磷氮阻燃剂的合成及其在环氧树脂中的应用
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摘要
由亚磷酸、乙腈和苯膦酰二氯(PPDC)合成了一种添加型阻燃剂——苯膦酰二氨基双乙基四膦酸(PAEPA)。通过FTIR和ESI-MS对PAEPA的结构进行了表征。并将PAEPA混入环氧树脂(EP)中制备了阻燃环氧树脂,通过TGA、UL-94测试和LOI测试考察了用三乙烯四胺(TETA)固化的环氧树脂的阻燃性和热性能。结果表明,当w(P)=2.6%时,环氧热固性材料表现出优异的阻燃性能,并通过了UL94实验的V-0等级,LOI为29.8%。热重分析结果表明:800℃的残炭量为17.7%。SEM结果表明:EP/TETA体系中的PAEPA明显促进环氧树脂形成更致密、丰富的密封炭层,以提高燃烧过程中基体的阻燃性能。
A novel flame retardant additive, phenylphosphonium diaminobisethyltetraphosphonic acid(PAEPA), was synthesized from phosphoric acid, acetonitrile and phenylphosphonic dichloride(PPDC). The structure of PAEPA was characterized by FTIR and ESI-MS. PAEPA was blended into epoxy resin to prepare flame-retardant epoxy resins. The flame-retardant and thermal properties of epoxy resins cured with triethylene tetramine(TETA) were investigated by TGA, vertical burning test(UL-94), and limiting oxygen index(LOI). The results revealed that the epoxy thermosets containing 2.6% phosphorus exhibited excellent flame retardancy and passed the UL 94 V-0 rating, its LOI value was 29.8%. The residual char yield at 800 ℃ was 17.7%. The morphology characterization of char residue by SEM showed that a denser, richer sealing residue char could be formed by the presence of PAEPA in EP/TETA system, which improved the flame-retardant properties of the matrix during combustion.
A novel flame retardant additive, phenylphosphonium diaminobisethyltetraphosphonic acid(PAEPA), was synthesized from phosphoric acid, acetonitrile and phenylphosphonic dichloride(PPDC). The structure of PAEPA was characterized by FTIR and ESI-MS. PAEPA was blended into epoxy resin to prepare flame-retardant epoxy resins. The flame-retardant and thermal properties of epoxy resins cured with triethylene tetramine(TETA) were investigated by TGA, vertical burning test(UL-94), and limiting oxygen index(LOI). The results revealed that the epoxy thermosets containing 2.6% phosphorus exhibited excellent flame retardancy and passed the UL 94 V-0 rating, its LOI value was 29.8%. The residual char yield at 800 ℃ was 17.7%. The morphology characterization of char residue by SEM showed that a denser, richer sealing residue char could be formed by the presence of PAEPA in EP/TETA system, which improved the flame-retardant properties of the matrix during combustion.
引文
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[25]YueX,LiJ,LiuP,etal.Investigationofflame-retardedpoly(butylenesuccinate)compositesusingMHSHassynergisticand reinforced agent[J]. Journal of Materials Science, 2017,(5):1-12.
[26]Xie C, Zeng B, Gao H, et al. Improving thermal and flame-retardant propertiesofepoxyresinsbyanovelreactivephosphorouscontainingcuringagent[J].PolymerEngineering&Science,2014,54(5):1192–1200.
[27]Jiao C, Zhang C,Dong J,et al. Combustion behavior and thermal pyrolysiskineticsofflame-retardantepoxycompositesbasedon organic–inorganic intumescent flame retardant[J]. Journal of Thermal Analysis&Calorimetry, 2015, 119(3):1759-1767.
[2]Dong Meili(董美丽). Effect of composite flame retardant on flame retardancy and mechanical properties of epoxy resin[D]. Shenyang:Shenyang Aerospace University(沈阳航空航天大学), 2018.
[3]HanMingxuan(韩明轩),XuMiaojun(许苗军),LiBin(李斌).Synthesisofnewphosphorus-containingflameretardantsand properties of flame retardant epoxy resins[J]. Plastic(塑料), 2015,44(5):65-69.
[4]GaoHuiyan(高慧妍),ZouQiang(邹强).Researchprogressof halogen-free flame retardant epoxy resin materials[J]. Petrochemical Technology(石化技术), 2017, 24(3):257-257.
[5]TanXing(谭行),ZengLiming(曾黎明),XuRenxin(徐任信).Synthesis of DOPO-PHBA reactive flame retardant and its effect on theperformanceofepoxyresinwithTGICcompositesystem[J].JournalofCompositeMaterials(复合材料学报),2018,35(3):485-492.
[6]XuMj,ZhaoW,LiB,etal.Synthesisofaphosphorusand sulfur-containing aromatic diamine curing agent and its application in flame retarded epoxy resins[J]. Fire and Materials, 2015, 39(5):518-532.
[7]XiaoL,SunDC,NiuTL,etal.SynthesesoftwoDOPO-based reactive additives as flame retardants and co-curing agents for epoxy resins[J]. Phosphorus, Sulfur, and Silicon and the Related Elements,2014, 189(10):1564-1571.
[8]LiuChuan(刘川).Preparationoftwophosphorus-nitrogenflame retardants and study on flame retardant epoxy resin[D]. Ha Erbing:Northeast Forestry University(东北林业大学), 2017.
