Soluble High Sulfur-Selenium Content Polymers via Inverse Vulcanization with Selenium Disulfide

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Abstract
Despite more than a decade of development, inverse vulcanization continues to produce sulfur-rich polymers with limited solubility, which impedes definitive structural characterization by solution-based techniques. The dominant hypothesis proposes that these materials form a cross-linked network. However, recent work by Pyun and co-workers demonstrated the coexistance of cross-linked and linear structures for the direct synthesis of vulcanized 1,3-diisopropenylbenzene (DIB) fragments by employing solid-state/solution nuclear magnetic resonance (NMR) and AlLiH4 reductive degradation of poly(S-DIB). To enable unambiguous structural elucidation, we employ selenium disulfide (SeS₂) as the sulfur source, which retains the eight-membered ring structure of S₈ but features a lower bond dissociation energy. The current protocol yields soluble sulfur/selenium-rich polymers. Structural characterization confirms the coexistence of linear and cross-linked components for the resultant polymers. The exceptional solubility enables comprehensive gel permeation chromatography (GPC) analysis. All polymers, synthesized at varying feed ratios, exhibit ultrahigh molecular weights (Mn > 1,300,000 g/mol). Additionally, poly(SeS2-DIB) synthesized with various feed ratios was comprehensively characterized using 1H NMR, FT-IR, PXRD, TGA, DSC, EA, and SEM to elucidate its structure and properties. This provides a critical foundation for investigating sulfur sequence length and degradation pathways.

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