(2-Me-3-ClPh)_2PBIMe_2FeCl_2racC_2H_4(Ind)_2ZrCl_2/MAO双功能催化体系乙烯原位共聚制备LLDPE  

LLDPE PREPARATION BY in situCOPOLYMERIZATION OF ETHYLENE USING MATALLOCENE/ (2-Me-3-ClPh)_2PBIMe_2FeCl_2/MAO TANDEM CATALYZERS

作　　者：王如义[1] 郑元锁[1] 崔楠楠[2] 张志成[2] 柯毓才[2] 胡友良[2] 

机构地区：[1]西安交通大学环境与化学工程学院高聚物复合材料研究所,西安710049 [2]中国科学院化学研究所高分子科学与材料联合实验室工程塑料重点实验室

出　　处：《高分子学报》2005年第1期132-136,共5页Acta Polymerica Sinica

基　　金：国家 8 63计划 (项目号 2 0 0 2AA3 3 3 0 5 0 );国家自然科学基金 (基金号 2 0 3 3 40 3 0 );SINOPEC联合资助

摘　　要：合成了后过渡金属铁 (2 Me 3 ClPh) 2 PBIMe2 FeCl2 低聚催化剂 ,并与亚乙基桥茂金属共聚催化剂rac C2 H4 (Ind) 2 ZrCl2 共用 ,用MAO(1 4mol L甲苯溶液 )作为助催化剂 ,原位共聚合成线性低密度聚乙烯 (LLDPE) .结果发现 ,这种后过渡铁催化剂具有很高的低聚催化活性 [1 0× 10 7goligomer (molFe·h) ],双功能催化体系的催化活性保持在 10 6 gPE (molFe·h)以上 ;1 3C NMR分析表明 ,得到了线性低密度聚乙烯 ,当Fe Zr比为 1 2时 ,也没有出现α 烯烃残留现象 ,说明这两种催化剂具有好的匹配性 ;随Fe Zr比和反应温度的变化 ,聚合物的熔点、结晶度、熔点等均表现出很好的规律性 .A novel late transitional metal catalyst-(2-Me-3-ClPh) 2PBIMe 2FeCl 2——has been synthesized having a high oligomerization activity up to 1.0×107g oligomer/(mol Fe·h).Using this oligomerization catalyst and metallocene catalyst—rac-C-2H-4(Ind) 2ZrCl 2—as a dual functional catalyst system,MAO as the only cocatalyst,Linear Low Density Polyethylene (LLDPE) has been prepared by in situ copolymerization of ethylene having a high activity [>106g PE/(mol cat·h)]. 13C-NMR shows that the LLDPE is obtained.In addition,the presence of unreacted α-olefin was not detected since there is no evident resonance signal at 29.29 and 29.42,which proves that this dual functional catalyst system has a good match during in situcopolymerization.With increasing the Fe/Zr ratio,the densities of polymers and the melting points of polymers obtained from DSC are in a descending trend.Meanwhile,the similar phenomenon is also found when the reaction temperature decreases.

关 键 词：原位共聚 催化体系 催化剂 C2H4 线性低密度聚乙烯 LLDPE 低聚 MAO 合成线 CL2 

分 类 号：TQ325.12[化学工程—合成树脂塑料工业]