[9]Xu Puqin(徐卜琴), Zhang Yanchong(张岩冲), Xu Guilong(徐桂龙),etal.Preparationofphosphorus-nitrogenmodifiedphenolic resin and study on flame retardant properties of cured epoxy resin[J].Journal of Chemical Engineering of Chinese Universities(高校化学工程学报), 2018, 32(3):653-658.
[10]ChenHaoran(陈浩然),ChenGuofu(陈国富),LiJinru(李金儒).Preparationofnewphosphorus-containingflameretardantandits application in epoxy resin system[J]. Fiber Composites(纤维复合材料), 2017(2):12-15.
[11]LuoHang(罗航),CaiXufu(蔡绪福).Synthesisofnitrogencontainingflameretardantanditsapplicationinepoxyresin[J].EngineeringScienceandTechnology(工程科学与技术),2018,50(4):1-7.
[12]WangZhiguo(王志国),LiangBing(梁兵).Synthesisof phosphorus-nitrogenflameretardantGAP-DOPOanditsflame retardant properties for epoxy resin[J]. Fine Chemicals(精细化工),2017, 34(4):382-388.
[13]Shao Zhiheng(邵志恒), Li Jilu(李纪录), Chen Xianming(陈显明).Synthesisofhalogen-freereactivephosphorousnitrogenflame retardantand studyonitsflameretardantmodifiedepoxyresin[J].Xiamen Journal of Xiamen University:Natural Science(厦门大学学报:自然科学版), 2018,(1):25-31.
[14]ShenDan(沈聃),ChenLi(陈力),XuYingjun(徐英俊).Flame retardantmodifiedepoxyresinofdiphenoxyphosphatemelamine salt[J].ChemicalResearchandApplication(化学研究与应用),2017, 29(7):1050-1055.
[15]LiPei(李霈),FuHai(付海),ZhaoOu(赵欧).Effectof polyphosphateflameretardantcombinedwithammonium polyphosphateonflameretardancyofepoxyresin[J].Chemical JournalofChineseUniversities(高等学校化学学报),2017,38(2):294-302.
[16]LaiFang(来方),FuHai(付海),ZhaoOu(赵欧).Effectof polyphenoxyphosphatebisphenolate/ammoniumpolyphosphate intumescent flameretardant on flameretardancy of epoxy resin[J].Acta Polymerica Sinica(高分子学报), 2017,(4):692-699.
[17]Ai C C, Xiao Y, Chen S P, et al. Solid state structures of anhydrous1-aminoethylidenediphosphonicacid[J].JournalofChemical Crystallography, 2011, 41(8):1202-1207.
[18]Liu Weishi(刘伟时), Zhang Tie(张铁), Chen Shanshan(陈珊珊).Boron-nitrogen flame retardant and magnesium hydroxide synergistic flameretardantepoxyresin[J].PolymerMaterialsScienceand Engineering(高分子材料科学与工程), 2017, 33(5):36-41.
[19]WangP,YangF,LiL,etal.Flame-retardantpropertiesand mechanismsofepoxythermosetsmodifiedwithtwophosphoruscontaining phenolic amines[J]. Journal of Applied Polymer Science,2016, 133(37). DOI:10.1002/app.43953.
[20]Song S Q, Ma J J, Cao K, et al. Synthesis of a novel dicyclic silicon/phosphorus hybrid and its performance on flame retardancy of epoxy resin[J]. Polymer Degradation and Stability, 2014, 99:43-52.
[21]VagapovaLI,GazizovAS,BurilovAR,etal.Newnucleoside analogsderivedfromadenosineandmethylenebisphosphonic acids[J]. Journal of General Chemistry, 2016, 86(11):2564-2566.
[22]Gu L-m, Chai C-p, Luo Y-j. Preparation and performance evaluation ofphosphorus-nitrogensynergismflame-retardantwater-borne coatingsforcottonandpolyesterfabrics[J].JournalofPolymer Research, 2016, 23(64):1-10.
[23]LiuXL,LiangB.Impactofanovelphosphorus-nitrogenflame retardant curing agent on the properties of epoxy resin[J]. Materials Research Express, 2017, 4(12). DOI:10. 1088/2053-1591/aa9dba.
[24]GuL,ChenG,YaoY.Twonovelphosphorus–nitrogen-containing halogen-free flame retardants of high performance for epoxy resin[J].England Polymer Degradation&Stability, 2014, 108:68-75.
[25]YueX,LiJ,LiuP,etal.Investigationofflame-retardedpoly(butylenesuccinate)compositesusingMHSHassynergisticand reinforced agent[J]. Journal of Materials Science, 2017,(5):1-12.
[26]Xie C, Zeng B, Gao H, et al. Improving thermal and flame-retardant propertiesofepoxyresinsbyanovelreactivephosphorouscontainingcuringagent[J].PolymerEngineering&Science,2014,54(5):1192–1200.
[27]Jiao C, Zhang C,Dong J,et al. Combustion behavior and thermal pyrolysiskineticsofflame-retardantepoxycompositesbasedon organic–inorganic intumescent flame retardant[J]. Journal of Thermal Analysis&Calorimetry, 2015, 119(3):1759-1767.