四硝基吡咯及其衍生物结构与性能的理论研究
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摘要
为了寻找新型高能量密度材料,设计了四硝基吡咯及其甲基、氨基、硝基衍生物。在DFT-B3LYP/6~(-3)1G*水平下对模型化合物进行了几何结构全优化。在DFT-B3LYP/6~(-3)11++G**水平计算了模型化合物的生成焓、爆轰性能。自然键轨道(NBO)分析了模型化合物引发键的强度进而考察了其热安全性。计算结果表明:1-甲基四硝基吡咯密度为1.88 g·cm~(~(-3)),爆速和爆压分别为8.66 km·s~(-1)和34.10 GPa,其爆轰性能具有与1,3,5-三硝基~(-1),3,5-三氮杂环己烷(RDX)相当的爆轰性能;四硝基吡咯、1-氨基四硝基吡咯密度分别为1.93 g·cm~(-3)和2.04 g·cm~(-3),爆速均为9.01 km·s~(-1),爆压分别为37.54 GPa和38.73 GPa,具有与1,3,5,7-四硝基~(-1),3,5,7-四氮杂环辛烷(HMX)相当的爆轰性能;由于五硝基吡咯中含有五个硝基,其热安全性最差,N(5)—NO2键离解能仅为60.8 k J·mol~(-1)。计算值与之前的实验值具有较好的一致性,表明计算值可靠。
In order to search new high-energy density materials,2,3,4,5-tetranitropyrrole( TNP) and its methyl-,amino-,nitro-substituted derivatives were designed. Their structures were optimized at the DFT-B3LYP/6~(-3)1G*level. Heats of formation,detonation properties were calculated at the DFT-B3LYP/6~(-3)11 + + G**level. Nature Bond Orbital( NBO) analysis was carried to understanding the strength of trigger bond and further to access the thermal stability of the model compounds. The calculated results are as follows: the density,detonation velocity and detonation pressure of 1-methyl-2,3,4,5-tetranitropyrrloe are 1. 88 g·cm~(-3),8. 66 km·s~(-1)and 34. 10 GPa,respectively,which is comparable to the detonation properties of 1,3,5-trinitro~(-1),3,5-triaza-cyclohexane( RDX). The densities of 2,3,4,5-tetranitropyrrole and 1-amino-2,3,4,5-tetranitropyrrole are 1. 93 g·cm~(-3)and 2. 04 g·cm~(-3),respectively; the detonation velocities are both 9. 01 km·s~(-1),and detonation pressures are 37. 54 GPa and 38. 73 GPa,which suggests that the detonation properties of TNP and ATNP are both comparable to that of 1,3,5,7-tetranitro~(-1),3,5,7-tetraza-cyclooctcme( HMX). With containing five nitro groups,the BDE of nitro group N( 5) —NO2is 60. 8 k J·mol~(-1),suggesting that pentanitropyrrole has the poorest thermal stability in all five model compounds. The calculated results and previous experimental work agree reasonably well one another,showing values in this paper are reasonable.
In order to search new high-energy density materials,2,3,4,5-tetranitropyrrole( TNP) and its methyl-,amino-,nitro-substituted derivatives were designed. Their structures were optimized at the DFT-B3LYP/6~(-3)1G*level. Heats of formation,detonation properties were calculated at the DFT-B3LYP/6~(-3)11 + + G**level. Nature Bond Orbital( NBO) analysis was carried to understanding the strength of trigger bond and further to access the thermal stability of the model compounds. The calculated results are as follows: the density,detonation velocity and detonation pressure of 1-methyl-2,3,4,5-tetranitropyrrloe are 1. 88 g·cm~(-3),8. 66 km·s~(-1)and 34. 10 GPa,respectively,which is comparable to the detonation properties of 1,3,5-trinitro~(-1),3,5-triaza-cyclohexane( RDX). The densities of 2,3,4,5-tetranitropyrrole and 1-amino-2,3,4,5-tetranitropyrrole are 1. 93 g·cm~(-3)and 2. 04 g·cm~(-3),respectively; the detonation velocities are both 9. 01 km·s~(-1),and detonation pressures are 37. 54 GPa and 38. 73 GPa,which suggests that the detonation properties of TNP and ATNP are both comparable to that of 1,3,5,7-tetranitro~(-1),3,5,7-tetraza-cyclooctcme( HMX). With containing five nitro groups,the BDE of nitro group N( 5) —NO2is 60. 8 k J·mol~(-1),suggesting that pentanitropyrrole has the poorest thermal stability in all five model compounds. The calculated results and previous experimental work agree reasonably well one another,showing values in this paper are reasonable.
