大位阻骨架策略在α-二亚胺镍钯烯烃聚合催化剂中的应用  

Bulky Backbone Strategy in α-Diimine Nickel and Palladium Catalyzed-Olefin Polymerization

作　　者：郑涵斗 高恒 杜诚 王凌志 钟柳 高海洋 伍青 ZHENG Han-dou;GAO Heng;DU Cheng;WANG Ling-zhi;ZHONG Liu;GAO Hai-yang;WU Qing(School of Materials Science and Engineering,Sun Yat-sen University,Guangzhou 510275,China)

机构地区：[1]中山大学材料科学与工程学院,广州510275

出　　处：《高分子通报》2021年第6期81-93,共13页Polymer Bulletin

基　　金：国家自然科学基金项目(51873234,21674130);广东省基础和应用基础重点项目(2019B1515120063)。

摘　　要：后过渡金属α-二亚胺镍钯聚合催化剂由于其单中心、高活性以及良好的极性基团容忍性,能够直接催化乙烯和极性单体共聚而引起广泛的关注。但此类催化剂的热稳定性差,远未达到工业上气相聚合生产对高温的要求,限制了其进一步的产业化应用。先前报道的提高催化剂热稳定性的策略主要集中在苯胺的邻位位阻修饰上。不同于先前的策略,本课题组采用增加骨架位阻的策略,也能够有效提高催化剂的热稳定性和聚合的可控性。本文主要介绍了本课题组近期大位阻骨架策略在α-二亚胺镍钯烯烃聚合催化剂中的应用,包括乙烯聚合、α-烯烃聚合、乙烯和极性单体共聚、苯乙烯类单体聚合以及一氧化碳和苯乙烯的交替共聚。Late transition metal catalysts, especially α-diimine nickel and palladium catalysts, have received intensive attention because of their unique catalytic properties including single active center, high activity, and outstanding tolerance toward polar groups that allow for direct copolymerization of ethylene and polar monomers. However, this kind of catalysts often show poor thermal stability and being unsuitable for many industrial synthetic processes that usually operate at high temperatures. Previously, the reported strategy to enhance the stability of α-diimine nickel and palladium catalysts mainly focused on the modifications of the N-aryl substituents. We provided an alternative approach by increasing the steric bulk of the α-diimine ligand backbone for effectively enhancing the thermal stability of catalysts and the controllability of polymerization. These advances in the bulky backbones strategy for α-diimine nickel and palladium catalysts toward olefin polymerization are summarized herein, including ethylene polymerization, α-olefin polymerization, copolymerization of ethylene and polar monomers, polymerization of styrene-based monomers and styrene/CO alternating copolymerization.

关 键 词：催化剂 位阻效应 热稳定性 活性聚合 

分 类 号：TQ426[化学工程] TQ325.1