氰乙基茂金属化合物合成及其催化乙烯聚合  

Synthesis and catalytic properties of novel cyanoethyl substituted cyclopentadienyl complexes

作　　者：梁成锋[1] 孙俊全[1] 胡蔚秋[1] 阳永荣[1] Herbert Schumann 

机构地区：[1]浙江大学联合化学反应工程研究所,浙江杭州310027 [2]柏林工业大学,德国柏林10623

出　　处：《浙江大学学报（工学版）》2002年第1期109-110,114,共3页Journal of Zhejiang University：Engineering Science

基　　金：国家自然科学基金资助项目 ( 2 0 0 740 2 8);中国石化集团基金资助项目 ( X5 0 0 0 30 )

摘　　要：合成了四种新型含氰乙基取代的茂金属化合物 ,Cp CNCp MCl2 (Cp CN=C5H4CH2 CH2 CN,M=Ti(1) ,Zr(2 ) ) ,Cp CNCp Sm Cl(3)和 Cp CN2 Zr Cl2 (4 ) .用四元 X衍射仪测定了化合物 1的晶体结构 .研究了其在乙烯聚合中的催化性能 ,两种茂锆化合物 (2 ,4)的活性明显要高于茂 (1)和茂 (3) .以 1作催化剂 ,MAO(甲基铝氧烷 )为助催化剂 ,详细研究了聚合反应条件对催化体系的影响 .研究表明 ,最佳的聚合温度和 Al/ Ti比分别为 6 0℃和 15 0 0 .随着聚合时间的延长 ,活性迅速下降 .所得聚合物的分子量随温度的升高而降低 .用 DSC(差示扫描热分析仪 )分析了聚合物的热性能 ,聚合物的熔点为 130℃左右 ,结晶度为 5 7%～ 6 5 % .Novel cyanoethyl substituted cyclopentadienyl complexes, Cp\+\{CN\}CpMCl\-2(Cp\+\{CN\}=C\-5H\-4CH\-2CH\-2CN, M=Ti(1), Zr(2)), Cp\+\{CN\}CpSmCl(3), and Cp\+\{CN\}\-2ZrCl\-2(4) were synthesized. The molecular structure of complex 1 was determined by X\|ray diffraction. Polymerization of ethylene catalyzed by these synthesized complexes were studied. Zirconocene 2 and 4 have higher activity than the titanocene 1 and samarocene 3. Effects of conditions on the ethylene polymerization catalyzed by (2)/MAO(methylaluminoxane)were studied in detail. The optimal temperature and molar ratio of Al/Ti are 60℃ and 1500 respectively. With the prolongation of polymerization time, the catalytic activity declined rapidly. The polymer has a higher molecular weight at low temperature and decreased rapidly with the rising of temperature. Thermal properties of the produced polyethylene were determined by DSC. The melt point is about 130 ℃ and the crystallinity is from 57% to 65%.

关 键 词：氰乙基茂金属催化剂 聚乙烯 晶体结构 催化活性 合成 氰乙基茂金属化合物 结晶度 

分 类 号：O623.76[理学—有机化学] O643.36[理学—化学]