三聚氰胺聚磷酸盐/季戊四醇配比、协效剂组及表面改性对聚丙烯基木塑复合材料的膨胀阻燃影响
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摘要
通过极限氧指数(LOI)、线性燃烧速率(LBR)、热重分析和锥形量热分析等技术手段研究膨胀型阻燃剂(IFRs)中三聚氰胺聚磷酸盐(MPP)和季戊四醇(PER)的质量比、组成为m(MgO):m(可膨胀石墨,EG):m(SiO_2)=1:5:5的协效剂组(MgO/EG/SiO_2)和硅烷偶联剂(KH550)对聚丙烯基木塑复合材料(WPC)阻燃性能的影响。结果表明,当IFRs中m(MPP):m(PER)=23:2(IFRs-M1)、质量分数为25%时的阻燃性能最佳,膨胀阻燃复合材料WPC/IFRs-M1的LOI和LBR分别为27. 1%和3. 89 mm/min,较未添加的WPC分别提高48. 1%和下降89. 79%,燃烧时的热释放速率、总热释放量、总烟释放量和CO_2释放量分别降低了76. 2%、50. 1%、6. 9%和65. 4%,600℃时的残炭率提高了498. 3%。协效剂组和KH550表面处理均可进一步改善WPC/IFRs-M1的阻燃性能,均对IFRs-M1具有良好的阻燃增效作用。相比于WPC/IFRs-M1,同时用这两种阻燃增效手段的WPC/IFRs-M1/MgO/EG/SiO_2/KH550,其LOI提高了3. 7%,LBR降低了20. 3%;材料的热稳定性明显提高,热失重降低;燃烧时的热释放速率、总热释放量、总烟释放量和CO_2释放量分别降低了36. 5%、37. 6%、57. 5%和33. 33%,600℃时的残炭率提高了84. 02%,显示出二者更好的协同效应。
The effect of the mass ratio and composition of melamine polyphosphate( MPP)/pentaerythritol( PER) in intumescent flame retardants( IFRs),synergist group MgO/EG/SiO_2 of which composition with m( MgO): m( expandable graphite,EG): m( SiO_2) = 1:5:5,and the silane coupling agent KH550 on the flame retardancy of polypropylene-based wood-plastic composites( WPC) were studied by means of limiting oxygen index( LOI),linear burning rate( LBR),thermogravimetric analysis and cone calorimetry. The results show that when m( MPP): m(PER) = 23:2 in IFRs( code IFRs-M1) and its mass fraction is 25%,the flame retardant performance is the best,and LOI and LBR of the intumescent flame retardant composite WPC/IFRsM1 are 27. 1% and 3. 89 mm/min,respectively,which are 48. 1% higher and 89. 79% lower than those of the unadded WPC. Compared with the unadded WPC,the heat release rate and total heat release during combustion decrease by 76. 2% and 50. 1%,the carbon residue rate at 600 ℃ increases by 498. 3%,the total smoke emission reduces by 6. 9%,and the release of CO_2 drops by 65. 4%. It also indicates that both the synergist group and KH550 surface treatment can further improve the flame retardant properties of WPC/IFRs-M1,and both have good flame retardant synergistic effect on IFRs-M1. Compared with WPC/IFRs-M1,LOI of WPC/IFRs-M1/MgO/EG/SiO_2/KH550 with both flame retardant means mentioned above is enhanced by 3. 7%,and its LBR declines by 20. 3%. At the same time,its thermal stability significantly improves,the thermal weight loss goes down,and its heat release rate and total heat release during combustion reduce by 36. 5% and 37. 6%,respectively. Its carbon residue rate at 600 ℃ increases by 84. 02%,the total smoke release reduces by 57. 5%,and the amount of CO_2 release reduces by 33. 33%,indicating a better synergistic effect.