引文
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[15]米向超.新型高能炸药TKX-50的结晶研究[D].太原:中北大学,2015.MI Xiang-chao.Research on the crystallization of the new high explosive TKX-50[D].Taiyuan:North University of China,2015.
[16]胡焕性,张志忠,赵凤起,等.高能量密度材料3,4-二硝基呋咱基氧化呋咱性能及应用研究[J].兵工学报,2004,25(2):155-158.HU Huan-xing,Zh ANG Zhi-zhong,Zh AO Feng-qi,et al.A study on the properties and application of high energetic density material DNTF[J].Acta Armamentarii,2004,25(2):155-158.
[17]Khan M K A,Morgan K J,Morrey D P.Carbonyl derivatives of heterocyclic compounds-Ⅲ[J].Tetrahedron,1966,22(7):2095-2105.
[18]Cooksey A R,Morgan K J,Morrey D P.Nitropyrroles—Ⅱ[J].Tetrahedron,1970,26(21):5101-5111.
[19]Morgan K J,Morrey D P.Nitropyrroles—Ⅲ[J].Tetrahedron,1971,27(1):245-253.
[20]Doddi G,Mencarelli P,Razzini A,et al.Cheminform abstract:nitration of 1-r-pyrrole:formation of polynitro-1-r-pyrroles and orienting effects in the reactions of 3-nitro-1-r-pyrroles[J].Chem Inform,1979,10(43):2199-2924.
[21]Jerald C H,Edward W W.Synthesis of 2,3,4,5-tetranitropyrrole[J].Journal of Heterocyclic Chemistry,1992,29(27):1721-1724.
[22]Cromer D T,Coburn M D,Ryan R R,et al.Structure of 1-methyl-2,3,4,5-tetranitropyrrole,a possible high-density explosive[J].Acta Crystallographica Section C,1986,42(10):1428-1430.
[23]Rashid M A M,Cho S G,Choi T H,et al.Heat of formation predictions of various nitro-substituted zaoles by G4MP2-SFM scheme[J].Theoretical Chemistry Accounts,2015,134(11):1-11.
[24]Frisch M J,Trucks G W,Schlegel H B,et al.Gaussian[CP],Inc.Wallingford CT,2013.
[25]Kamlet K M,Jacob S J.Chemistry of detonation a simple method for calculating detonation properties of C—H—N—O explosives[J].Journal of Chemical Physics,1967,48(1):23-35.
[26]Wang F,Du H C,Zhang J Y,et al.Comparative theoretical studies of energetic azo s-triazines[J].Journal of Physical Chemistry A,2011,115(42):11852-11860.
[27]Mortimer R G.Physical Chemistry,3rd ed.[M].Oxford:Elsevier.Academic Press,2008.
[28]Zhou Y,Long X P,Shu Y J.Theoretical studies on the heats of formation,densities,and detonation properties of substituted s-tetrazine compounds[J].Journal of Molecular Modelling,2009,16(16):1021-1027.
[29]Ju X H.Theoretical study on thermodynamic and detonation properties of polynitrocubanes[J].Propellants,Explosives,Pyrotechnics,2009,34(34):106-109.
[30]Politzer P,Murray J S.Relationships between dissociation energies and electrostatic potentials of C—NO2bonds:applications to impact sensitivities[J].Journal of Molecular Structure,1996,376(1-3):419-424.
[31]Steward J J P.Optimization of parameters for semiempirical methodsⅠ[J].Journal of Computational Chemistry,1989,10(2):209-220.
[32]Carpenter J E,Weinhold F.Analysis of the geometry of the hydroxymethyl radical by the“different hybrids for different spins”natural bond orbital procedure[J].Journal of Molecular Structure,1988,169:41-62.
[33]Bondi A.Van der Waals volumes and radii[J].Journal of Physical Chemistry,1964,68(3):441-451.
[34]Sutor D J.The C—H…O Hydrogen Bond in Crystals[J].Nature,1962,195(4836):68-69.
[35]Klaptke T M,Mayer P,Schulz A,et al.1,5-diamino-4-methyltetrazolium dinitramide[J].Journal of the American Chemical Society,2005,127(7):2032-2033.
[36]Scott A P,Radom L G.Harmonic vibrational frequencies:An evaluation of Hartree—Fock,Mller—Plesset,quadratic configuration interaction,density functional theory,and semiempirical scale factors[J].Journal of Physical Chemistry,1996,100:16502-16513.
