Center for Energetic Concepts Development, Department of Mechanical Engineering, University of Maryland

Synthesis

1. Synthesis and Performance of Polyaryloxyphosphazene
WANG Zhi-feng1,CAO Ji-ping2,YAO Nan2,WANG Jian-zhong1
1.Ningbo Branch of Academy of Ordnance Science,Ningbo 315103,China
2.Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: Polyaryloxyphosphazene was obtained with aryloxy substituting chlorine atom of the linear polydichlorophosphazene,which was synthesized by solution polymerization of hexachlorocyclotriphosphazene.The polymer was characterized by IR spectrum and analyzed by GPC,DMA,TGA,and thermal conductivity.The results show that the polymer obtained is polyaryloxyphosphazene with number-average molecular weight ranging from 38343 to 44625 and dispersion degree ranging from 3.0305 to 4.8857.The peak temperature of the initial thermal decomposition is 374.23℃ and of main decomposition reaction is 397.78℃.The weight of the polymer which shows obvious weight loss at the temperature of 461.14℃ and 529.95℃ could remain 45.40% at the temperature of 565.37℃ and then keep constant.It can be expected that the polymer has good thermal stability at high temperature.The glass transition temperature of the polymer is-24.09℃ and the thermal conductivity 0.21W/(m•K).

2. Synthesis of HMX from DPT by Green Nitrolysis with Dinitrogen Pentoxide
HE Zhi-yong1,LUO Jun1,Lü Chun-xu1,XU Rong2,LI Jin-shan1
1.School of Chemical Engineering,Nanjing University of Science and Technology,Nanjing 210094,China
2.Institute of Chemical Materials,CAEP,Mianyang Sichuan 621900,China)

Abstract: In order to achieve a clean synthesis process of HMX,nitrolysis of DPT in two nitration systems was investigated.Nitrolysis of DPT in N2O5/organic solvent systems was investigated to yield little HMX but mainly complex by-products with low melting point,indicating that the solutions of N2O5 in organic solvents was not suitable for this process.Nitrolysis in N2O5/HNO3 system was investigated.The effect of reaction time,reaction temperature,amount of ammonium nitrate and ratio of raw materials on the yield of HMX were studied,finding that yield of HMX increases first and then decreases along with the increasing usage of N2O5 and N2O5/HNO3 system was suitable for the nitrolysis of DPT because it could give HMX in a high yield up to 58% and purity of 99% under optimized conditions:n(N2O5):n(DPT)=2:1,n(HNO3):n(DPT)=36:1,react time 30min and react temperature 25℃.

3. Progress of Study on the Synthesis of Azole Energetic Ionic Compounds
LIU Xiao-jian1,ZHANG Hui-juan1,LIN Qiu-han1,LI Yu-chuan1,LI Ya-yu2,PANG Si-ping1
1.School of Life Science,Beijing Institute of Technology,Beijing 100081,China
2.Beijing Institute of Aerospace Testing Technology,Beijing 100074,China)

Abstract: The synthesis of energetic salts comprising imidazole,triazole,tetrazole and pentazole as precursors are reviewed with 36 references.The physiochemical properties of these new energetic salts,such as melting point,density,enthalpy of formation and detonation performance,as well as the effect of molecular structure and substituted groups on properties are summarized.The applications of these compounds in explosives and propellants are discussed.

4. Synthesis of 3,4-Epoxybutanol Nitrate
MO Hong-chang,GAN Xiao-xian,LI Na,XING Ying,HAN Tao,ZHANG Zhi-gang,LI Lei
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China

Abstract: 3,4-Epoxybutanol nitrate was synthesized with 3-butane-1-ol as raw matieral via two-step reactions,nitration and epoxidation,and characterized by IR,1HNMR and elemental analysis.The optimum nitration reaction conditions are as follows: n(HNO3)∶n(EBO)=1.5∶1.0,reaction temperature,-10℃ and the reaction was quenched after addition was over when temperature began to descend.The yield of nitrating reaction is 65.2%.The purity of the product is 98.2%.

