无卤阻燃增强PA10T和PA66的阻燃机理
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摘要
采用二乙基次膦酸铝(Alpi)阻燃剂对质量分数30%的玻璃纤维增强聚对苯二甲酰癸二胺(PA10T)和聚己二酰己二胺(PA66)进行阻燃改性,通过垂直燃烧法、锥形量热仪、热重和扫描电子显微镜(SEM)等手段研究了二者阻燃机理的差异。结果表明,少量Alpi(质量分数为12%)即可使PA10T垂直燃烧等级达到V–0级,总热释放量(THR)从80.4 MJ/m~2下降至59.5 MJ/m~2,峰值热释放速率(pkHRR)从296.4 kW/m~2下降至140.9 kW/m~2,单位质量损失下的CO释放(TCOR/TML)提高了132%,具有良好的凝聚相和气相阻燃效果;而在PA66体系中,Alpi的添加改变了PA66的热分解过程,TCOR/TML提高了265%,气相阻燃得到明显的增强,但THR从86.5 MJ/m~2下降至72.9 MJ/m~2,凝聚相阻燃不足,单独使用Alpi时薄试样的垂直燃烧等级难以达到V–0级。利用SEM对其锥形燃烧后残炭进行分析表明,PA10T材料的炭层较为平整且致密,而PA66材料的炭层相对疏松且凹凸不平。
The effect of Aluminum phosphinate(Alpi) on the flame retardancy of 30 wt% glass fiber reinforced poly(decamethylene terephthalamide)(PA10 T) and poly(hexamethylene adipamide)(PA66) was examined. The difference of ?ame retarding mechanism between PA10 T and PA66 in this ?ame retardant system was studied by means of UL 94 test,cone calorimeter method(CONE), thermogravimetric analysis(TGA) method and scanning electron microscope(SEM). The results show that when the added Alpi content is 12 wt%,the PA10 T/GF/Alpi sample can reach UL94 V–0 level with the reduction of THR from 80.4 MJ/m~2 to 59.5 MJ/m~2,the reduction of pkHRR from 296.4 kW/m~2 to 140.9 kW/m~2 and the rate of CO release under unit mass loss(TCOR/TML) increases 132%,which means PA10 T/GF/Alpi has good gas-phase and solid-phase ?ame retardant effect. The addition of Alpi can change the thermal decomposition process of PA66,which enhance the gas-phase ?ame retardant effect with the increasing of TCOR/TML in 265%. However,it's hard to reach UL94 V–0 of the PA66/GF/Alpi sample only using Alpi as ?re retardant due to the weak solid-phase ?ame retardant effect. The analysis of residual carbon after conical combustion by SEM shows that PA10 T/GF/Alpi has dense carbon layer while PA66/GF/Alpi has loose carbon layer.
The effect of Aluminum phosphinate(Alpi) on the flame retardancy of 30 wt% glass fiber reinforced poly(decamethylene terephthalamide)(PA10 T) and poly(hexamethylene adipamide)(PA66) was examined. The difference of ?ame retarding mechanism between PA10 T and PA66 in this ?ame retardant system was studied by means of UL 94 test,cone calorimeter method(CONE), thermogravimetric analysis(TGA) method and scanning electron microscope(SEM). The results show that when the added Alpi content is 12 wt%,the PA10 T/GF/Alpi sample can reach UL94 V–0 level with the reduction of THR from 80.4 MJ/m~2 to 59.5 MJ/m~2,the reduction of pkHRR from 296.4 kW/m~2 to 140.9 kW/m~2 and the rate of CO release under unit mass loss(TCOR/TML) increases 132%,which means PA10 T/GF/Alpi has good gas-phase and solid-phase ?ame retardant effect. The addition of Alpi can change the thermal decomposition process of PA66,which enhance the gas-phase ?ame retardant effect with the increasing of TCOR/TML in 265%. However,it's hard to reach UL94 V–0 of the PA66/GF/Alpi sample only using Alpi as ?re retardant due to the weak solid-phase ?ame retardant effect. The analysis of residual carbon after conical combustion by SEM shows that PA10 T/GF/Alpi has dense carbon layer while PA66/GF/Alpi has loose carbon layer.
引文
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[2]陈俊,胡建华,张译方,等.滑石粉-玻纤协同增强尼龙复合材料[J].广东化工,2018,45(9):33-35.Chen Jun,Hu Jianhua,Zhang Yifang,et al.Synergistic reinforcing effects of pa6 composites filled with talc and glass fiber[J].guangdong chemical industry,2018,45(9):33-35.
[3]张鹏飞,陆波.增韧剂对玻纤增强尼龙66力学性能的影响[J].橡塑技术与装备,2017,43(12):43-45.Zhang Pengfei,Lu Bo.Effects of toughening agents on performances of glass fiber reinforced PA66[J].China Rubber/Plastics Technology and Equipment,2017,43(12):43-45.
