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

Abstract

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 °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 (∼90%) was achieved in 2 min. ¹H 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 ¹H NMR and FT-IR analysis.