Mechanically Promoted Synthesis of Polymer Organogels via Disulfide Bond Cross-Linking,ACS Macro Letters

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Mechanically Promoted Synthesis of Polymer Organogels via Disulfide Bond Cross-Linking
ACS Macro Letters ( IF 5.1 ) Pub Date : 2021-06-14 , DOI: 10.1021/acsmacrolett.1c00337
Jorge Ayarza ₁ , Zhao Wang ₁ , Jun Wang ₁ , Aaron P Esser-Kahn ₁

Affiliation

Mechanically adaptive polymers could significantly improve the life-cycle of current materials. Piezo-polymerization is a novel approach that harnesses vibrational mechanical energy through piezoelectric nanoparticles to generate chemical promoters for linear polymerization and cross-linking reactions. However, the available piezo-polymerization systems rely on reactions forming irreversible covalent bonds. Dynamic covalent linkages could impart further adaptability to these polymeric systems. Here we show the first example of the piezoelectrochemical synthesis of disulfide bonds to form organogels from polymers with thiol side groups. We demonstrate that the reaction proceeds via piezo-oxidation of the thiol to disulfide in the presence of ZnO nanoparticles and iodide anions under mechanical agitation. We use mechanical energy in the form of ultrasound (40 kHz) and low frequency vibrations (2 kHz) to synthesize a variety of organogels from common synthetic polymers. Additionally, we show that the polymers in these gels can be chemically recycled with a reducing agent. Finally, we study the thermal and mechanical properties of the composites obtained after drying the gels. We believe this new system adds to the piezo-polymerization repertoire and serves as the basis to fabricate mechanically adaptive polymeric materials via dynamic covalent bonds.

中文翻译：

通过二硫键交联机械促进合成聚合物有机凝胶

机械适应性聚合物可以显着改善当前材料的生命周期。压电聚合是一种新颖的方法，它通过压电纳米粒子利用振动机械能来生成用于线性聚合和交联反应的化学促进剂。然而，可用的压电聚合系统依赖于形成不可逆共价键的反应。动态共价键可以赋予这些聚合物系统进一步的适应性。在这里，我们展示了压电电化学合成二硫键以从具有硫醇侧基的聚合物形成有机凝胶的第一个例子。我们证明，在机械搅拌下，在存在 ZnO 纳米颗粒和碘化物阴离子的情况下，该反应通过硫醇的压电氧化为二硫化物进行。我们使用超声波 (40 kHz) 和低频振动 (2 kHz) 形式的机械能，从常见的合成聚合物中合成各种有机凝胶。此外，我们表明这些凝胶中的聚合物可以用还原剂进行化学回收。最后，我们研究了凝胶干燥后获得的复合材料的热性能和机械性能。我们相信这个新系统增加了压电聚合的功能，并作为通过动态共价键制造机械适应性聚合物材料的基础。我们研究了凝胶干燥后获得的复合材料的热性能和机械性能。我们相信这个新系统增加了压电聚合的功能，并作为通过动态共价键制造机械适应性聚合物材料的基础。我们研究了凝胶干燥后获得的复合材料的热性能和机械性能。我们相信这个新系统增加了压电聚合的功能，并作为通过动态共价键制造机械适应性聚合物材料的基础。

更新日期：2021-07-20

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