Nano-Sb_2O_3/BEO/PP复合材料阻燃性能
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摘要
球磨混入溴化环氧树脂(BEO)和改性nano-Sb_2O_3以提高聚丙烯(PP)的阻燃性能,采用垂直燃烧(UL94)和极限氧指数(LOI)研究nano-Sb_2O_3/BEO/PP复合材料的阻燃性能,用扫描电镜(SEM)分析燃烧产物微观形貌,借助傅里叶变换红外光谱(FT-IR)和热重分析(TGA)研究Sb-Br阻燃体系协同作用机理。结果表明:改性nano-Sb_2O_3与BEO的反应可延长Br·在燃烧区的时间,从而消耗更多OH·和H·达到阻燃的目的。当改性nano-Sb_2O_3含量为7%(质量分数,下同),BEO含量为21%时,nano-Sb_2O_3/BEO/PP复合材料具有优异的阻燃性能,其极限氧指数值为28.6%,垂直燃烧等级UL94为V-0级。
To improve flame retardant properties of polypropylene,the brominated epoxy resin(BEO) and nano-Sb_2O_(3 )were added into polypropylene by using a high energy ball milling technique. Flame retardant properties of polypropylene composites were evaluated by UL94 vertical combustion tests and limit oxygen index(LOI). The surface morphology of combustion products of composites was characterized by scanning electron microscopy(SEM) and the flame-retardant mechanism of flame retardant additives acting on the polymer matrix was studied by using thermo gravimetric analysis(TGA) and Fourier transform infrared(FT-IR) spectroscopy. The results show that the reaction between modified nano-Sb_2O_3 and BEO can prolong residence of the halogens in the combustion area, resulting in more hydroxyl and hydrogen radicals are replaced by the bromine radicals. When the content of modified nano-Sb_2O_3 is 7%(mass fraction, the same below) and that of BEO is 21%, the nano-Sb_2O_3/BEO/PP composite has excellent flame retardant performance with 28.6% of LOI value and V-0 of UL94 grade of vertical combustion.
To improve flame retardant properties of polypropylene,the brominated epoxy resin(BEO) and nano-Sb_2O_(3 )were added into polypropylene by using a high energy ball milling technique. Flame retardant properties of polypropylene composites were evaluated by UL94 vertical combustion tests and limit oxygen index(LOI). The surface morphology of combustion products of composites was characterized by scanning electron microscopy(SEM) and the flame-retardant mechanism of flame retardant additives acting on the polymer matrix was studied by using thermo gravimetric analysis(TGA) and Fourier transform infrared(FT-IR) spectroscopy. The results show that the reaction between modified nano-Sb_2O_3 and BEO can prolong residence of the halogens in the combustion area, resulting in more hydroxyl and hydrogen radicals are replaced by the bromine radicals. When the content of modified nano-Sb_2O_3 is 7%(mass fraction, the same below) and that of BEO is 21%, the nano-Sb_2O_3/BEO/PP composite has excellent flame retardant performance with 28.6% of LOI value and V-0 of UL94 grade of vertical combustion.
引文
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[16] 刘刚, 张代军, 张晖. 纳米粒子改性环氧树脂及其复合材料力学性能研究[J]. 材料工程,2010(1): 47-53. LIU G, ZHANG D J, ZHANG H. Mechanical properties of nanoparticles modified epoxy matrix and composites[J]. Journal of Materials Engineering,2010(1): 47-53.
[17] 高田田. 高效聚丙烯阻燃剂的研究和开发[D]. 广州:华东理工大学, 2014. GAO T T. Research and development of efficient flame retardant polypropylene [D]. Guangzhou: East China University of Science and Technology, 2014.
[18] 甘小荣,薛方红,黄昊,等. SiC/C纳米复合材料的制备与性能表征[J]. 材料工程,2014(2):75-82. GAN X R, XUE F H, HUANG H, et al. Preparation and characterization of SiC/C nano-composites[J].Journal of Materials Engineering, 2014(2): 75-82.
[19] GHOLAMIAN F, NABIYOUNI G, GHANBARI D. Synergistic effect between Sb2O3 nanostructure and brominated compound on the flame retardant properties of the polymeric matrixes[J].High Temperature Materials and Processes,2013,32(2):125-132.
[2] LI N, XIA Y, MAO Z W, et al. Influence of antimony oxide on flammability of polypropylene/intumescent flame retardant system[J]. Polymer Degradation and Stability, 2012, 97(9): 1737-1744.
[3] MIRDAMADIAN Z, GHANBARI D. Synergistic effect between Sb2O3 nanoparticles-trichloromelamine and carbon nanotube on the flame retardancy and thermal stability of the cellulose acetate[J].Journal of Cluster Science, 2014, 25(4): 925-936.
