Design and synthesis of a dual-DOPO-based flame retardant: performance evaluation and mechanistic study in waterborne polyurethane systems

IF 6.5 2区材料科学 Q1 CHEMISTRY, APPLIED

Progress in Organic Coatings Pub Date : 2025-04-22 DOI:10.1016/j.porgcoat.2025.109330

Yanbo Ding , Libo Sun , Jiale Qu , Guangxian Yang , Jianing Wang , Xinrui Pan , Quanjie Wang , Lianxiang Feng , Baorong Duan , Yonggen Weng

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Abstract

Waterborne polyurethane (WPU) has gained extensive applications in eco-friendly coatings, adhesives, and related fields owing to its inherent safety, environmental compatibility, and superior performance. Nevertheless, its high flammability severely restricts practical implementation. In the present research, a dual-DOPO-based nitrogen‑phosphorus flame retardant (PHED) was designed and subsequently incorporated into WPU to develop flame-retardant PHED-WPU. Remarkably, the incorporation of 12 wt% PHED elevated the limiting oxygen index of WPU from 21.2 % to 28.6 %. Additionally, PHED-WPU demonstrated exceptional flame inhibition characteristics, reaching a V-0 grade in the vertical burning tests (UL-94, compared to no rating for pristine WPU), along with 43.6 % and 30.5 % reductions in total smoke production and total heat release, respectively. It was found that the char formation of 12 % PHED-WPU at 600 °C could reach 7.37 %, 47.99 % higher than WPU (4.98 %). The enhanced flame retardancy is attributed to a synergistic mechanism involving: 1) gas-phase dilution by non-combustible volatiles, 2) quenching of free radicals via phosphorus-containing species at the condensed phase, and 3) formation of a protective phosphorus-rich characeous barrier. Meanwhile, while the flame retardancy performance was significantly improved, the inherent mechanical properties of WPU were maintained. These findings offer valuable insights for developing environmentally friendly flame-retardant WPU systems with superior comprehensive performance.

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双dopo基阻燃剂的设计与合成：水性聚氨酯体系的性能评价与机理研究

水性聚氨酯（WPU）因其固有的安全性、环境兼容性和卓越性能，在环保涂料、粘合剂和相关领域获得了广泛应用。然而，它的高易燃性严重限制了其实际应用。在本研究中，我们设计了一种基于双 DOPO 的氮磷阻燃剂（PHED），随后将其加入到 WPU 中，开发出了阻燃 PHED-WPU。令人瞩目的是，12 wt% PHED 的加入将 WPU 的极限氧指数从 21.2% 提高到了 28.6%。此外，PHED-WPU 还表现出优异的阻燃特性，在垂直燃烧测试中达到了 V-0 级（UL-94，而原始 WPU 未达标），同时总产烟量和总放热量分别减少了 43.6% 和 30.5%。研究发现，12% PHED-WPU 在 600 °C 时的成炭率可达 7.37%，比 WPU（4.98%）高出 47.99%。阻燃性能的增强归因于一种协同机制，其中包括1) 气相被不可燃挥发物稀释；2) 凝聚相中的含磷物质淬灭自由基；3) 形成富磷炭质保护屏障。同时，在阻燃性能显著提高的同时，WPU 的固有机械性能得以保持。这些发现为开发具有优异综合性能的环境友好型阻燃 WPU 系统提供了宝贵的启示。

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来源期刊

Progress in Organic Coatings 工程技术-材料科学：膜

CiteScore

11.40

自引率

15.20%

发文量

577

审稿时长

48 days

期刊介绍： The aim of this international journal is to analyse and publicise the progress and current state of knowledge in the field of organic coatings and related materials. The Editors and the Editorial Board members will solicit both review and research papers from academic and industrial scientists who are actively engaged in research and development or, in the case of review papers, have extensive experience in the subject to be reviewed. Unsolicited manuscripts will be accepted if they meet the journal''s requirements. The journal publishes papers dealing with such subjects as: • Chemical, physical and technological properties of organic coatings and related materials • Problems and methods of preparation, manufacture and application of these materials • Performance, testing and analysis.