六(2,4,6-三溴苯氧基)环三磷腈对固体推进剂三元乙丙橡胶包覆层性能的影响
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摘要
为了提高自由装填固体推进剂包覆层的综合性能,制备了不同六(2,4,6-三溴苯氧基)环三磷腈(BPCPZ)含量的三元乙丙橡胶(EPDM)包覆层,分析了BPCPZ含量对包覆层理化性能、硫化特性参数、耐高温和耐烧蚀性能、阻燃性能的影响。结果表明,随着包覆层配方中BPCPZ的质量分数由0增至13.55%,EPDM包覆层胶料的焦烧时间(t_(s1))未发生明显变化,而正硫化时间(t_(90))则出现了先升高后降低的趋势;包覆层在20℃时的拉伸强度由3.52M Pa增至6.09M Pa,而延伸率则由750.0%降至328.4%;EPD M包覆层的耐高温和耐烧蚀性能也随着BPC PZ含量的增加而提高,线烧蚀率由0.18mm/s降至(0.065～0.143)mm/s,800℃时的质量残留率由5.24%最大升至17.5%;当包覆层配方中BPCPZ的质量分数达到3.37%以上时,极限氧指数大于27,包覆层表现出难燃特性。
In order to improve the comprehensive performance of inhibitor of free-loading solid propellant,ethylene propylene diene monomers EPD M inhibitor w ith different contents of hexa(2,4,6-tribromophenoxy)cyclotriphosphazene(BPCPZ)were prepared.The effects of BPCPZ on the physicochemical properties,curing characteristic parameters,heatand ablative-resistance and fire-resistance of inhibitor w ere conducted.T he results show that there is no significant change of the scorch time(t_(s1)),whereas the optimum cure time(t_(90))increases at first and then decreases with increasing the mass fraction of BPC PZ from 0 to 13.55%.T he tensile strength(20℃)of inhibitor increased from 3.52M Pa to 6.09M Pa,w hereas the elongation(20℃)decreased from 750.0%to 328.4%.T he thermostability and ablation resistance of EPD M inhibitor w ere improved w ith increasing the mass fraction of BPC PZ,the linear ablation rate reduces from 0.18mm/s to(0.065—0.143)mm/s and the maximum residual rate at 800℃increases from 5.24% to 17.5%.T he limiting oxygen index is higher than 27 and the inhibitor samples show s high flame retardancy w hen the mass fraction of BPC PZ is above 3.37%.
In order to improve the comprehensive performance of inhibitor of free-loading solid propellant,ethylene propylene diene monomers EPD M inhibitor w ith different contents of hexa(2,4,6-tribromophenoxy)cyclotriphosphazene(BPCPZ)were prepared.The effects of BPCPZ on the physicochemical properties,curing characteristic parameters,heatand ablative-resistance and fire-resistance of inhibitor w ere conducted.T he results show that there is no significant change of the scorch time(t_(s1)),whereas the optimum cure time(t_(90))increases at first and then decreases with increasing the mass fraction of BPC PZ from 0 to 13.55%.T he tensile strength(20℃)of inhibitor increased from 3.52M Pa to 6.09M Pa,w hereas the elongation(20℃)decreased from 750.0%to 328.4%.T he thermostability and ablation resistance of EPD M inhibitor w ere improved w ith increasing the mass fraction of BPC PZ,the linear ablation rate reduces from 0.18mm/s to(0.065—0.143)mm/s and the maximum residual rate at 800℃increases from 5.24% to 17.5%.T he limiting oxygen index is higher than 27 and the inhibitor samples show s high flame retardancy w hen the mass fraction of BPC PZ is above 3.37%.
引文
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[18]Shui-Yu Lu,Ian Hamerton.Recent developments in the chemistry of halogen free flame retardant polymers[J].Progress in Polymer Science,2002,27:1661-1712.
[19]徐应麟,王元宏,夏国梁.高聚物材料的实用阻燃技术[M].北京:化学工业出版社,1987.
[20]Tokuyasu,Noriaki.Flame retardants for resins and flameretardanted resin compositions containing the same:EP,1219677[P].2002.
[2]侯林法,张春森,周学刚,等.复合固体推进剂[M].北京:宇航出版社,1994.
[3]阿兰·达文纳斯.固体火箭推进技术[M].北京:航天工业总公司第三十一研究所,1995.
[4]吴战鹏,张腾,吴德珍,等.低特征信号绝热层及衬层基体材料发展新趋势---聚磷腈[C]∥2006年中国宇航学会年会.北京:中国宇航学会,2006:241-247.
[5]Proebster M.Filler-containing,low-smoke insulation for solid rocket propelants:D E,3544634[P].1987.
[6]Schreuder G H.Adhesion of solid rocket materials[J].Rubber world,1990,11:928-931.
[7]Weil E.Melamine phosphates and pyrophosphates in flame-retardant coatings:old products with newpotential[J].Journal of Coatings Technology,1994,66(839):75-82.
[8]赵凤起,王新华.应用于绝热包覆层中的填料及其选用的某些规律初探[J].火炸药学报,1994(1):34-38.
[9]詹惠安,郑邯勇,赵文忠,等.固体推进剂包覆层的研究进展[J].舰船防化,2009(3):1-5.
[10]Allcock H R.Polyphosphazenes:newpolymers with inorganic backbone atoms[J].Science,1976,193:1214.
[11]Li Z,Li J.Synthesis of polyphosphazenes as potential photorefractive materials[J].Reactive and Functional.Polymers,2001,48:113-118.
[12]刘亚青,赵贵哲,宋福田.芳氧基取代聚磷腈合成方法的改进[J].兵工学报,2005,26(1):90-93.LIU Ya-qing,Z HAO Gui-zhe,SO N G Fu-tian.Improvements in the synthesis of polyaryloxyphosphazene[J].Acta Armamentarii,2005,26(1):90-93.
[13]Philip L M.Flame retardant polymeric compositions containing halogen substituted hexakis(substitutedphenoxy)cyclotriphosphazene:U S,4029634[P].1977.
[14]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.XIAO Xiao,GAN Xiao-xian,LIU Q ing,et al.Synthesis,thermal property and application of hexakis(2,4,6-tribromophenoxy)cyclotriphosphazene(BPC PZ)[J].C hinese Journal of Explosives&Propellants(Huoz hayao Xuebao),2011,34(5):16-19.
[15]王建中,王志锋,曹继平.芳氧基聚磷腈绝热包覆材料的性能表征[J].固体火箭技术,2015,38(2):278-280.WAN G Jian-zhong,WAN G Z hi-feng,C AO Ji-ping.Performance characterization of polyaryloxyphosphazene insulation coating material[J].Journal of Solid Rocket Technology,2015,38(2):278-280.
[16]Qian S Y,Huang J F,Guo WH,et al.Investigation of carbon black network in natural rubber with different bound rubber contents[J].Journal of Macromolecular Science Part B,2007,46(3):453-466.
[17]Tokuyasu,Noriaki.Flame retardants for resins and flameretardanted resin compositions containing the same:EP,1219677[P].2002.
[18]Shui-Yu Lu,Ian Hamerton.Recent developments in the chemistry of halogen free flame retardant polymers[J].Progress in Polymer Science,2002,27:1661-1712.
[19]徐应麟,王元宏,夏国梁.高聚物材料的实用阻燃技术[M].北京:化学工业出版社,1987.
[20]Tokuyasu,Noriaki.Flame retardants for resins and flameretardanted resin compositions containing the same:EP,1219677[P].2002.