一种DOPO衍生物合成及其对PLA阻燃性能的影响
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摘要
为了开发阻燃性能优良的聚乳酸(PLA)材料,扩大该生物可降解材料的应用范围,以9,10–二氢–9–氧杂–10–磷杂菲–10–氧化物(DOPO)为原料,与1,2–丙二胺反应合成了一种含双P—N键的DOPO衍生物6H–二苯并[c,e][1,2]氧代磷酸甘油酯–6,6′–(1,2–丙二胺)双–6,6′–二氧化物(12AP–DOPO)阻燃剂,通过傅里叶变换红外光谱、核磁共振表征证实合成了目标产物。将12AP–DOPO作为阻燃剂对PLA进行阻燃改性,通过垂直燃烧、极限氧指数和锥形量热分析等测试,研究了12AP–DOPO对PLA材料阻燃性能的影响。结果表明,制备的12AP–DOPO具有良好的阻燃效果,当添加量为5%时,可以使PLA材料达到UL–94 V–0阻燃级别,极限氧指数为36.3%,热释放速率峰值比纯PLA降低了15%,表现出良好的阻燃效果。
In order to develop polylactic acid(PLA) materials with excellent flame retardancy and expand the application scope of the biodegradable materials,a novel DOPO–phosphate amide derivative 6H-dibenzo[c,e][1,2] glycerol phosphate-6,6′–(1,2-propanediamine) bis-6,6′-dioxide(12 AP–DOPO) was prepared from 9,10–dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO) and 1,2–diaminopropane. FTIR,~1H NMR and ~(31)P NMR were used to characterize the product. The effect of 12 AP–DOPO on the flame retardancy of PLA was studied by means of vertical combustion,limit oxygen index and thermal analysis. The results show that the prepared 12 AP–DOPO has good flame retardant effect. When the content of 12 AP–DOPO is 5%,the material can reach UL–94 V–0 flame retardant rating,the limiting oxygen index is 36.3%,and the peak heat release rate is reduced by 15%compared with that of pure PLA,which indicates that 12 AP–DOPO has good flame retardant effect on PLA.
In order to develop polylactic acid(PLA) materials with excellent flame retardancy and expand the application scope of the biodegradable materials,a novel DOPO–phosphate amide derivative 6H-dibenzo[c,e][1,2] glycerol phosphate-6,6′–(1,2-propanediamine) bis-6,6′-dioxide(12 AP–DOPO) was prepared from 9,10–dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO) and 1,2–diaminopropane. FTIR,~1H NMR and ~(31)P NMR were used to characterize the product. The effect of 12 AP–DOPO on the flame retardancy of PLA was studied by means of vertical combustion,limit oxygen index and thermal analysis. The results show that the prepared 12 AP–DOPO has good flame retardant effect. When the content of 12 AP–DOPO is 5%,the material can reach UL–94 V–0 flame retardant rating,the limiting oxygen index is 36.3%,and the peak heat release rate is reduced by 15%compared with that of pure PLA,which indicates that 12 AP–DOPO has good flame retardant effect on PLA.
引文
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[6]Chen X,Zhuo J,Jiao C.Thermal degradation characteristics of flame retardant polylactide using TG-IR[J].Polymer Degradation&Stability,2012,97(11):2 143-2 147.
[7]Lin H J,Liu S R,Han L J,et al.Effect of a phosphorus-containing oligomer on flame-retardant,rheological and mechanical properties of poly(lactic acid)[J].Polymer Degradation&Stability,2013,98(7):1 389-1 396.
[8]Yuan X Y,Wang D Y,Chen L,et al.Inherent flame retardation of bio-based poly(lactic acid)by incorporating phosphorus linked pendent group into the backbone[J].Polymer Degradation&Stability,2011,96(9):1 669-1 675.
[9]Gaan S,Neisius M,Mercoli P,et al.Synthèse de nouveaux phosphonamidates et utilisation comme ignifuge[P].WO 2013/020696 A2.2013-02-14.
[10]Buczko A,Stelzig T,Bommer L,et al.Bridged DOPO derivatives as flame retardants for PA6[J].Polymer Degradation and Stability,2014,107:158-165.
[11]Chang Q,Long L,He W,et al.Thermal degradation behavior of PLA composites containing bis DOPO phosphonates[J].Thermochimica Acta,2014,639:84-90.
[12]Zhan J,Song L,Nie S,et al.Combustion properties and thermal degradation behavior of polylactide with an effective intumescent flame retardant[J].Polymer Degradation and Stability,2009,94(3):291-296.
[13]Jing J,Zhang Y,Fang Z.Diphenolic acid based biphosphate on the properties of polylactic acid:Synthesis,fire behavior and flame retardant mechanism[J].Polymer,2017,108:29-37.
[14]张阳,代培刚,陈英杰,等.基于锥形量热仪试验的典型聚合物材料燃烧性能研究[J].广东化工,2015,42(7):53-54.zhang Yang,Dai Peigang,Chen Yingjie,et al.Study on combustion performance of typical polymeric materials based on cone calorimeter test[J].Guangdong Chemical Industry,2015,42(7):53-54.
[15]Zhang F,Gao W,Jia Y,et al.A concise water-solvent synthesis of highly effective,durable,and eco-friendly flame-retardant coating on cotton fabrics[J].Carbohydrate Polymers,2018,199:256-265.
[16]司明明,丁率,郝建薇,等.纳米Sb2O3与次膦酸铝阻燃聚对苯二甲酸乙二醇酯协同作用研究[J].高分子学报,2013(12):1 483-1 491.Si Mingming,Ding Shuai,Hao Jianwei,et al.Synergistic effect of nano-Sb2O3 and aluminium phosphinate on flame retardancy of PET[J].Acta Polymerica Sinica,2013(12):1 483-1 491.