In Situ Kinetics Reveal the Influence of Solvents and Monomer Structure on the Anionic Ring‐Opening Copolymerization of Epoxides

Abstract In‐depth understanding of copolymerization kinetics and the resulting polymer microstructure is crucial for design materials with well‐defined properties. Further, insights regarding impact solvents on allows precisely tuned materials. In this regard, in situ 1 H NMR spectroscopy enables precise monitoring living anionic ring‐opening (AROP) ethylene oxide (EO) glycidyl ethers allyl ether (AGE) ethoxy vinyl (EVGE), respectively. Determination reactivity ratios reveals slightly higher both compared to EO, emphasizing a pronounced counterion chelation effect by AROP. Implementation density functional theory (DFT) calculations further illustrates complexation capability ether‐containing side groups ethers, analogy crown (“crown effect”). Investigation i) THF‐ d 8 ii) DMSO‐ 6 shows an increasing disparity clearly related decreasing solvent polarity.