Tailor-made polymethacrylate bearing bicyclo-alkenyl functionality via selective ATRP at ambient temperature and its post-polymerization modification by 'thiol-ene' reaction

This investigation reports a facile synthetic route for the preparation of tailor-made polymers bearing reactive pendant bicyclo-alkenyl functionality via selective atom transfer radical polymerization at ambient temperature (AT-ATRP). In this case dicyclopentenyloxyethyl methacrylate (DCPMA) was polymerized at ambient temperature (30 degrees C) using CuBr or CuCl as the catalyst in combination with different ligands, such as N,N,N',N '',N ''-pentamethyldiethylenetriamine (PMDETA) and 4,4'-di(5-nonyl)-2,2'-bipyridine (dNbpy). The polymerization was very fast and very high conversion (similar to 90%) was achieved in 2 min. H-1 NMR and MALDI-TOF-MS analysis confirmed the presence of a bicyclic alkenyl pendant group in the polymer prepared by ATRP. This alkenyl functionality was successfully modified by the 'thiol-ene' reaction, as evidenced by H-1 NMR and FT-IR analysis.