5. Synthesis of 3,4-Diphenylfuroxan with High Efficiency
XUE Yun-na,YANG Jian-ming,LI Chun-ying,Lü Jian
Xi′an Modern Chemistry Research Institute,Xi′an 710065, China)

Abstract: 3,4-Diphenylfuroxan was synthesized using benzil as starting material via hydro amine addition and oxidative cyclization.Its molecular structure has been identified with IR,1H NMR,13C NMR and elemental analyses.The effect of the category,dosage,mass fraction of oxidants and reaction temperature on the cyclization were investigated.Under the condition of HClO(mass fraction 7.39%) as oxidant,n(HClO)∶n(diphenylgly-oxime)=3,reaction temperature 80℃,atmospheric pressure and reaction time 1.5h,the yield of 3,4-diphenylfuroxan was 92.8%.

6. Syntheses of CHZ and PA Energetic Compounds and Their Effects on Thermal Decomposition of CL-20
ZHANG Guo-tao,ZHANG Tong-lai,LIU Jun-wei,ZHANG Jian-guo,YANG Li
State Key Laboratory of Explosion Science and Technology,Beijing Institute of Technology,Beijing 100081,China)

Abstract: Three kinds of energetic complexes,Co(CHZ)4(PA)2•3H2O,Cu(CHZ)4(PA)2•4H2O and Pb(CHZ)2(PA)2•4H2O(CHZ= carbodihydrazide,PA=picric acid),were synthesized with carbohydrazide,picric acid and corresponding metallic(Co,Cu,Pb) salts.The molecular formulas of these coordination compounds were derived by using elemental analyses and FTIR techniques.The friction,impact and flame sensitivities of the complexes were tested followed by the standard methods.The effects of the energetic complexes on the thermal decomposition of CL-20 were studied by means of DSC and TG-DTG techniques.The results show that the addition of those complexes make the onset temperature and peak temperature of CL-20 shift to low temperature.The kinetic parameters Ea and A of the first exothermic decomposition process for complexes/CL-20 mixture were calculated by Kissingér′s method and Ozawa-Doylés method.Cu(CHZ)(PA) and(CHZ)(PA) make the Ea value of the exothermic processes of CL-20 decrease from 222.8kJ/mol to 186.6kJ/mol and 183.0kJ/mol.

7. Synthesis,Crystal Structure and Sensitivity of [Mn(IMI)_6](ClO_4)_2
REN Yan1,YAN Ying-jun2,YANG Li1,ZHANG Tong-lai1,ZHANG Jian-guo1,YU Kai-bei1
1.State Key Laboratory of Explosion Science and Technology,Beijing Institute of Technology,Beijing 100081, China
2.Jiangxi Journalism and Publication College,Nanchang 330224,China)

Abstract: An energetic compound [Mn(IMI)6](ClO4)2(IMI:imidazolium) was synthesized by reaction of imidazolium with Mn(ClO4)2 in aqueous solution.Single crystal of [Mn(IMI)6](ClO4)2 was obtained.The compound was characterized by elemental analysis,TG-DTG and single crystal X-ray diffraction analysis.The results show that the crystal belongs to a monoclinic system with P2(1)/n space group and cell parameters of a=11.721(2)nm,b=7.2191(13)nm,c=16.402(3)nm,β=90.064(3)°,V=1387.9(4)nm3;Dc=1.585g/cm3;Z=2;F(000)= 678,μ=0.160mm,R1=0.0367,ωR2=0.1372.The title compound [Mn(IMI)6](ClO4)2formed by [Mn(IMI)6]2+ and(ClO4)-belongs to an ionic compound.The central Mn(II) ion is six-coordinated with six imidazole molecules.At a heating rate of 10K/min,the thermal decomposition process of the title compound consists of one endothermic peak and one exothermic peak with 9.9% residues.The mechanic sensitivity test results show that this compound is an insensitive energetic compound.

8. Synthesis and Thermal Decomposition Kinetics of TATB without Chloride
MA Xiao-ming,LI Bin-dong,Lü Chun-xu,LU Ming
School of Chemical Engineering,Nanjing University of Science and Technology,Nanjing 210094,China)

Abstract: In order to solve the influence of chloride in the traditional synthesis of TATB,taking phoroglucinol as primary material,1,3,5-triamino-2,4,6-trinitrobeneze(TATB) was synthesized by nitration with N2O5,methylation and amination,and its structure was identified by NMR,IR and MS.The effect of amination reaction on the yield and thermal decomposition property of TATB was investigated,the total yield of crude TATB was 92%.High-purity TATB was obtained by organic solvent recrystallization with yield of 75%.Thermal properties of TATB was analyzed by DSC and TG,the thermal decompositon activation energy and pre-exponential factor of TATB obtained by Owaza′s equation are ETATB=135.28kJ/mol,ATATB=2.340×109s-1.

