Yang Hongjun, Zhang Jikai, Huang Wenyan, Zhang Guangzhao
Key Laboratory of Environmentally Friendly Polymeric Materials, School of Materials Science and Engineering, Jiangsu Collaborative Innovation Centre of Photovoltaic Science and Engineering, Changzhou University, Changzhou, 213164, Jiangsu, P. R. China.
Changzhou University Huaide College, Jingjiang, 214500, Jiangsu, P. R. China.
Angew Chem Int Ed Engl. 2025 Jan 10;64(2):e202414244. doi: 10.1002/anie.202414244. Epub 2024 Oct 30.
The utilization of sulfur has been a global issue. Copolymerization of element sulfur (S) with other monomers is a promising route to convert it to useful materials but is limited by the comonomers. Here, we report anionic hybrid copolymerization of S with acrylate and epoxide at room temperature, where S does not copolymerize with epoxide in the absence of acrylate. Yet, the proton transfer from the methyne in acrylate to the oxygen anion enables the ring-opening of the cyclic comonomer and hence the copolymerization. The cyclic comonomers can be expanded to lactone and cyclic carbonate. Specifically, the copolymer of S with bisphenl A diglycidyl ether and diacrylate displays mechanical properties comparable to those of most common plastics, namely, it has ultimate tensile strength as high as 60.8 MPa and Young's modulus up to 680 MPa. It also exhibits high UV resistance and good transparency. Particularly, it has excellent UV-induced self-healing, reprocessability and closed-loop recyclability due to the abundant dynamic S-S bonds and ester groups. This study provides an efficient strategy to turn element sulfur into closed-loop recyclable polymer with high mechanical and optical performances.
硫的利用一直是一个全球性问题。将元素硫（S）与其他单体共聚是将其转化为有用材料的一条有前景的途径，但受到共聚单体的限制。在此，我们报道了硫与丙烯酸酯和环氧化物在室温下的阴离子杂化共聚反应，在没有丙烯酸酯的情况下，硫不会与环氧化物共聚。然而，丙烯酸酯中亚甲基上的质子转移到氧阴离子上，使得环状共聚单体开环，从而实现共聚。环状共聚单体可以扩展到内酯和环状碳酸酯。具体而言，硫与双酚A二缩水甘油醚和二丙烯酸酯的共聚物表现出与大多数常见塑料相当的机械性能，即其极限拉伸强度高达60.8 MPa，杨氏模量高达680 MPa。它还具有高耐紫外线性和良好的透明度。特别地，由于存在大量动态S-S键和酯基，它具有优异的紫外光诱导自愈性、可再加工性和闭环可回收性。本研究提供了一种将元素硫转化为具有高机械和光学性能的闭环可回收聚合物的有效策略。
