Debsharma, TapasTapasDebsharmaSchmidt, BerndBerndSchmidtLaschewsky, AndreAndreLaschewskySchlaad, HelmutHelmutSchlaad2022-03-062022-03-062021https://publica.fraunhofer.de/handle/publica/26661110.1021/acs.macromol.0c02821A series of biomass-derived levoglucosenyl alkyl ethers (alkyl = methyl, ethyl, n-propyl, isopropyl, and n-butyl) were synthesized and polymerized by ring-opening olefin metathesis polymerization using the Grubbs catalyst C793 at room temperature. Polymerizations were successfully performed in conventional solvents such as 1,4-dioxane and dichloromethane as well as in polar aprotic green solvents such as 2-methyltetrahydrofuran, dihydrolevoglucosenone (Cyrene), and ethyl acetate. The prepared polyacetals with degrees of polymerization of ~100 exhibit SchulzFlory-type molar mass distributions and are thermoplastic materials with rather low glass transition temperatures in the range of 430 °C depending on the length of the alkyl substituent. Kinetic studies revealed that the polymerization proceeded rapidly to a steady state with a certain minimum monomer concentration threshold. When the steady state was reached, just about half of the [Ru] catalyst had been effective to initiate the polymerization, indicating that the initiation step was a slow process. The remaining catalyst was still active and did no longer react with monomers but with in-chain double bonds, cutting the formed polymer chains into shorter fragments. In the long term, all catalyst was consumed and propagating [Ru] chain ends were deactivated by the elimination of [Ru] from the chain ends to form inactive chains with terminal aldehyde groups.enbiopolymersthermoplasticsring opening metathesis polymerizationmechanism668547journal article