›› 2023, Vol. 37 ›› Issue (3): 83-87.

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Ni-MOF与焦磷酸哌嗪对环氧树脂的协同阻燃及抑烟

满婷莉,沈文涛,许苗军   

  1. 东北林业大学
  • 收稿日期:2022-12-19 修回日期:2022-12-28 出版日期:2023-03-26 发布日期:2023-03-26

Synergistic flame retardancy and smoke suppression of epoxy thermosets with Ni?MOF and piperazine pyrophosphate

  • Received:2022-12-19 Revised:2022-12-28 Online:2023-03-26 Published:2023-03-26

摘要: 将含镍金属有机框架材料(Ni-MOF)与焦磷酸哌嗪(PPAP)复配后添加到环氧树脂(EP)中,通过极限氧指数(LOI)、垂直燃烧(UL 94)及锥形量热(CONE)测试研究了材料的阻燃性能及烟释放行为。结果表明,添加6 %(质量分数,下同)的PPAP时,材料的LOI值为27.9 %,垂直燃烧测试通过了UL 94 V-0级;当PPAP与Ni-MOF以质量比99∶1混合,总添加量为5 %时,材料的LOI值达到29.3 %并通过了UL 94 V-0级;极少量Ni-MOF的加入,有效提高了材料的阻燃效率。CONE测试表明,在相同阻燃剂添加量下,EP/PPAP/Ni-MOF材料的热释放速率、总热释放量、烟释放速率及总烟释放量,与EP/PPAP材料相比均得到了明显降低;Ni-MOF的引入,降低了材料的燃烧强度,减少了烟气的释放;Ni离子与PPAP受热分解形成的磷酸及多聚磷酸发生交联,将更多的磷留在了凝聚相中,促进了材料形成更加丰富、强度更高的炭层,有效抑制EP燃烧过程中热量和烟气的释放,从而提高了EP材料的火安全性能。

关键词: 环氧树脂, 阻燃, 抑烟, 含镍金属有机框架材料, 焦磷酸哌嗪

Abstract: A mixture of nickel ion-containing metal organic frameworks (Ni-MOF) and piperazine pyrophosphate (PPAP) was incorporated into epoxy resin (EP) to form compounding EP thermosets, and their flame-retardant performance and smoke release behaviors were investigated by means of limiting oxygen index (LOI), vertical burning test, and cone calorimeter (CONE). The results indicated that the compounding EP thermosets achieved a UL 94 V-0 classification in the vertical burning test, and their LOIs reached 27.9 vol% with the addition of 6 % PPAP. However, the EP/PPAP/Ni-MOF compounding thermosets obtained a UL 94 V-0 classification together with a LOI of 29.3 vol% with the addition of 5 wt% PAPP/Ni-MOF at a mass ratio of 99∶1. These results demonstrated that the addition of a small amount of Ni-MOF effectively improved the flame retardancy for EP thermosets. Cone calorimetric test results indicated that the EP/PPAP/Ni-MOF compounding thermosets exhibited an obviously lower heat release rate, total heat release, smoke release rate and total smoke release than the EP/PPAP ones under the same loading of flame retardants. The addition of Ni-MOF inhibited the combustion intensity and smoke release of EP thermosets. Nickel ions in Ni-MOF could be cross-linked with the phosphoric acid and polyphosphoric acid generated from the thermal degradation of PPAP, which resulted in more phosphorus components remaining in the condensed phase. Consequently, sufficient char layers with good strength were formed to effectively inhibit the release of heat and smoke during combustion. This enhanced the fire safety performance of EP thermosets significantly.

Key words: epoxy resin, flame retardant, smoke suppression, nickel-containing metal organic framework material, piperazine pyrophosphate