Thermoset polyurethane is an important polymer material due to high strength and adjustable performance. However, the thermoset polyurethane only based on dynamic urethane bond shows poor reprocessing performance. To improve the reprocessability and recyclability, multiple dynamic covalent bonds (ester, urethane, and thiourethane bonds) were introduced into molecular chains to develop a thermoset shape memory polythiourethane (PCTU) with high transparency, excellent mechanical properties, solid state plasticity, reprocessability, and recyclability. The PCTU samples show good mechanical properties and have the highest reprocessing efficiencies with η_σ of 144.4% and η_ε of 160.1%. Moreover, the samples can realize complex 3D shapes via the combination of solid-state plasticity and shape memory property. Notably, for the prepared PCTU/CFs composites, carbon fibers (CFs) can be easily recycled under mild conditions and can be reused in other polymer composites. Thus, this work provides a new way for developing recyclable, reconfigurable, and thermadapt shape memory polythiourethane fiber composites.

热固性聚氨酯由于强度高、性能可调，是一种重要的高分子材料。然而，仅基于动态氨基甲酸酯键的热固性聚氨酯表现出较差的再加工性能。为了提高可再加工性和可回收性，将多个动态共价键（酯键、氨基甲酸酯键和硫氨基甲酸酯键）引入分子链中，开发出一种热固性形状记忆聚硫氨酯（PCTU），具有高透明度、优异的机械性能、固态可塑性、可再加工性和可回收性。PCTU 样品显示出良好的机械性能，并具有最高的后处理效率，η _σ为 144.4% 和 η _ε160.1%。此外，样品可以通过固态塑性和形状记忆特性的结合实现复杂的 3D 形状。值得注意的是，对于制备的 PCTU/CFs 复合材料，碳纤维 (CFs) 可以在温和条件下轻松回收，并可在其他聚合物复合材料中重复使用。因此，这项工作为开发可回收、可重构和热适应形状记忆聚硫氨酯纤维复合材料提供了一种新方法。