含能增塑剂一缩二甘油四硝酸酯的基本性能
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摘要
以硝酸铵为硝化剂,浓硫酸为脱水剂,一缩二甘油为前驱体,制备了含能增塑剂一缩二甘油四硝酸酯(DGTN);采用核磁共振确认了产物的分子结构;对DGTN进行了DSC分析,计算了DGTN热分解的表观活化能(E_K)、指前因子(A_K)、速率常数(k)、活化焓(ΔH~≠)、活化自由能(ΔG~≠)和活化熵(ΔS~≠)。同时,利用TG-IR分析研究了DGTN的热分解产物。测试了DGTN的撞击感度,计算了DGTN单元推进剂的标准比冲(I_(sp))、特征速度(C~*)、燃烧室温度(T_c)和燃烧产物平均相对分子质量(M_c),并与NG进行了对比。另外,利用DSC分析研究了DGTN与AP和HMX的相容性。结果表明,DGTN的分解峰温在199～208℃之间,表观热分解活化能为164.4 k J/mol,分解产物为CO_2、NO_2、CH_4和H_2O,还有少量CO、NO和CH_2O生成。DGTN的撞击感度明显低于NG,能量性能与NG相近。DGTN的加入未影响AP和HMX的热分解过程,AP和HMX也未影响DGTN的热分解过程,说明DGTN与AP和HMX有较好的化学相容性。
By using ammonium nitrate as a nitrating agent,concentrated sulfuric acid as dehydrant,and diglycerol as precursor,an energetic plasticizer diglycerol tetranitrate(DGTN)has been synthesized.The molecular structure of the prepared material has been confirmed as DGTN via 1H NMR analysis.The DSC analyses have been performed at different heating rate,and the kinetic and thermodynamic parameters such as activation energy(E_K),pre-exponential factor(A_K),rate constant(k),activation enthalpy(ΔH~≠),activation free energy(ΔG~≠),and activation entropy(ΔS~≠)were calculated.Meanwhile,employing TG-IR analysis,decomposition products of DGTN have been disclosed.The impact sensitivity of DGTN was tested and its energy performances such as standard specific impulse(I_(sp)),characteristic velocity(C~*),temperature of combustion chamber(T_c),and average molecular weight of combustion products(M_c)were calculated.Additionally,the compatibilities of DGTN with ammonium perchlorate(AP)and octogen(HMX)are also investigated.The results indicate that the decomposition peak temperature range of DGTN is located at 199～208℃.The activation energy of thermal decomposition of DGTN was 164.4 k J·mol~(-1).The main decomposition products of DGTN are CO_2,NO_2,CH_4,and H_2O.A few CO,NO,and CH_2O are also detected.The impact sensitivity of DGTN is obviously lower than that of NG and the energy performance of DGTN was similar as that of NG.In presence of DGTN does not affect decomposition processes of AP and HMX.The contact with AP and HMX also does not affect decomposition process of DGTN.It means that the DGTN had good chemical compatibility with AP and HMX.
By using ammonium nitrate as a nitrating agent,concentrated sulfuric acid as dehydrant,and diglycerol as precursor,an energetic plasticizer diglycerol tetranitrate(DGTN)has been synthesized.The molecular structure of the prepared material has been confirmed as DGTN via 1H NMR analysis.The DSC analyses have been performed at different heating rate,and the kinetic and thermodynamic parameters such as activation energy(E_K),pre-exponential factor(A_K),rate constant(k),activation enthalpy(ΔH~≠),activation free energy(ΔG~≠),and activation entropy(ΔS~≠)were calculated.Meanwhile,employing TG-IR analysis,decomposition products of DGTN have been disclosed.The impact sensitivity of DGTN was tested and its energy performances such as standard specific impulse(I_(sp)),characteristic velocity(C~*),temperature of combustion chamber(T_c),and average molecular weight of combustion products(M_c)were calculated.Additionally,the compatibilities of DGTN with ammonium perchlorate(AP)and octogen(HMX)are also investigated.The results indicate that the decomposition peak temperature range of DGTN is located at 199～208℃.The activation energy of thermal decomposition of DGTN was 164.4 k J·mol~(-1).The main decomposition products of DGTN are CO_2,NO_2,CH_4,and H_2O.A few CO,NO,and CH_2O are also detected.The impact sensitivity of DGTN is obviously lower than that of NG and the energy performance of DGTN was similar as that of NG.In presence of DGTN does not affect decomposition processes of AP and HMX.The contact with AP and HMX also does not affect decomposition process of DGTN.It means that the DGTN had good chemical compatibility with AP and HMX.
引文
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[12]Andrew J Sanderson,North Ogden,Laura J Martins,et al.Method of synthesizing diglycerol tetranitrate and solid rocket motor propellant containing the same[P].US Patent,US 20030089435A1,2003.
[2]何利明,郑剑,罗运军.含Bu NENA钝感交联改性双基推进剂能量分析[J].固体火箭技术,2015,38(1):90-94.HE Liming,ZHENG Jian,LUO Yunjun.Energy properties of the insensitive and cross-linked Bu NENA propellant[J].Journal of Solid Rocket Technology,2015,38(1):90-94.
[3]刘亚静,莫洪昌,汪营磊,等.含能增塑剂DAMNP的合成与性能[J].含能材料,2015,23(7):712-714.LIU Yajing,MO Hongchang,WANG Yinglei,et al.Synthesis and properties of energetic plasticizer DAMNP[J].Chinese Journal of Energetic Materials,2015,23(7):712-714.
[4]张杏芬.国外火炸药原材料性能手册[M].北京:兵器工业出版社,1991.
[5]田德余.固体推进剂配方优化设计[M].北京:国防工业出版社,2013.TIAN Deyu.Optimization design of solid propellant formulation[M].Beijing:National Defence Industry Press,2013.
[6]Sanderson A J.Development of very energetic binder system ingredients(PGN and DGTN)[C]//The 32nd International Annual Conference of the ICT.Karlsruhe Germany:July2001,3-6.
[7]Nicholas Straessler,Manfai Lee.Synthesis and characterization of diglycerol tetranitrate(DGTN)-an energetic plasticizer for use in explosive and propellant formulations[J].Journal of Energetic Materials,2017,35(1):1-8.
[8]Kissinger H E.Reaction kinetics in different thermal analysis[J].Analytical Chemistry,1957,29(11):1702-1706.
[9]Sovizi M R,Hajimirsadeghi S S,Naderizadeh B.Effect of particle size on thermal decomposition of nitrocellulose[J].Journal of Hazardous Materials,2009,168(2):1134-1139.
[10]宋小兰,王毅,王晶禹,等.1,2,3,4-丁四醇四硝酸酯的合成、表征和性能研究[J].含能材料,2014,22(4):458-461.SONG Xiaolan,WANG Yi,WANG Jingyu,et al.Synthesis,characterization of 1,2,3,4-erythrityl tetranitrate[J].Chinese Journal of Energetic Materials,2014,22(4):458-461.
[11]Wang Yi,Song Xiaolan,Song Dan,et al.Synthesis,thermolysis,and sensitivities of HMX/NC energetic nanocomposites[J].Journal of Hazardous Materials,2016,312:73-83.
[12]Andrew J Sanderson,North Ogden,Laura J Martins,et al.Method of synthesizing diglycerol tetranitrate and solid rocket motor propellant containing the same[P].US Patent,US 20030089435A1,2003.