Insertion Homo‐ and Copolymerization of Diallyl Ether

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.