离子液体协效芳纶纤维阻燃热塑性聚氨酯
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摘要
使用1-乙酸乙酯基-3-甲基咪唑六氟磷酸盐([EOOEMIm][PF_6])协效芳纶纤维(AF)阻燃热塑性聚氨酯(TPU),采取锥形量热仪(CCT)、热重分析(TGA)和热重-红外联用(TG-IR)等手段对阻燃TPU的燃烧性能及热解性能进行了测试研究。研究结果表明[EOOEMIm][PF_6]协效AF阻燃体系可以有效地提高TPU的热稳定性,AF和[EOOEMIm][PF_6]的添加量(质量分数)各为0.5%时效果最为明显,其中热释放速率峰值(PHRR)降低至253.2 kW·m~(-2),较纯TPU降低了67.22%,此外,烟参数也得到了明显改善;TGA结果显示,AF和[EOOEMIm][PF_6]的添加可以提高阻燃TPU的炭渣余量;TG-IR结果表明,[EOOEMIm][PF_6]协效AF阻燃体系可以降低TPU热解过程中CO_2、H_2O及挥发性有机物的释放量。这说明[EOOEMIm][PF_6]协效AF体系具有良好的阻燃效果和应用前景。
In this paper, a system of 1-ethylacetate-3-methylimidazolium hexafluorophosphate([EOOEMIm][PF_6]) synergistic aramid fiber(AF) were used to prepare flame retardant thermoplastic polyurethane, the combustion performance and pyrolysis performance of flame-retardant TPU were tested by cone calorimetry(CCT), thermogravimetric analysis(TGA) and thermogravimetric analysis/infrared spectrometry(TG-IR). The results of the study showed that the flame-retardant system of [EOOEMIm][PF_6] synergistic AF could improve the thermal stability of TPU effectively. The effect was most pronounced when 0.5% of AF and [EOOEMIm][PF_6] were added, the peak heat release rate(PHRR) was reduced to 253.2 kW·m~(-2), which was 67.22% lower than that of pure TPU, and the smoke parameters also improved significantly. The TGA results showed that the addition of AF and [EOOEMIm] [PF_6] could improve the residual carbon residue of flame-retardant TPU. The TG-IR results showed that the flame-retardant system of [EOOEMIm][PF_6] synergistic AF could reduce the release of CO_2, H_2O and volatile organic compounds during the pyrolysis of TPU. These results proved that the [EOOEMIm][PF_6] co-efficient AF system has a good flame-retardant effect and application prospects.
In this paper, a system of 1-ethylacetate-3-methylimidazolium hexafluorophosphate([EOOEMIm][PF_6]) synergistic aramid fiber(AF) were used to prepare flame retardant thermoplastic polyurethane, the combustion performance and pyrolysis performance of flame-retardant TPU were tested by cone calorimetry(CCT), thermogravimetric analysis(TGA) and thermogravimetric analysis/infrared spectrometry(TG-IR). The results of the study showed that the flame-retardant system of [EOOEMIm][PF_6] synergistic AF could improve the thermal stability of TPU effectively. The effect was most pronounced when 0.5% of AF and [EOOEMIm][PF_6] were added, the peak heat release rate(PHRR) was reduced to 253.2 kW·m~(-2), which was 67.22% lower than that of pure TPU, and the smoke parameters also improved significantly. The TGA results showed that the addition of AF and [EOOEMIm] [PF_6] could improve the residual carbon residue of flame-retardant TPU. The TG-IR results showed that the flame-retardant system of [EOOEMIm][PF_6] synergistic AF could reduce the release of CO_2, H_2O and volatile organic compounds during the pyrolysis of TPU. These results proved that the [EOOEMIm][PF_6] co-efficient AF system has a good flame-retardant effect and application prospects.
引文
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[13] BANGALORE A S,SHAFFER R E,SMALL G W,et al.Genetic algorithm-based method for selecting wavelengths and model size for use with partial least-squares regression:Application to near-infrared spectroscopy[J].Analytical Chemistry,1996,68(23):4200-4212.
