Controlled Insertion Reaction of Thiirane into Carbamothioate: Novel Synthesis of Well-Defined Polysulfide

Abstract

The insertion reaction of propylene sulfide (PS) into p-tolylcarbamothioate (PTCT) was examined in the presence of tetrabutylammonium chloride (TBAC) in 1-methyl-2-pyrrolidinone at 60 °C in the feed ratio of PTCT/PS = 1/1−1/40, affording the corresponding polysulfides in satisfactory yields. It was found that the molecular weights (M n′s) coincided with the feed ratios PS and molecular dispersity ratios (M w/M n) were very narrow (M w/M n <1.10). i.e., this insertion reaction could be performed under the living system. Furthermore, the insertion living reaction of PS using tricarbamothioate was examined to give the controlled three-arms star-shaped polysulfides.

New Polymeric Materials Based on Element-Blocks

“…These data are explained by three issues. First, similarly to Nishikubo's reports, 44 the fragment density of polysulfides could be enhanced by the connection with POSS. Second, because of the strong hydrophobicity of the silica cube, there is possible to generate strong interaction between the POSS units and the polymer chains.…”

Transformation of sulfur to organic-inorganic hybrids employed by networks and their application for the modulation of refractive indices

“…Without adding the heavy atoms involving sulfur element or aromatic compounds which can efficiently elevate the refractive indices of matrices, it is possible to increase the refractive indices of materials. Nishikubo et al reported the significant enhancement of refractive indices of polymeric materials by modulating the polymer morphology . They prepared the sulfur element‐containing polymers with or without connection of the end of polymer chains.…”

“…In addition, the molecular motions of polymer chains should be efficiently suppressed. These effects are favorable for increasing the refractive indices of polymers …”

“…Nishikubo et al reported the significant enhancement of refractive indices of polymeric materials by modulating the polymer morphology. [28][29][30] They prepared the sulfur element-containing polymers with or without connection of the end of polymer chains. Accordingly, from the series of the refractive index measurements with the polymeric samples with the same sulfur contents, they found that the dendritic polymers showed the highest refractive indices of the samples.…”

Protected thiol strategies in macromolecular design

“…Thiiranes can be polymerized in a controlled fashion, as demonstrated by Nishikubo and coworkers [257] who presented a living system for the synthesis of well-defined polysulfides.…”