超支化极性官能团化烯烃齐聚物的合成及表征  

Synthesis and Characterization of Hyperbranched Polar Functionalized Olefin Oligomers

作　　者：严正鹏 李帅康 代胜瑜 YAN Zheng-peng;LI Shuai-kang;DAI Sheng-yu(Institutes of Physical Science and Information Technology, Anhui University, Hefei 230601, China)

机构地区：[1]安徽大学物质科学与信息技术研究院,安徽合肥230601

出　　处：《合成化学》2021年第12期1033-1044,共12页Chinese Journal of Synthetic Chemistry

基　　金：国家自然科学基金资助项目(51703215)。

摘　　要：设计、合成并表征了2种不同烷基链长取代的大位阻二芳基甲基吡啶亚胺配体及其相应的钯配合物。这些钯催化剂在乙烯与丙烯齐聚中表现出高活性(1.6×10^(5) g·mol^(-1)h^(-1)),反应能够生成低分子量的超支化(BD=112~238/1000C)乙烯与丙烯齐聚物(M_(HNMR)=258~478 g·mol^(-1))。最为重要的是,通过利用这些吡啶亚胺钯催化剂催化乙烯或丙烯与丙烯酸甲酯共齐聚,能够得到超支化高插入率(24.3 mol%)的极性官能团化的乙烯与丙烯齐聚物。这些极性官能团位于齐聚物支链的末端。这类新型的钯催化剂为解决超支化极性官能团化烯烃齐聚物制备过程中稳定性差和插入率低等问题提供了可能。A series of iminopyridyl ligands and the corresponding Pd(II)catalysts containing bulky diarylmethyl substituents with alkyl groups of different lengths were synthesized and characterized.The Pd(II)catalysts possessing high catalytic activities(up to 1.6×10^(5) g mol^(-1) h^(-1)),are capable of producing hyperbranched(BD=112~238/1000C)ethylene and propylene oligomers(M_(HNMR)=258~478 g mol^(-1))in ethylene and propylene oligomerization.Most interestingly,hyperbranched(BD=117~215/1000C)polar functionalized ethylene and propylene oligomers(M_(HNMR)=317~392 g mol^(-1))with high incorporations(up to 24.3 mol%)can be accessible from ethylene-MA and propylene-MA co-oligomerization by using the iminopyridyl Pd(II)catalysts.The polar functionalized groups are located at the end of the oligomer branches.These new Pd(II)catalysts provide the possibility to solve the problems of poor stability and low insertion rate in the preparation of hyperbranched polar functionalized olefin oligomers.

关 键 词：吡啶亚胺配体 钯催化剂 超支化齐聚物 官能团化 合成 表征 

分 类 号：O62[理学—有机化学] O63[理学—化学]