9. Application of Crystal Modifier in the Synthesis of Nitrophenol Potassium Salts
TANG Zhan1,YANG Li1,YAN Ying-jun2,ZHANG Tong-lai1,ZHANG Jian-Guo1,QIAO Xiao-jing1
1.State Key Laboratory of Explosion Science and Technology,Beijing Institute of Technology,Beijing 100081,China
2.Jiangxi Journalism and Publication College,Nanchang 330224,China)

Abstract: In order to attain the amount of crystal modifier in synthesis of nitrophenol potassium salts,the grained KPA was synthesized with the nonionic surfactant that containing H in the functional group served as crystal modifier.The surface tension and data of the surfactant,which will provide theoretical support for the dosage of surfactant,was studied.The grained KPA obtained in different conditions was studied with X-ray powder diffraction and the important growth facet that has more influence on the morphology was analyzed.The results show that the surfactant can reduce the strongest diffraction peaks and affect the dominant crystal facet,so they can control crystal morphology of KPA.Grained crystal can be gained if choosing appropriate surfactant and dosage through measuring surface tension of surfactant.

10. Structure,Thermodynamics and Sensitivity Property of (TAGH)ClO_4
QI Shu-yuan1,ZHANG Tong-lai1,AO Guo-jun2,ZHANG Jian-guo1,YANG Li1
1.State Key Laboratory of Explosion Science and Technology,Beijing Institute of Technology,Beijing 100081,China
2.East China Research Institute of Microelectronics,Hefei 230022,China)

Abstract: Triaminoguandine perchlorate was synthesized with triaminoguandine and perchloric acid as primary materials.The crystal structure was determined by X-ray single crystal diffraction analysis.The results show that the title compound belongs to monoclinic system with P2(1)/c space group and cell parameters of a=1.0213(11)nm,b=1.4869(15)nm,c=1.0936(11)nm,β=102.91(2)°.The title compound,with formula of CH9ClN6O4,is an ionic compound formed by [C(N2H3)3]+ and ClO-4.There are a lot of intramolecular and intermolecular hydrogen bonds,which make it stable.The title compound was characterized by elemental analysis,FTIR,DSC,TG-DTG.The results show that the title compound lost 99.7% at 457.03℃ with a heating rate of 10℃/min.The sensitivity test results show that it has low friction sensitivity and has no frame sensitivity and impact sensitivity under the sensitivity test conditions.

11. Synthesis and Characterization of 3,4-Bis(pyrazine-2′yl)furoxan
LI Ya-nan,ZHANG Zhi-zhong,ZHOU Yan-shui,CHEN Bin,WANG Bo-zhou
Xi′an Modern Chemistry Research Institute,Xi′an 710065, China

Abstract: 3,4-Bis(pyrazine-2′-yl)furoxan(DPF) was synthesized using 2-cyanopyrazine as raw material,via four-step reactions of oxime,diazotization,denitrification and cyclization and the overall yield was 51.0%.The structures of target compound and intermediates were characterized by IR,NMR,MS and elemental analysis.The mechanism of cyclization reaction was investigated.The affecting factors of reactions were optimized. The optimum reaction conditions of cyclization were:molar ratio nexp∶ntheory=1.10-1.25 for Na2CO3,reaction temperature 2 to 10℃ and reaction time 4h.The yield of DPF is about 75.6% and purity 99.0%.

12. Synthesis,Crystal Structure and Quantum Chemistry of C_3N_2H_5~+C_6N_3O_7H_2~-
LI Dan1,REN Ying-hui1,ZHAO Feng-qi2,YI Jian-hua2,CHANG Chun-ran2,SONG Ji-rong1,3
1.School of Chemical Engineering/Shaanxi Key Laboratory of Physico-inorganic Chemistry,Northwest University,Xi′an 710069,China
2.Xi′an Modern Chemistry Research Institute,Xi′an 710065,China
3.Conservation Technology Department,The Palace Museum,Beijing 100009,China

Abstract: C3N2H+5C6N3O7H-2 was prepared by mixing imidazole ethanol solution and picric acid(PA)ethanol solution.Single crystals suitable for X-ray measurement were cultured at room temperature.The crystal is rhombic system,space group Pbca with crystal parameters of a=0.8950nm,b=1.3474(3)nm,c=2.0164nm,α=β=γ=90°,V=2.4317(3)nm3,Dc=1.624g/cm3,Z=8,F(000)=1216.The theoretical investigation of the title compound as a structure unit was carried out by HF/6-311+G(d) and B3LYP/6-311+G(d) methods in Gaussian 03 package,and the atomic net charges and the population analysis was discussed.

