Raman analysis of inverse vulcanised polymers

Dodd, Liam J.; Lima, Cássio; Costa-Milan, David; Neale, Alex R.; Saunders, Benedict; Zhang, Bowen; Sarua, Andrei; Goodacre, Royston; Hardwick, Laurence J.; Kuball, Martin; Hasell, Tom

doi:10.1039/d2py01408d

Cited by 13 publications

(15 citation statements)

References 36 publications

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“…With that said, subtle differences in the S–S signals of the Raman spectra could be resolved for linear disulfide and trisulfide small molecule models and the cyclic trisulfide and pentasulfide monomers (S18–S19). This important series of control experiments indicate the possibility for distinguishing sulfur ranks by Raman spectroscopy, in line with a recent report by Dodd, Hasell and co-workers . Furthermore, reduction of the polymer with LiAlH 4 produced dithiol 5 , corroborating the proposed polymer structure (Figure G).…”

Section: Resultssupporting

confidence: 90%

“…FTIR spectra of the polymer showed broadened peaks compared to monomer 4 (Figure E), and Raman spectroscopy revealed fluorescence when analyzed with either a 532 nm laser (Figure F) or a 785 nm laser (S51). This fluorescence is consistent with previous reports of dicyclopentadiene-sulfur copolymers, which makes it difficult to draw conclusions from the Raman spectra with regards to sulfur rank . With that said, subtle differences in the S–S signals of the Raman spectra could be resolved for linear disulfide and trisulfide small molecule models and the cyclic trisulfide and pentasulfide monomers (S18–S19).…”

Section: Resultssupporting

confidence: 84%

“…This fluorescence is consistent with previous reports of dicyclopentadiene-sulfur copolymers, which makes it difficult to draw conclusions from the Raman spectra with regards to sulfur rank. 38 With that said, subtle differences in the S−S signals of the Raman spectra could be resolved for linear disulfide and trisulfide small molecule models and the cyclic trisulfide and pentasulfide monomers (S18−S19). This important series of control experiments indicate the possibility for distinguishing sulfur ranks by Raman spectroscopy, in line with a recent report by Dodd, Hasell and co-workers.…”

Section: ■ Introductionmentioning

confidence: 99%

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Electrochemical Synthesis of Poly(trisulfides)

et al. 2023

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With increasing interest in high sulfur content polymers, there is a need to develop new methods for their synthesis that feature improved safety and control of structure. In this report, electrochemically initiated ring-opening polymerization of norbornene-based cyclic trisulfide monomers delivered well-defined, linear poly(trisulfides), which were solution processable. Electrochemistry provided a controlled initiation step that obviates the need for hazardous chemical initiators. The high temperatures required for inverse vulcanization are also avoided resulting in an improved safety profile. Density functional theory calculations revealed a reversible "self-correcting" mechanism that ensures trisulfide linkages between monomer units. This control over sulfur rank is a new benchmark for high sulfur content polymers and creates opportunities to better understand the effects of sulfur rank on polymer properties. Thermogravimetric analysis coupled with mass spectrometry revealed the ability to recycle the polymer to the cyclic trisulfide monomer by thermal depolymerization. The featured poly(trisulfide) is an effective gold sorbent, with potential applications in mining and electronic waste recycling. A water-soluble poly(trisulfide) containing a carboxylic acid group was also produced and found to be effective in the binding and recovery of copper from aqueous media.

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Section: Resultssupporting

confidence: 90%

Section: Resultssupporting

confidence: 84%

Section: ■ Introductionmentioning

confidence: 99%

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Electrochemical Synthesis of Poly(trisulfides)

et al. 2023

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“…This important series of control experiments indicate the possibility for distinguishing sulfur ranks by Raman spectroscopy, in line with a recent report by Dodd, Hasell and co-workers. 36 Furthermore, reduction of the polymer with LiAlH4 produced dithiol 5, corroborating the proposed polymer structure (Fig. 4G).…”

Section: Electrochemical Polymerizationsupporting

confidence: 80%

“…This fluorescence is consistent with previous reports of dicyclopentadiene-sulfur copolymers, which makes it difficult to draw conclusions from the Raman spectra with regards to sulfur rank. 36 With that said, subtle differences in the S-S signals of the Raman spectra could be resolved for linear disulfide and trisulfide small molecule models and the cyclic trisulfide and pentasulfide monomers (S18). This important series of control experiments indicate the possibility for distinguishing sulfur ranks by Raman spectroscopy, in line with a recent report by Dodd, Hasell and co-workers.…”

Section: Electrochemical Polymerizationmentioning

confidence: 99%

Electrochemical synthesis of poly(trisulfides)

Pople

Nicholls

Pham

et al. 2023

Preprint

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With increasing interest in high sulfur content polymers, there is a need to develop new methods for their synthesis that feature better safety and control of structure. In this report, electrochemically-initiated ring-opening polymerization of norbornene-based cyclic trisulfide monomers delivered well-defined, linear poly(trisulfides), which were solution processable. Electrochemistry provided a controlled initiation step that obviates the need for hazardous chemical initiators. The high temperatures required for inverse vulcanization are also avoided resulting in an improved safety profile. Density functional theory calculations revealed a reversible ‘self-correcting’ mechanism that ensures trisulfide linkages between monomer units. This control over sulfur rank is a new benchmark for high sulfur content polymers and creates opportunities to better understand the effects of sulfur rank on polymer properties. Thermogravimetric analysis coupled with mass spectrometry revealed the ability to recycle the polymer to the cyclic trisulfide monomer by thermal depolymerization. The featured poly(trisulfide) is an effective gold sorbent, with potential applications in mining and electronic waste recycling. A water-soluble poly(trisulfide) containing a carboxylic acid group was also produced and found to be effective in the binding and recovery of copper from aqueous media.

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