Dang Haichun, Zhang Ziliang, Sun Ruibing, Li Yunlun, Lin Mengyu, Yang Siting, He Maoyong, Xu Zhaozan, Bian Xiangcheng
Department of Materials Engineering, Taiyuan Institute of Technology, Taiyuan 030008, China.
Institute of Resources and Environmental Engineering, Shanxi University, Taiyuan 030006, China.
Polymers (Basel). 2025 May 2;17(9):1243. doi: 10.3390/polym17091243.
Integrating strong mechanical properties and excellent optical properties for self-healing materials is challenging in both academia and industry. Robust self-healing polyurethane elastomers are expected to have superior mechanical properties, transparency, remarkable healing capability, and shape-memory performance via the adjustment of chemical and microphase separation structure. Herein, a robust transparent self-healable 4,4'-diphenylmethane diisocyanate (MDI)-based polyurethane elastomer containing disulfide bonds and branched structure (MPUE-SS) was synthesized. The chemical and topological structures, compatibility of soft-hard phases, and hard domain size of polyurethane could be adjusted via branched structure and mixed chain extender containing disulfide bonds and 1,4-butanediol (BDO), leading to enhanced self-healing, transparency, and mechanical properties. MPUE-SS exhibited a maximal tensile strength of 40 MPa. The microphase separation structure and reduced crystallinity led to a high transparency of about 91%, close to that of alicyclic polyurethane elastomers. After cutting in half and splicing, the MPUE-SS film recovered more than 95% of the original mechanical properties in 24 h. The shape recovery ratio at 40 °C and shape fixity ratio at -20 °C of MPUE-SS were 96.0% and 99.6%, respectively, higher than those of MPUE without disulfide bonds. Therefore, the chemical, topological structures, and microphase separation of polyurethane could be adjusted to achieve desired self-healing, transparency, shape-memory, and mechanical properties.
在学术界和工业界,将强机械性能和优异光学性能集成到自愈材料中都具有挑战性。通过调整化学和微相分离结构,有望使坚固的自愈聚氨酯弹性体具有卓越的机械性能、透明度、显著的自愈能力和形状记忆性能。在此,合成了一种基于4,4'-二苯基甲烷二异氰酸酯(MDI)的含二硫键和支化结构的坚固透明可自愈聚氨酯弹性体(MPUE-SS)。通过支化结构以及含二硫键的混合扩链剂和1,4-丁二醇(BDO),可以调整聚氨酯的化学和拓扑结构、软硬相的相容性以及硬区尺寸,从而提高自愈性、透明度和机械性能。MPUE-SS的最大拉伸强度为40MPa。微相分离结构和降低的结晶度使其具有约91%的高透明度,接近脂环族聚氨酯弹性体。将MPUE-SS薄膜切成两半后拼接,在24小时内恢复了超过95%的原始机械性能。MPUE-SS在40℃时的形状恢复率和在-20℃时的形状固定率分别为96.0%和99.6%,高于不含二硫键的MPUE。因此,可以通过调整聚氨酯的化学、拓扑结构和微相分离来实现所需的自愈、透明、形状记忆和机械性能。