Confined polymerization: RATRP of GMA in the bicontinuous PolyHIPE

Controlled free radical polymerization in confined spaces has great potential for obtaining new materials with specific properties and predetermined structures. In this work, polymerized high internal phase emulsion (PolyHIPE) monoliths with bicontinuous structure were synthesized and used as confined reactors for reverse atom transfer radical polymerization (RATRP) of glycidyl methacrylate (GMA). Compared to PGMAs by conventional polymerization, the PGMA obtained in the PolyHIPE exhibits a larger molecular weight, higher glass transition temperature (Tg) and a higher isotactic configuration. The proportion of isotactic configuration in the PGMAs polymerized in the PolyHIPE increased notably, with the highest reaching 65%. All the results exerted evidence for the confining effect of PolyHIPE to the RATRP of GMA. In particular, the PolyHIPE with the largest surface area showed the most significant confining effect. The PGMA obtained within it exhibited the largest molecular weight, the highest isotactic configuration ratio, and the highest Tg.