[37]Zhang X L,Gong X D.Theoretical study of the stabilities and detonation performance of 5-nitro-3-trinitromethyl-1H-1,2,4-triazole and its derivatives[J].Journal of Molecular Modelling,2015,21(2):1-11.
[38]Zhang X W,Zhu W H,Xiao H M.Theoretical studies on heats of formation,detonation properties,and bond dissociation energies of monofurazan derivatives[J].International Journal of Quantum Chemistry,2010,110(8):1549-1558.
[39]Chen Z X,Xiao H M.Quantum chemistry derived criteria for impact sensitivity[J].Propellants,Explosives,Pyrotechnics,2014,39(4):487-495.
[40]Zhang C Y,Shu Y J,Huang Y G,et al.Investigation of correlation between impact sensitivities and nitro group charges in nitro compounds[J].Journal of Physical Chemistry B,2005,109(18):8978-8982.
[2]Agrawal J P.High energy materials:propellants explosives and pyrotechnics[M].England:John Wiley&Sons,2010:1-3.
[3]Klaptke T M.High energy density materials[M].Berlin:Springer Verlag,2007:2-4.
[4]李云路,薛梅,王建龙,等.多硝基呋咱类含能化合物的合成研究进展[J].有机化学,2016,36(7):1528-1538.LI Yun-lu,XUE Mei,WANG,Jian-long,et al.Advances in the synthesis of poly-nitro furazans[J].Chinese Journal of Organic Chemistry,2016,36(7):1528-1538.
[5]Gao H X,Shreeve J M.Azole-based energetic salts[J].Chemical Reviews,2011,111(11):7377.
[6]De Hope A,Pagoria P F,Parrish D.New polynitro alkylamino furazans[R].LLNL-CONF-624954:2013.
[7]Badgujar D M,Talawar M B,Asthana S N,et al.Advances in science and technology of modern energetic materials:An overview[J].Journal of Hazardous Materials,2008,151(2-3):289-305.
[8]Talawar M B,Sivabalan R,Mukundan T,et al.Environmentally compatible next generation green energetic materials(GEMs)[J].Journal of Hazardous Materials,2009,161(2-3):589-607.
[9]Schmitt D,Eyerer P,Elsner P.Insensitive high-performance energetic materials:applied research for optimized products[J].Propellants,Explosives,Pyrotechnics,1997,22(3):69-87.
[10]LI Bao-hui,SHI Wen-jin,REN Fu-de,et al.A B3LYP and MP2 theoretical investigation on the cooperativity effect;between the X-H center dot center dot center dot H-M(X=F,Cl,Br;M=Li,Na,K)dihydrogen-bonding and H-M center dot center dot center dot;pi interactions involving C6H6[J].Computational&Theoretical Chemistry,2013,1020(2):81-90.
[11]Fried L E,Ruggiero A J.Energytransfer rates in primary,secondary,and insensitive explosives[J].Journal of Physical Chemistry,1994,98(39):9786-9791.
[12]冯露露,曹端林,王小军,等.1-甲基-2,4,5-三硝基咪唑的晶体形貌预测[J].含能材料,2015,23(5):443-449.FENG Lu-lu,CAO Duan-lin,WANG Xiao-jun,et al.Prediction of crystal morphology of MTNI[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2015,23(5):443-449.
[13]Cho J R,Cho S G,Kim K J.et al.A candidate of new insensitive high explosive;MTNI[C]∥Insensitive Materials&Energetic Materials Technology Symposium,Enschede,2000:393-400.
[14]Fischer N,Fischer D,Klaptke T M.Pushing the limits of energetic materilas:the synthesis and characterization of dihydroxylammonium5,5'-bistetrazole-1,1-diolate[J].Journal of Material Chemistry,2012,22(38):20418-20422.
[15]米向超.新型高能炸药TKX-50的结晶研究[D].太原:中北大学,2015.MI Xiang-chao.Research on the crystallization of the new high explosive TKX-50[D].Taiyuan:North University of China,2015.
[16]胡焕性,张志忠,赵凤起,等.高能量密度材料3,4-二硝基呋咱基氧化呋咱性能及应用研究[J].兵工学报,2004,25(2):155-158.HU Huan-xing,Zh ANG Zhi-zhong,Zh AO Feng-qi,et al.A study on the properties and application of high energetic density material DNTF[J].Acta Armamentarii,2004,25(2):155-158.
[17]Khan M K A,Morgan K J,Morrey D P.Carbonyl derivatives of heterocyclic compounds-Ⅲ[J].Tetrahedron,1966,22(7):2095-2105.
