Kay Christopher J, Goring Paul D, Burnett Connah A, Hornby Ben, Lewtas Kenneth, Morris Shaun, Morton Colin, McNally Tony, Theaker Giles W, Waterson Carl, Wright Peter M, Scott Peter
Department of Chemistry , University of Warwick , Coventry CV4 7AL , U.K.
Infineum UK Ltd , Milton Hill , Abingdon OX13 6BB , U.K.
J Am Chem Soc. 2018 Oct 24;140(42):13921-13934. doi: 10.1021/jacs.8b09039. Epub 2018 Oct 12.
A new metallocene-based polymerization mechanism is elucidated in which a zirconium hydride center inserts α-methylstyrene at the start of a polymer chain. The hydride is then regenerated by hydrogenation to release a polyolefin containing a single terminal α-methylstyrenyl group. Through the use of the difunctional monomer 1,3-diisopropenylbenzene, this catalytic hydride insertion polymerization is applied to the production of linear polyethylene and ethylene-hexene copolymers containing an isopropenylbenzene end group. Conducting simple radical polymerizations in the presence of this new type of macromonomer leads to diblock copolymers containing a polyolefin attached to an acrylate, methacrylate, vinyl ester, or styrenic segments. The new materials are readily available and exhibit interfacial phenomena, including the mediation of the mixing of immiscible polymer blends.
阐明了一种基于茂金属的新型聚合机理，其中氢化锆中心在聚合物链起始处插入α-甲基苯乙烯。然后通过氢化使氢化物再生，以释放出含有单个末端α-甲基苯乙烯基的聚烯烃。通过使用双官能单体1,3-二异丙烯基苯，这种催化氢化物插入聚合反应被应用于制备含有异丙烯基苯端基的线性聚乙烯和乙烯-己烯共聚物。在这种新型大分子单体存在下进行简单的自由基聚合反应，可得到含有连接到丙烯酸酯、甲基丙烯酸酯、乙烯基酯或苯乙烯链段上的聚烯烃的二嵌段共聚物。这些新材料易于制备，并表现出界面现象，包括介导不相容聚合物共混物的混合。
