Effects of Illuminance and Heat Rays on Photo-Controlled/Living Radical Polymerization Mediated by 4-Methoxy-2,2,6,6-Tetramethylpiperidine-1-Oxyl

Abstract

The effects of illuminance and heat rays released from the light source on the photo-controlled/living radical polymerization of methyl methacrylate were investigated with the aim of strict control of molecular weight. The bulk polymerization was performed at room temperature using 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl as the mediator and (2RS,RS)-azobis(4-methoxy-2,4-dimethylvaleronitrile) as the initiator in the presence of (4-tert-butylphenyl)diphenylsulfonium triflate as the accelerator by irradiation with a high-pressure mercury lamp. The polymerization by the direct irradiation from the light source yielded polymers containing an uncontrolled high-molecular-weight polymer and having the molecular weight distribution over 3. On the other hand, the polymerization by the indirect irradiation with reflective light using a mirror produced polymers with controlled molecular weights with comparatively narrow molecular weight distribution at ca. 1.4. Too high an illuminance caused an increase in the molecular weight distribution. During the polymerization, the monomer conversion increased as the illuminance increased. It was found that the elimination of heat rays from the illuminating light was indispensable for the molecular weight control by the photo-controlled/living radical polymerization.