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

A novel acrylic monomer, 4-cyanophenyl acrylate (CPA) was synthesized by reacting 4-cyanophenol dissolved in methyl ethyl ketone with acryloyl chloride in the presence of triethylamine as a catalyst. Copolymers of CPA with methyl methacrylate (MMA) at different composition was prepared by free radical solution polymerization at 70 ± 1 °C using benzoyl peroxide as an initiator. The copolymers were characterized by FT-IR, ¹H-NMR and ¹³C-NMR spectroscopic techniques. The solubility tests were checked in various polar and non polar solvents. The molecular weight and polydispersity indices of the copolymers were estimated by using gel permeation chromatography. The glass transition temperature of the copolymers increases with increases MMA content. The thermal stability of the copolymer increases with increases in mole fraction of CPA content in the copolymer. The copolymer composition was determined by using ¹H-NMR spectra. The monomer reactivity ratios determined by the application of linearization methods such Fineman–Ross (r ₁ = 0.535, r ₂ = 0. 0.632), Kelen–Tudos (r ₁ = 0.422, r ₂ = 0.665) and extended Kelen–Tudos methods (r ₁ = 0.506, r ₂ = 0. 0.695).