13. Synthesis and Characterization of 7-Chloro-4,6-dinitro-benzofuroxans
HUO Huan,WANG Bo-zhou,LIU Qian,LUO Yi-fen,ZHANG Ye-gao
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: Taking 4-chloro-2-nitroaniline as primary material,7-chloro-4,6-dinitro-benzfuroxan was synthesized by the process of oxidation,cyclization,nitration and rearrangement.Its structure was characterized by IR,NMR and elemental analysis.The effect of the nitration reaction temperature and 5-chlorobenzfuroxan/nitric acid mole ratio on the yield was studied.The best condition of nitration reaction were reaction temperature,60℃;5-chlorobenzfuroxan/nitric acid mole ratio,1∶10.The yield is 39%.

14. Energized Synthesis and Characterization of 1,3,5-Tris(2-hydroxy ethyl)-1,3,5-triazinane-2,4,6-trione
XU Ruo-qian,JI Yue-ping,DING Feng,YANG Wei,LIU Wei-xiao
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: Taking 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione as primary material,1,3,5-tris(2-nitroethyl)-1,3,5-triazinane-2,4,6-trione(TNEIC) and 1,3,5-tris(2-azidoethyl)-1,3,5-triazinane-2,4,6-trione(TAEIC) were synthesized via nitration and azidonation.The optimum conditions of nitration were:HNO3/H2SO4(volume ratio),1∶1;reaction temperature,25℃;reaction time,0.25h and the optimum reaction yield is 92.0%.The structure of the final product was confirmed by IR,1 HNMR,and elemental analysis.The thermal properties of the compounds were determined by DSC and TG.The results show that TAEIC has a low melting point and will be used in melt-cast explosive.

15. Preparation of Fe_2O_3/CNTs and Its Catalytic Mechanism on Thermal Decomposition of RDX
CUI Qing-zhong,JIAO Qing-jie,ZHAO Wei-dong
National Key Laboratory of Explosive Science and Technology,Beijing Institute of Technology,Beijing 100081,China)

Abstract: Nano-Fe2O3/CNTs catalyzers were synthesized by the sol-gel methods.The technology parameters were optimized by an orthogonal test.The appearance of products was characterized by SEM, TEM and XRD.The catalytic properties of Fe2O3/CNTs on thermal decomposition of RDX were determined by using DSC method.The results show that the surface of CNTs is coated with Fe2O3.When mass fraction of Fe2O3/CNTs is about 5%,Fe2O3/CNTs catalyzers make the peak temperature of DSC curve for thermal decomposition of RDX decrease by 14.1℃,and the activation energy of thermal decomposition reaction of RDX obtained by Kissinger method decrease by 38.5%.

16. New Technology for Synthesis of 1-Methyl-2,4,5-trinitroimidazoles
WANG Xiao-jun,CAO Duan-lin,LI Yong-xiang,SONG Lei,WANG Jian-long
College of Chemical Engineering and Environment,North University of China,Taiyuan 030051,China)

Abstract: 1-Methyl-2,4,5-trinitroimidazoles(MTNI) was synthesized with 1-methylimidazole as initial material by two steps nitrification reaction.Its structure was characterized by IR,1 H NMR and elemental analysis.The effect of the drip order,ratios of volume for nitric and sulfuric acid,reaction time,temperature on the yield of 2,4-dinitroimidasole(2,4-MDNI) and MTNI was investigated.The results show that the conditions of good yields are: the drip order of additive of the first step,ratios of volume for nitric and sulfuric acid 1∶2,the drip order of anti-additive for the second step, ratios volume for nitric and sulfuric acid 1∶4,reaction time 2 h,temperature110～115 ℃.

