Li Donghan, Yu Lu, Ning Shurui, Li Ping, Chen Changle, Zhao Dawei, Liao Mingyi, Meng Qingshi, Zhang Shixin, Fang Qinghong, Kang Hailan, Li Long, Yang Jia
College of Materials Science and Engineering, Shenyang University of Chemical Technology, Shenyang, 110142, China.
Liaoning Key Laboratory of Polymer Materials Application Technology, Shenyang University of Chemical Technology, Shenyang, 110142, China.
Adv Sci (Weinh). 2025 Aug;12(31):e01460. doi: 10.1002/advs.202501460. Epub 2025 May 28.
To address the challenges of recycling and high-value utilization of waste fluororubbers, an effective method is reported for producing novel photocurable vinyl-terminated liquid fluororubbers (VTLF) with elevated fluorine content (63.1%), superior temperature resistance (T = 335 °C) from commercial waste fluororubbers. The approach employs a streamlined, multifaceted system (oxidative degradation/condensation reaction) integrating microwave, mechanical, and steady-state temperature fields. This system facilitates both efficient recycling and high-value transformation of waste fluororubbers. Initially, waste fluororubbers undergo controlled/oxidative degradation induced by alkali and hydrogen peroxide to yield carboxyl-terminated liquid fluororubbers (CTLF). Subsequently, condensation reaction system efficiently converts carboxyl groups into photoreactive vinyl groups. Ultimately, environmentally friendly and efficient photocuring of VTLF is achieved. The nonthermal effects of microwave fields reduce the total process time to just 1 h. The resulting photocured VTLF exhibits not only the comprehensive properties of conventional fluororubbers but also excellent chemical stability and unique light transmittance (94.21%). This study proposes a green, straightforward upcycling strategy within the circular economy framework to mitigate environmental issues associated with rubber's covalent crosslinking. Furthermore, it opens avenues for designing and synthesizing novel fluoropolymers for diverse applications.
为应对废弃氟橡胶回收利用及高值化利用的挑战，本文报道了一种有效方法，可从商用废弃氟橡胶制备含氟量更高（63.1%）、耐高温性能更优（T = 335 °C）的新型光固化乙烯基封端液态氟橡胶（VTLF）。该方法采用了一种集成微波、机械和稳态温度场的简化多方面系统（氧化降解/缩合反应）。该系统有助于废弃氟橡胶的高效回收和高值化转化。首先，废弃氟橡胶在碱和过氧化氢的作用下进行可控氧化降解，生成羧基封端液态氟橡胶（CTLF）。随后，缩合反应体系将羧基高效转化为光反应性乙烯基。最终，实现了VTLF的环保高效光固化。微波场的非热效应将总工艺时间缩短至仅1小时。所得光固化VTLF不仅具有传统氟橡胶的综合性能，还具有优异的化学稳定性和独特的透光率（94.21%）。本研究在循环经济框架内提出了一种绿色、直接的升级循环策略，以缓解与橡胶共价交联相关的环境问题。此外，它为设计和合成用于各种应用的新型含氟聚合物开辟了道路。
