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Hendrik K.-H. Volz, Seema Agarwal

Macromolecular Chemistry and Physics, 2026, https://doi.org/10.1002/macp.202500366

In free radical ring-opening copolymerization of cyclic ketene acetals (CKA) with vinyl monomers, a major challenge is the often-low reactivity of CKAs and thus insufficient ester incorporation and homogeneity. Most workarounds, like semibatch copolymerization, require a considerable change in the system. In this work, we report a method to improve ester incorporation into the backbone and homogeneity of the polymer by using a batch copolymerization in 1,4-dioxane above solvent boiling point. The monomer system of 2-methylene-4-phenyl-1,3-dioxolane (MPDL) and syringyl methacrylate (SM) showed improved copolymerization parameters (r_MPDL = 0.032 and r_SM = 2.464) compared to the polymers obtained at 70°C in anisole. Basic hydrolysis with potassium hydroxide (KOH) in tetrahydrofuran (THF)/methanol (MeOH) was conducted to study structural homogeneity and was compared with semibatch experiments.