空心玻璃微珠与咪唑型离子液体组合阻燃热塑性聚氨酯弹性体
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摘要
采用空心玻璃微珠(HGM)与1-乙酸乙酯基-3-甲基咪唑四氟硼酸盐([EOOEMIm]·[BF_4])离子液体组合阻燃热塑性聚氨酯弹性体(TPU),并通过锥形量热仪(CCT)、烟密度仪(SDT)和热重红外联用(TG-IR)等手段研究了阻燃TPU的燃烧和热降解性能。锥形量热仪实验结果表明,HGM与[EOOEMIm][BF_4]的组合物能够显著提高TPU的阻燃性能。其中0.005%(质量分数)[EOOEMIm][BF_4]和0.995%(质量分数)HGM组合使TPU的热释放速率峰值(PHRR)降至最低(431.44kW·m~(-2))(TPU4),比纯TPU(1 417.37kW·m~(-2))与只含空心玻璃微珠的复合材料(537.80kW·m~(-2))分别降低了69.56%和19.78%。烟密度实验表明,无焰条件下HGM与[EOOEMIm][BF_4]的组合物能够使得光通量(LF)显著提高。TG-IR结果显示,HGM与[EOOEMIm][BF_4]的组合物能够提高TPU的热稳定性,降低有毒气体的生成。
In this paper,a series of flame retardant thermoplastic polyurethane(TPU)composites were prepared based on the combination of hollow glass microspheres(HGM)and 1-((ethoxycarbonyl)methyl)-3-methylimidazolium tetrafluoroborate([EOOEMIm][BF_4]).The combustion behavior and thermal degradation properties of TPU composites were investigated by cone calorimeter test(CCT),smoke density test(SDT),and thermogravimetric analysis/infrared spectrometry(TG-IR),respectively.The CCT results showed that the introduction of HGM and[EOOEMIm][BF_4]into TPU can significantly improve the flame re-tardant performance of TPU.The peak value of heat release rate(PHRR)from the composite containing 0.995%(mass content)HGM and 0.005% [EOOEMIm][BF_4]was the lowest(431.44 kW·m~(-2)),reduced by 69.56% and 19.78% respectively,compared with pure TPU and the composite only containing HGM.The SDT results indicated that the combination of HGM and[EOOEMIm][BF_4]could greatly improve the luminous flux(LF)of flame retardant TPU composites in the test without flame.TG-IR data revealed that the combination of HGM and[EOOEMIm][BF_4]could improve the thermal stability of TPU and reduce the production of some toxic gases.
In this paper,a series of flame retardant thermoplastic polyurethane(TPU)composites were prepared based on the combination of hollow glass microspheres(HGM)and 1-((ethoxycarbonyl)methyl)-3-methylimidazolium tetrafluoroborate([EOOEMIm][BF_4]).The combustion behavior and thermal degradation properties of TPU composites were investigated by cone calorimeter test(CCT),smoke density test(SDT),and thermogravimetric analysis/infrared spectrometry(TG-IR),respectively.The CCT results showed that the introduction of HGM and[EOOEMIm][BF_4]into TPU can significantly improve the flame re-tardant performance of TPU.The peak value of heat release rate(PHRR)from the composite containing 0.995%(mass content)HGM and 0.005% [EOOEMIm][BF_4]was the lowest(431.44 kW·m~(-2)),reduced by 69.56% and 19.78% respectively,compared with pure TPU and the composite only containing HGM.The SDT results indicated that the combination of HGM and[EOOEMIm][BF_4]could greatly improve the luminous flux(LF)of flame retardant TPU composites in the test without flame.TG-IR data revealed that the combination of HGM and[EOOEMIm][BF_4]could improve the thermal stability of TPU and reduce the production of some toxic gases.
引文
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[11]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.
[12]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.
[13]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.
[2]张军,纪奎江,夏延致.聚合物燃烧与阻燃技术[M].北京:化学工业出版社,2005:57-105,387-389.ZHANG Jun,JI Kuijiang,XIA Yanzhi.Polymer Combustion and Flame Retardant Technology[M].Beijing:Chemistry Industry Press,2005:57-105,387-389.
[3]韩非,辛浩波,张云峰.聚氨酯弹性体的合成及表征[J].青岛科技大学学报(自然科学版),2008,29(1):43-46.HAN Fei,XIN Haobo,ZHANG Yunfeng.Synthesis and characterization of polyurethane elastomers[J].Journal of Qingdao University of Science and Technology(Natural Science Edition),2008,29(1):43-46.
[4]孙立艳.阻燃聚氨酯泡沫塑料的制备及性能研究[D].天津:天津工业大学,2013.SUN Liyan.Preparation of Flame Retardant Polyurethane and Its Study on Performance[D].Tianjin:Tianjin Polytechnic University,2013.
[5]翟金国,许肖丽,尹亮.硅烷微胶囊包覆聚磷酸铵的制备及其阻燃TPU的研究[J].聚氨酯工业,2015,30(6):8-11.ZHAI Jinguo,XU Xiaoli,YIN Liang.Preparation of silanemodified ammonium polyphosphate and its application in flame retardancy of TPU[J].China Plastics Industry,2015,30(6):8-11.
[6]DOUMBIA A S,BOURMAUD A,JOUANNET D,et al.Hollow microspheres-poly-(propylene)blends:Relationship between microspheres degradation and composite properties[J].Polymer Degradation&Stability,2015,114:146-153.
[7]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.
[8]李思源,党晓容.1-丁基-3-甲基咪唑甲磺酸盐离子液体对聚碳酸酯阻燃性能及热降解行为的影响[J].高分子通报,2010(11):78-85.LI Siyuan,DANG Xiaorong.Effect of ionic liquid[Bmim]OTM on the flame retardancy and thermal degradation of polycarbonate[J].Chinese Polymer Bulletin,2010(11):78-85.
[9]李艳伟,王桂兴,叶建,等.咪唑型离子液体对聚氨酯硬泡阻燃性能的影响研究[J].聚氨酯工业,2012,27(3):5-8.LI Yanwei,WANG Guixing,YE Jian,et al.The study in effect of imidazole ionic liquid on the flame retardancy of rigid polyurethane foam[J].Polyurethane Industry,2012,27(3):5-8.
[10]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 flame retardant 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.
[11]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.
[12]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.
[13]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.