The effect of the mass ratio and composition of melamine polyphosphate( MPP)/pentaerythritol( PER) in intumescent flame retardants( IFRs),synergist group MgO/EG/SiO_2 of which composition with m( MgO): m( expandable graphite,EG): m( SiO_2) = 1:5:5,and the silane coupling agent KH550 on the flame retardancy of polypropylene-based wood-plastic composites( WPC) were studied by means of limiting oxygen index( LOI),linear burning rate( LBR),thermogravimetric analysis and cone calorimetry. The results show that when m( MPP): m(PER) = 23:2 in IFRs( code IFRs-M1) and its mass fraction is 25%,the flame retardant performance is the best,and LOI and LBR of the intumescent flame retardant composite WPC/IFRsM1 are 27. 1% and 3. 89 mm/min,respectively,which are 48. 1% higher and 89. 79% lower than those of the unadded WPC. Compared with the unadded WPC,the heat release rate and total heat release during combustion decrease by 76. 2% and 50. 1%,the carbon residue rate at 600 ℃ increases by 498. 3%,the total smoke emission reduces by 6. 9%,and the release of CO_2 drops by 65. 4%. It also indicates that both the synergist group and KH550 surface treatment can further improve the flame retardant properties of WPC/IFRs-M1,and both have good flame retardant synergistic effect on IFRs-M1. Compared with WPC/IFRs-M1,LOI of WPC/IFRs-M1/MgO/EG/SiO_2/KH550 with both flame retardant means mentioned above is enhanced by 3. 7%,and its LBR declines by 20. 3%. At the same time,its thermal stability significantly improves,the thermal weight loss goes down,and its heat release rate and total heat release during combustion reduce by 36. 5% and 37. 6%,respectively. Its carbon residue rate at 600 ℃ increases by 84. 02%,the total smoke release reduces by 57. 5%,and the amount of CO_2 release reduces by 33. 33%,indicating a better synergistic effect.
引文
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[15]Nguyen T H,Hoang D Q,Kim J. Effect of Ammonium Polyphosphate and Melamine Pyrophosphate on Fire Behavior and Thermal Stability of Unsaturated Polyester Synthesized from Poly(ethylene terephthalate)Waste[J]. Macromol Res,2018,26(1):22-28.
[16]Umemura T,Arao Y,Nakamura S,et al. Synergy Effects of Wood Flour and Fire Retardants in Flammability of WoodPlastic Composites[J]. Energy Procedia,2014,(56):48-56.
[17] ZHU Deqin,ZHENG Shouyang,SHENG Yu. Flame-Retardant Synergistic Effect of Synergists on Intumescent FlameRetardant Wood Flour-Polypropylene Composites[J]. Chinese J Appl Chem,2017,34(2):195-203(in Chinese).朱德钦,郑守扬,生瑜.协效剂对膨胀阻燃聚丙烯基木塑复合材料的阻燃增效研究[J].应用化学,2017,34(2):195-203.
[18]Ye L,Zhang Y J,Wang S H,et al. Synergistic Effects and Mechanism of Zn Cl2on Intumescent Flame-Retardant Polypropylene[J]. J Therm Anal Calorim,2014,115(2):1065-1071.
[19]Li B,He J M. Investigation of Mechanical Property,Flame Retardancy and Thermal Degradation of LLDPE-Wood-Fibre Composites[J]. Polym Degrad Stab,2004,83(2):241-246.
[2]ZHANG Jinkai,MA Li,GE Weijuan,et al. Research Status of Intumescent Flame-Retarded Polypropylene[J]. Mater Rev,2015,29(5):68-72(in Chinese).张金凯,马丽,葛维娟,等.膨胀型阻燃剂阻燃聚丙烯的研究进展[J].材料导报,2015,29(5):68-72.
[3]Wu Z P,Hu Y C,Shu W Y. Effect of Ultrafine Zinc Borate on the Smoke Suppression and Toxicity Reduction of a LowDensity Polyethylene/Intumescent Flame-Retardant System[J]. J Appl Polym Sci,2010,117(1):443-449.
[4]Ye L,Zhang Y J,Wang S H,et al. Synergistic Effects and Mechanism of Zn Cl2on Intumescent Flame-Retardant Polypropylene[J]. J Therm Anal Calorim,2014,115(2):1065-1071.
[5]Nie S B,Song L,Bao C L,et al. Synergistic Effects of Ferric Pyrophosphate(Fe PP)in Intumescent Flame-Retardant Polypropylene[J]. Polym Adv Technol,2011,22(6):870-876.
[6]Dong Q X,Liu M M,Ding Y F,et al. Synergistic Effect of DOPO Immobilized Silica Nanoparticles in the Intumescent Flame Retarded Polypropylene Composites[J]. Polym Adv Technol,2013,24(8):732-739.
