›› 2023, Vol. 37 ›› Issue (7): 80-86.

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新型氮磷硅阻燃剂的合成及其在聚丙烯中的应用

冯明珠,张泽,万里,崔永岩   

  1. 天津科技大学化工与材料学院
  • 收稿日期:2023-03-01 修回日期:2023-03-13 出版日期:2023-07-26 发布日期:2023-07-26

Synthesis and application of novel nitrogen and phosphorus flame retardants for polypropylene

  • Received:2023-03-01 Revised:2023-03-13 Online:2023-07-26 Published:2023-07-26

摘要: 采用9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)、1,3,5-三缩水甘油异氰脲酸酯(TGIC)和γ-氨乙基氨丙基三甲氧基硅烷(KH792),合成了一种新型含氮、磷、硅的阻燃剂(TDK),然后将TDK与聚磷酸铵(APP)、三聚氰胺焦磷酸盐(MPP)共混制备膨胀阻燃聚丙烯,并与传统膨胀阻燃配方聚丙烯(PP)/APP/双季戊四醇(Di-PE)/MPP复合材料进行性能比较。TDK的结构和成分通过傅里叶变换红外光谱、31P-固态核磁共振和元素分析进行验证。结果表明,在膨胀型阻燃剂(IFR)的添加量为30份时,纯PP在329.0 ℃开始降解,而PP/APP/MPP/TDK复合材料的成炭反应先于PP基体发生,复合材料的分解温度为273.8 ℃,且PP/APP/MPP/TDK复合材料的残炭率较纯PP提高了13.8 %。此外,PP/APP/MPP/TDK的极限氧指数提高到了30.5 %,垂直燃烧可以达到UL 94 V-0级别,热释放率降低了86 %,产烟率降低了78.8 %,且具有比PP/APP/MPP/Di-PE更好的力学性能。通过扫描电子显微镜、傅里叶变换红外光谱、能量色散光谱法进一步分析了阻燃性能和阻燃机理,发现磷、氮、硅的协同作用主要在凝聚相中发挥优异的阻燃作用。

关键词: 聚丙烯, 膨胀阻燃, 合成, 无卤, 抑烟

Abstract: A novel flame retardant (TDK) containing nitrogen, phosphorus, and silicon elemetns was synthesized by using 9,10-dihydro-9-oxa-10-phosphoxanthophosphor-10-oxide (DOPO), 1,3,5-three glycidyl different melamine urea acid ester, and gamma-ammonia ethyl ammonium propyl silane as raw materails. The resultant TDK was blended with ammonium polyphosphate (APP) and melamine pyrophosphate (MPP) to prepare intumescent-flame-retardant polypropylene, and its performance was compared with the traditional intumescent-flame-retardant PP/APP/MPP/dipentaerythritol (Di-PE) composite. The structure and composition of TDK were verified by FTIR, 31P solid-state NMR, and elemental analysis. Thermogravimetric analysis indicated that PP began to degrade at 329.0 ℃ when 30 phr of IFR was added. On the other hand, the carbonization reaction of the PP/APP/MPP/TDK composite was earlier than that of PP matrix, and its decomposition temperature was 273.8 ℃. Moreover, the carbon residue rate of the PP/APP/MPP/TDK composite was 13.8 % higher than that of pure PP. In addition, the PP/APP/MPP/TDK composite presented a limiting oxygen index of 30.5 wt%, and its flame retardant classification reached V-0 level classification in the vertical combustion. Its heat release rate was reduced by 86 %, its smoke production rate was reduced by 78.8 %, and its mechanical properties were better than those of the PP/APP/MPP/Di-PE composite. The flame retardant performance and corresponding mechanism of the developed composite were further analyzed by using scanning electron microscopy, infrared spectroscopy, and energy dispersion spectroscopy. The results indicated that there was a synergistic effect of phosphorus, nitrogen and silicon on the flame retardancy of PP in the condensed phase.

Key words: polypropylene, intumescent flame retardant, synthesis, halogen-free, smoke suppression