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Abstract Organosulfur polymers prepared via the inverse vulcanization of elemental sulfur with olefinic comonomers represent a new class of high‐chalcogenide content organic/inorganic macromolecules. Extensive reporting on new synthetic advances and materials derived from the inverse vulcanization process have been explored in the past decade. However, detailed structural analysis of these sulfur copolymers have not been rigorously conducted, due to the poor solubility of many of these materials, coupled with the numerous side‐reactions that result in complex microstructures from these synthetic methods. In the current report, we revisit analysis of the solution13C NMR spectral data for poly(S‐r‐Sty) and identify for the first time previously unidentified carbon peaks that offer new insights into a corrected repeating unit structure of this sulfur copolymer.
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Sulfur-Containing Polymers Prepared from Fatty Acid-Derived Monomers: Application of Atom-Economical Thiol-ene/Thiol-yne Click Reactions and Inverse Vulcanization Strategies
This paper is review with 119 references. Approaches to supplant currently used plastics with materials made from more sustainably-sourced monomers is one of the great contemporary challenges in sustainable chemistry. Fatty acids are attractive candidates as polymer precursors because they can be affordably produced on all inhabited continents, and they are also abundant as underutilized by-products of other industries. In surveying the array of synthetic approaches to convert fatty acids into polymers, those routes that produce organosulfur polymers stand out as being especially attractive from a sustainability standpoint. The first well-explored synthetic approach to fatty acid-derived organosulfur polymers employs the thiol-ene click reaction or the closely-related thiol-yne variation. This approach is high-yielding under mild conditions with up to 100% atom economy and high functional group tolerance. More recently, inverse vulcanization has been employed to access high sulfur-content polymers by the reaction of fatty acid-derived olefins with elemental sulfur. This approach is attractive not only because it is theoretically 100% atom economical but also because elemental sulfur is itself an underutilized by-product of fossil fuel refining. The thiol-ene, inverse vulcanization, and mechanistically-related thiol-yne and classic vulcanization are therefore discussed as promising routes to access polymers and composites from fatty acid-derived precursors.
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- Award ID(s):
- 1708844
- PAR ID:
- 10199255
- Date Published:
- Journal Name:
- Sustainable Chemistry
- Volume:
- 1
- Issue:
- 3
- ISSN:
- 2673-4079
- Page Range / eLocation ID:
- 209 to 237
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/suschem1030015
