Synthesis of clickable hydrogels and linear polymers by type II photoinitiation

A facile synthesis method for the preparation of clickable hydrogels and linear polymers is described. The strategy pertains to the photochemical generation of initiating radicals by hydrogen abstraction of excited camphorquinone from acetylenic alcohol followed by free radical polymerization. For hydrogels, poly(ethylene glycol) methyl ether methacrylate and poly(ethylene glycol) diacrylate were used in the system as monomer and crosslinker, respectively. Fluorescent pyrene groups were anchored onto the hydrogels through copper-catalyzed Huisgen 1,3-dipolar azide/alkyne click reaction by using 2-azidomethyl pyrene as evidenced by Fourier transform infrared and fluorescence spectroscopy. The applicability of the method for macromolecular synthesis is also demonstrated. For this purpose, poly(methyl methacrylate) with alkyne terminal groups was prepared by photoinitiated free radical polymerization of methyl methacrylate using camphorquinone and 3-(trimethylsilyl)propargyl alcohol as sensitizer and hydrogen donor, respectively. After deprotection, the click reaction with azido polystyrene obtained by atom transfer radical polymerization followed by azidation resulted in the formation of polystyrene-b-poly(methyl methacrylate). The intermediates at various stages and the final block copolymer were characterized by spectral analysis and gel permeation chromatography. (c) 2014 Society of Chemical Industry