Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 54, Issue 52, Pages 15845-15849Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201508930
Keywords
allyl monomer; homogeneous catalysis; insertion; palladium; polymerization
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Funding
- Alexander von Humboldt Foundation
- University of Konstanz within the EU FP7 Marie Curie Zukunftskolleg Incoming Fellowship Programme [291784]
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The previously unresolved issue of polymerization of allyl monomers CH2= CHCH2X 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 approximate to 44.
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