Radical Polymerization and Copolymerization of 12-[(N-Methacryloyl)carbamoyloxy]octadecanoic Acid

Abstract

Radical polymerization of 12‐[(N‐methacryloyl)carbamoyloxy] octadecanoic acid (1) was kinetically and ESR spectroscopically investigated in acetone, using dimethyl 2,2′‐azobisisobutyrate (2) as initiator. The polymerization rate (Rp) is given by Rp = k [2]0.7[1]1.4 at 50°C. Propagating poly(1) radical was observed as a 13‐lines spectrum by ESR under the actual polymerization conditions. The ESR‐determined kp values (1.8–7.9 L/mol·s) are much lower than those of usual methacrylate monomers. The rate constant (kt) of termination was determined to be kt = 1.0–2.7·104 L/mol·s from decay curve of the propagating radical. The Arrhenius plots of kp and kt gave the activation energies of propagation (63 kJ/mol) and termination (24 kJ/mol). A significant solvent effect was observed on the radical polymerization of 1. The copolymerizations of 1 with styrene(St) and acrylonitrile were examined at 50°C. Copolymerization parameters obtained for the 1 (M1)/St (M2) system are as follows; r1 = 0.73, r2 = 0.57, Q1 = 0.83, and e1 = 0.13.

Kinetic and ESR studies on radical polymerization behavior ofN-(2-phenylethoxycarbonyl)methacrylamide

“…Liaw et al studied the radical homo‐ and copolymerizations of such monomers from phenol derivatives and pointed out the low polymerizability of them 2, 3. We reported kinetic and ESR results on the radical polymerization of 12‐[( N ‐methacryloyl)carbamoyloxy]octadecanoic acid (MCOA) as such a monomer where the rate constants of propagation ( k p ) and termination ( k t ) of MCOA are much lower than those of methacrylate monomers 5. Such unique behaviors of MCOA may be due to a steric effect of the long sec ‐alkyl group as bulky substituent.…”

“…Methacryloyl isocyanate (MAI) has been successfully used for syntheses of new types of methacryl monomers,1–5 where the isocyanate group of MAI is allowed to react with alcohols, phenols, thiols, and amines. The reaction of MAI with a hydroxylic compound yields a monomer carrying an alkoxycarbonylcarbamoyl group as a new conjugative substituent.…”

Kinetic study of the radical polymerization behavior of N‐(1‐phenylethylaminocarbonyl)methacrylamide

“…Methacryloylisocyanate (MAI) has been satisfactorily employed for syntheses of new types of methacryl monomers, where the isocyanate group of MAI is allowed to easily react with alcohols, phenols, thiols, and amines 1–6. The reaction of MAI with a hydroxylic compound yields a monomer carrying an alkoxycarbonylcarbamoyl group as a conjugative substituent involving urethane moiety.…”