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Living Ring-Expansion Polymerization of Thiirane with Cyclic Monocarbamothioates

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journal contribution
posted on 08.06.2020, 20:04 authored by Hiroto Kudo, Kazunori Naritomi, Shuto Onishi, Hiroyuki Maekawa, Evan A. Q. Mondarte, Kasinan Suthiwanich, Tomohiro Hayashi
We synthesized two kinds of monocarbamothioates TZO­(R) containing a thiazolidin-2-one (TZO) skeleton and TZD­(R) containing a thiazolidine-2,4-dione (TZD) skeleton. In the reaction of TZO­(R) and phenoxypropyrenesulfide (PPS) using tetrabutylammonium chloride (TBAC) as a catalyst in 1-methyl-2-pyrrolidinone at 60 °C, anionic ring-opening polymerization of PPS proceeded to give the corresponding linear polysulfides, polyPPS, with Mn = 75 860–206 700 (Mw/Mn = 1.54–1.73) in high yield. In contrast, in the reaction of TZD­(R) and PPS, the continuous insertion reaction of PPS into TZD­(R), i.e., living ring-expansion polymerization, occurred to afford cyclic polysulfides TZD­(R)-c-poly­(PPS)n with Mn = 1870–33 420 (Mw/Mn = 1.07–1.26) in high yield. The ring size could be controlled by the feed ratio of TZD­(R)/PPS in the range of 1/5–1/100.