Autoren:	Dreier, Philip Matthes, Rebecca Barent, Ramona D. Schüttner, Sandra Müller, Axel H. E. Frey, Holger
Titel:	In situ kinetics reveal the influence of solvents and monomer structure on the anionic ring-opening copolymerization of epoxides
Online-Publikationsdatum:	30-Jan-2023
Erscheinungsdatum:	2022
Sprache des Dokuments:	Englisch
Zusammenfassung/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-Sachgruppe:	540 Chemie 540 Chemistry and allied sciences
Veröffentlichende Institution:	Johannes Gutenberg-Universität Mainz
Organisationseinheit:	FB 09 Chemie, Pharmazie u. Geowissensch.
Veröffentlichungsort:	Mainz
ROR:	https://ror.org/023b0x485
DOI:	http://doi.org/10.25358/openscience-8699
Version:	Published version
Publikationstyp:	Zeitschriftenaufsatz
Nutzungsrechte:	CC BY-NC-ND
Informationen zu den Nutzungsrechten:	https://creativecommons.org/licenses/by-nc-nd/4.0/
Zeitschrift:	Macromolecular chemistry and physics 224 1
Seitenzahl oder Artikelnummer:	2200209
Verlag:	Wiley-VCH
Verlagsort:	Weinheim
Erscheinungsdatum:	2023
ISSN:	1521-3935
DOI der Originalveröffentlichung:	10.1002/macp.202200209
Enthalten in den Sammlungen:	DFG-491381577-H