可交换键在二烯烃橡胶-纳米颗粒界面的构筑方法和性能效应

Realizing the plastic processing of cross-linked rubber materials and expanding their application gallery in intelligent materials are two important issues in rubber science and technology. The cross-linked polymers with exchangeable bonds can rearrange the network topology under thermal stimulus due to the exchange reactions among exchangeable bonds, which endows the cross-linked polymers with plasticity. In this proposal, nanoparticles are used as crosslinking points and reinforcement in diene rubbers, and the interfaces with exchangeable bonds are constructed between rubbers and nanoparticles. Based on the function mechanism of exchangeable bonds and the design of network structure, the rubber nanocomposites with high performance and reconfigurable/multiple shape memory rubber materials are prepared. The main research aspects include: (1) Accurate modification of diene rubbers and controllable decoration of nanoparticles; (2) Revealing the mechanism and influence factors of the interfacial crosslinking and exchange reactions; (3) Structure design, performance regulation and applications of the resulting rubber nanocomposites. In the proposal, due to the interfacial cross-linking and exchange reactions, the crosslinking, reinforcement, plastic processing, and functionalization of rubbers are synchronously implemented, which offers a novel methodology to solve the shortage of raw rubbers and environmental pollution caused by rubber scrap, and provides new opportunities for the design and preparation of functional rubber materials. The studies are believed to be of great scientific and practical significance.

实现交联橡胶材料的可塑加工和拓展其功能性应用是橡胶科学与技术领域的两个重要问题。含可交换键的交联高分子在热激发作用下可通过键的交换反应实现网络拓扑结构的重排，为制备可塑交联高分子提供了新途径。本项目提出以纳米颗粒作为交联点和增强体，在二烯烃橡胶-纳米颗粒界面构筑可交换键，利用可交换键的作用原理并结合网络结构的设计，制备可塑高性能弹性体和可重塑形/多重形状记忆材料。主要研究内容包括：（1）二烯烃橡胶的精准改性和纳米颗粒可控修饰研究；（2）阐明橡胶-颗粒界面交联反应和交换反应的机理与影响因素；（3）可塑橡胶纳米复合材料的结构设计、性能调控和应用研究。本项目提出的基于橡胶-纳米颗粒界面交联和交换反应，同步实现橡胶交联、增强、可塑加工和功能化的策略，为解决生胶资源匮乏和橡胶报废带来的环境污染等问题提供了全新思路，为设计和制备橡胶基功能材料提供了新机遇，具有重要的科学意义和现实意义。

含可交换键的交联高分子在热激发作用下可通过键的交换反应实现网络拓扑结构的重排，为制备可塑交联高分子提供了新途径。本项目提出以纳米颗粒作为交联点和增强体，在二烯烃橡胶-纳米颗粒界面构筑可交换键，利用可交换键的作用原理和结合网络结构的调控，制备可塑高性能弹性体和可重塑形/多重形状记忆橡胶材料。主要研究内容包括：发展了几类典型的二烯烃橡胶的精准改性和纳米颗粒可控修饰方法；揭示了橡胶-颗粒界面交联反应和交换反应的机理与影响因素；探讨了可塑橡胶纳米复合材料的结构调控、构-效关系和应用研究。另外，本项目提出在动态共价键交联的橡胶网络中引入非共价键牺牲键策略，利用非共价键的可逆断裂-重构机理耗散能量，实现对网络的增强增韧；利用牺牲键在低温下充当物理交联点和在高温下解离的特征，提高动态共价键的低温抗蠕变性且不影响其高温动态性。.本项目提出的基于界面交联/交换反应和牺牲键策略制备高性能可重复加工橡胶材料，为解决生胶资源匮乏和橡胶报废带来的环境污染等问题提供了全新思路，为设计和制备橡胶基功能材料提供了新机遇，具有重要的科学意义和现实意义。