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Authors: Dreier, Philip
Matthes, Rebecca
Barent, Ramona D.
Schüttner, Sandra
Müller, Axel H. E.
Frey, Holger
Title: In situ kinetics reveal the influence of solvents and monomer structure on the anionic ring-opening copolymerization of epoxides
Online publication date: 30-Jan-2023
Year of first publication: 2022
Language: english
Abstract: In-depth understanding of copolymerization kinetics and the resulting polymer microstructure is crucial for the design of materials with well-defined properties. Further, insights regarding the impact of solvents on copolymerization kinetics allows for precisely tuned materials. In this regard, in situ 1H NMR spectroscopy enables precise monitoring of the living anionic ring-opening copolymerization (AROP) of ethylene oxide (EO) with the glycidyl ethers allyl glycidyl ether (AGE) and ethoxy vinyl glycidyl ether (EVGE), respectively. Determination of reactivity ratios reveals slightly higher reactivity of both glycidyl ethers compared to EO, emphasizing a pronounced counterion chelation effect by glycidyl ethers in AROP. Implementation of density functional theory (DFT) calculations further illustrates the complexation capability of ether-containing side groups in glycidyl ethers, in analogy to crown ethers (“crown ether effect”). Investigation of the copolymerization in i) THF-d8 and ii) DMSO-d6 shows an increasing disparity of reactivity ratios for both glycidyl ethers compared to EO, clearly related to decreasing solvent polarity.
DDC: 540 Chemie
540 Chemistry and allied sciences
Institution: Johannes Gutenberg-Universität Mainz
Department: FB 09 Chemie, Pharmazie u. Geowissensch.
Place: Mainz
Version: Published version
Publication type: Zeitschriftenaufsatz
License: CC BY-NC-ND
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Journal: Macromolecular chemistry and physics
Pages or article number: 2200209
Publisher: Wiley-VCH
Publisher place: Weinheim
Issue date: 2023
ISSN: 1521-3935
Publisher DOI: 10.1002/macp.202200209
Appears in collections:DFG-491381577-H

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