TY - JOUR A1 - Debsharma, Tapas A1 - Behrendt, Felix Nicolas A1 - Laschewsky, Andre A1 - Schlaad, Helmut T1 - Ring-opening metathesis polymerization of biomass-derived levoglucosenol JF - Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker N2 - The readily available cellulose-derived bicyclic compound levoglucosenol was polymerized through ring-opening metathesis polymerization (ROMP) to yield polylevoglucosenol as a novel type of biomass-derived thermoplastic polyacetal, which, unlike polysaccharides, contains cyclic as well as linear segments in its main chain. High-molar-mass polyacetals with apparent weight-average molar masses of up to 100kgmol(-1) and dispersities of approximately 2 were produced despite the non-living/controlled character of the polymerization due to irreversible deactivation or termination of the catalyst/active chain ends. The resulting highly functionalized polyacetals are glassy in bulk with a glass transition temperature of around 100 degrees C. In analogy to polysaccharides, polylevoglucosenol degrades slowly in an acidic environment. KW - degradable polymers KW - metathesis KW - ring-opening polymerization KW - sustainable chemistry KW - thermoplastics Y1 - 2019 U6 - https://doi.org/10.1002/anie.201814501 SN - 1433-7851 SN - 1521-3773 VL - 58 IS - 20 SP - 6718 EP - 6721 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Kaya, Kerem A1 - Debsharma, Tapas A1 - Schlaad, Helmut A1 - Yagci, Yusuf T1 - Cellulose-based polyacetals by direct and sensitized photocationic ring-opening polymerization of levoglucosenyl methyl ether JF - Polymer Chemistry N2 - This study aims to explore the photoinitiated cationic ring-opening polymerization of levoglucosenyl methyl ether (LGME), a chemical obtained from the most abundant biomass - cellulose. Direct and sensitized photopolymerizations of LGME using photoinitiators acting at the near UV or visible range in conjunction with diphenyliodonium hexafluoroantimonate (DPI) yielded unsaturated polyacetals with varying molar masses and distributions. Y1 - 2020 U6 - https://doi.org/10.1039/d0py01307b SN - 1759-9954 SN - 1759-9962 VL - 11 IS - 43 SP - 6884 EP - 6889 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Debsharma, Tapas A1 - Schmidt, Bernd A1 - Laschewsky, Andre A1 - Schlaad, Helmut T1 - Ring-opening metathesis polymerization of unsaturated carbohydrate derivatives BT - levoglucosenyl alkyl ethers JF - Macromolecules : a publication of the American Chemical Society N2 - A 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 similar to 100 exhibit Schulz-Flory-type molar mass distributions and are thermoplastic materials with rather low glass transition temperatures in the range of 43-0 degrees 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. Y1 - 2021 U6 - https://doi.org/10.1021/acs.macromol.0c02821 SN - 0024-9297 SN - 1520-5835 VL - 54 IS - 6 SP - 2720 EP - 2728 PB - American Chemical Society CY - Washington ER -