Polymerization of methacrylates. I. Polymerization reactivity of picryl methacrylate

Abstract

Abstract The polymerization of picryl (PMA), 2,4‐dinitrophenyl (2,4‐DNMA),2,6‐dinitrophenyl (2,6‐DNMA), 2‐methyl‐4,6‐dinitrophenyl (MDNMA), and 2,6‐dimethylphenyl methacrylates (DMMA) was carried out in benzene at 60°C. PMA, 2,6‐DNMA, and MDNMA did not undergo radical homopolymerization, while 2,4‐DNMA and DMMA did. The results suggest that the growing radical readily attacks the oxygen atom of the nitro group at the 2 position of the terminal phenyl group due to the steric effect of the substituent at the 6 position, resulting in chain termination. PMA formed a charge‐transfer complex with 2‐naphthyl methacrylate (NMA). The stoichiometric composition of this complex was shown to be 1:1 molar complex. PMA was readily copolymerized with NMA. The amount of solvent affected the composition of the copolymer obtained at a given same mole fraction in feed. The results suggest that charge‐transfer interaction between the ester groups affects the copolymerization mechanism.