Polymerization of propylene sulphide by the Zn(C2H5)2-H2O catalyst system

Belonovskaja, G. P.; Kuznetsov, Yu. P.; Dolgoplosk, A.; Eskin, V. E.

doi:10.1016/0014-3057(79)90206-4

Cited by 11 publications

(4 citation statements)

References 14 publications

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“…The produced PPS was pure without any thiocarbonate units or other possible linkages, as revealed by the 1 H NMR and 13 C NMR spectra (Figure ). Remarkably, the reaction was highly regioselective that was confirmed by around 96% of head-to-tail diad content in PPS based on the 13 C NMR spectra . Interestingly, propylene sulfide (PS) was detected during the ROP by 1 H NMR spectra (Figure S3) at 120 °C and was completely consumed in the end (Figure S2).…”

Section: Resultsmentioning

confidence: 81%

Poly(thioether)s from Closed-System One-Pot Reaction of Carbonyl Sulfide and Epoxides by Organic Bases

et al. 2019

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The synthesis of poly(thioether), a highly desired sulfur-containing polymer, is still a key challenge. Herein, we report a simple and facile approach to poly(thioether)s by closed-system one-pot reaction of carbonyl sulfide (COS) and epoxides. This route underwent the coupling reaction of COS with epoxides, followed by decarboxylative ring-opening polymerization (ROP) of the generated mixed cyclic thiocarbonates with releasing of CO2 and a little bit of COS. Organic base was used as catalyst and initiator in the two steps, respectively. The oxygen/sulfur exchange reaction was driven by successive regioselective elementary reactions and spontaneous releasing of CO2 (COS), leading to the sulfur atom of COS transferring to poly(thioether)s, which was well demonstrated by DFT studies. This work provides an easy-to-handle, metal-free route to poly(thioether)s bearing diverse structures by using readily available chemicals.

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Section: Resultsmentioning

confidence: 81%

Poly(thioether)s from Closed-System One-Pot Reaction of Carbonyl Sulfide and Epoxides by Organic Bases

et al. 2019

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“…Chain Microstructures of the Poly(thioether)s. The exclusive thioether repeating units of the prepared poly-(thioether)s from the terminal epoxides were revealed by 1 H NMR and 13 C NMR spectra (Figures S6−S12). The resultant PPS (entry 1, Table 1) has around 92% of head-to-tail (H−T) diad content determined by the 13 C NMR spectrum (Figure S6b), 37,38 suggesting a regioselective manner of the process.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Chemoselective Coupling of CS₂ and Epoxides for Producing Poly(thioether)s and COS via Oxygen/Sulfur Atom Exchange

Zhang

2019

Macromolecules

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Utilization of carbon disulfide (CS2), a low-cost and sulfur-rich one-carbon (C1) feedstock, for making sulfur-containing polymers is important for both polymer chemistry and applied environmental science. However, the production of well-defined sulfur-containing polymers from CS2 and epoxides remains a key challenge. Here, we report a robust coupling reaction of CS2 and epoxides for chemoselectively producing poly(thioether)s and carbonyl sulfide (COS) in one pot. The resultant polymer has exclusive thioether units and a thiol (−SH) terminal. This route takes advantage of oxygen/sulfur exchanges through two consecutive reactions, i.e., cycloaddition of CS2 to epoxides and dethiocarboxylative ring-opening polymerization of the generated cyclic dithiocarbonates. The process can be conducted in ambient air with several commercially available organic bases as catalysts (initiators) and extended to a variety of epoxides, yielding COS and diverse poly(thioether)s with tens of grams. This work furnishes an original and practical strategy for utilizing CS2 as a sulfur feedstock in polymer synthesis.

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“…(Figure S7). 14 Notably, the complicated 13 C NMR spectrum is likely due to regioselectivity and stereoregularity of PPS in the copolymer 42,43 . To verify the nature of the copolymer rather than the mixture of two separate homopolymers, we then performed the diffusion‐ordered spectroscopy (DOSY) NMR experiment.…”

Section: Resultsmentioning

confidence: 99%

“…14 Notably, the complicated 13 C NMR spectrum is likely due to regioselectivity and stereoregularity of PPS in the copolymer. 42,43 To verify the nature of the copolymer rather than the mixture of two separate homopolymers, we then performed the diffusion-ordered spectroscopy (DOSY) NMR experiment. As shown in Figure 2B, only a single diffusion coefficient value of 9.48 Â 10 À7 cm 2 s À1 was observed, which confirmed the structure of PES-co-PPS.…”

Section: Resultsmentioning

confidence: 99%

One‐pot, one‐step, and selective terpolymerization of ethylene oxide, propylene oxide, and COS to copoly(thioether)s with tunable thermal properties

Kiriratnikom

Zhang

Cao

et al. 2021

Journal of Polymer Science

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Facile construction of sulfur-rich polymers using readily available raw chemicals is an area aggressively pursued but challenging. Herein we use common feedstocks of ethylene oxide (EO), propylene oxide (PO), and carbonyl sulfide (COS) to synthesize copoly(thioether)s which are traditionally produced from unpleasant and difficult to store episulfides. In this protocol, the EO/COS coupling selectively generates a pure poly(ethylene sulfide) (PES) with melting temperature (T m ) values up to 172 C and high yields up to 98%. The EO/PO/COS terpolymerization leads to the incorporation of soft poly(propylene sulfide) (PPS) and hard PES segments together, affording a random PES-co-PPS copoly(thioether) with the complete consumption of EO and PO. Additionally, by simply varying the EO/PO feeding ratio, the obtained copoly(thioether)s possess tunable thermal properties, T m values in the range of 76-144 C, and excellent solubility. These copolymerizations are conducted in one-pot/one-step at industrially favored reaction temperatures of 100-120 C using catalysts of common organic bases, suggesting a facile and practical manner. Especially, the copoly(thioether) exhibits high refractive indices up to 1.68 owing to its high sulfur content, suggesting a broad application prospect in optical materials.

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Polymerization of propylene sulphide by the Zn(C2H5)2-H2O catalyst system

Cited by 11 publications

References 14 publications

Poly(thioether)s from Closed-System One-Pot Reaction of Carbonyl Sulfide and Epoxides by Organic Bases

Poly(thioether)s from Closed-System One-Pot Reaction of Carbonyl Sulfide and Epoxides by Organic Bases

Chemoselective Coupling of CS₂ and Epoxides for Producing Poly(thioether)s and COS via Oxygen/Sulfur Atom Exchange

One‐pot, one‐step, and selective terpolymerization of ethylene oxide, propylene oxide, and COS to copoly(thioether)s with tunable thermal properties

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Polymerization of propylene sulphide by the Zn(C2H5)2-H2O catalyst system

Cited by 11 publications

References 14 publications

Poly(thioether)s from Closed-System One-Pot Reaction of Carbonyl Sulfide and Epoxides by Organic Bases

Poly(thioether)s from Closed-System One-Pot Reaction of Carbonyl Sulfide and Epoxides by Organic Bases

Chemoselective Coupling of CS2 and Epoxides for Producing Poly(thioether)s and COS via Oxygen/Sulfur Atom Exchange

One‐pot, one‐step, and selective terpolymerization of ethylene oxide, propylene oxide, and COS to copoly(thioether)s with tunable thermal properties

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Chemoselective Coupling of CS₂ and Epoxides for Producing Poly(thioether)s and COS via Oxygen/Sulfur Atom Exchange