Proton-Transfer Polymerization by N-Heterocyclic Carbenes: Monomer and Catalyst Scopes and Mechanism for Converting Dimethacrylates into Unsaturated Polyesters

Journal of the American Chemical Society
Miao HongEugene Y-X Chen

Abstract

This contribution presents a full account of experimental and theoretical/computational investigations into the N-heterocyclic carbene (NHC)-catalyzed proton-transfer polymerization (HTP) that converts common dimethacrylates (DMAs) containing no protic groups into unsaturated polyesters. This new HTP proceeds through the step-growth propagation cycles via enamine intermediates, consisting of the proposed conjugate addition-proton transfer-NHC release fundamental steps. This study examines the monomer and catalyst scopes as well as the fundamental steps involved in the overall HTP mechanism. DMAs having six different types of linkages connecting the two methacrylates have been polymerized into the corresponding unsaturated polyesters. The most intriguing unsaturated polyester of the series is that based on the biomass-derived furfuryl dimethacrylate, which showed a unique self-curing ability. Four MeO- and Cl-substituted TPT (1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene) derivatives as methanol insertion products, (Rx)TPT(MeO/H) (R = MeO, Cl; x = 2, 3), and two free carbenes (catalysts), (OMe2)TPT and (OMe3)TPT, have been synthesized, while (OMe2)TPT(MeO/H) and (OMe2)TPT have also been structurally characterized. The s...Continue Reading

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Citations

Jul 15, 2016·Chemical Communications : Chem Comm·Camille Bakkali-HassaniDaniel Taton
Jul 26, 2017·Philosophical Transactions. Series A, Mathematical, Physical, and Engineering Sciences·Ravikumar R Gowda, Eugene Y-X Chen
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Apr 3, 2019·Chemical Reviews·Christene A SmithCathleen M Crudden
Oct 24, 2018·Chemical Reviews·Miao HongEugene Y-X Chen

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