Abstract
Radical polymerizations of vinyl monomer in which vinyl group directly bind to a tetraphenyl porphyrin (TPP) moiety, 5-(4-vinylphenyl)-10,15,20-triphenylporphyrin (VTPP), were investigated. Homopolymerization occurred and high-molecular weight polymers (M̅w>100000) were obtained. Copolymerizations of VTPP (M1) and styrene (M2) were performed with 2,2′-azobis(isobutyronitrile) (AIBN) at 60°C. Monomer reactivity ratios were r1=0.65±0.15 and r2=0.51±0.15, Q and e for VTPP being 0.85 and 0.24, respectively. These values suggest a slightly distorted structure of propagating radicals. Rate constant of the addition of diphenyl phosphinoyl radicals (Ph2Ṗ=O), generated by the photolysis of 2,4,6-trimethylbenzoyl di-phenylphosphine oxide (TMDPO), to VTPP was directly determined by time-resolved electron spin resonance (ESR) spectroscopy. The rate constant ∼14×106 s−1M−1, was one order of magnitude smaller than that of styrene (∼1.1×107 s−1M−1), due to decrease of resonance stabilization caused from a steric hindrance of TPP moiety.
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Kajiwara, A., Aramata, K., Kamachi, M. et al. Radical Polymerization of 5-(4-Vinylphenyl)-10,15,20-triphenyl Porphyrin. Polym J 26, 215–223 (1994). https://doi.org/10.1295/polymj.26.215
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DOI: https://doi.org/10.1295/polymj.26.215