17. Synthesis of Acrylated Span80 and Its Application in Emulsion Explosive
QIAN Hua,LIU Da-bin,YE Zhi-wen
Collage of Chemical and Engineering,Nanjing University of Science and Technology,Nanjing 210094,China)

Abstract: The acrylated Span80 was synthesized by the starifying method of acryloyl chloride.The effect of reaction time,temperature and solvent etc on acrylated Span80 were investigated.The optimum conditions of the reaction were: triethylamine as catalyst,n(acrylic acid)∶n(thionyl chloride)∶n(Span80)∶n(triethylamine)=1.0∶2.1∶1.0∶1.4,reaction time 3 h,reaction temperature 50℃ and 80 mL toluene /mol-acrylic acid as solvent.The iodine value of acrylated Span80 obtained by using optimum conditions was 94.9 7 g I2/100 g sample.The effect of acrylated Span80 and ordinary Span80 on properties of emulsion explosive was compared by SEM and the performance test.The results show that this acrylated Span80 has better emulsified property than ordinary Span80.

18. Green Synthesis of Glycidyl Nitrate
WANG Qing-fa1,SHI Fei2,ZHANG Xiang-wen1,WANG Li1,MI Zhen-tao1
1.Key Laboratory for Green Chemical Technology of State Education Ministry,School of Chemical Engineering and Technology,Tianjin Universtiy,Tianjin 300072,China
2.Shandong Silk Textile Vocation College,Zibo Shandong 255300,China)

Abstract: A mild and high efficient method to prepare glycidyl nitrate by selective nitration of glycidol with dinitrogen pentoxide as the nitrating agent was developed.The influences of molar ratio of dinitrogen pentoxide to glycidol,reaction temperature and reaction time on the nitration of glycidol were investigated.The results indicated that the selectivity of 100% and the yield of 94% for glycidyl nitrate were obtained by carrying out the reaction at-15℃ for 6 min with the molar ratio of dinitrogen pentoxide to glycidol at 1∶1.

19. Preparation of Zirconium 3-Nitrophthalate and Its Effect on Combustion of Double-base Propellant and RDX-CMDB Propellant
ZHANG Heng,ZHAO Feng-qi,ZHANG Xiao-hong,PEI Qing,HAO Hai-xia
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: Zirconium 3-nitrophthalate(Zr(3-NO2-PHT)2•2H2O) was synthesized by using 3-nitrophthalic acid,sodium hydroxide,and zirconyl nitrate as raw materials,and the structure was determined by elemental analysis,X-ray fluorescence diffraction and FT-IR spectra.The catalytic action of zirconium 3-nitrophthalate on double-base propellant and RDXCMDB propellant was analyzed.The results show that the burning rates of the double-base propellant and RDX-CMDB propellant increase obviously in the low pressure range,and the pressure exponents of the double-base propellant decrease obviously in the middle and high pressure range.Especially,when Zirconium 3-nitrophthalate together with copper salts is used,the catalytic efficiency is higher.

20. Synthesis and Crystal Structure of 3,3′-Dinitro-5,5′-azo-1H-1,2,4-triazole(DNAT)
JIA Si-yuan,WANG Xi-jie,WANG Bo-zhou,XIONG Cun-liang,LIU Qian
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: 3,3′-Dinitro-5,5′-azo-1H-1,2,4-triazole(DNAT) was synthesized by the oxidative coupling of 5-amino-5-nitro1,2,4-triazole(ANTA) as raw material.Its structure was characterized by IR,NMR and elemental analyses.The crucial factors and mechanism in the coupling reaction were explored and the synthetical conditions were optimized.Some properties of DNAT were measured.The H50of 17.08cm(drop hammer 5kg) and friction sensitivity of 60%(pressure 3.92MPa,pendulum angle 90°)were obtained.The single crystal of DNAT•4H2O was cultivated,and its crystal structure was determined by X-ray crystallogaphy.The crystal of DNAT•4H2O is monoclinic crystal system with space group P2(1)/n and Dc=1.550g•cm-3.

21. Synthesis and Characterization of 5-Vinyltetrazole
LIU Qing,GAN Ning,HAN Tao,ZHANG Zhi-gang,LI Na,MO Hong-chang
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: Hydroxyethyltetrazole was synthesized by the 1,3-polar cycloaddition of 3-hydroxypropanenitrile and NH4N3 that produced by the reaction of NaN3 and NH4Cl.The ultrasonic technology was applied in this reaction and the yield was up to 90.5%.5-Chloroethyltetrazole was prepared by the halogenation of hydroxyethyltetrazole and SO2Cl2 and the yield was 77%.5-Vinyltetrazole was obtained by the elimination of 5-chloroethyltetrazole under the condition of alkaline,and the yield was 70%.5-Chloroethyltetrazole and 5-vinyltetrazole were characterized by IR,1 HNMR and elemental analyses.The results show that the final product was the target product.This method has the advantages of high and stable yield and convenient preparation.

