非茂钯催化剂催化乙烯/丙烯/ω-Cl-α-乙烯基单体三元共聚合的研究  

The investigation of terpolymerization of ethylene/propylene/ω-cl-α-vinyl monomers catalyzed by Cat.L-Pd catalyst

作　　者：王帆[1] 石向辉[1,2] 南枫 李红明[1] 王秋璨[1] 于洪超 黄启谷 杨万泰[1] Fan Wang;Xianghui Shi;Feng Nan;Hongming Li;Qiucan Wang;Hongchao Yu;Qigu Huang;Wantai Yang(State Key Laboratory of Chemtcal Resource Engineering, Key Laboratory of Carbon Fiber and Functional Polymers, Ministry of Education, College of Material Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China;State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China)

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材料科学与工程学院,北京100029 [2]中国科学院长春应用化学研究所高分子物理与化学国家重点实验室,长春130022

出　　处：《中国科学：化学》2018年第6期609-619,共11页SCIENTIA SINICA Chimica

基　　金：国家自然科学基金(编号:U1462102)资助项目

摘　　要：本文探索了乙烯/丙烯/极性单体三元共聚物的合成方法.乙烯/丙烯/ω-Cl-α-乙烯基单体三元共聚物由于分子中引入了ω-Cl-α-乙烯基极性单体,改变了乙烯丙烯共聚物的化学惰性.我们采用催化剂Cat.L-Pd配位催化乙烯/丙烯/ω-Cl-α-乙烯基单体三元共聚合,合成了极性三元无规共聚物.探讨了催化剂结构、聚合条件对三元共聚合行为的影响,并优化了聚合条件.采用红外光谱(FTIR)、核磁共振碳谱(氢谱)(^(13)C(~1H)NMR)、示差扫描量热(DSC)和高温凝胶渗透色谱(GPC)等方法研究了共聚物的结构与性能.FTIR与^(13)C(~1H)NMR结果表明,催化剂Cat.L-Pd能够有效催化乙烯/丙烯/ω-Cl-α-乙烯基单体三元共聚合,共聚物中ω-氯代极性单体的插入量达3.6 mol%.极性单体不发生均聚合反应,但能够有效参与乙烯和丙烯的共聚合反应,形成三元无规共聚物.丙烯能够发生均聚合反应,但是不能形成聚丙烯长链段,主要发生乙烯与丙烯共聚合反应.乙烯最易发生聚合反应,并能够形成较长链段的聚乙烯.共聚物的Mw高于2×10~5g/mol.分子量分布在1.6～3.0,说明该类催化剂催化乙烯/丙烯/ω-Cl-α-乙烯基单体三元共聚合行为遵循单中心聚合机理.We investigated the terpolymerization of ethylene/propylene/ω-Cl-α-vinyl monomers to obtain polar terpolymers by non-metallocene catalyst Cat.L-Pd through coordination polymerization directly. The functional ω-Cl-α-vinyl monomer inserted into the polymeric molecules changed the properties of the obtained polymers. The optimum catalyst Cat.L-Pd and polymerization conditions were optimized for the terpolymerization. The structure and properties of the terpolymers were characterized by FTIR,^13C（^1H）NMR, DSC and GPC. The optimum incorporation content of11-chloro-1-undecylene within the terpolymer chains is up to 3.58 mol%. The polar monomers did not carry out the homopolymerization itself, but efficiently joined the terpolymerization with ethylene and propylene. Propylene monomer was in favor of the copolymerization with ethylene beside its homopolymerization. But polypropylene segments were not observed within the terpolymer chains. Compared to the polar monomers and propylene, ethylene was the most efficient monomer for joining the terpolymerization of ethylene/propylene/ω-Cl-α-vinyl monomers, and longer segments of polyethylene were produced within the terpolymer chains. Mwup to 2×10^5 g/mol of the terpolymers was obtained by the catalyst system. The terpolymer molecular weight distribution（MWD） was about 2 to 3, implying the terpolymerization behavior followed the single-site mechanism.

关 键 词：非茂钯催化剂 乙烯 丙烯 极性单体 三元共聚合 

分 类 号：O631.5[理学—高分子化学]