Organophosphate-intercalated high-entropy LDHs for high-performance fire-safe thermoplastic polyurethane composites

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability Pub Date : 2025-08-17 DOI:10.1016/j.polymdegradstab.2025.111613

Chuanshen Wang , Hongliang Ding , Lu Liu , Hongfei He , Bicheng Lin , Na Sun , Keqing Zhou , Wei Wang , Yuan Hu , Bin Yu

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引用次数: 0

Abstract

Polymer materials pose significant fire hazards, including rapid heat release and the emission of toxic smoke. Herein, we report a flame-retardant thermoplastic polyurethane (TPU) composite engineered with organophosphonic acid-intercalated high-entropy layered double hydroxides (HE-LDHs), achieving synergistic flame retardancy, smoke suppression, and mechanical enhancement. Meanwhile, tensile strength was enhanced to 38 MPa. The NiCoFeAlZn/DPA/TPU system demonstrated 42.1 % reduction in peak heat release rate (pHRR), 48.5 % decrease in total smoke release (TSR), and 36.4 % decrease in CO production rate compared to pure TPU, attributed to a hierarchical flame-retardant mechanism involving gas-phase dilution, physical barrier formation, and catalytic charring. The synergistic effect of multi-metal components of HE-LDHs and the intercalation (diphenylphosphoric acid, phenylphosphinic acid) agents restructured the thermal decomposition pathway of the material. Early-stage fire warning through HE-LDHs decomposition of interlayer water and organic acid anions releases CO₂/H₂O to dilute flammable gases; Intermediate flame inhibition through HE-LDHs catalyze dehydrogenation crosslinking of TPU, capture by PO· radicals from phosphonates, effectively suppressing flame propagation; High-temperature protection through collapse of LDH layers generates metal oxides and phosphorus-carbon hybrid barriers, triggering endothermic phase transitions, with an increase in the amount of residual carbon. This work establishes a theoretical framework for regulating the structure-property relationship of HE-LDHs and pioneers an integrated, active-passive design for fire-safe, high-risk polymer applications.

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高性能防火热塑性聚氨酯复合材料的有机磷酸酯插层高熵LDHs

聚合物材料具有重大的火灾隐患，包括快速放热和释放有毒烟雾。在此，我们报告了一种阻燃热塑性聚氨酯（TPU）复合材料与有机膦酸插入高熵层状双氢氧化物（HE-LDHs）工程，实现协同阻燃，抑烟和机械增强。同时，拉伸强度提高到38 MPa。与纯TPU相比，NiCoFeAlZn/DPA/TPU体系的峰值放热率（pHRR）降低了42.1%，总烟雾释放率（TSR）降低了48.5%，CO产出率降低了36.4%，这归功于分层阻燃机制，包括气相稀释、物理屏障形成和催化炭化。HE-LDHs的多金属组分与插层剂（二苯基磷酸、苯基膦酸）的协同作用重构了材料的热分解途径。早期火灾预警通过HE-LDHs分解层间水和有机酸阴离子释放CO2/H2O稀释可燃性气体；通过HE-LDHs催化TPU脱氢交联，捕获磷酸盐中的PO·自由基，有效抑制火焰传播；LDH层坍塌产生的高温保护产生金属氧化物和磷碳杂化屏障，引发吸热相变，残余碳量增加。这项工作为调节HE-LDHs的结构-性能关系建立了理论框架，并开创了一种用于防火、高风险聚合物应用的集成、主动式被动设计。

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来源期刊

Polymer Degradation and Stability 化学-高分子科学

CiteScore

10.10

自引率

10.20%

发文量

325

审稿时长

23 days

期刊介绍： Polymer Degradation and Stability deals with the degradation reactions and their control which are a major preoccupation of practitioners of the many and diverse aspects of modern polymer technology. Deteriorative reactions occur during processing, when polymers are subjected to heat, oxygen and mechanical stress, and during the useful life of the materials when oxygen and sunlight are the most important degradative agencies. In more specialised applications, degradation may be induced by high energy radiation, ozone, atmospheric pollutants, mechanical stress, biological action, hydrolysis and many other influences. The mechanisms of these reactions and stabilisation processes must be understood if the technology and application of polymers are to continue to advance. The reporting of investigations of this kind is therefore a major function of this journal. However there are also new developments in polymer technology in which degradation processes find positive applications. For example, photodegradable plastics are now available, the recycling of polymeric products will become increasingly important, degradation and combustion studies are involved in the definition of the fire hazards which are associated with polymeric materials and the microelectronics industry is vitally dependent upon polymer degradation in the manufacture of its circuitry. Polymer properties may also be improved by processes like curing and grafting, the chemistry of which can be closely related to that which causes physical deterioration in other circumstances.