磷-氮多元醇浸渍可膨胀石墨协同增强硬质聚氨酯泡沫的隔热及阻燃性能
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摘要
采用湿化学浸渍法将反应型磷-氮多元醇(DHP,N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯)与膨胀石墨(EG)混合,制备了DHP-EG阻燃剂。显著提高了DHP-EG在多元醇原料中的分散稳定性,降低了阻燃多元醇体系的黏度。在表征DHP-EG中组分相互作用的基础上,研究了DHP-EG对硬质聚氨酯泡沫(RPUF)隔热、吸水、压缩强度及阻燃性能的影响。结果表明,15%DHP-EG(DHP与EG的质量比为1∶2)阻燃RPUF表现了良好的协同作用。阻燃RPUF的泡孔分布趋向均匀,导热系数低至0.0237 W/(m·K),吸水率及压缩强度分别为1.52%和0.24 MPa。与纯RPUF比较,阻燃RPUF氧指数由20.1%提高到了28.3%,热释放速率峰值与总烟释放量分别降低了53%和73%。文中采用湿化学浸渍法将反应型与添加型阻燃剂相结合,为提高阻燃RPUF综合应用性能提供了参考。
Through the interaction between a reactive phosphorus flame retardant(diethyl bis(2-hydroxyethyl) aminomethylphosphonate, DHP) and expandable graphite(EG) via wet chemistry approaches, a novel flame retardant DHP-EG was prepared. The effect of this interaction was characterized by rotational rheometer and Fourier transform infrared spectroscopy(FT-IR). The results indicate that the dispersion stability of DHP-EG in polyether and polyester polyols is improved apparently. Meanwhile, the viscosity of the flame-retardancy polyols is reduced dramatically. In addition, the influence on the cell structure, thermal insulation, water absorption, compressive strength and flame retardancy of rigid polyurethane foams(RPUF) was investigated. The results show that 15% DHP-EG(the mass ratio of 1∶2) has great synergetic effect. The cellular distribution of this sample is the most homogeneous with a smaller cell diameter compared with other flame-retardancy RPUF, and then the thermal conductivity of the sample is as low as 0.0237 W/(m·K). In addition, the water absorption rate and compressive strength of the sample are 1.52% and 0.24 MPa respectively. Relative to pure RPUF, the limit oxygen index(LOI) of flame-retardancy RPUF is increased from 20.1% to 28.3%. Meanwhile, the cone calorimeter testing results show that the peak heat release rate and total smoke release are reduced by 53% and 73% respectively.
Through the interaction between a reactive phosphorus flame retardant(diethyl bis(2-hydroxyethyl) aminomethylphosphonate, DHP) and expandable graphite(EG) via wet chemistry approaches, a novel flame retardant DHP-EG was prepared. The effect of this interaction was characterized by rotational rheometer and Fourier transform infrared spectroscopy(FT-IR). The results indicate that the dispersion stability of DHP-EG in polyether and polyester polyols is improved apparently. Meanwhile, the viscosity of the flame-retardancy polyols is reduced dramatically. In addition, the influence on the cell structure, thermal insulation, water absorption, compressive strength and flame retardancy of rigid polyurethane foams(RPUF) was investigated. The results show that 15% DHP-EG(the mass ratio of 1∶2) has great synergetic effect. The cellular distribution of this sample is the most homogeneous with a smaller cell diameter compared with other flame-retardancy RPUF, and then the thermal conductivity of the sample is as low as 0.0237 W/(m·K). In addition, the water absorption rate and compressive strength of the sample are 1.52% and 0.24 MPa respectively. Relative to pure RPUF, the limit oxygen index(LOI) of flame-retardancy RPUF is increased from 20.1% to 28.3%. Meanwhile, the cone calorimeter testing results show that the peak heat release rate and total smoke release are reduced by 53% and 73% respectively.
引文
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[3] Xi W,Qian L,Huang Z,et al.Continuous flame-retardant actions of two phosphate esters with expandable graphite in rigid polyurethane foams [J].Polym.Degrad.Stab.,2016,130:97-102.
[4] Liu X,Salmeia K A,Rentsch D,et al.Thermal decomposition and flammability of rigid PU foams containing some DOPO derivatives and other phosphorus compounds [J].J.Anal.Appl.Pyrol.,2017,124:219-229.
[5] 张汪强,郭刚,邱进俊,等.反应型磷氮复合阻燃多元醇制备聚氨酯阻燃硬泡及性能[J].高分子材料科学与工程,2015,31(9):141-146.Zhang W Q,Guo G,Qiu J J,et al.Preparation and properties of reactive flame-retardant polyurethane rigid foam with phosphorus- and nitrogen-containing polyol[J].Polymer Materials Science & Engineering,2015,31(9):141-146.
[6] Zhang A,Zhang Y,Lv F,et al.Synergistic effects of hydroxides and dimethyl methylphosphonate on rigid halogen-free and flame-retarding polyurethane foams[J].J.Appl.Polym.Sci.,2013,128:347-353.
[7] Singh H,Jain A K.Ignition,combustion,toxicity,and fire retardancy of polyurethane foams:a comprehensive review[J].J.Appl.Polym.Sci.,2009,111:1115-1143.
[8] Wang C,Wu Y,Li Y,et al.Flame-retardant rigid polyurethane foam with a phosphorus‐nitrogen single intumescent flame retardant[J].Polym.Adv.Technol.,2017,29:DOI:10.1002/pat.4105.
[9] Xi W,Qian L,Chen Y,et al.Addition flame-retardant behaviors of expandable graphite and [bis(2-hydroxyethyl)amino]-methyl-phosphonic acid dimethyl ester in rigid polyurethane foams [J].Polym.Degrad.Stab.,2015,122:36-43.
[10] Schütt F,Signetti S,Krüger H,et al.Hierarchical self-entangled carbon nanotube tube networks[J].Nat.Commun.,2017,8:1215.
[11] 边炳鑫.石墨加工与石墨材料 [M].徐州:中国矿业大学出版社,2014:29-30,148-149.
[12] Yuan Y,Yang H,Yu B,et al.Phosphorus and nitrogen-containing polyols:synergistic effect on the thermal property and flame retardancy of rigid polyurethane foam composites [J].Ind.Eng.Chem.Res.,2016,55:10813-10822.