Novel copolymers of N-(4-bromophenyl)-2-methacrylamide with glycidyl methacrylate: Synthesis, characterization, monomer reactivity ratios and thermal properties

The acrylamide monomer, N-(4-bromophenyl)-2-methacrylamide (BrPMAAm) has been synthesized by reacting 4-bromoaniline with methacryloyl chloride in the presence of triethylamine(NR3) at 0-5 °C. Copolymers of N-(4-bromophenyl)-2-methacrylamide (BrPMAAm), with glycidyl methacrylate (GMA) were synthesized in 1,4-dioxane solution at 70 ± 1 °C using 2,2′-azobisisobutyronitrile (AIBN) as an initiator with different monomer-to-monomer ratios in the feed. The copolymers were characterized by FTIR, 1H-and 13C NMR spectroscopy. The copolymer composition was evaluated by nitrogen content (N for BrPMAAm-units) in polymers led to the determination of reactivity ratios. The monomer reactivity ratios for BrPMAAm (M1)-GMA (M2) pair were determined by the application of conventional linearization methods such as Fineman-Ross (r1 = 0.2893; r2 = 0.7114), Kelen-Tüdös (r1 = 0.3361; r2 = 0.8645) and extended Kelen-Tüdös (r1 = 0.3096; r2 = 0.8577) as well as by a non-linear error variables model (EVM) method using a computer program, RREVM (r1 = 0.3453; r2 = 0.8606). The mean sequence lengths determination indicated that the copolymer was statistically in nature. The polydispersity indices of the polymers determined using gel permeation chromatography suggest a strong tendency for chain termination by disproportionation. Thermal decomposition of the polymers occurred in three stages in the temperature range of 100-500 °C and the glass transition temperature (Tg) range of 94-165 °C.