四氟硼酸盐离子液体改性漂珠的制备及其阻燃热塑性聚氨酯弹性体的研究
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摘要
采用离子液体[EOOEMIm][BF4]改性粉煤灰漂珠(FB)制备了一种新型阻燃剂FB@[EOOEMIm][BF4],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FB@[EOOEMIm][BF4]的结构与元素分布特点,并且通过锥形量热仪(CCT)、烟密度仪(SDT)、热重(TG)及热重红外联用(TG-IR)等手段研究了TPU的阻燃及热降解性能。CCT实验表明:FB@[EOOEMIm][BF4]能够显著提高TPU的阻燃性能,热释放速率(HRR)、总热释放(THR)和生烟速率(SPR)等参数明显降低,其中当FB@[EOOEMIm][BF4]添加量质量分数为1.000%时,HRR峰值(356.3kW·m-2)较纯TPU(1 172.9kW·m-2)和含相同含量FB的样品(588.8kW·m-2)的HRR峰值分别降低了69.6%和39.5%。SDT实验表明:在无焰条件下,FB@[EOOEMIm][BF4]能够显著提高TPU的光通量,降低烟的产量。TG实验表明:FB@[EOOEMIm][BF4]能够显著提高TPU的热稳定性能,提高TPU的成炭能力。TG-IR实验表明:FB@[EOOEMIm][BF4]能够提高TPU的热稳定性,降低烟颗粒及有毒、有害气体的生成。
In this paper,a new type of flame retardant FB@[EOOEMIm][BF4]was prepared by modifying fly-ash floating beads(FB)with ionic liquid[EOOEMIm][BF4]and applied in flame retardant thermoplastic polyurethane(TPU).The structure and element distribution properties of FB@[EOOEMIm][BF4]tested by scanning electron microscope-energy disper-sive spectrometer(SEM-EDS).And the flame retardant and thermal degradation characteristics of TPU composites were tested using cone calorimeter test(CCT),smoke density test(SDT),thermogravimetric(TG)and thermogravimetric/fourier transform infrared spectroscopy(TG-IR),etc.The CCT revealed that FB@[EOOEMIm][BF4]can greatly enhance the flame retardant of TPU.And the heat release rate(HRR),total heat release(THR)and smoke production rate(SPR)of TPU composites with FB@[EOOEMIm][BF4]were significantly reduced.Remarkably,the peak of HRR of the sample with 1.000% FB@ [EOOEMIm][BF4](356.3 kW·m-2)was reduced by 69.6% and 39.5% compared with pure TPU(1 172.9 kW·m-2)and the sample with the same loading of FB(588.8 kW·m-2).The SDT results indicated that FB@[EOOEMIm][BF4]could greatly improve the luminous flux(LF)of TPU composites in the test without flame and reduce the production of smoke.The TG test showed that FB@[EOOEMIm][BF4]can improve the thermal stability of TPU composites and promote the char formation in the combustion process of TPU.
In this paper,a new type of flame retardant FB@[EOOEMIm][BF4]was prepared by modifying fly-ash floating beads(FB)with ionic liquid[EOOEMIm][BF4]and applied in flame retardant thermoplastic polyurethane(TPU).The structure and element distribution properties of FB@[EOOEMIm][BF4]tested by scanning electron microscope-energy disper-sive spectrometer(SEM-EDS).And the flame retardant and thermal degradation characteristics of TPU composites were tested using cone calorimeter test(CCT),smoke density test(SDT),thermogravimetric(TG)and thermogravimetric/fourier transform infrared spectroscopy(TG-IR),etc.The CCT revealed that FB@[EOOEMIm][BF4]can greatly enhance the flame retardant of TPU.And the heat release rate(HRR),total heat release(THR)and smoke production rate(SPR)of TPU composites with FB@[EOOEMIm][BF4]were significantly reduced.Remarkably,the peak of HRR of the sample with 1.000% FB@ [EOOEMIm][BF4](356.3 kW·m-2)was reduced by 69.6% and 39.5% compared with pure TPU(1 172.9 kW·m-2)and the sample with the same loading of FB(588.8 kW·m-2).The SDT results indicated that FB@[EOOEMIm][BF4]could greatly improve the luminous flux(LF)of TPU composites in the test without flame and reduce the production of smoke.The TG test showed that FB@[EOOEMIm][BF4]can improve the thermal stability of TPU composites and promote the char formation in the combustion process of TPU.
引文
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[14]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]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]CHATTOPADHYAY D K,WEBSTER D C.Thermal stability and flame retardancy of polyurethanes[J].Progress in Polymer Science,2009,34(10):1068-1133.
[4]LIN M,LI B,LI Q,et al.Synergistic effect of metal oxides on the flame retardancy and thermal degradation of novelintumescent flame-retardant thermoplastic polyurethanes[J].Journal of Applied Polymer Science,2011,121(4):1951-1960.
[5]成沂南,田留华,吕文晏,等.阻燃型聚酰胺66的研究进展[J].合成树脂及塑料,2017,34(1):81-84.CHENG Yinan,TIAN Liuhua,LYU Wenyan,et al.Research progress of flame retardant PA 66[J].China Synthetic Resin and Plastics,2017,34(1):81-84.
[6]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.
[7]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.
[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):76-83.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):76-83.
[9]CHEN X L,FENG X L,JIAO C M.Combustion and thermal degradation properties of flame-retardant TPU based on EMIMPF6[J].Journal of Thermal Analysis and Calorimetry,2017,129(2):851-857.
[10]ZHOU K Q,GUI Z,HU Y.The influence of graphene based smoke suppression agents on reduced fire hazards of polystyrene composites[J].Composites Part A,2016,80:217-227.
[11]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.
[12]RICCIARDI M R,ANTONUCCI V,ZARRELLI M,et al.Fire behavior and smoke emission of phosphate based inorganic fire-retarded polyester resin[J].Fire and Materials,2012,36(3):203-215.
[13]JIAO C M,ZHANG C J,DONG J.Combustion behavior and thermal pyrolysis kinetics of flame-retardant epoxy composites based on organic-inorganic intumescent flame retardant[J].Journal of Thermal Analysis and Calorimetry,2015,119(3):1759-1767.
[14]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.