[4] 范望喜, 李文元, 任家强, 等.高分子阻燃材料的研究进展[J]. 天津化工, 2010, 24(5): 17-19. FAN W X, LI W Y, REN J Q, et al. Research progress of acylhydrazone compounds[J]. Tianjin Chemical Industry, 2010, 24(5): 17-19.
[5] LU H D, WILKIE C A. Synergistic effect of carbon nanotubes and decabromodiphenyl oxide/Sb2O3 in improving the flame retardancy of polystyrene[J].Polymer Degradation and Stability, 2010, 95(4): 564-571.
[6] MELAMED L, EDEN E, LEIFER M, et al. Performances of blends between poly (pentabromobenzyl acrylate) and magnesium hydroxide as flame retardants for polypropylene block copolymers[J]. Fire Technology, 2015, 51(1):41-52.
[7] 奚溪,张群朝,赵辉, 等. 卤-锑阻燃体系对热塑性聚酯弹性体性能的影响[J].工程塑料应用,2013,41(5):82-89. XI X, ZHANG Q C, ZHAO H, et al. Effect of halogen-antimony flame retardant system on thermoplastic polyester elastomer[J]. Engineering Plastics Application, 2013,41(5):82-89.
[8] CHEN S J, WANG C L, LI J. Effect of alkyl groups in organic part of polyoxo-metalates based ionic liquids on properties of flame retardant polypropylene[J].Thermochimica Acta,2016, 631:51-58.
[9] DUAN L J, YANG H Y, SONG L.Hyperbranched phosphorus/nitrogen-containing polymer incombination with ammonium polyphosphate as a novel flameretardant system for polypropylene[J].Polymer Degradation and Stability, 2016, 134:179-185.
[10] SHI Y Q, GUI Z, XU B. Graphite-like carbon nitride and functionalized layered double hydroxide filled polypropylene-grafted maleic an hydride nanocomposites: comparison in flame retardancy, and thermal,mechanical and UV-shielding properties[J]. Composites Part B, 2015, 79:277-284.
[11] GALLO E, SCHARTEL B, ACIERNO D, et al. Flame retardant biocomposites: synergism between phosphinate and nanometric metal oxides[J]. European Polymer Journal,2011, 47(7):1390-1401.
[12] 徐建林,周生刚,牛磊,等.Sb2O3/聚氯乙烯复合材料的制备及阻燃性能[J]. 材料热处理学报,2015,36(11):1-6. XU J L, ZHOU S G, NIU L, et al. Preparation and flame retardancy of Sb2O3/polyvinyl chloride composites[J]. Transactions of Materials and Heat Treatment,2015,36(11):1-6.
[13] 张荣良. 纳米Sb2O3/环氧复合材料阻燃耐热及力学性能研究[J].热固性树脂,2011, 26(4):46-49. ZHANG R L. Research in flame-retardance, heat resistance and mechanical properties of nano-Sb2O3/epoxy composites[J]. Thermosetting Resin, 2011, 26(4):46-49.
[14] 张心亚, 沈慧芳, 黄洪, 等.纳米粒子材料的表面改性及其应用研究进展[J]. 材料工程,2005(10): 58-63. ZHANG X Y, SHEN H F, HUANG H, et al. Novel progress of application and surface-modification technique for nano-particles materials[J]. Journal of Materials Engineering, 2005(10):58-63.
[15] 唐星三,孟烨,刘杰. 溴化环氧树脂阻燃剂应用户综述与发展[J].塑料工业,2011, 39(增刊1): 47-49. TANG X S, MENG Y, LIU J. Review on the application and prospect of bromated epoxy resin flame retardant[J]. China Plastics Industry, 2011, 39(Suppl 1): 47-49.
[16] 刘刚, 张代军, 张晖. 纳米粒子改性环氧树脂及其复合材料力学性能研究[J]. 材料工程,2010(1): 47-53. LIU G, ZHANG D J, ZHANG H. Mechanical properties of nanoparticles modified epoxy matrix and composites[J]. Journal of Materials Engineering,2010(1): 47-53.
[17] 高田田. 高效聚丙烯阻燃剂的研究和开发[D]. 广州:华东理工大学, 2014. GAO T T. Research and development of efficient flame retardant polypropylene [D]. Guangzhou: East China University of Science and Technology, 2014.
[18] 甘小荣,薛方红,黄昊,等. SiC/C纳米复合材料的制备与性能表征[J]. 材料工程,2014(2):75-82. GAN X R, XUE F H, HUANG H, et al. Preparation and characterization of SiC/C nano-composites[J].Journal of Materials Engineering, 2014(2): 75-82.
[19] GHOLAMIAN F, NABIYOUNI G, GHANBARI D. Synergistic effect between Sb2O3 nanostructure and brominated compound on the flame retardant properties of the polymeric matrixes[J].High Temperature Materials and Processes,2013,32(2):125-132.
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