A New Initiator System for the Living Thiiranes Ring-Opening Polymerization: A Way toward Star-Shaped Polythiiranes

Nicol, Erwan; Bonnans-Plaisance, C.; Lévesque, Guy

doi:10.1021/ma9900434

Cited by 37 publications

(34 citation statements)

References 13 publications

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“…On this basis, we envisioned that the STA/PS copolymerization could proceed smoothly in an anionic manner once triggered by a nucleophilic initiator. Initially, we focused on the copolymerization using DBU (1,8‐diazabicyclo[5.4.0]undec‐7‐ene), an effective initiator for the living episulfide ring‐opening polymerization . With a PS/STA/DBU feed ratio of 1000:250:1 at 25 °C, the copolymerization can proceed with an STA conversion of 30 % within 1 h (Table , entry 1).…”

Section: Methodsmentioning

confidence: 99%

Precise Synthesis of Poly(thioester)s with Diverse Structures by Copolymerization of Cyclic Thioanhydrides and Episulfides Mediated by Organic Ammonium Salts

Yue

Zhang

et al. 2018

Angew Chem Int Ed

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The precise synthesis of poly(thioester)s with diverse structures is still a significant challenge in the polymeric materials field. Herein, we report a novel approach to the synthesis of well‐defined poly(thioester)s by the controlled alternating copolymerization of cyclic thioanhydrides and episulfides induced by simple organic ammonium salts. Both the cation and anion have strong effects on the copolymerization. [PPN]OAc ([PPN]=bis(triphenylphosphine)iminium) with a bulky cation was proven to be efficient in initiating this polymerization, yielding poly(thioester)s with a completely alternating structure, controlled molecular weight, and narrow polydispersity. The poly(thioester) obtained from succinic thioanhydride and propylene sulfide is a typical semicrystalline material, possessing a high refractive index of up to 1.78. Because it uses readily available monomers, this method is expected to open up a new route to poly(thioester)s with diverse structures and properties.

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Section: Methodsmentioning

confidence: 99%

Precise Synthesis of Poly(thioester)s with Diverse Structures by Copolymerization of Cyclic Thioanhydrides and Episulfides Mediated by Organic Ammonium Salts

Yue

Zhang

et al. 2018

Angew Chem Int Ed

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“…S2), and GPC measurement revealed a large M n of 160,000 and a broad M w /M n of 2.36. These results indicate that a typical ringopening polymerization of thiirane occurs, initiated by thiolate anion, [43][44][45][46] which was presumably produced by the nucleophilic attack of chloride anion of TBAC on PPS. On the other hand, the large polymeric product obtained in the above control experiment was not observed in the REP in the presence of BT, indicating that the thiourethane structure based on the BT initiator effectively regulated the polymerization by trapping the thiolate anion intermediate (Intermediate I in Scheme 1) to lead to an acyl-transfer mechanism instead of the intrinsic ring-opening polymerization of thiiranes.…”

Section: Ring-expansion Polymerization Of Ppsmentioning

confidence: 98%

Controlled ring‐expansion polymerization of thiiranes based on cyclic aromatic thiourethane initiator

Takahashi

Yuzaki

Ishida

et al. 2019

J. Polym. Sci. Part A: Polym. Chem.

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Ring‐expansion polymerization (REP) of thiiranes was investigated using 3H‐benzothiazol‐2‐one (BT) as the cyclic aromatic thiourethane initiator in the presence of tetrabutylammonium chloride (TBAC) catalyst. The polymerization proceeded in a well‐controlled manner to afford cyclic polysulfides with one BT moiety per macrocycle, as confirmed by MALDI‐TOF MS spectroscopy. Differential scanning calorimetry (DSC) measurement of the obtained cyclic polysulfides revealed slight decrease in the glass‐transition temperature as the increase in the molecular weight, supporting the cyclic topology of the products. Postpolymerization of thiiranes using the BT‐initiated cyclic polysulfide as the macroinitiator afforded the ring‐expanded product while maintaining the narrow polydispersity and well‐defined cyclic structure, which enabled precise synthesis of cyclic block copolymer with different thiirane combination. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2442–2449

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“…There is an issue, however, regarding the precise identity of the propagating species: Boileau and Sigwalt showed that the PS polymerisation was much accelerated when the thiolates were in the form of free ions rather than ion pairs, or, similarly, when sodium ions were replaced by more bulky tetrabutyl ammonium ions or complexed by cryptating agents 100–102. This finding was later applied by the group of Bonnans‐Plaisance, who utilised bulky organic counterions103, 104 for the polymerisation of a number of functional episulfides, for example, bearing liquid crystalline side chains,105, 106 protected aldehydes107, 108 or comb polymer chains [poly(ethylene glycol); PEG] 109…”

Section: Preparative Strategies For Polysulfidesmentioning

confidence: 99%

Polymers and Sulfur: what are Organic Polysulfides Good For? Preparative Strategies and Biological Applications

Kilcher

Tirelli

2009

Macromol. Rapid Commun.

106

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Sulfur(II)-containing polymers (polysulfides) combine flexible synthetic and processing techniques with a unique responsiveness to oxidants. Here, the polysulfide oxidative sensitivity is put into the biological context of the development of new anti-inflammatory therapies - the development of new anti-inflammatory methodologies, adopted interactions and the minimisation of foreign-body reactions - through the review of 50 years of research on polysulfide synthetic methodologies. Attention is paid to the identification of the most flexible and robust preparative techniques.

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A New Initiator System for the Living Thiiranes Ring-Opening Polymerization: A Way toward Star-Shaped Polythiiranes

Cited by 37 publications

References 13 publications

Precise Synthesis of Poly(thioester)s with Diverse Structures by Copolymerization of Cyclic Thioanhydrides and Episulfides Mediated by Organic Ammonium Salts

Precise Synthesis of Poly(thioester)s with Diverse Structures by Copolymerization of Cyclic Thioanhydrides and Episulfides Mediated by Organic Ammonium Salts

Controlled ring‐expansion polymerization of thiiranes based on cyclic aromatic thiourethane initiator

Polymers and Sulfur: what are Organic Polysulfides Good For? Preparative Strategies and Biological Applications

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