M. Seno, Tomoya Fukui, Tsuneyuki Sato
Feb 1, 2001
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Journal
Macromolecular Chemistry and Physics
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 (R p ) 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 k p values (1.8-7.9 L/mos) are much lower than those of usual methacrylate monomers. The rate constant (k t ) of termination was determined to be k t = 1.0-2.7 10 4 L/mo.s from decay curve of the propagating radical. The Arrhenius plots of k p and k t gave the activation energies of propagaton (63 kJ/mol) and termination (24 kJ/mol). A significant solvent effect was observed on the radial polymerization of 1. The copolymerizations of 1 with styrene(St) and acrylonitrile were examined at 50°C. Copolymerization parameters obtained for the 1(M t )/S t (M 2 ) system are as follows; r 1 = 0.73, r 2 = 0.57, Q 1 = 0.83, and e 1 = 0.13.