Et(Ind)2ZrCl2／MAO催化乙烯和ω-对甲苯基-α-烯烃共聚合的研究  

COPOLYMERIZATION OF ETHYLENE WITH ω-p-METHYLPENYL-α-OLEFIN USING ET(IND)_2ZrCl_2/MAO AS A CATALYST

作　　者：李化毅[1] 张辽云[2] 李金阁[1] 胡友良[1] 

机构地区：[1]中国科学院化学研究所北京分子科学国家实验室高分子科学与材料联合实验室工程塑料重点实验室,北京100080 [2]中国科学院研究生院,北京100039

出　　处：《高分子学报》2008年第4期371-377,共7页Acta Polymerica Sinica

基　　金：国家自然科学重点基金(基金号20734002);国家自然科学基金(基金号50703044);SINOPEC(中国石油化工集团公司)资助项目

摘　　要：使用Et(Ind)2ZrCl2/MAO催化剂催化乙烯和3种ω-对甲苯基-α-烯烃(对甲苯基-1-丙烯,4-对甲苯基-1-丁烯,6-对甲苯基-1-己烯)共聚,主要研究了共单体加入量对催化剂活性和所得共聚物性能的影响.4-对甲苯基-1-丁烯表现出最好的共聚性能.使用1H-NMR、13C-NMR、GPC和DSC对共聚物进行了表征.Modification of polyethylene with polar groups and/or polar polymer side chains has been an issue forboth academic and industry fields for a long time. Many method have been presented to prepare functional polyethylene, among which the post-functional method has find its industry applications. However, this method shows many disadvantages in controlling polymer structure. The reactive monomer method is characterized by good control of polymer chain structure. We have prepared an ethylene/p-allyholuene copolymer by Et （Ind）2ZrCl2/MAO. Thiscopolymer can be transferred to polyethylene graft copolymers using graft-from technique from the site of benzyl groups. In this paper,copolymerization of ethylene with three kinds of ω-p-methylphenyl-α-olefins,p-methylphenyl-1-propylene （ AC3 ）, 4-p-methylphenyl-l-butene （ BC4 ） and 6-p-methylphenyl-1-hexene （ HC6 ） using Et （Ind）2 ZrCI2/MAO as a catalyst was performed in order to compare the copolymerization abilities of the three reactive comonomers. Three comonomers were synthesized by the coupling reactions between benzyl or aryl metal （magnesium or lithium） and alkenyl halide. The comonomers were purified to get the polymerization grade. Ethylene/reactivecomonomer copolymerization was carried out under 1.01 × 10^5 Pa of ethylene with variations of the comonomer quality in the feed. The copolymers were characterized with ^1H-NMR, ^13 C-NMR, GPC and DSC. With the feed of comonomers the catalyst activity increased, reached a maximum value and then decreased. Under the same concentration of comonomers,the highest catalyst activity occurred in the BC4 system. The content of comonomer in copolymers increased with the comonomer in the feed. Under the same concentration of comonomers,the content ofcomonomer in copolymers could be used to compare the copolymerization ability of the comonomers. The examination results showed that the best copolymerization ability came from BC4. With the increase of the content of comonomer in copolymers, the melting point o

关 键 词：聚乙烯 对甲苯基烯烃 共聚合 茂金属 功能化 

分 类 号：O631.5[理学—高分子化学]