Preparation of trinity intumescent flame retardants to enhance the flame retardancy of polyurea composites
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摘要: 聚合物材料存在易燃、易被氧化的缺点,以及传统膨胀型阻燃体系存吸湿性大、阻燃效率较低、与基体相容性差等缺陷。结合气相阻燃、凝聚相阻燃的设计理念,制备出三位一体膨胀型阻燃剂(PTA-PA)。研究不同含量的PTA-PA对聚脲(PUA)的阻燃性能及力学的影响,分析材料在燃烧、热解过程中气相和凝聚相产物,探究PTA-PA阻燃剂的阻燃机制,建立膨胀型阻燃剂与复合材料热稳定性、阻燃性能和火灾安全性之间的关系。结果表明:和纯PUA相比,添加20.0wt% PTA-PA 的PUA复合材料(PUA-4)具有较高的热稳定性,800 ℃下残炭量为21.9%;PUA-4复合材料的垂直燃烧等级从V-2级提高到V-0级,LOI分别从22.2%提高到28.4%,线烧蚀率、热释放速率峰值和总热释放量分别降低19.8%,71.7%和18.3%。本研究为高性能阻燃聚合物复合材料的制备提供理论基础和事实依据。Abstract: Polymeric materials are inherently flammable and prone to oxidation. Traditional intumescent flame retardants exhibit drawbacks, including significant moisture absorption, limited flame-retardant efficacy, and suboptimal matrix compatibility. To address these challenges, a trinity intumescent flame retardant (PTA-PA) was synthesized, integrating the principles of gas-phase and condensed-phase flame retardation. This study examined the influence of varying PTA-PA concentrations on the flame resistance and mechanical properties of polyurea (PUA). It entailed analyzing combustion and pyrolysis byproducts to elucidate the mechanism of flame retardance provided by these novel agents. Additionally, the study correlated the introduction of PTA-PA with enhancements in thermal stability, flame retardance, and overall fire safety of the composites. The findings indicate that the PUA composite with a 20.0wt% loading of PTA-PA (PUA-4) exhibits increased thermal stability, evidenced by a residual carbon content of 21.9% at 800℃. Notably, the vertical burn rating of PUA-4 improved from V-2 to V-0, the limiting oxygen index (LOI) rose from 22.2% to 28.4%, and the rates of line ablation, peak heat release, and total heat release diminished by 19.8%, 71.7%, and 18.3%, respectively. This investigation provides a theoretical and empirical foundation for developing advanced flame-retardant polymeric composites.
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图 7 样品PUA-4的TG-IR分析: (a)Gram-Schmidt曲线;(b)Gram-Schmidt曲线峰值下FTIR光谱;(c)全过程NH3吸收光谱;(d)全过程饱和烷烃吸收光谱
Figure 7. TG-IR of PUA-4: (a) Gram-Schmidt curve; (b) FTIR of sample at the peaks of Gram-Schmidt curve; (c) whole process absorption spectrum of NH3; (d) whole process absorption spectrum of saturated alkane
表 1 喷涂耐烧蚀绝热材料配方
Table 1. 1 Formulation of sprayed ablation resistant material
Sample Component A/
wt%Component B/
wt%PTA-PA/wt% PUA 66.7 33.3 - PUA-1 63.3 31.7 5.0 PUA-2 60.0 30.0 10.0 PUA-3 56.7 28.3 15.0 PUA-4 53.3 26.7 20.0 Notes: PUA−Neat polyurea; PTA-PA−Flame retardant. 表 2 PUA复合材料LOI、UL-94、氧乙炔烧蚀和锥形量热仪测试数据
Table 2. Results of LOI, UL-94, OTA and cone calorimeter testsfor EVA composites
Sample UL-94 LOI LAR PHRR TPHRR THR FPI FGI TTI Dripping Rating % mm/s kW/m2 s MJ/m2 m2·s/kW kW/m2·s s PUA Y V-2 22.2 0.853 654 158 68.3 0.032 4.139 21 PUA-1 Y V-2 24.1 0.774 454 168 68.0 0.042 2.702 19 PUA-2 Y V-2 26.5 0.701 326 227 66.9 0.055 1.436 18 PUA-3 N V-0 27.0 0.695 268 264 66.0 0.063 1.015 17 PUA-4 N V-0 28.4 0.684 185 329 55.8 0.092 0.562 17 Notes: N−No; Y−Yes; LOI−Limiting oxygenindex; LAR−Linear ablation rate; PHRR−Peak heat release rate; TPHRR−Peak time corresponding to the heat release rate; THR−Total heat release; FPI−Fire performance index (FPI = TTI/PHRR); FGI−Fire growth index(FGI = PHRR/T PHRR); TTI−Ignition time. -
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