利用多重氢键或金属配位作用制备高性能可再生型超分子橡胶

Recycled rubber material has become third largest source of rubber in China. However, due to the degradation of rubber molecules during unvulcanisation process, the mechanical properties of recycled rubber are greatly impaired. This proposal aims at the fabrication of recyclable supramolecular rubber with good mechanical properties by reversibly crosslinking rubber via multiple hydrogen bonds or coordination interaction. Based on the synthesis of sulfhydryl group modified crosslinkers that have hydrogen bond or coordination interaction, moieties with hydrogen bond or coordination interactions can be easily grafted onto rubber molecules via thiol-ene reaction. Study the influence of the structure of crosslinkers on the degree of crosslinking of obtained supramolecular rubber. Through adjusting the molecular structure of the crosslinker, and studying the mechanical properties of the as-prepared supramolecular rubber, how these factors affect the mechanical performance and remoldability of the supramolecular rubber is investigated in detail. Finally, nano-fillers were used to enhance the mechanical properties of these supramolecular rubber. This proposal not only offers a new route to graft moieties that have supramolecular interactions onto rubber molecules, but also a guidance on the fabrication of recyclable supramolecular rubber.

再生橡胶已经成为我国第三大橡胶来源，但是由于断键再生过程中的不可控性导致橡胶高分子链断裂，使得再生橡胶的强度大幅下降。本项目拟以多重氢键或金属配位键这两类可逆作用力对通用橡胶进行交联，制备兼具良好力学性质和重塑性的可再生超分子橡胶。以合成两大类修饰有巯基的多重氢键型和金属配位型交联剂为基础，通过巯基与通用橡胶上的烯键之间的点击化学反应高效地将多重氢键和金属配位作用引入到通用橡胶中。研究超分子交联剂的分子构型对通用橡胶交联效率的影响。通过调节氢键给受体以及配位金属的种类的方法，研究超分子作用力强弱与超分子橡胶的力学性能、稳定性和重塑性之间的关系。明确超分子作用力的引入对纳米填料在超分子橡胶内的分散性和增强作用的影响。本项目的实施，不仅为超分子作用力引入到通用橡胶材料内提供了新思路，也为高性能可再生超分子橡胶的设计提供指导。

合成具有良好的重塑性和自修复性的超分子橡胶，不但可以降低橡胶合成和回收过程中产生的污染，还可以有效的提高橡胶材料的使用寿命和可靠性。本项目从分子设计入手，将具有金属配位键或氢键作用的官能团引入到橡胶材料中，得到了一系列具有良好重塑性和自修复性能的超分子橡胶材料。这些超分子橡胶包括锌金属离子交联的羧基修饰的聚丁二烯，具有氢键作用的PDMS聚脲和同时具有氢键和金属配位作用的过渡金属离子交联的组氨酸修饰的聚油酸。通过对所得到的超分子橡胶的详细测试，总结了超分子作用力的种类对超分子橡胶的弹性、重塑性和自修复性能的影响。该项目验证了利用超分子橡胶替代普通橡胶材料的可行性，并为后续的超分子橡胶的合成提供了指导。将纳米填料分散到超分子橡胶内，研究了纳米填料的掺杂对超分子橡胶的弹性、重塑性和自修复性能的影响，为超分子橡胶的增强提供了指导。此外，本项目还首次利用超分子橡胶制备了具有自修复性能的超疏水多孔材料和透明防污涂层，拓展了超分子橡胶的应用范围。