Abstract
The addition reaction mechanism of thiophenol with styrene was studied as a model of the polyaddition of 1,4-benzenedithiol to 1,4-divinylbenzene. The addition reaction of thiophenol to styrene occurred without a side reaction and an adduct of the anti-Markownikoff’s structure (φSCH2CH2φ) was quantitatively obtained. The kinetic study shows that the rate-determining step of the addition reaction is the chain transfer reaction between thiophenol and β-phenylthiostyryl radical. The substituent effect of the chain transfer reaction was determined on various thiophenols and styrenes. Fairly good linear correlation was obtained for the Hammett plot of logktr to σ+ on both monomers (ρ(ktr(St))=−0.60, ρ(ktr(TP))=+0.64). These results are discussed in detail by comparing with polyaddition.
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Kobayashi, E., Obata, T., Aoshima, S. et al. Polyaddition of Dithiol Compounds to Divinyl Compounds: The Kinetics of the Model Addition Reaction of Thiophenols to Styrenes. Polym J 22, 803–813 (1990). https://doi.org/10.1295/polymj.22.803
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DOI: https://doi.org/10.1295/polymj.22.803