[14] ASLZADEH M M,ABDOUSS M,SADEGHI G M M.Preparation and characterization of new flame retardant polyurethane composite and nanocomposite[J].Journal of Applied Polymer Science,2013,127(3):1683-1690.
[2] 孙杰,焦传梅.氧化锌与膨胀型阻燃剂对聚丙烯的协效阻燃[J].青岛科技大学学报(自然科学版),2012,32(2):172-176.SUN Jie,JIAO Chuanmei.Synergistic flame resistant effect of zinc oxide and intumescent flame retardant in polypropylene[J].Journal of Qingdao University of Science and Technology (Natural Science Edition),2012,32(2):172-176.
[3] 王庆国,张军,张峰.锥形量热仪的工作原理及应用[J].现代科学仪器,2003(6):36-39.WANG Qingguo,ZHANG Jun,ZHANG Feng.The principle and application of the cone calorimeter[J].Modern Scientific Instruments,2003(6):36-39.
[4] CHEN X L,JIANG Y F,JIAO C M.Synergistic effects between hollow glass microsphere and ammonium polyphosphate on flame-retardant thermoplastic polyurethane[J].Journal of Thermal Analysis and Calorimetry,2014,117(2):857-866.
[5] 居亚庆,王佳辉,王新龙.改性硅树脂微球阻燃PP的制备及性能[J].塑料,2015,44(2):18-21.JU Yaqing,WANG Jiahui,WANG Xinlong.Preparation and property of flame retardant PP by modified silicone resin particles[J].Plastics,2015,44(2):18-21.
[6] 霍莉莉,王月月,焦传梅,等.聚苯乙烯泡沫保温材料的燃烧性能及热解动力学[J].青岛科技大学学报(自然科学版),2013,34 (5):501-505.HUO Lili,WANG Yueyue,JIAO Chuanmei,et al.Combustion properties and pyrolysis kinetics of polystyrene foam insulation materials[J].Journal of Qingdao University of Science and Technology(Natural Science Edition),2013,34(5):501-505.
[7] 李晓俊,刘小兰,刘宪增,等.硅树脂阻燃聚碳酸酯的研究[J].工程塑料应用,2005,33(2):16-18.LI Xiaojun,LIU Xiaolan,LIU Xianzeng,et al.Study on silicone flame retardant polycarbonate[J].Application of Engineering Plastics,2005,33(2):16-18.
[8] MENACHEM L.Synergistic and catalytic effects in flame retardancy of polymeric materials-an overview[J].Journal of Fire Sciences,1999,17(1):3-19.
[9] 周玉彬,韩文,刘丽娜,等.锥形量热法研究可膨胀石墨对微孔聚氨酯弹性体的阻燃作用[J].青岛科技大学学报(自然科学版),2016,37(4):429-432.ZHOU Yubin,HAN Wen,LIU Lina,et al.Intumescent flameretardant effect of graphite on microcellular polyurethane elastomers by cone method[J].Journal of Qingdao University of Science and Technology (Natural Science Edition),2016,37(4):429-432.
[10] YANG X F,GE N L,HU L Y,et al.Synthesis of a novel ionic liquid containing phosphorus and its application in intumescent flame retardant polypropylene system[J].Polymers for Advanced Technologies,2013,24(6):568-575.
[11] JIAO C,WANG H,LI S,et al.Fire hazard reduction of hollow glass microspheres in thermoplastic polyurethane composites[J].Journal of Hazardous Materials,2017,332:176-184.
[12] 黎丹,吴俊,王业强.粉煤灰综合利用研究现状[J].绿色科技,2013(7):197-199.LI Dan,WU Jun,WANG Yeqiang.Research status of comprehensive utilization of fly ash[J].Journal of Green Science and Technology,2013(7):197-199.
[13] BANGALORE A S,SHAFFER R E,SMALL G W,et al.Genetic algorithm-based method for selecting wavelengths and model size for use with partial least-squares regression:Application to near-infrared spectroscopy[J].Analytical Chemistry,1996,68(23):4200-4212.
[14] ASLZADEH M M,ABDOUSS M,SADEGHI G M M.Preparation and characterization of new flame retardant polyurethane composite and nanocomposite[J].Journal of Applied Polymer Science,2013,127(3):1683-1690.