The case of 4-vinyl-1,3-dioxolane-2-one: determination of its pseudo-living behavior and preparation of allyl carbonate-styrene co-polymers

This article describes for the first time the pseudo-living radical activity of 4-vinyl-1,3-dioxolane-2-one (VEC) monomer towards a free radical homo-polymerization: a kinetic study of VEC homo-polymerization was performed up to 168 hours and it was found that molecular weights, determined via gel permeation chromatography (GPC), and VEC conversion, measured via H-1 NMR spectroscopy, continue to grow over time showing a molecular weights distribution typical of pseudo-living polymerizations. Until today, in co-polymerization with styrene, just a few VEC moieties could be inserted into VEC-styrene co-polymers; in this work VEC controlled radical activity allows, for the first time, the synthesis of di-block co-polymers between styrene and vinyl groups bearing cyclic carbonate functionalities that can be used for further cross-linking reactions. VEC-styrene copolymers were synthesized with different molar ratios between co-monomers and characterized by GPC analyses and H-1 NMR spectra; excellent reaction yields and solubility in apolar solvents were obtained.