六(4-硝基苯氧基)环三磷腈的合成及其热稳定性研究
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摘要
六(4-硝基苯氧基)环三磷腈(HNCTP)是一种环境友好型阻燃剂,因具有良好的耐热性和阻燃性而备受关注。以六氯环三磷腈(HCCP)、对硝基苯酚为原料合成了HNCTP,经傅里叶红外光谱(FT-IR)、核磁共振(NMR)、元素分析(EA)、热重-差示扫描量热分析(TGA-DSC)等分析手段对产物的结构和热稳定性进行了表征,并考察了反应溶剂、投料比例和反应时间3个因素对HNCTP收率的影响。结果表明,以丙酮为溶剂,n(对硝基苯酚)∶n(HCCP)=9∶1,56℃回流反应18h,HNCTP的收率为90.5%。热稳定性研究表明,HNCTP的热稳定性较好,在N2气氛下的初始分解温度为371.5℃,可作为添加型阻燃剂应用于聚合物基材中,而且适用于加工温度较高的体系。
Hexa(4-nitrophenoxy)cyclotriphosphazene(HNCTP)is an environmentally friendly flame retardant and it has attracted significant attention because of its excellent heat-resistance and flame-resistance.In the study,HNCTP was synthesized by the reaction of hexachlorocyclotriphosphazene(HCCP)with 4-nitrophenol,and characterized by means of Fourier transform infrared spectroscopy(FT-IR),nuclear magnetic resonance(NMR),elemental analysis(EA),thermogravimetric analysis and differential scanning calorimetry(TGADSC).The influences of solvent,raw material ratio and reaction time(t)on the yield of HNCTP were investigated.The results showed when n(4-nitrophenol)∶n(HCCP)=9∶1,T=56℃,t=18h,acetone as solvent,the yield of HNCTP was the highest and amounted up to 90.5%.Thermal analysis results showed that the onset decomposition temperature of HNCTP was 371.5℃.Therefore,HNCTP is a flame retardant with perfect thermal stability,and it can be applied in high processing temperature system.
Hexa(4-nitrophenoxy)cyclotriphosphazene(HNCTP)is an environmentally friendly flame retardant and it has attracted significant attention because of its excellent heat-resistance and flame-resistance.In the study,HNCTP was synthesized by the reaction of hexachlorocyclotriphosphazene(HCCP)with 4-nitrophenol,and characterized by means of Fourier transform infrared spectroscopy(FT-IR),nuclear magnetic resonance(NMR),elemental analysis(EA),thermogravimetric analysis and differential scanning calorimetry(TGADSC).The influences of solvent,raw material ratio and reaction time(t)on the yield of HNCTP were investigated.The results showed when n(4-nitrophenol)∶n(HCCP)=9∶1,T=56℃,t=18h,acetone as solvent,the yield of HNCTP was the highest and amounted up to 90.5%.Thermal analysis results showed that the onset decomposition temperature of HNCTP was 371.5℃.Therefore,HNCTP is a flame retardant with perfect thermal stability,and it can be applied in high processing temperature system.
引文
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[2]Zima V,Svoboda J,Benes L,et al.Synthesis and characterization of new strontium 4-carboxyphenylphosphonates[J].Journal of Solid State Chemistry,2007,180(3):929-939.
[3]Bao Dongmei,Liu Jiping,Xie Bing,et al.Research on synthesis and thermal stability of hexa(phenoxy)cyclotriphosphazene[J].Journal of functional materials,2016,47(5):05165-05169(in Chinese).宝冬梅,刘吉平,谢兵,等.六苯氧基环三磷腈的合成及其热稳定性研究[J].功能材料,2016,47(5):05165-05169.
[4]Hou Ruifeng,Li Shunxiang,Ma Aili.Phosphazene phosphor-nitrogen flame retardant[J].Shanxi Chemical Industry,1998,(4):30-31(in Chinese).侯锐锋,李顺香,马爱丽.磷腈系列磷-氮系阻燃剂[J].山西化工,1998,(4):30-31.
[5]Chen Sheng,Zheng Qingkang.Research progress of cyclophosphazene flame retardants[J].China Textile Leader,2004,(5):92-96(in Chinese).陈胜,郑庆康.环状磷腈阻燃剂的研究进展[J].纺织导报,2004,(5):92-96.
[6]Shao Zonglong,Liang Jun,Shi Hu,et al.Studies on heat decomposition and combustion of polyethylene modified by flame retardants[J].Fire Safety Science,1998,7(1):39-43(in Chinese).邵宗龙,梁军,时虎,等.阻燃聚乙烯热解燃烧特性的研究[J].火灾科学,1998,7(1):39-43.
[7]Li Shizhen.Synthesis of cyclotriphosphazene derivatives and new synthetic process discussion of polyphosphazenes[D].Changsha:Hunan University,2007(in Chinese).李时珍.环三磷腈衍生物合成与聚磷腈合成新工艺探讨[D].长沙:湖南大学,2007.
[8]Dez I,De Jaeger R.Synthesis and radical polymerization of methacrylate monomers containing cyclotriphosphazene.Thin-layer grafts of their polymers on a poly(vinyl alcohol)surface[J].Macromolecules,1997,30(26):8262-8269.
[9]Meng Xinjing.Synthesis and characterization of hexachlorocyclotriphosphazene and derivatives containing phenoxy group[D].Nanjing:Nanjing University of Science and Technology,2004(in Chinese).孟新静.六氯环三磷腈及其苯氧基衍生物的合成与表征[D].南京:南京理工大学,2004.
[10]Wu Xiangwen,Fang Changshui,Wang Min,et al.Synthesis of hexakis(4-nitrophenoxy)cyclotriphosphazene by an improved method[J].Acta Chimica Sinica,2002,60(5):955-956(in Chinese).吴祥雯,房昌水,王民,等.一种改进方法合成六(4-硝基酚氧)环三磷腈[J].化学学报,2002,60(5):955-956.
[11]He Lanlan.Synthesis of cyclophosphazene containing silicon group and study on its application in non-halogen flame retardant polypropylene[D].Beijing:Beijing Institute of Technology,2011(in Chinese).何兰岚.含硅官能团磷腈阻燃剂的合成及其在无卤阻燃聚丙烯中的作用研究[D].北京:北京理工大学,2011.
[12]Xiao Xiao,Gan Xiaoxian,Liu Qing,et al.Synthesis,thermal property and application of hexakis(2,4,6-tribromophenoxy)cyclotriphosphazene(BPCPZ)[J].Chinese Journal of Explosives&Propellants,2011,34(5):16-19(in Chinese).肖啸,甘孝贤,刘庆,等.六(2,4,6-三溴苯氧基)环三磷腈(BPCPZ)的合成、热性能及应用[J].火炸药学报,2011,34(5):16-19.
[13]Wu Yong.Synthesis and study of cyclotriphosphazenes derivatives containing oxygen group and their flame-retardant for epoxy resin[D].Zhengzhou:Henan University of Technology,2011(in Chinese).吴勇.环三磷腈含氧衍生物的合成及其对环氧树脂的阻燃研究[D].郑州:河南工业大学,2011.
[14]Kong Xiangjian.Study on LLDPE modified by non-halogen flame retardant[D].Guangzhou:South China University of Technology,2008(in Chinese).孔祥建.无卤阻燃改性LLDPE的研究[D].广州:华南理工大学,2008.
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