[7]Qiao Z H,Tai Q L,Song L,et al. Synergistic Effects of Cerium Phosphate and Intumescent Flame Retardant on EPDM/PP Composites[J]. Polym Adv Technol,2011,22(12):2602-2608.
[8]SHENG Yu,ZHENG Shouyang,ZHU Deqin. Orthogonal Optimization on Flame Retardant Polypropylene-Based Wood Plastic Composite[J]. J Northeast Forestry Univ,2017,45(4):88-93(in Chinese).生瑜,郑守扬,朱德钦.阻燃型聚丙烯基木塑复合材料的正交优化[J].东北林业大学学报,2017,45(4):88-93.
[9]WANG Zhangyu. Study on the Flame Retardance of Glass Fiber Rejnforeced Polyamide 6 and Polyamide 66 by Melamine Polyphosphate[D]. Chengdu:Sichuan University,2007(in Chinese).王章郁.三聚氰胺聚磷酸盐阻燃玻纤增强尼龙6及尼龙66的研究[D].成都:四川大学,2007.
[10]GUO Wei. Study on Properties of Melamine Polyphosphate Flame Retarded Polyethylene/Wood Flour Composites[D].Haerbin:Northeast Forestry University,2016(in Chinese).果威.三聚氰胺聚磷酸盐复合阻燃聚乙烯/木粉复合材料的性能研究[D].哈尔滨:东北林业大学,2016.
[11]WANG Qingwen,FANG Yiqun,GAO Hua,et al. Flame Retardant Wood Plastic Composite and Its Preparation Method:CN,200910072237. X[P]. 2009-06-10(in Chinese).王清文,房轶群,高华,等.阻燃型木塑复合材料及其制备方法:中国,200910072237. X[P]. 2009-06-10.
[12]Bai P,Li B,Gao S,et al. Investigation on Flame Retardancy and Antidripping of New Intumescent Flame Retardant Polypropylene Film[J]. Polym Polym Compos,2010,18(9):495-502.
[13]LI Xiaoyun,WANG Zhengzhou,LIANG Haojun. Flame Retardation of EVA Copolymer Using Melamine Phosphate and Pentaerythritol as Intumescent Flame Retardants[J]. Polym Mater Sci Eng,2007,23(1):145-148(in Chinese).李小云,王正洲,梁好均.三聚氰胺磷酸盐和季戊四醇在EVA中的阻燃研究[J].高分子材料科学与工程,2007,23(1):145-148.
[14]WANG Yun,WANG Zhengzhou,HU Yuan. Study on Flame Retardation of Epoxy Resin Composites Containing Melamine Phosphate and Pentaerythritol[J]. Fire Saf Sci,2008,17(2):88-92(in Chinese).王云,王正洲,胡源.三聚氰胺磷酸盐及季戊四醇阻燃环氧树脂研究[J].火灾科学,2008,17(2):88-92.
[15]Nguyen T H,Hoang D Q,Kim J. Effect of Ammonium Polyphosphate and Melamine Pyrophosphate on Fire Behavior and Thermal Stability of Unsaturated Polyester Synthesized from Poly(ethylene terephthalate)Waste[J]. Macromol Res,2018,26(1):22-28.
[16]Umemura T,Arao Y,Nakamura S,et al. Synergy Effects of Wood Flour and Fire Retardants in Flammability of WoodPlastic Composites[J]. Energy Procedia,2014,(56):48-56.
[17] ZHU Deqin,ZHENG Shouyang,SHENG Yu. Flame-Retardant Synergistic Effect of Synergists on Intumescent FlameRetardant Wood Flour-Polypropylene Composites[J]. Chinese J Appl Chem,2017,34(2):195-203(in Chinese).朱德钦,郑守扬,生瑜.协效剂对膨胀阻燃聚丙烯基木塑复合材料的阻燃增效研究[J].应用化学,2017,34(2):195-203.
[18]Ye L,Zhang Y J,Wang S H,et al. Synergistic Effects and Mechanism of Zn Cl2on Intumescent Flame-Retardant Polypropylene[J]. J Therm Anal Calorim,2014,115(2):1065-1071.
[19]Li B,He J M. Investigation of Mechanical Property,Flame Retardancy and Thermal Degradation of LLDPE-Wood-Fibre Composites[J]. Polym Degrad Stab,2004,83(2):241-246.