勃姆石/MPP二元协效AlPi阻燃PA66/GF复合材料研究
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摘要
采用勃姆石部分替代传统的三聚氰胺聚膦酸盐(MPP)构成二元协效剂,与二乙基次膦酸铝(AlPi)复配协效阻燃尼龙66 (PA66)/玻璃纤维(GF)复合材料。勃姆石的引入对复合材料的力学性能影响较小,但是能显著提高流动性,提高材料的可加工性。采用勃姆石1∶1替代MPP后,复合材料的阻燃性能并没有显著提升,但是部分替代MPP后,锥形量热和垂直燃烧测试结果均显示,复合材料的阻燃性能提升明显,热释放速率峰值(pHRR)由279.4kW/m~2降低至158.6 kW/m~2,垂直燃烧阻燃等级由V–1级提高至V–0级。扫描电子显微镜(SEM)结果表明,勃姆石和MPP构成二元协效体系,能够提高材料的成炭性能以及炭层的致密度。在相同的阻燃效率条件下,勃姆石和MPP二元协效能够降低MPP和AlPi的用量,体现出良好的经济性。同时,勃姆石的部分引入能够减少材料在湿热老化过程中阻燃剂的析出数量。
Combining with melamine polyphosphate(MPP),the boehmite was used to partly replace MPP as synergists of aluminum diethylphosphinate(AlPi) to improve the flame retardancy of nylon 66(PA66)/glass fiber(GF) composites. The addition of boehmite has less influence on the mechanical properties of PA66/GF composites,but can enhance the fluidity of the material,resulting in better molding performance. The flame retardancy of composite keep changeless while replaced the MPP with boehmite at the mass ratio of 1∶1,however,when partly replaced MPP with boehmite,the results of cone calorimeter and vertical combustion show that binary synergists of boehmite and MPP can enhance the solid phase flame retardancy of composites,the peak heat release rate is reduced by 158.6 kW/m~2 from 279.4 kW/m~2,the flame retardant rating is improved to V–0 from V–1. The scanning electron micro(SEM) results show that binary synergist of boehmite and MPP can improve charring process and compactness of char layer. Binary synergist of boehmite and MPP can reduce the dosage of MPP and AlPi while keep the flame retardancy constant,which shows great efficiency. Besides,the addition of boehmite can reduce the precipitation of flame retardants in composites after hydrothermal aging.
Combining with melamine polyphosphate(MPP),the boehmite was used to partly replace MPP as synergists of aluminum diethylphosphinate(AlPi) to improve the flame retardancy of nylon 66(PA66)/glass fiber(GF) composites. The addition of boehmite has less influence on the mechanical properties of PA66/GF composites,but can enhance the fluidity of the material,resulting in better molding performance. The flame retardancy of composite keep changeless while replaced the MPP with boehmite at the mass ratio of 1∶1,however,when partly replaced MPP with boehmite,the results of cone calorimeter and vertical combustion show that binary synergists of boehmite and MPP can enhance the solid phase flame retardancy of composites,the peak heat release rate is reduced by 158.6 kW/m~2 from 279.4 kW/m~2,the flame retardant rating is improved to V–0 from V–1. The scanning electron micro(SEM) results show that binary synergist of boehmite and MPP can improve charring process and compactness of char layer. Binary synergist of boehmite and MPP can reduce the dosage of MPP and AlPi while keep the flame retardancy constant,which shows great efficiency. Besides,the addition of boehmite can reduce the precipitation of flame retardants in composites after hydrothermal aging.
引文
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[19]Braun U,Schartel B,Fichera M A,et al.Flame retardancy mechanisms of aluminium phosphinate in combination with melamine polyphosphate and zinc borate in glass-fibre reinforced polyamide6,6[J].Polymer Degradation and Stability,2007,92:1 528-1 545.
[2]Chen Jun,Wu Wei,Chen Chuan,et al.Toughened nylon66/nylon6 ternary nanocomposites by elastomers[J].Journal of Applied Polymer Science,2010,115:588-598.
[3]Kundu C K,Wang Wei,Zhou Shun,et al.A green approach to constructing multilayered nanocoating for flame retardant treatment of polyamide 66 fabric from chitosan and sodium alginate[J].Carbohydrate Polymers,2017,166:131-138.
[4]Li Yuanyuan,Liu Ke,Xiao Ru.Preparation and characterization of flame-retarded polyamide 66 with melamine cyanurate by in situ polymerization[J].Macromolecular Research,2017,25:779-785.