[4]许军,马静,丁会利.工程塑料PA6增韧改性的研究进展[J].塑料工业,2015,43(12):1-4.Xu Jun,Ma Jing,Ding Huili.Study Progress in toughening engineering plastics nylon 6[J].China Plastic Industry,2015,43(12):1-4.
[5]宋海硕,周登凤,张道海,等.短玻纤增强尼龙10T复合材料的热氧老化性能[J].材料工程,2017,45(12):43-49.Song Haishuo,Zhou Dengfeng,Zhang Daohai,et al.Thermaloxidative aging properties of short glass fiber reinforced nylon 10t composites[J].Journal of Materials Engineering,2017,45(12):43-49.
[6]吕文涛,马永梅,杨伏良,等.聚合法制备无卤阻燃尼龙的研究进展[J].化学通报,2017,80(2):157-163.Lyu Wentao,Ma Yongmei,Yang Fuliang,et al.Research progress in preparation of non-halogen flame retardant nylon by polymerization[J].Chemistry Bulletin,2017,80(2):157-163.
[7]Bhaskar T,KanekoJ,Muto A,et al.Effect of poly(ethylene terephthalate)on the pyrolysis of brominated flame retardant containing high impact polystyrene and catalytic debromination of the liquid products[J].Journal of Analytical and Applied Pyrolysis,2004,71:765-777.
[8]Uddin M A,Bhaskar T,Kaneko J,et al.Dehydrohalogenation druing pyrolysis of brominated flame retardant containing high impact polystyrene(HIPS-Br)mixed with polyvinylchoride(PVC)[J].Fuel,2002,81:1819-1825.
[9]赵泽文,肖淑娟,于守武.尼龙无卤阻燃研究进展[J].塑料科技,2018,46(12):128-132.Zhao Zewen,Xiao Shujuan,Yu Shouwu.Research progress in nonhalogen flame retardant of nylon[J].Plastics Science and Technology,2018,46(12):128-132.
[10]Feng Jianxiang,Su Shengpei,Zhu Jin.An intumescent flame retardant system usingβ-cyclodextrin as a carbon source in polylactic acid(PLA)[J].Polymers for Advanced Technologies,2011,22(7):1115-1122.
[11]王影洲,丁欣茹,姜浩,等.新型无卤阻燃剂二乙基次膦酸铝的合成及阻燃应用[J].南京师大学报,2016,39(2):33-37.Wang Yingzhou,Ding Xinru,Jiang Hao,et al.Synthesis and application of novel halogen-free flame retardant aluminum diethylphosphinate[J].Journal of Normal University,2016,39(2):33-37.
[12]Wang Deyi,Andreas L,Wang Yuzhong,et al.Preparation and burning behaviors of flame retarding biodegradable poly(lactic acid)nanocomposite based on zinc aluminum layered double hydroxide[J].Polymer Degradation and Stability,2010,95(12):2 474-2 480.
[13]Liu Xueqi,Wang Deyi,Wang Xxiuli,et al.Synthesis of organo-modifiedα-zirconium phosphate and its effect on the flame retardancy of IFR poly(lactic acid)systems[J].Polymer Degradation and Stability,2011,96(5):771-777.
[14]Braun U,Schartel B,Fichera M A,et al.Flame retardancy mechanism of aluminum phosphinate in combination with melamine polyphosphate and zinc borate in glass-fibre reinforced polyaminde66[J].Polymer Degradation and Stability,2007,92(8):1 528-1 545.
[15]Hu Zhi,Chen Li,Lin Gongpeng,et al.Flame Retardantion of Glass-fibre-reinforced Polyaminde 6 by a Novel Metal Salt of Alkylphosphinic Acid[J].Polymer Degradation and Stability,2011,96(9):1 538-1 545.
[16]陈先敏,兰修才,李谦,等.无卤阻燃增强尼龙66提高氧指数的研究[J].塑料工业,2015,43(8):95-98.Chen Xianmin,Lan Xiucai,Li Qian,et al.Study on improving the oxygen index in non-halogen flame retardant reinforced nylon66[J].China Plastic Industry,2015,43(8):95-98.
[17]刘志文,常晓文,周军杰,等.高性能无卤阻燃PA66的制备和性能研究[J].塑料工业,2016,44(6):5-7.Liu Zhiwen,Chang Xiaowen,Zhou Junjie,et al.Study on preparation and properties of high performance halogen-free flame retardant nylon 66[J].China Plastics Industry,2016,44(6):5-7.
[18]Braun U.Flame retardancy of glass fiber reinforced high temperature polyamide by use of aluminum diethylphosphinate:thermal and thermo-oxidative effects[J].Polymer International,2013,62(11):1 608-1 616.