Abstract
Novel α-substituted acrylates having various functional groups containing a sulfur atom at the α-position, such as benzyl α-(butylthiomethyl)acrylate, benzyl α-(t-butylthiomethyl)acrylate, benzyl α-(benzylthiomethyl)acrylate, benzyl α-(triphenylmethylthiomethyl)acrylate, ethyl α-(2-thienylmethyl)acrylate, benzyl α-(benzylsulfinylmethyl)acrylate, and benzyl α-(benzylsulfonylmethyl)acrylate, were synthesized, and polymerizability and stereoregularity of the obtained polymers using lithium reagents were investigated. In the anionic polymerization of α-(alkylthiomethyl)acrylates and ethyl α-(2-thienylmethyl)acrylate in toluene, highly isotactic polymers were obtained in good yields. A bulky α-substituent, triphenylmethylthiomethyl group, prevents polymerization. The anionic polymerization of α-(alkylthiomethyl)acrylates in tetrahydrofuran (THF) resulted in low yields and isotacticities, ethyl α-(2-thienylmethyl)acrylate gave an isotactic polymer in a good yield. A side reaction, the elimination of alkylthiolate anion from the propagating end, seems to take place in the polymerization of α-(alkylthiomethyl)acrylates in THF.
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Habaue, S., Shibagaki, T. & Okamoto, Y. Stereospecific Anionic Polymerization of α-(Alkylthiomethyl)acrylates and α-(2-Thienylmethyl)acrylate. Polym J 31, 942–947 (1999). https://doi.org/10.1295/polymj.31.942
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DOI: https://doi.org/10.1295/polymj.31.942
