Polymerization of methacrylates. I. Polymerization reactivity of picryl methacrylate

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.