Kinetics of the base‐catalyzed reactions of cyclo‐octameric and catenapolymeric sulfur with dithiol

Bordoloi, Binoy K.; Pearce, Eli M.

doi:10.1002/app.1979.070230920

Cited by 11 publications

(11 citation statements)

References 9 publications

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“…The high acidity of thiol group facilitates a condensation reaction with elemental sulfur while offering selectivity in polysulfide order through simple stoichiometry, thus making it a suitable choice . When utilizing dithiols (HS–R–SH), it has been shown that this reaction yields oligomers and polymers at room temperatures under the catalytic action of bases such as secondary amines. − …”

Section: Resultsmentioning

confidence: 99%

Rationally Designed High-Sulfur-Content Polymeric Cathode Material for Lithium–Sulfur Batteries

Bhargav

Chang

et al. 2019

ACS Appl. Mater. Interfaces

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Polyethylene hexasulfide (PEHS) is investigated as a cathode material in lithium batteries. By utilizing a condensation reaction, ethylene groups are inserted between six linear sulfurs in a chain to obtain PEHS while simultaneously exercising control over the polysulfur chain length. Additionally, by selecting a low-molecular-weight organic group, PEHS contains 87 wt % sulfur, thus maximizing the material-level specific capacity to 1217 mA h g–1. Furthermore, this synthesis method is validated using a host of materials characterization techniques. In a battery, PEHS prevents the formation of soluble long-chain intermediates that plague traditional sulfur cathodes. This enables a high material-level capacity of 774 mA h g–1 at 1C-rate alongside a stable performance over 350 cycles with a capacity fade rate of only 0.083% per cycle. We also elucidate the unique reaction pathway of our short-chain polysulfur material and provide a useful foundation for further development of sulfur-containing polymer-based cathode materials.

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Section: Resultsmentioning

confidence: 99%

Rationally Designed High-Sulfur-Content Polymeric Cathode Material for Lithium–Sulfur Batteries

Bhargav

Chang

et al. 2019

ACS Appl. Mater. Interfaces

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“…A variant of the thiol–ene reaction between sulfur and dithiols in the presence of base was adopted by Bordoloi et al. to generate the mentioned polymers . Intriguingly, as the molecular weight of the polymer increased during the polymerization, the sulfur rank plateaued to a value of 2.5.…”

Section: Chemistrymentioning

confidence: 99%

Sulfur Chemistry in Polymer and Materials Science

Mutlu

Ceper

et al. 2018

Macromol. Rapid Commun.

254

220

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The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/marc.201800650. ChemistryBefore moving to the recent advances within the last 5 years in the diverse applications of sulfur chemistry in polymer and Sulfur-Containing PolymersSulfur and its functional groups are major players in an area of exciting research taking place in modern polymer and materials science, both in academia and industry. In fact, manifold sulfur-based reactions that are both exceptionally versatile as well as tremendously useful have been implemented, and further utilized for the design and preparation of polymeric materials that lead to a plethora of applications ranging from medicine to optics and nanotechnology to separation science. Hence, within this review, an overview of strategies and developments used over the last 5 years to reinforce the importance of the sulfur functional group in modern polymer and materials science is presented. In particular, many important references in the primary literature of sulfur chemistry are referred to, including thiol-ene, thiol-yne, thiol-Michael addition, disulfide cross-linking, and thiol-disulfide exchange, among others, by explaining and illustrating the important principles. Last but not least, the grand aim to underpin the importance of sulfur in modern polymer and materials science is achieved by presenting selected examples in diverse fields and postulating the respective potential for real-world applications. he is now a full professor at KIT.sulfur atoms, and tetraphenylethene-bearing di(alkyl bromide) (Scheme 3). The yield of the polymerization was dependent on the di(alkyl bromide) monomer; the longer spacer between the aromatic moiety and the reactive bromide end groups Scheme 1. The discussion henceforth focuses on the synthesis of polymers possessing the depicted sulfur functional groups. Scheme 2.Representative examples of polythioethers prepared via A) the nucleophilic substitution reaction between an electrophilic dihalide with nucleophilic derivatives of dithiols under alkaline conditions; B) the thiol-ene/yne addition reaction between AA and BB type monomers (i.e., dithiols and dienes/diynes); and C) radical or ionic ring-opening of sulfurcontaining strained rings.Scheme 3. The thiol-bromo polymerization of conformationally fixed monomers to provide multifunctional polymers. [19] Macromol. Rapid Commun. 2019, 40, 1800650 Scheme 4. The regioselective selective nucleophilic aromatic substitution between thiol and fluorinated aromatic compounds, the para-fluorothiol reaction (PFTR).Scheme 5. Synthesis of a linear polymer via PFTR-reaction. [21]

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“…The Arrhenius analysis yields an activation energy for the formation of the photoluminescent species of 92 kJ/mol. This activation energy is similar to the value measured for the polymerization of S 8 initiated by thiol in the presence of base …”

Section: Resultsmentioning

confidence: 99%

“…This activation energy is similar to the value measured for the polymerization of S 8 initiated by thiol in the presence of base. 20 The kinetics of the colorimetric changes in S/ODE require a mechanism that forms a structurally disperse set of air-stable species, is thermally irreversible, and is accelerated by the presence of carbon−carbon double bonds. Sulfur melts undergo a discontinuous change in their viscosity at 158 °Cknown as the "lambda transition"during which the cyclooctasulfur rings that comprise elemental sulfur begin to homolytically cleave sulfur−sulfur bonds and polymerize to produce catena-sulfur, which is composed of variable-length polysulfur chains.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Role of Organosulfur Compounds in the Growth and Final Surface Chemistry of PbS Quantum Dots

McPhail

Weiss

2014

Chem. Mater.

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This paper describes the mechanism by which reaction of sulfur with 1-octadecene (ODE) induces a change in the shape of PbS quantum dots (QDs), synthesized from the S/ODE precursor and lead(II) oleate, from cubic to hexapodal by altering the ligand chemistry of the growing QDs. 1 H NMR and optical spectroscopies indicate that extended heating of sulfur and ODE at 180 °C produces a series of organosulfur compounds with optical transitions in the visible region and that the binding of organosulfur ligands to the growing QD induces a preferential growth at the ⟨100⟩ faces (over the ⟨111⟩ faces) and, therefore, a hexapodal geometry for the particles. The study shows that S/ODE can be made a more reliable precursor by reducing the temperature and duration of the sulfur dissolution step and that any metal sulfide QD synthesis using elemental sulfur heated to high temperatures should take steps to reduce the in situ yield of organosulfur byproducts by avoiding olefinic solvents.

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Kinetics of the base‐catalyzed reactions of cyclo‐octameric and catenapolymeric sulfur with dithiol

Abstract: SynopsisThe base-catalyzed sulfur-1,2-ethanedithiol reactions appear to follow pseudo first-order kinetics as determined by TGA. The activation energy has been determined to be 26.1 kcal/mol with either cyclo-octameric or catenapolymeric sulfur.

Cited by 11 publications

References 9 publications

Rationally Designed High-Sulfur-Content Polymeric Cathode Material for Lithium–Sulfur Batteries

Rationally Designed High-Sulfur-Content Polymeric Cathode Material for Lithium–Sulfur Batteries

Sulfur Chemistry in Polymer and Materials Science

Role of Organosulfur Compounds in the Growth and Final Surface Chemistry of PbS Quantum Dots

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