|538. Dreier, Ph.; Matthes, R.; Barent, R.D.; Schüttner, S.; Müller, A.H.E.; Frey, H.: In Situ Kinetics Reveal the Influence of Solvents and Monomer Structure on the Anionic Ring-Opening Copolymerization of Epoxides, , 202200209 (2022) -- DOI: 10.1002/macp.202200209|
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 revealed 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 showed an increasing disparity of reactivity ratios for both glycidyl ethers compared to EO, clearly related to decreasing solvent polarity.