伊利石基锌MOFs杂化阻燃剂的制备及在环氧树脂中的应用研究

Preparation of illite-based zinc MOFs hybrid flame retardant and its application in epoxy resin

  • 摘要: 环氧树脂(EP)易燃、热释放和烟气释放量高,限制了其在火灾安全领域的应用。本文以伊利石为载体,利用Zn2+与1,1′-二茂铁二甲酸(FDA)和氨基三亚甲基膦酸(ATMP)配位,制备伊利石基锌金属有机框架材料杂化阻燃剂(IAZnMOF),并引入EP制备IAZnMOF/EP复合材料。采用SEM、FTIR、XRD、XPS和TGA分析IAZnMOF结构及热稳定性,并通过LOI、UL-94、锥形量热、TG-FTIR和力学性能测试评价复合材料性能。结果表明,Zn、P、N和Fe等元素被引入伊利石体系,IAZnMOF在800℃时残余质量分数为91.64%。与纯EP相比,添加2份IAZnMOF的EP复合材料的LOI由23.8%提高至28.7%,UL-94由NR提高至V-1;相比纯EP,热释放速率峰值、烟释放速率峰值、CO产生速率峰值和CO2产生速率峰值分别降低73.5%、67.0%、78.4%和76.1%,燃烧后残余质量由10.3%提高至18.9%。残炭和TG-FTIR结果表明,IAZnMOF可促进致密膨胀炭层形成,并抑制可燃及有害挥发物释放;其阻燃作用以凝聚相促炭和阻隔为主,并伴随含磷活性物种的气相淬灭作用,从而提高EP的阻燃、抑烟和成炭性能,同时较好保持复合材料的力学性能。

     

    Abstract: Epoxy resin (EP) is flammable and releases large amounts of heat and smoke during combustion, which limits its application in fields with high fire safety requirements. To improve the flame retardancy, smoke suppression and char-forming ability of EP, an illite-based Zn metal-organic hybrid flame retardant (IAZnMOF) was prepared by coordination of Zn2+ with 1,1′-ferrocenedicarboxylic acid (FDA) and aminotrimethylene phosphonic acid (ATMP) using illite as the carrier, and then introduced into EP to prepare IAZnMOF/EP composites. The structure and thermal stability of IAZnMOF were characterized by SEM, FTIR, XRD, XPS and TGA. The properties of the composites were evaluated by LOI, UL-94, cone calorimetry, TG-FTIR and mechanical property tests. The results show that Zn, P, N and Fe were introduced into the illite system, and the residual mass fraction of IAZnMOF at 800℃ is 91.64%. Compared with pure EP, the LOI of 2IAZnMOF/EP increases from 23.8% to 28.7%, and the UL-94 rating improves from NR to V-1. The peak heat release rate, peak smoke production rate, peak CO production rate and peak CO2 production rate decrease by 73.5%, 67.0%, 78.4% and 76.1%, respectively, and the residual mass after combustion increases from 10.3% to 18.9%. Char residue and TG-FTIR results show that IAZnMOF promotes the formation of a compact intumescent char layer and suppresses the release of flammable and harmful volatile products. Its flame-retardant action is dominated by condensed-phase char formation and barrier effects, accompanied by gas-phase quenching by phosphorus-containing active species. As a result, the flame retardancy, smoke suppression and char-forming ability of EP are improved, while the mechanical properties of the composites are well maintained.

     

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