苯并嗪协效二乙基次磷酸铝阻燃PA66的研究
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摘要
以双酚A型苯并嗪(BOZ)为成炭协效剂,二乙基次磷酸铝(ADP)为阻燃剂,通过熔融共混制备了阻燃尼龙66(PA66)复合材料。通过垂直燃烧测试(UL94)、极限氧指数(LOI)、锥形量热(Cone)、SEM以及TGA等考察了复合材料的协同阻燃性能及作用机制。结果表明:BOZ和ADP具有良好的协同阻燃效应。适量BOZ的引入不但可以提高材料的阻燃性能,还可以改善材料的热稳定性,并且对材料的力学性能影响不大。添加占体系质量分数0.3%BOZ和质量分数7.7%ADP时,ADP/BOZ阻燃PA66复合材料的垂直燃烧达到UL94V-0级,LOI达到了32.8%,拉伸强度、弯曲强度分别为81.52、111.11 MPa。阻燃机理研究表明:ADP/BOZ和ADP都是以气相阻燃作用为主的气相和凝聚相协同阻燃机制。
Flame-retardant nylon 66(PA66) composites were prepared by melt blending process using bisphenol A benzoxazine(BOZ) as synergist and diethyl-phosphate aluminum(ADP) as flame retardant. The synergistic flame retardant effects and mechanism of PA66 composites were investigated by means of UL94 vertical combustion test, limiting oxygen index(LOI) value, cone calorimeter test(Cone), SEM and TGA. The results showed that BOZ and ADP had good synergistic effect on flame retardant properties of PA66. The introduction proper amount of BOZ could not only improve the flame retardant properties of the PA66 composites, but also enhance the thermal stability, and have little influence on the mechanical properties of the material. When the adding amounts of BOZ and ADP were 0.3% and 7.7%(mass fraction), respectively, the prepared ADP/BOZ/PA66 composites could pass UL94 V-0 flammability rating, the LOI value reached 32.8%, the tensile strength was 81.52 MPa, and the bending strength was 111.11 MPa. The flame retardant mechanism revealed that both ADP/BOZ and ADP were dominated by gas phase flame-retardant mechanism and accompanying condensed phase flame-retardant mechanism simultaneously.
Flame-retardant nylon 66(PA66) composites were prepared by melt blending process using bisphenol A benzoxazine(BOZ) as synergist and diethyl-phosphate aluminum(ADP) as flame retardant. The synergistic flame retardant effects and mechanism of PA66 composites were investigated by means of UL94 vertical combustion test, limiting oxygen index(LOI) value, cone calorimeter test(Cone), SEM and TGA. The results showed that BOZ and ADP had good synergistic effect on flame retardant properties of PA66. The introduction proper amount of BOZ could not only improve the flame retardant properties of the PA66 composites, but also enhance the thermal stability, and have little influence on the mechanical properties of the material. When the adding amounts of BOZ and ADP were 0.3% and 7.7%(mass fraction), respectively, the prepared ADP/BOZ/PA66 composites could pass UL94 V-0 flammability rating, the LOI value reached 32.8%, the tensile strength was 81.52 MPa, and the bending strength was 111.11 MPa. The flame retardant mechanism revealed that both ADP/BOZ and ADP were dominated by gas phase flame-retardant mechanism and accompanying condensed phase flame-retardant mechanism simultaneously.
引文
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[4]RathiS,DahiyaJB.Effectonthermalbehaviourofpolyamide66/clay nanocomposites with inorganic flame retardant additives[J].Indian Journal of Chemistry,2012, 51(12):1677-1685.
[5]Kelnar I, Stephan M, Jakisch L,et al. Influence of the component reactivity on the properties of ternary reactive blends Nylon 6/rigid brittlepolymer/elastomer[J].JournalofAppliedPolymerScience,2000, 78(9):1597-1603.
[6]Zhan Z S, Li B, Xu M J, et al. Synergistic effects of nano-silica on aluminumdiethylphosphinate/polyamide66systemforfire retardancy[J]. High Performance Polymers, 2016, 28(2):140-146.
