Ring-opening metathesis polymerization of unsaturated carbohydrate derivatives
- 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 thatA 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.…
Author details: | Tapas DebsharmaORCiDGND, Bernd SchmidtORCiDGND, Andre LaschewskyORCiDGND, Helmut SchlaadORCiDGND |
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DOI: | https://doi.org/10.1021/acs.macromol.0c02821 |
ISSN: | 0024-9297 |
ISSN: | 1520-5835 |
Title of parent work (English): | Macromolecules : a publication of the American Chemical Society |
Subtitle (English): | levoglucosenyl alkyl ethers |
Publisher: | American Chemical Society |
Place of publishing: | Washington |
Publication type: | Article |
Language: | English |
Date of first publication: | 2021/03/12 |
Publication year: | 2021 |
Release date: | 2023/11/10 |
Volume: | 54 |
Issue: | 6 |
Number of pages: | 9 |
First page: | 2720 |
Last Page: | 2728 |
Funding institution: | University of Potsdam |
Organizational units: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie |
DDC classification: | 5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften |
Peer review: | Referiert |
Publishing method: | Open Access |