A linear combination fitting in sulfur K-edge X-ray absorption near edge structure (S-XANES) measurements reveals each fraction of monosulfidic, disulfidic and polysulfidic linkages in solvent extracted sulfur cross-linked isoprene rubbers. The sulfidic linkage of a disulfidic type is found for the first time to be dominant when zinc stearate and -(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine are used as the activator and accelerator, respectively, for the sulfur cross-linking reaction at 140 °C. The presence of the bridging bidentate zinc/stearate complex as an intermediate for the sulfur cross-linking reaction is supposed to induce the generation of abundant disulfidic linkages in the rubber networks. This unexpected observation is of use for the material design of high performance rubber products with anti-aging and thermal stabilities. S-XANES is a powerful tool that was used to reveal the characteristics of the sulfur cross-linking of rubber. These results will contribute to the development of rubber science and technology.
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http://dx.doi.org/10.1039/c8ra00544c | DOI Listing |
J Am Chem Soc
January 2025
State Key Laboratory of Fine Chemicals, Frontier Science Center for Smart Materials, Dalian University of Technology, West Campus, 2# Linggong Road, Dalian 116024, China.
The macroscopic properties of elastomers are intimately linked to their molecular reactivity and mechanisms. Here, we propose a new strategy for designing strengthening materials based on the synergy of weak covalent bonds and mechanochemistry. After mechanical treatment, the failure strength and toughness of the elastomer increased from 2.
View Article and Find Full Text PDFJ Phys Chem B
January 2025
Nordbayerisches NMR-Zentrum, Universität Bayreuth, 95447 Bayreuth, Germany.
Rubbers prepared from technical poly(butadiene) and natural poly(isoprene) are studied by field-cycling (FC) H NMR relaxometry to elucidate the changes of the relaxation spectrum. Starting with the non-cross-linked polymer successively cross-links are introduced via sulfur or peroxide vulcanization. Applying an advanced home-built relaxometer allows one to probe entanglement dynamics in addition to Rouse dynamics.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Polymer Chemistry Research group, Centre of Macromolecular Chemistry (CMaC) and Laboratory of Organic Synthesis, Department of Organic and Macromolecular Chemistry, Faculty of Sciences, Ghent University, Krijgslaan, 281-S4, Ghent, 9000, Belgium.
Recycling thermosetting materials presents itself as a major challenge in achieving sustainable material use. Dynamic covalent cross-linking of polymers has emerged as a viable solution that can combine the structural integrity of thermosetting materials with the (re-)processability of thermoplastics. Thioether linkages between polymer chains are quite common, and their use dates back to the vulcanization of rubbers.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2024
Institute of Low-Dimensional Materials Genome Initiative, College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen, 518060, China.
Environ Res
December 2024
College of Environmental Science and Engineering, Ocean University of China, Qingdao, 266100, China; Key Laboratory of Marine Environmental and Ecology, Ministry of Education, Ocean University of China, Qingdao, 266100, China. Electronic address:
Elemental iron provides a viable strategy to improve the denitrification efficiency by expediting electron transport. However, the roles of magnetic iron powder (FeO) on mixotrophic denitrification remains unknown. In this study, the intra/extracellular electron transfer (IET/EET) and microbial metabolism mechanisms were explored in a FeO-mediated sulfide-autotrophic and heterotrophic denitrification system.
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