22. Synthesis and Characterization of Picrylfurazanether Compounds
GE Zhong-xue,QIU Shao-jun,JIANG Jun,WANG Xi-jie
Xi'an Modern Chemistry Research Institute,Xi'an 710065,China)

Abstract: In order to obtain high energy density materials with excellent synthetic performances,picryl(3-nitrofurazan-4) ether(FOP) and bis(3-nitrofurazan-4) picryl ether(DFOP) were synthesized by condensation of sodium hydroxyl nitrofurazan with picryl chloride(PcCl) and 2,4-dichloro-1,3,5-trinitrobenzene(DCPc),respectively.The products were characterized by FTIR,1H NMR,13 C NMR,MS and elemental analyses.The optimal reaction conditions obtained are:FOP of the yield as 31% from PcCl,the mole ratio of PcCl to sodium nitrohydrofurazan 1.0∶1.1,reaction temperature 80℃,reaction time 16h,and for DFOP of the yield as 42% from DCPc,the mole ratio of DCPc to sodium nitrohydrofurazan 1.0∶2.7,reaction temperature 80℃,reaction time 2h.

23. Synthesis and Characterization of 1-Methyl-2,4,5-trinitroimidazole
WANG Wei,YANG Wei,JI Yue-ping,DING Feng
Xi'an Modern Chemistry Research Institute,Xi'an 710065,China)

Abstract: 1-Methyl-2,4,5-trinitroimidazole(MTNI) was synthesized with imidazole as starting material via a 5-step sequence of reactions(nitration,thermal rearrangement,methylation,etc).The total yield is 15.6%,and its purity is more than 98%.The structure of MTNI was characterized by IR,NMR and elemental analyses.The thermal decomposition performance of MTNI was tested by DSC.The results show that the detonation performances were comparable to those of RDX,and better than TATB.MTNI is a new insensitive high explosive with its friction sensitivity similar with TNT and impact sensitivity similar with comp B.The exothermic decomposition of MTNI proceeds in three stages.The corresponding peak temperature are 177,223 and 298℃,and decomposition heat 327.67,11.2 and 54.84kJ/mol,respectively.

24. Synthesis and Characterization of Energetic Intermediate 5-Hydrazinotetrazole
ZHU Ya-hong,SHENG Di-lun,CHEN Li-kui,MA Feng-e
Shaanxi Applied Physicochemical Research Institute,Xi'an 710061,China)

Abstract: 5-Hydrazinotetrazole was synthesized with 5,5'-azotetrazolate as starting material by the acidizing of hydrochloric acid and recrystallizing of sodium acetate processes.Its structure was characterized by Fourier transform infrared,melting point and elemental analyses.The key factors affecting acidizing and recrystallizing of synthesis were discussed.The results show that the mass fraction of material used during acidizing is 10% for 5,5'-azotetrazolate solution and 10%-15% for hydrochloric acid solution.The yield of 5-hydrazinotetrazole is 55%-60%,and melting point is 196-198.9℃.

25. Synthesis and Characterization of 4,4′-Dinitrodifurazalyl Ether
WANG Xi-jie,GE Zhong-xue,JIANG Jun,WANG Bo-zhou,ZHANG Ye-gao
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: 4,4′-Dinitrodifurazalyl ether(FOF-1)was synthesized from 3,4-diamino-furazan(DAF) after Caro-acid oxidation and etherification of nitro-group.Its structure was characterized by IR,MS,NMR and elemental analysis.The reaction mechanism of intermolecular etherification of nitro-group was preliminarily discussed.In addition,the synthetic procedures were optimized,and the optimal conditions of oxidization and intermolecular etherification reaction were determined.The best condition was obtained as follows: the oxidation reaction time is 3.5h,initial content of H2SO4 is 51.7%,the etherification reaction time is 2.5h,content of water is less tan 0.03%,the overall yields is 42% and the purity is 99.6%.

