硅烷偶联剂改性聚磷酸铵的制备及其阻燃热塑性聚氨酯弹性体的性能研究
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摘要
采用硅烷偶联剂KH550(AMEO)无水条件下改性聚磷酸铵(APP),并用于阻燃热塑性聚氨酯弹性体(TPU)。通过扫描电镜-能谱分析(SEM-EDS)手段研究了APP@AMEO的结构与元素分布特点。并且通过锥形量热仪(CCT)、微型量热仪(MCC)、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。CCT结果表明:APP@AMEO能够明显降低TPU复合材料的热释放速率(HRR)、总热释放(THR),生烟速率(SPR)等,其中含有质量分数为12.5%APP@AMEO的TPU复合材料(TPU/APP-2)的HRR峰值比含相同含量APP的TPU复合材料(TPU/APP)的HRR峰值降低了8.7%。SDT结果表明:无焰条件下APP@AMEO能够使得TPU复合材料的光通量(LF)显著提高。TG-IR结果显示:APP@AMEO不仅能够显著提高TPU的热稳定性,而且能够降低有毒有害气体的生成。
In this paper,the ammonium polyphosphate(APP)was modified by the silane coupling agent KH-550 without water and applied in flame retardant thermoplastic polyurethane(TPU).The structure and element distribution properties of APP@AMEO were characterized by SEM-EDS methods.And the combustion behavior and thermal degradation properties of TPU composites were investigated by cone calorimeter test(CCT),microscale combustion colorimeter test(MCC),smoke density test(SDT)and thermogravimetric analysis/infrared spectrometry(TG-IR),respectively.The CCT results showed that the heat re-lease rate(HRR),total heat release(THR),and smoke production rate(SPR)of the TPU composite was significantly reduced by APP@AMEO.Remarkably,the peak HRR of the sample with 12.5% APP@AMEO(TPU/APP-2)was reduced by 8.7% compared with the sample with the same loading of APP(TPU/APP).The SDT results indicated that APP@AMEO could greatly improve the luminous flux(LF)of TPU composites in the test without flame.TG-IR data revealed that APP@AMEO could not only improve the thermal stability of TPU,but also reduce the production of some toxic and hazardous gases.In conclusion,APP@AMEO will have a good application prospect in the field of flame retardant.
In this paper,the ammonium polyphosphate(APP)was modified by the silane coupling agent KH-550 without water and applied in flame retardant thermoplastic polyurethane(TPU).The structure and element distribution properties of APP@AMEO were characterized by SEM-EDS methods.And the combustion behavior and thermal degradation properties of TPU composites were investigated by cone calorimeter test(CCT),microscale combustion colorimeter test(MCC),smoke density test(SDT)and thermogravimetric analysis/infrared spectrometry(TG-IR),respectively.The CCT results showed that the heat re-lease rate(HRR),total heat release(THR),and smoke production rate(SPR)of the TPU composite was significantly reduced by APP@AMEO.Remarkably,the peak HRR of the sample with 12.5% APP@AMEO(TPU/APP-2)was reduced by 8.7% compared with the sample with the same loading of APP(TPU/APP).The SDT results indicated that APP@AMEO could greatly improve the luminous flux(LF)of TPU composites in the test without flame.TG-IR data revealed that APP@AMEO could not only improve the thermal stability of TPU,but also reduce the production of some toxic and hazardous gases.In conclusion,APP@AMEO will have a good application prospect in the field of flame retardant.
引文
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[8]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.
[9]JIAO C M,WANG H Z,ZHANG Z B,et al.Preparation and properties of an efficient smoke suppressant and flame-retardant agent for thermoplastic polyurethane[J].Polymers for Advanced Technologies,2017,28(12):1690-1698.
[10]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.
[11]JIAO C,ZHAO X,SONG W,et al.Synergistic flame retardant and smoke suppression effects of ferrous powder with ammonium polyphosphate in thermoplastic polyurethane composites[J].Journal of Thermal Analysis and Calorimetry,2015,120(2):1173-1181.
[12]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.
[13]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.
[14]霍莉莉,王月月,焦传梅.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.
[15]王洪志,焦传梅.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的研究[J].青岛科技大学学报(自然科学版),2018,39(4):60-67.WANG Hongzhi,JIAO Chuanmei.Flame retardant thermoplastic polyurethane based on the combination of hollow glass microspheres and imidazole ionic liquids[J].Journal of Qingdao University of Science and Technology(Natural Science Edition),2018,39(4):60-67.
[2]CHATTOPADHYAY D K,WEBSTER D C.Thermal stability and flame retardancy of polyurethanes[J].Progress in Polymer Science,2009,34(10):1068-1133.
[3]LIN M,LI B,LI Q,et al.Synergistic effect of metal oxides on the flame retardancy and thermal degradation of novel intumescent flame-retardant thermoplastic polyurethanes[J].Journal of Applied Polymer Science,2011,121(4):1951-1960.
[4]王洪志,焦传梅.硅胶低聚物阻燃热塑性聚氨酯弹性体的研究[J].青岛科技大学学报(自然科学版),2017,38(1):87-92.WANG Hongzhi,JIAO Chuanmei.Research of flame retardant thermoplastic polyurethane elastomer based on silicone oligomer[J].Journal of Qingdao University of Science and Technology(Natural Science Edition),2017,38(1):87-92.
[5]李剑波.我国阻燃剂的发展建议与展望[J].橡胶科技,2010,8(4):8-10.LI Jianbo.Development suggestion and prospect of flame retardant in China[J].Rubber Science and Technology,2010,8(4):8-10.
[6]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,2005:93-98.ZHANG Jun,JI Kuijiang,XIA Yanzhi.Polymer Combustion and Flame Retardant Technology[M].Beijing:Chemistry Industry Press,2005:93-98.
[7]CHEN X L,MA C Y,JIAO C M.Synergistic effects between iron-graphene and ammonium polyphosphate in flame-retardant thermoplastic polyurethane[J].Journal of Thermal Analysis&Calorimetry,2016,126(2):1-10.
[8]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.
[9]JIAO C M,WANG H Z,ZHANG Z B,et al.Preparation and properties of an efficient smoke suppressant and flame-retardant agent for thermoplastic polyurethane[J].Polymers for Advanced Technologies,2017,28(12):1690-1698.
[10]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.
[11]JIAO C,ZHAO X,SONG W,et al.Synergistic flame retardant and smoke suppression effects of ferrous powder with ammonium polyphosphate in thermoplastic polyurethane composites[J].Journal of Thermal Analysis and Calorimetry,2015,120(2):1173-1181.
[12]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.
[13]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.
[14]霍莉莉,王月月,焦传梅.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.
[15]王洪志,焦传梅.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的研究[J].青岛科技大学学报(自然科学版),2018,39(4):60-67.WANG Hongzhi,JIAO Chuanmei.Flame retardant thermoplastic polyurethane based on the combination of hollow glass microspheres and imidazole ionic liquids[J].Journal of Qingdao University of Science and Technology(Natural Science Edition),2018,39(4):60-67.