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以9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物修饰的海胆状镍钴基双金属氢氧化物作为高疏水性阻燃剂,用于显著降低聚(L-乳酸)的火灾危险性。

Urchin-like NiCo-based bimetallic hydroxide decorated with DOPO as highly hydrophobic flame retardant for remarkably reducing fire hazard of poly (L-lactic acid).

作者信息

Luo Qian, Ding Chi-Jie, Zhong Cheng-Zhi, Wang Lei, Wang Niang-Liang, Li Wei-Du, Tang Zhe-Hong, Xu Sheng

机构信息

School of Chemical Engineering, Xiangtan University, Xiangtan 411105, Hunan, China.

School of Chemical Engineering, Xiangtan University, Xiangtan 411105, Hunan, China.

出版信息

Int J Biol Macromol. 2024 Sep 25;280(Pt 3):136028. doi: 10.1016/j.ijbiomac.2024.136028.

Abstract

Designing high-performance flame retardants for poly (L-lactic acid) (PLA) materials and exploring a simple and scalable strategy have been hot topics in research. In this work, a novel and highly efficient flame retardant, that is, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) decorated urchin-like NiCo-based bimetallic hydroxide (NiCo-BH@DOPO), was synthesized and incorporated into PLA to prepare PLA and NiCo-BH@DOPO (PLA/NiCo-BH@DOPO) composite. Benefiting from the DOPO organic modification, NiCo-BH@DOPO had superb hydrophobicity and presented excellent dispersion in the PLA matrix. When 20 wt% NiCo-BH@DOPO was added, the LOI value of PLA/NiCo-BH@DOPO composites reached 33.2 %, passed the V-0 level of UL-94 grade, and its maximum peak heat release rate (PHRR) and total heat release (THR) were reduced by 13.2 % and 17.3 %, respectively, compared with PLA/NiCo-BH composites. Furthermore, the residue of PLA/NiCo-BH@DOPO at 800 °C reached 19.8 wt% and the T (temperature at 10 % weight loss) increased by 33 °C. More importantly, the residual PLA/NiCo-BH@DOPO char exhibits a significantly reduced presence of large cracks compared to PLA/NiCo-BH, indicating a more compact formation of residual char. NiCo-BH@DOPO endowed PLA with outstanding flame retardancy, thermal stability and carbonization properties, which were owing to the multi-coordinating effect transition metal (NiCo-BH) catalyzed the char formation to form a char layer barrier and DOPO free radicals captured to inhibit the combustion reaction chain. This investigation provided a facile strategy for the novel multi-function NiCo-based bimetallic hydroxide flame retardant, expanding NiCo-BH potential applications in PLA.

摘要

设计用于聚(L-乳酸)(PLA)材料的高性能阻燃剂并探索一种简单且可扩展的策略一直是研究中的热门话题。在这项工作中,合成了一种新型高效阻燃剂,即9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)修饰的海胆状镍钴基双金属氢氧化物(NiCo-BH@DOPO),并将其引入PLA中制备PLA与NiCo-BH@DOPO(PLA/NiCo-BH@DOPO)复合材料。受益于DOPO的有机改性,NiCo-BH@DOPO具有优异的疏水性,并在PLA基体中表现出良好的分散性。当添加20 wt%的NiCo-BH@DOPO时,PLA/NiCo-BH@DOPO复合材料的极限氧指数(LOI)值达到33.2%,通过了UL-94等级的V-0级,与PLA/NiCo-BH复合材料相比,其最大热释放峰值速率(PHRR)和总热释放量(THR)分别降低了13.2%和17.3%。此外,PLA/NiCo-BH@DOPO在800℃时的残炭率达到19.8 wt%,热失重10%时的温度(T)提高了33℃。更重要的是,与PLA/NiCo-BH相比,PLA/NiCo-BH@DOPO的残余炭层中明显减少了大裂纹的存在,表明残余炭层的形成更加致密。NiCo-BH@DOPO赋予了PLA优异的阻燃性、热稳定性和碳化性能,这是由于过渡金属(NiCo-BH)的多配位效应催化形成炭层屏障,以及DOPO自由基捕获抑制燃烧反应链。本研究为新型多功能镍钴基双金属氢氧化物阻燃剂提供了一种简便策略,拓展了NiCo-BH在PLA中的潜在应用。

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