Chair of Chemical Materials Science, Department of Chemistry, University of Konstanz, Universitätsstrasse 10, 78457 Konstanz (Germany).
Angew Chem Int Ed Engl. 2015 Dec 21;54(52):15845-9. doi: 10.1002/anie.201508930. Epub 2015 Nov 13.
The previously unresolved issue of polymerization of allyl monomers CH2 CHCH2 X is overcome by a palladium-catalyzed insertion polymerization of diallyl ether as a monomer. An enhanced 2,1-insertion of diallyl ether as compared to mono-allyl ether retards the formation of an unreactive five-membered cyclic O-chelate (after 1,2-insertion) that otherwise hinders further polymerization, and also enhances incorporation in ethylene polymers (20.4 mol %). Cyclic ether repeat units are formed selectively (96 %-99 %) by an intramolecular insertion of the second allyl moiety of the monomer. These features even enable a homopolymerization to yield polymers (poly-diallyl ether) with degrees of polymerization of DPn ≈44.
先前未解决的烯丙基单体 CH2 CHCH2 X 聚合问题通过钯催化的二烯丙基醚作为单体的插入聚合得到克服。与单烯丙基醚相比，二烯丙基醚的增强的 2,1-插入会延迟形成无反应性的五元环 O-螯合物（在 1,2-插入之后），否则会阻碍进一步聚合，并且还会增强在乙烯聚合物中的掺入（20.4 mol%）。环状醚重复单元通过单体的第二个烯丙基部分的分子内插入选择性地形成（96%-99%）。这些特点甚至可以实现均聚合，从而得到聚合度 DPn ≈44 的聚合物（聚二烯丙基醚）。
