Extension of Living Radical Polymerization Accompanied by Phase Separation to Methacrylate- and Acrylamide-based Polymer Monoliths

Abstract

Rigid methacrylate-based and acrylamide-based polymer monoliths with well-defined macropores have been synthesized from different monomers by organotellurium-mediated living radical polymerization (TERP) accompanied by phase separation. Glycerol 1,3-dimethacrylate (GDMA), trimethylolpropane trimethacrylate (Trim), and N,N-methylenebis(acrylamide) (BIS) were used as monomers. In each system, poly(ethylene oxide) (PEO) effectively induced spinodal decomposition with the progress of polymerization. The resultant polymer monoliths possessed macropores with narrow size distributions and the macropore size can be controlled simply by varying the amount of PEO. Starting from GDMA and BIS, polymer monoliths with unimodal macropores can be obtained due to the collapse of micro- and mesopores, which were originally embedded in macropore skeletons, by large shrinkage during drying. In contrast, starting from Trim, the obtained polymer monoliths included not only macropores but also micro- and mesopores, which led to high specific surface area (470 m2 g−1), owing to the higher crosslinking density.