| 韩旭,张晓华,张松利,周恒.化学通报,2021,84(10):1066-1073. |
| 含磷氮POSS改性乙烯基树脂的阻燃性和热性能的研究 |
| Study on the Flame Retardant and Thermal Properties of POSS modified vinyl resin containing phosphorus and nitrogen |
| 投稿时间：2021-03-04 修订日期：2021-04-03 |
| DOI： |
| 中文关键词: 乙烯基树脂 POSS 阻燃 热稳定性 磷氮协同 |
| 英文关键词:Vinyl resin POSS Flame retardant Thermal stability P/N Synergistic effect |
| 基金项目:国家自然科学基金项目(51873215和52003272)和北京市自然科学基金项目(2204101)资助 |
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| 中文摘要: |
| 乙烯基树脂（VE）具有优异的耐腐蚀特性及良好的机械强度，但由于其易燃烧的缺点，极大地限制了其在轨道交通、船舶运输等领域的应用。本文采用多聚甲醛(POM)，γ-氨丙基三乙氧基硅烷(KH550)和9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)为原料，通过经典的Kabachnik反应制备了含磷、氮的笼型和半笼型结构的低聚倍半硅氧烷（N/P-POSS）。然后，通过与商品化MFE-711乙烯基树脂共混/共聚的方法制备得到改性乙烯基树脂。采用红外光谱（FTIR）、核磁共振氢谱（1H-NMR）和基质辅助激光解析飞行时间质谱（MALDI-TOF）对阻燃剂（N/P-POSS）进行了结构表征；采用氧指数（LOI）、UL-94垂直燃烧、锥形量热、热重分析（TGA）以及动态力学分析（DMA）等方法对乙烯基树脂固化物的阻燃性能和耐热性能进行了研究。结果表明，当N/P-POSS的添加量为4 wt%时，乙烯基树脂固化物的LOI从19.5提高至27.5，并通过UL-94 V-1测试。并且热释放速率峰值(PHRR)和总热释放量（THR）分别降低了47.2 %和20.9 %。同时N/P-POSS的引入显著提高了乙烯基树脂的耐热性能，热分解温度提高了近10 ℃。采用扫描电镜（SEM）和热重红外（TG-FTIR）分析了其阻燃机理，主要为含磷自由基的淬灭效应，以及生成致密二氧化硅陶瓷相和含氮不可燃气体的阻隔作用，表现出了良好的磷、氮、硅协同阻燃效应。 |
| 英文摘要: |
| Vinyl resin (VE) has excellent corrosion resistance and good mechanical strength, but due to its combustible shortcoming, its application in rail transportation, ship transportation and other fields is greatly limited. The cage and half-cage polyhedral silsesquioxane (N/P-POSS) flame retardants containing phosphorus and nitrogen were synthesized by classical kabachnik-fields between polyoxymethylene (POM), γ-aminopropyltriethoxysilane (KH550) and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO). Then, the modified vinyl resin was prepared by blending/copolymerization with commercial MFE-711 vinyl resin. The chemical structure of N/P-POSS was characterized by Fourier transform infrared spectroscopy (FTIR), 1H nuclear magnetic resonance (NMR) spectroscopy, matrix-assisted laser desorption ionization time of flight (MALDI-TOF), and the flame retardancy and heat resistance were studied by the limiting oxygen index value (LOI), UL-94 vertical combustion, cone calorimetry, thermal gravimetric analysis (TGA) and dynamic mechanical analysis (DMA) tests. The results show that with the addition of 4 wt% N/P-POSS, the LOI increased from 19.5 to 27.5 and vertical burning (UL-94) V-1 rating was achieved. The peak heat release rate (PHRR) and total heat release (THR) decreased by 47.2 % and 20.9 %, respectively. At the same time, the introduction of N/P-POSS can significantly improve the heat resistance of the vinyl resin, and the thermal decomposition temperature increased by nearly 10 ℃. Scanning electron microscopy (SEM) and TG-FTIR analysis showed that the main flame retardant mechanism was the quenching of phosphorus containing free radicals, and the formation of dense silica ceramic phase and the barrier effect of nitrogen containing noncombustible gas, showing a good synergistic flame retardant effect of phosphorus, nitrogen and silicon. |
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