Abstract
o-Benzoquinones initiate radical polymerization of methacrylates under visible light irradiation in the presence of tertiary amines. Spectral sensitivity of the initiating system coincides with absorption bands of o-benzoquinone attributed to the S(π→π*) (λmax ≈ 400 nm) and S(n→π*) (λmax ≈ 600 nm) transitions. The amine radicals (Am·) initiating polymerization are generated by the photoreduction of Q in the presence of AmH from the triplet radical pair 3(QH·, Am·). The yield of Am· depends on the difference between the volumes of substituents in the 3 and 6 positions of the quinoid ring and is maximal for symmetrically substituted o-benzoquinones. For a series of derivatives of symmetrical 3,6-di-tert-butyl-o-benzoquinone, the rate of photopolymerization of α,ω-bis(methacryloyloxyethyleneoxycarbonyloxy)ethyleneoxyethylene (OCM-2) in the presence of N,N-dimethylaniline is determined by the free energy (ΔG e) of electron transfer from the amine to photoexcited o-benzoquinone. The ΔG e value includes the energies of oxidation of the amines and reduction of the o-quinones and the energy of the 0→0 transition of the triplet excited state of o-benzoquinones, which are equal to their redox potentials. The photopolymerization rate is maximal for ΔG e ≈ 0.
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Chesnokov, S.A., Cherkasov, V.K., Abakumov, G.A. et al. Influence of o-benzoquinone nature on initiation of radical polymerization by the o-benzoquinone—tert-amine system. Russian Chemical Bulletin 50, 2366–2371 (2001). https://doi.org/10.1023/A:1015079328446
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DOI: https://doi.org/10.1023/A:1015079328446