[18]Cooksey A R,Morgan K J,Morrey D P.Nitropyrroles—Ⅱ[J].Tetrahedron,1970,26(21):5101-5111.
[19]Morgan K J,Morrey D P.Nitropyrroles—Ⅲ[J].Tetrahedron,1971,27(1):245-253.
[20]Doddi G,Mencarelli P,Razzini A,et al.Cheminform abstract:nitration of 1-r-pyrrole:formation of polynitro-1-r-pyrroles and orienting effects in the reactions of 3-nitro-1-r-pyrroles[J].Chem Inform,1979,10(43):2199-2924.
[21]Jerald C H,Edward W W.Synthesis of 2,3,4,5-tetranitropyrrole[J].Journal of Heterocyclic Chemistry,1992,29(27):1721-1724.
[22]Cromer D T,Coburn M D,Ryan R R,et al.Structure of 1-methyl-2,3,4,5-tetranitropyrrole,a possible high-density explosive[J].Acta Crystallographica Section C,1986,42(10):1428-1430.
[23]Rashid M A M,Cho S G,Choi T H,et al.Heat of formation predictions of various nitro-substituted zaoles by G4MP2-SFM scheme[J].Theoretical Chemistry Accounts,2015,134(11):1-11.
[24]Frisch M J,Trucks G W,Schlegel H B,et al.Gaussian[CP],Inc.Wallingford CT,2013.
[25]Kamlet K M,Jacob S J.Chemistry of detonation a simple method for calculating detonation properties of C—H—N—O explosives[J].Journal of Chemical Physics,1967,48(1):23-35.
[26]Wang F,Du H C,Zhang J Y,et al.Comparative theoretical studies of energetic azo s-triazines[J].Journal of Physical Chemistry A,2011,115(42):11852-11860.
[27]Mortimer R G.Physical Chemistry,3rd ed.[M].Oxford:Elsevier.Academic Press,2008.
[28]Zhou Y,Long X P,Shu Y J.Theoretical studies on the heats of formation,densities,and detonation properties of substituted s-tetrazine compounds[J].Journal of Molecular Modelling,2009,16(16):1021-1027.
[29]Ju X H.Theoretical study on thermodynamic and detonation properties of polynitrocubanes[J].Propellants,Explosives,Pyrotechnics,2009,34(34):106-109.
[30]Politzer P,Murray J S.Relationships between dissociation energies and electrostatic potentials of C—NO2bonds:applications to impact sensitivities[J].Journal of Molecular Structure,1996,376(1-3):419-424.
[31]Steward J J P.Optimization of parameters for semiempirical methodsⅠ[J].Journal of Computational Chemistry,1989,10(2):209-220.
[32]Carpenter J E,Weinhold F.Analysis of the geometry of the hydroxymethyl radical by the“different hybrids for different spins”natural bond orbital procedure[J].Journal of Molecular Structure,1988,169:41-62.
[33]Bondi A.Van der Waals volumes and radii[J].Journal of Physical Chemistry,1964,68(3):441-451.
[34]Sutor D J.The C—H…O Hydrogen Bond in Crystals[J].Nature,1962,195(4836):68-69.
[35]Klaptke T M,Mayer P,Schulz A,et al.1,5-diamino-4-methyltetrazolium dinitramide[J].Journal of the American Chemical Society,2005,127(7):2032-2033.
[36]Scott A P,Radom L G.Harmonic vibrational frequencies:An evaluation of Hartree—Fock,Mller—Plesset,quadratic configuration interaction,density functional theory,and semiempirical scale factors[J].Journal of Physical Chemistry,1996,100:16502-16513.
[37]Zhang X L,Gong X D.Theoretical study of the stabilities and detonation performance of 5-nitro-3-trinitromethyl-1H-1,2,4-triazole and its derivatives[J].Journal of Molecular Modelling,2015,21(2):1-11.
[38]Zhang X W,Zhu W H,Xiao H M.Theoretical studies on heats of formation,detonation properties,and bond dissociation energies of monofurazan derivatives[J].International Journal of Quantum Chemistry,2010,110(8):1549-1558.
[39]Chen Z X,Xiao H M.Quantum chemistry derived criteria for impact sensitivity[J].Propellants,Explosives,Pyrotechnics,2014,39(4):487-495.
[40]Zhang C Y,Shu Y J,Huang Y G,et al.Investigation of correlation between impact sensitivities and nitro group charges in nitro compounds[J].Journal of Physical Chemistry B,2005,109(18):8978-8982.