[7]HeWT,ZhuH,ZhangPC,etal.Pyrolysisandflammability behavior of long(glass fiber)-reinforced polyamide 6 by aluminum alkylphosphinate-based flame retardants in combination with organic montmorillonite[J]. Journal of Vinyl&Additive Technology, 2018,24(1):27-36.
[8]TangG,WangX,JiangSD,etal.Thermaldegradationand combustionbehaviorsofflameretardedglassfiberreinforced polyamide 6 composites based on cerium hypophosphite[J]. Polymer Composites, 2016, 37(10):3073-3082.
[9]Huang W J, He W T, Long L J, et al. Highly efficient flame-retardant glass-fiber-reinforcedpolyamide6Tsystembasedonanovel DOPO-basedderivative:Flameretardancy,thermaldecomposition,andpyrolysisbehavior[J].PolymerDegradation&Stability,2018,148:26-41.
[10]LuZhehong(鲁哲宏),BanDasai(班大赛),LiHao(李豪),etal.Researchprogressofflameretardantmodifiednylon[J].Chemical Research(化学研究),2018, 29(3):310-316.
[11]Xiao X, Hu S, Zhai J G, et al. Thermal properties and combustion behaviors of flame-retarded glass fiber-reinforced polyamide 6 with piperazinepyrophosphateandaluminumhypophosphite[J].Journal of Thermal Analysis&Calorimetry,2016, 125(1):1-11.
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[13]JinSong(金松),XiangYushu(向宇姝),YuJie(于杰),etal.Synthesis of a novel alkyl-substituted phosphinate and its application in PA6[J]. China Plastics Industry(塑料工业),2017, 45(1):9-13.
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[15]Cheng Baofa(程宝发), Ma Tenghao(马腾昊), Li Xiangmei(李向梅), et al. Flame retardant performance of PA 6/ADP composites[J].China Synthetic Resin and Plastics(合成树脂与塑料), 2016, 33(4):24-28.
[16]Wang Junliang(王军亮), Lu Zhehong(鲁哲宏), Li Hao(李豪), et al. Research progress of polybenzoxazines:design and synthesis[J].Chemical Research(化学研究),2018, 29(2):213-220.
[17]ZhangHC,GuW,ZhuRQ,etal.Nitrogenconfigurationof polybenzoxazinecarbide[J].HighTemperatureMaterialsand Processes,2015, 34(3):245-250.
[18]Wang Junliang(王军亮),Lu Zhehong(鲁哲宏), Li Hao(李豪), et al.Progressonflameretardantmodificationofpolybenzoxazines[J].PolymerMaterialsScience&Engineering(高分子材料科学与工程), 2018, 34(5):183-190.
[19]KiskanB,YagciY.Self-healingofpoly(propyleneoxide)-polybenzoxazine thermosets by photoinduced coumarine dimerization[J].JournalofPolymerScience,PartA:PolymerChemistry,2015,52(20):2911-2918.
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[24]Standardization Administration of the People's Republic of China(中国国家标准化管理委员会).Plastics—Determinationofburning behaviourbyoxygenindex—Part2:Ambient-temperaturetest(塑料用氧指数法测定燃烧行为第2部分:室温试验):GB/T2406. 2-2009[S]. Beijing:Standards Press of China(北京:中国标准出版社), 2009:6-15.
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[27]Standardization Administration of the People's Republic of China(中国国家标准化管理委员会).Plastics—Determinationofflexural properties(塑料-弯曲性能的测定):GB/T9341-2008[S]. Beijing:Standards Press of China(北京:中国标准出版社), 2008:8-4.
[28]Standardization Administration of the People's Republic of China(中国国家标准化管理委员会).Plastics-Determinationofcharpy impactproperties(塑料-简支梁冲击性能的测定):GB/T1043-2008[S].Beijing:StandardsPressofChina(北京:中国标准出版社), 2008:8-4.