Photopolymerization of a high internal phase emulsion (HIPE) containing a polyemrizable ATRP initiator resulted in polyHIPE with ATRP initiator groups on the surface available for polymer grafting reactions. This was initially shown for the grafting of MMA. Further functionalization of the polyHIPE was obtained by the grafting of glycidyl methacrylate (GMA). The macroporous morphology and the up to 800 nm thick grafted pGMA layer was clearly visible in SEM micrographs. Epoxide ring-opening reactions of the epoxide groups with sodium azide yielded near quantitative azidation of the PGMA layer. Under optimized conditions, azide conversions of around 80 % were estimated from IR. Further modification was achieved by Huisgens-type 'click' chemistry with various alkynes, for example amino acids and a fluorescent alkyne. Moreover, amino functional silica microparticles were attached to the PGMA modified pHIPE.
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