Photo-controlled/living radical polymerization of tert-butyl methacrylate in the presence of a photo-acid generator using a nitroxide mediator |
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Authors: | Eri Yoshida |
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Institution: | (1) Department of Environmental and Life Sciences, Toyohashi University of Technology, 1-1 Hibarigaoka, Tempaku-cho, Toyohashi Aichi, 441-8580, Japan |
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Abstract: | The photo-controlled/living radical polymerization of tert-butyl methacrylate was performed using a (2RS,2′RS)-azobis(4-methoxy-2,4-dimethylvaleronitrile) initiator and a 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl
(MTEMPO) mediator in the presence of a (4-tert-butylphenyl)diphenylsulfonium triflate photo-acid generator. The bulk polymerization was carried out at 25 °C by irradiation
with a high-pressure mercury lamp. Whereas the polymerization in the absence of MTEMPO produced a broad molecular weight distribution,
the MTEMPO-mediated polymerization provided a polymer with a comparatively narrow molecular weight distribution around 1.4
without elimination of the tert-butyl groups. The living nature of the polymerization was confirmed on the basis of the linear correlations for the first-order
time–conversion plots and conversion–molecular weight plots in the range below 50% conversion. The block copolymerization
with methyl methacrylate also supported the livingness of the polymerization based on no deactivation of the prepolymer. |
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Keywords: | |
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