离子液体改性漂珠对聚氨酯复合材料的燃烧及热解行为影响研究
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摘要
利用离子液体[EOOEMIm][PF_6]对粉煤灰漂珠(FB)进行改性,制得了一种新型阻燃剂(FB@[EOOEMIm][PF_6]),并应用于热塑性聚氨酯弹性体(TPU)当中。采用烟密度仪(SDT)、锥形量热仪(CCT)、热重红外联用(TG-IR)等手段研究了复合材料的燃烧及热降解性能。SDT实验表明,在无焰或有焰条件下,FB@[EOOEMIm][PF_6]均能够增加TPU复合材料的光通量。CCT实验表明,FB@[EOOEMIm][PF_6]能够使得TPU复合材料的生烟速率(SPR)、总生烟量(TSR)、热释放速率(HRR)等参数较纯FB阻燃TPU显著降低,因而降低材料的生热及生烟性能。热重(TG)及热重红外联用(TG-IR)实验结果显示,FB@[EOOEMIm][PF_6]能够提高TPU复合材料的热稳定性,降低烟颗粒及有毒、有害气体的生成。所有实验结果证实,FB@[EOOEMIm][PF_6]在提高TPU的燃烧及热降解性能方面将会有较好的前景。
In this paper,a new type of flame retardant(FB@[EOOEMIm][PF_6])was prepared by modifying fly-ash floating beads(FB)with ionic liquid[EOOEMIm][PF_6]and applied in thermoplastic polyurethane(TPU).Then,the combustion and thermal degradation properties of the composites was evaluated using smoke density test(SDT),cone calorimeter test(CCT)and thermogravimetric analysis/infrared spectrometry(TG-IR),respectively.The SDT results indicated that FB@[EOOEMIm][PF_6]could improve the luminous flux of TPU composites in the test with or without flame.The CCT results demonstrated that the smoke production rate(SPR),total smoke release(TSR)and heat release rate(HRR)of the composites with FB@[EOOEMIm][PF_6]were significantly decreased than those of the composites with FB.Thus,the heat and smoke generation properties of the materials were decreased.The TG and TG-IR results showed that the thermal stability of TPU composites was improved by FB@ [EOOEMIm][PF_6]and the production of smoke particles,toxic and harmful gas were also reduced.All above results illustrated that FB@[EOOEMIm][PF_6]would have a good prospect in improving the combustion and thermal degradation properties of TPU.
In this paper,a new type of flame retardant(FB@[EOOEMIm][PF_6])was prepared by modifying fly-ash floating beads(FB)with ionic liquid[EOOEMIm][PF_6]and applied in thermoplastic polyurethane(TPU).Then,the combustion and thermal degradation properties of the composites was evaluated using smoke density test(SDT),cone calorimeter test(CCT)and thermogravimetric analysis/infrared spectrometry(TG-IR),respectively.The SDT results indicated that FB@[EOOEMIm][PF_6]could improve the luminous flux of TPU composites in the test with or without flame.The CCT results demonstrated that the smoke production rate(SPR),total smoke release(TSR)and heat release rate(HRR)of the composites with FB@[EOOEMIm][PF_6]were significantly decreased than those of the composites with FB.Thus,the heat and smoke generation properties of the materials were decreased.The TG and TG-IR results showed that the thermal stability of TPU composites was improved by FB@ [EOOEMIm][PF_6]and the production of smoke particles,toxic and harmful gas were also reduced.All above results illustrated that FB@[EOOEMIm][PF_6]would have a good prospect in improving the combustion and thermal degradation properties of TPU.
引文
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[11]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.
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[13]CHEN X,WANG W,JIAO C.A recycled environmental friendly flame retardant by modifying para-aramid fiber with phosphorus acid for thermoplastic polyurethane elastomer[J].Journal of Hazardous Materials,2017,331:257-264.
[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]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.
[3]李梅.几种纳米阻燃热塑性聚氨酯复合材料的制备、表征与燃烧、力学性能研究[D].青岛:青岛科技大学,2016.LI Mei.Prepared,Characterization,Combustion and Mechanical Properties of Several Nano-materials in Flame Retardant TPU Composite[D].Qingdao:Qingdao University of Science and Technology,2016.
[4]杨赞中,刘玉金,杨赞国,等.粉煤灰漂珠的物理化学性能及综合利用[J].矿产保护与利用,2002(5):46-49.YANG Zanzhong,LIU Yujin,YANG Zanguo,et al.Physicalchemical properties and utilization of floating beads in fly-ash from power plant[J].Conservation and Utilization of Mineral Resources,2002(5):46-49.
[5]王洪志,焦传梅.粉煤灰漂珠对热塑性聚氨酯弹性体的阻燃性能影响研究[J].青岛科技大学学报(自然科学版),2018,39(6):63-70.WANG Hongzhi,JIAO Chuanmei.Influence of fly-ash floating beads on flame retardant properties of thermoplastic polyurethane[J].Journal of Qingdao University of Science and Technology(Natural Science Edition),2018,39(6):63-70.
[6]HE Y,ZHANG Q,ZHAN X,et al.Synthesis of efficient SBA-15immobilized ionic liquid catalyst and its performance for Friedel-Crafts reaction[J].Catalysis Today,2016,276:112-120.
[7]RAN S,GUO Z,HAN L,et al.Effect of Friedel-Crafts reaction on the thermal stability and flammability of high-density polyethylene/brominated polystyrene/graphene nanoplatelet composites[J].Polymer International,2015,63(10):1835-1841.
[8]GANN R G,BABTAUSKAS V,PEACOCK R D,et al.Fire conditions for smoke toxicity measurement[J].Fire&Materials,2010,18(3):193-199.
[9]JIAO C M,WANG H Z,LI S X,et al.Fire hazard reduction of hollow glass microspheres in thermoplastic polyurethane composites[J].Journal of Hazardous Materials,2017,332:176-184.
[10]RICCIARDI M R,ANTONUCCI V,ZARRELLI M,et al.Fire behavior and smoke emission of phosphate-based inorganic fire-retarded polyester resin[J].Fire&Materials,2012,36(3):203-215.
[11]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.
[12]ZHOU K,GUI Z,HU Y.The influence of grapheme based smoke suppression agents on reduced fire hazards of polystyrene composites[J].Composites Part A,2016,80:217-227.
[13]CHEN X,WANG W,JIAO C.A recycled environmental friendly flame retardant by modifying para-aramid fiber with phosphorus acid for thermoplastic polyurethane elastomer[J].Journal of Hazardous Materials,2017,331:257-264.
[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.