TiCl_4/XROH/MgCl_2/Et_3Al催化剂合成宽分子量分布乙烯/1-己烯共聚物  

Ethylene/1-Hexene Copolymer with Broadened Molecular Mass Distribution Obtained by Catalysis of TiCl_4/XROH/MgCl_2/Et_3Al

作　　者：孔媛[1] 汪红丽[1] 义建军 张明革 黄启谷[1] 杨万泰[1] 

机构地区：[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

出　　处：《应用化学》2010年第6期626-631,共6页Chinese Journal of Applied Chemistry

基　　金：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);"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

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0.45MPa,聚合温度80℃,聚合时间2h,共聚单体(1-hexene)浓度0.25mol/L时,催化效率达23.2kg/gcat。采用13CNMR、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%。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%.

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 

分 类 号：O632.1[理学—高分子化学]