, ZHANG Ming-Ge2, HUANG Qi-Gu1*, YANG Wan-Tai1   

  1. (1.State Key Laboratory of Chemical Resource Engineering,Key Laboratory of Carbon Fiber
    and Functional Polymers,Ministry of Education,Beijing University of Chemical Technology,Beijing 100029;
    2.Laboratory for Synthetic Resin Research Institution of Petrochemical Technology,
    China National Petroleum Corporation,Beijing)
  • Received:2009-09-03 Revised:2009-11-30 Published:2010-06-10 Online:2010-06-10

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摘要：

采用MgCl2负载TiCl4及1,3-二氯-2-丙醇给电子体(XROH)，与三乙基铝助催化剂组成的催化剂体系，合成了1-己烯共聚率高且宽分子量分布的乙烯/1-己烯共聚物。 讨论了催化体系的组成、配比和聚合条件对乙烯/1-己烯共聚合行为，共聚物结构、分子量及分子量分布的影响。 结果表明，n(Ti)∶n(Mg)=10∶1,n(XROH)∶n(MgCl2)=2.6∶1,n(Al)∶n(Ti)=100∶1,乙烯压力0.45 MPa,聚合温度80 ℃,聚合时间2 h,共聚单体(1-hexene)浓度0.25 mol/L时,催化效率达23.2 kg/g cat。 采用13C NMR、X-ray、SEM、WAXD、DSC、GPC等测试技术对催化剂、共聚物的结构进行了表征。 结果表明，在Zieglar-Natta(Z-N)催化体系中，给电子体多卤代醇与TiCl4结合，载体MgCl2的晶体结构发生了变化。 结晶度降低，有利于催化剂负载量的提高(ω(Ti)=4.8%)和催化效率增大。 催化体系产生了多种活性中心，使聚烯烃分子量分布变宽(15~20)。 多卤代醇还可增强1-己烯与乙烯的共聚能力，在共聚物中1-己烯的摩尔分数达5.1%。

关键词: 负载型Z-N催化剂, 多官能团内给电子体, 烯烃共聚物, 宽分子量分布

Abstract:

The synthesis of copolymer with high comonomer incorporation and broadened molecular mass distribution from ethylene with 1-hexene catalyzed by co-catalyst TiCl4/XROH/MgCl2 and Et3Al is described. The influences of the catalyst system composition and the polymerization conditions on the behavior of ethylene/1-hexene copolymerization, the structure, molecular mass and molecular mass distribution(MMD) of the obtained copolymer have been discussed in detail. When the copolymerization was performed under the optimum conditions:n(Ti)∶n(Mg)=10∶1, n(XROH)∶n(MgCl2)=2.6∶1, n(Al)∶n(Ti)=100∶1, P=0.45 MPa, t=80 ℃, Time=2 h and the comonomer concentration in feed=0.25 mol/L, the catalytic activity reached 23.2 kg/g cat. The catalyst particle shape and the structure and properties of the ethylene/1-octene copolymer are characterized with 13C NMR, X-ray, SEM, WAXD, DSC and GPC. These results show that the catalytic activity, molecular mass distribution and higher 1-hexene incorporation were considerably improved when the multi-halogen alcohol(XROH) was added into the catalyst system. By adding XROH in the catalyst system made Ti mass fraction of the catalyst increased up to 4.8%; the molar ratio of MMD of the copolymer became broader, ranging from 15 to 20; 1-hexene incorporation within the copolymer chain was higher, up to 5.1%.

Key words: supported Z-N catalyst, multi-group internal donor, copolymer of olefins, broaden molecular weight distribution

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