AbstractThe acrylic monomer, 4‐cyanophenyl acrylate (CPA), was synthesized by reacting 4‐cyanophenol dissolved in methyl ethyl ketone (MEK) with acryloyl chloride in the presence of triethylamine as a catalyst. The homopolymer and copolymers were synthesized by using free‐radical techniques. Characterization by FTIR, 1H NMR, and 13C NMR spectroscopic analysis confirms the chemical structure. The solubility of the polymers was tested in various polar and nonpolar solvents. The polydispersity index values of polymers suggest a strong tendency for chain termination by disproportionation in all cases, and the tendency increases with the increasing GMA content in the feed. The initial decomposition temperatures for poly(GMA) (188°C), poly(CPA‐co‐GMA) (280°C), and poly(CPA) (290°C) reveal that the thermal stability of the copolymer increases with an increase in CPA content. DSC analysis showed Tg for poly(CPA) (25°C), poly(GMA) (74°C), and copolymer (0.4007 : 0.5993) (39°C) indicates that Tg of the copolymers decreases with the increase in CPA content. The copolymer composition was determined using 1H NMR spectra. The monomer reactivity ratios were determined by the application of linearization methods such as Fineman‐Ross (r1 = 0.5806, r2 = 0.6651), Kelen‐Tudos (r1 = 0.5442, r2 = 0.6472), and extended Kelen‐Tudos methods (r1 = 0.5372, r2 = 0.6352). The reactivity ratio values indicate that the copolymerization has a tendency to alternation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008