Copolymerization of 4-cyanophenyl methacrylate with methyl methacrylate: Synthesis, characterization and determination of monomer reactivity ratios

Abstract

A novel methacrylic monomer, 4-cyanophenyl methacrylate (CPM) was synthesized by reacting 4-cyanophenol dissolved in methyl ethyl ketone (MEK) with methacryloyl chloride in the presence of triethylamine as a catalyst. Copolymers of CPM with methyl methacrylate(MMA) at different composition was prepared by free radical solution polymerization at 70 ± 1°C using benzoyl peroxide as initiator. The copolymers were characterized by FT-IR, 1 H-NMR and 13 C-NMR spectroscopic techniques. The solubility of the polymers was tested in various polar and non polar solvents. The molecular weight and polydispersity indices of the copolymers were determined using gel permeation chromatography. The glass transition temperature of the copolymers increases with increase in mole fraction of MMA content. The thermal stability of the copolymer increases with increases in mole fraction of CPM content in the copolymer. The copolymer composition was determined by using 1 H-NMR spectroscopy. The monomer reactivity ratios estimated by the application of linearization methods such as Fineman-Ross (r 1 = 2.524 ± 0.038, r 2 = 0.502 ± 0.015), Kelen-Tudos (r 1 = 2.562 ± 0.173, r 2 = 0.487 ± 0.005) and extended Kelen-Tudos methods (r 1 = 2.735 ± 0.128, r 2 = 0.492 ± 0.002).