[5]Matsunaga T,Sato Y,Goda K.Major cause of strength improvement of a ramie/PA composite with low fiber contents[J].Advanced Industrial and Engineering Polymer Research,2018,1:93-98.
[6]吴长波,郑一泉,金雪峰,等.缩合磷酸铝在二乙基次膦酸铝阻燃PA66/GF材料中应用评估[J].合成材料老化与应用,2018,47(5):15-18,35.Wu Changbo,Zheng Yiquan,Jin Xuefeng,et al.The application assessment of aluminium phosphate used in aluminium diethyl phosphonate flame retarded PA66/GF composite[J].Synthetic Materials Aging and Application,2018,47(5):15-18,35.
[7]吴长波,张永,丁超,等.湿热老化对二乙基次膦酸铝阻燃增强PA66的影响研究[J].塑料工业,2018(8):95-99,115.Wu Changbo,Zhang Yong,Ding Chao,et al.Study on the Influences of Hydrothermal Aging on Halogen-free Flame-retarded Glass Fiber Reinforced PA66 Composite[J].China Plastics Industry,2018(8):95-99,115.
[8]薛妮娜,姜宏伟.二乙基次膦酸铝协效氢氧化铝阻燃EVA的研究[J].绝缘材料,2010,43(3):16-19.Xue Nina,Jiang Hongwei.Study and preparation of EVA composites with non-halogen and high efficient flame retardancy[J].Insulating Materials,2010,43(3):16-19.
[9]李胜男,郑洋洋,赵井博.二乙基次膦酸铝的合成及其协同阻燃软线材料研究[J].塑料工业,2018,46(4):138-141.Li Shengnan Zheng Yangyang,Zhao Jingbo,et al.Synthesis of aluminum salts of diethyl phosphinic acid and its synergistic effect on flame retardant thermalplastic elastomer[J].China Plastics Industry,2018,46(4):138-141.
[10]Karger-Kocsis J,Lendvai L.Polymer/boehmite nanocomposites:Areview[J].Journal of Applied Polymer Science,2018,135:45 573-45 604.
[11]Huang Pei-Hsuan,Chang Shinn-Jen,Li Chia-Chen,et al.Boehmite-based microcapsules as flame-retardants for lithium-ion batteries[J].Thermochimica Acta,2017,228:597-603.
[12]Ghamari M,Farzi G.Surface morphology of PMMA/boehmite hybrid nanostructures prepared via facile one-pot process[J].Applied Physics A:Materials Science&Processing,2017,123:508-516.
[13]王娜,赵莹,朱明,等.勃姆石阻燃改性PP复合材料的制备及性能研究[J].塑料科技,2017,45(11):36-40.Wang Na,Zhao Ying,Zhu Ming,et al.Study on Properties of Boehmite Flame Retardant Modified PP Composites and Its Preparation[J].Plastics Science and Technology,2017,45(11):36-40.
[14]Cai Yuhuang,Zhao Mengmeng,Wang Henti,et al.Synthesis and properties of flame-retardant poly(vinyl alcohol)/pseudo-boehmite nanocomposites with high transparency and enhanced refractive index[J].Polymer Degradation and Stability,2014,99:53-60.
[15]Hamdani-Devarennes S,El Hage R A,Dumazert L,et al.Waterbased flame retardant coating using nano-boehmite for expanded polystyrene(EPS)foam[J].Progress in Organic Coatings,2016,99:32-46.
[16]Sun Tao,Zhuo Qin,Chen Yingpu,et al.Synthesis of boehmite and its effect on flame retardancy of epoxy resin[J].High Performance Polymers,2014,27:100-104.
[17]Alongi J,Poskovic M,Visakh P M,et al.Cyclodextrin nanosponges as novel green flame retardants for PP,LLDPE and PA6[J].Carbohydrate Polymers,2012,88:1 387-1 394.
[18]罗观晃,冉进成,刘典典,等.尼龙66/勃姆石复合材料性能研究[J].工程塑料应用,2015,43(12):25-29.Luo Guanhuang,Ran Jincheng,Liu Diandian,et al.Study on Properties of Nylon 66/Boehmite Composites[J].Engineering Plastics Application,2015,43(12):25-29.
[19]Braun U,Schartel B,Fichera M A,et al.Flame retardancy mechanisms of aluminium phosphinate in combination with melamine polyphosphate and zinc borate in glass-fibre reinforced polyamide6,6[J].Polymer Degradation and Stability,2007,92:1 528-1 545.