芳纶纤维协效聚钛酸丁酯对热塑性聚氨酯弹性体火灾安全性的研究
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摘要
通过熔融共混法制备了含有不同含量芳纶纤维(AF)和聚钛酸丁酯(BTP)的热塑性聚氨酯弹性体(TPU)复合材料,并研究了AF和BTP在提高TPU火灾安全性方面的协效性。通过氧指数、锥形量热仪、烟密度测试仪研究样品的阻燃生烟特性,通过热重分析研究样品的热分解特性。锥形量热仪实验结果表明:AF与BTP能够明显降低样品的热释放速率(HRR)、总热释放速率(THR)、烟释放速率(SPR)、总烟释放(TSR)和烟因子(SF),并且能够提高成炭量,其中含有0.50%AF和0.50%BTP的样品(AF/BTP~(-2))的热释放速率峰值(pHRR)仅为409kW·m~(-2),相比TPU样品和AF样品分别下降73.0%和49.8%,炭渣质量也达到了14.6%,高于纯TPU的8.8%。烟密度测试结果表明:BTP的添加进一步提高了燃烧时的光通量。热重分析实验表明:BTP水解生成的TiO_2能够进一步促进成炭,改善炭层质量,从而起到阻燃抑烟的效果。
Thermoplastic polyurethane elastomer(TPU)composites containing different amounts of aramid fiber(AF)and poly butyl titanate(BTP)were prepared by molten blending method.And thesynergistic fire safety effect between AF and BTP in TPU has been studied by a series tests.The flame retardancy and smoke generation characteristics of samples were studied by LOI,cone calorimeter and smoke density tester.The thermal decomposition characteristics of samples were studied by thermogravimetric analysis.The cone calorimeter test showed that AF and BTP could significantly reduce the HRR,THR,SPR,TSRand SF of the samples,and could improve the char forming progress.Remarkably,the pHRR of the sample containing 0.50% AF and 0.50% BTP(AF/BTP~(-2))was only 409 kW·m~(-2),decreased by 73%and 49.8%compared with TPU and AF samples respectively.The residual mass reached 14.6%,which was higher than that of pure TPU(8.8%).The smoke density test results showed that the addition of BTP could further improve the luminous flux of the TPU composites.Thermogravimetric analysis results showed that the TiO_2 hydrolyzed from BTP could further promote the char forming progress and improve the structure of carbon layer,so as to achieve an excellent flame retardancy and smoke suppression property.
Thermoplastic polyurethane elastomer(TPU)composites containing different amounts of aramid fiber(AF)and poly butyl titanate(BTP)were prepared by molten blending method.And thesynergistic fire safety effect between AF and BTP in TPU has been studied by a series tests.The flame retardancy and smoke generation characteristics of samples were studied by LOI,cone calorimeter and smoke density tester.The thermal decomposition characteristics of samples were studied by thermogravimetric analysis.The cone calorimeter test showed that AF and BTP could significantly reduce the HRR,THR,SPR,TSRand SF of the samples,and could improve the char forming progress.Remarkably,the pHRR of the sample containing 0.50% AF and 0.50% BTP(AF/BTP~(-2))was only 409 kW·m~(-2),decreased by 73%and 49.8%compared with TPU and AF samples respectively.The residual mass reached 14.6%,which was higher than that of pure TPU(8.8%).The smoke density test results showed that the addition of BTP could further improve the luminous flux of the TPU composites.Thermogravimetric analysis results showed that the TiO_2 hydrolyzed from BTP could further promote the char forming progress and improve the structure of carbon layer,so as to achieve an excellent flame retardancy and smoke suppression property.
引文
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[20]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 Applied Science&Manufacturing,2015,80:217-227.
[21]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.
[2]CHEN X L,MA C Y,JIAO C M.Enhancement of flame-retardant performance of thermoplastic polyurethane with the incorporation of aluminum hypophosphite and iron-graphene[J].Polymer Degradation and Stability,2016,129:275-285.
[3]TOLDY A,HARAKLY G,SZOLNOKI B,et al.Flame retardancy of thermoplastics polyurethanes[J].Polymer Degradation and Stability,2012,97(12):2524-2430.
[4]LI H X,NING N Y,ZHANG L Q,et al.Different flame retardancy effects and mechanisms of aluminium phosphinate in PPO,TPU and PP[J].Polymer Degradation and Stability,2014,105:86-95.
[5]CHEN X L,WANG W D,JIAO C M.In situ synthesis of flame retardant organic-inorganic hybrids by molten blending method based on thermoplastic polyurethane elastomer and polybutyl titanate[J].RSC Advances,2016,6(95):92276-92284.
[6]CHEN X L,WANG W D,JIAO C M.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.
[7]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.
[8]AKATO K,BHAT G.10-High Performance Fibers from Aramid Polymers[M].Structure and Properties of High-Performance Fibers.Oxford:Woodhead Publishing,2017:245-266.
[9]ZENG C X.Test and research on heat resistance of aramid 1313blended fabric[J].Shanghai Textile Science&Technology,2008,37(3):47-48.
[10]SA R,YANY,WEI Z H,et al.Surface modification of aramid fibers by bio-inspired poly(dopamine)and epoxy functionalized silane grafting[J].ACS Applied Materials&Interfaces,2014,6(23):21730-21738.
[11]ELSHEREKSI N W,GHAZALI M J,MUCHTAR A,et al.Studies on the effects of titanate and silane coupling agents on the performance of poly(methyl methacrylate)/barium titanate denture base nanocomposites[J].Journal of Dentistry,2017,56:121-132.
[12]ENGIN SAGIRLI F Z,UNSAL C,KAYALI E S,et al.In-situ preparation and characterization of pyrrole and tert-butyl 1-pyrrole-carboxylate on barium titanate/poly(acrylonitrile-comethylacrylate)nanoparticles[J].Reactive and Functional Polymers,2016,100:1-11.
[13]王文多,陈希磊.碱式钼酸铜的制备及其对膨胀型防火涂料的防火抑烟性能影响研究[J].青岛科技大学学报(自然科学版),2017,38(4):66-70.WANG Wenduo,CHEN Xilei.Fire and smoke suppression properties of copper molybdate in intumescent flame retardant coating[J].Journal of Qingdao University of Science and Technology(Natural Science Edition),2017,38(4):66-70.
[14]CHEN X L,ZHUO J L,JIAO C M.Thermal degradation characteristics of flame retardant polylactide using TG-IR[J].Polymer Degradation and Stability,2012,97(11):2143-2147.
[15]TIAN L N,YANG W,CHEN Z H,et al.Sulfur behavior during coal combustion in oxy-fuel circulating fluidized bed condition by using TG-FTIR[J].Journal of the Energy Institute,2016,89(2):264-270.
[16]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),2012,33(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),2012,33(2):172-176.
[17]BONATI A,RAINIERI S,BOCHICCHIO G,et al.Characterization of thermal properties and combustion behaviour of asphalt mixtures in the cone calorimeter[J].Fire Safety Journal,2015,74:25-31.
[18]FENG C M,LIANG M Y,JIANG J L,et al.Preparation and characterization of oligomeric char forming agent and its effect on the thermal degradation and flame retardant properties of LDPE with ammonium polyphosphate[J].Journal of Analytical and Applied Pyrolysis,2016,119:75-86.
[19]JIN E,CHUNG Y J.Combustion characteristics of Pinus rigida specimens treated with mixed phosphorus-nitrogen additives[J].Journal of Industrial and Engineering Chemistry,2016,36:74-79.
[20]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 Applied Science&Manufacturing,2015,80:217-227.
[21]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.