26. Synthesis and Properties of Energetic Binder PNIMMO
MO Hong-chang,GAN Xiao-xian,XING Ying,LI Na
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: Using 1,4-butanediol as initiator,boron trifluoride etherate as catalyst and CH2Cl2 as solvent,poly(3-nitratomethyl-3-methyl oxetane)(PNIMMO) was prepared by 3-nitratomethyl-3-methyloxetane via cationic ring-opening polymerization.The effect of molar ratio for catalyst and initiator,reaction temperature and the dropping rate of monomer on polymerization was discussed.The optimum conditions were determined as: molar ratio for catalyst and initiator was 0.50-0.75,reaction temperature was around 10℃ and dropping monomer slowly.The polymer was characterized by IR and 13CNMR.The results show that the glass transition temperature,the enthalpy of decomposition and the decomposition peak temperature of the polymer are-24.52℃,+1212J/g and 221.78℃,respectively.The mechanical properties of polyurethane film cured by N-100 are 3.5-3.7MPa for δ and 260%-280% for ε at room temperature.

27. Research Progress on Polynitroimidazoles and Their Derivatives
YANG Wei,JI Yue-ping
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: Synthesis and properties of polynitroimidazoles,such as dinitroimidazole,trinitroimidazole and their derivatives and their application in energetic materials and medicines were summarized with 26 references.Nitroimidazole was synthesized by nitration,thermal rearrangement and methylation with the imidazole or iodoimidazole as primary substance.Considering that trinitroimidazole is a new insensitive high explosives with high formation enthalpy,fine thermal stability and relatively good safety characteristics.

28. Synthesis and Characterization of 3-Propargyl-5,5-dimethylhydantoin
ZHANG Li-na,YANG Rong-jie
School of Materials Science and Engineering,Beijing Institute of Technology, Beijing 100081,China)

Abstract: In order to improve the mechanical properties of solid propellant,a new bonding agent,3-propargyl-5,5-dimethylhydantoin(PDMH) was synthesized by the Gabriel method.The condition of the reaction was n(DMH)∶n(propargylbromine)∶n(methyl alcohol solvent of KOH)=1∶1∶1,water as solvent,reaction temperature 65℃,reaction time 3h.The yield of PDMH was 50%.Chemical structure of PDMH was identified by FT-IR,NMR,MS and TGA-DTA.Melting point of PDMH is 170-171℃ and its decomposition temperature 185.5℃,it is expected to be used in composite solid propellant.

29. Synthesis and Characterization of 1,5-Diazido-3-nitrazapentane(DIANP)
JI Yue-ping,LAN Ying,LI Pu-rui, WANG Wei,DING Feng,LIU Ya-jing
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: 1,5-Diazido-3-nitrazapropant(DIANP) was synthesized from DINA and sodium azide,via azidation,extraction,washing,decolor,filtration and vacuum distillation.Its structure was characterized by IR,NMR and elemental analyses.Relative properties were analysed.The parameters affecting the yield,such as ratio,solvent,temperature and reaction time,were discussed.The results show that the optimum reaction condition of synthesizing DIANP are:the mass ratio of DINA to sodium azide,about 1∶0.59;solvent, DMSO;reaction temperature,80-85℃ and reaction time,7-8h.The yield of DIANP is about 80% and purity 98%.

30. Synthesis of 1,3,5-Tri-Substituted Perhydro-s-triazines
YU Qin-wei,YANG Jian-ming,ZHAO Feng-wei,Lü Jian
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: 1,3,5-Tri-substituted perhydro-s-triazines were synthesized from nitriles(acetonitrile,propionitrile,butyronitxle and benzonitrile),and 1,3,5-trioxane.The products were characterized by 1HNMR,IR,MS and elemental analysis.The effects of ratios of raw materials,reaction temperature and reaction time on the yield were investigated by orthogonal experiment.Results show that on the optimal reaction conditions,the yields of the corresponding 1,3,5-tri-substituted perhydro-s-triazines synthesized from acetonitrile,propionitrile,butyronitrile,benzonitrile and 1,3,5-trioxane were 95.7%,96.1%,84.2% and 98.1%,respectively.

31. Synthesis and Properties of ETPE Based on BAMO/AMMO
GAN Xiao-xian,LI Na,LU Xian-ming,HAN Tao,XING Ying,LIU Qing
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: Bromopolyether was prepared from 3-bromomethyl-3-methyl oxetane(BrMMO) by cation ring-opening polymerization.Azide polyether PAMMO was synthesized by theazido reaction of bromopolyether.Azide polyether PBAMO was prepared from 3,3-bisbromomethyl oxetane(BAMO) by directly ring-opening polymerization.Using tetrahydrofuran as solvent,PBAMO as hard block,PAMMO as soft block,2,4-toluene diisocyanate(TDI) as diisocyanate monomer,butane-1,4-diol urethane oligomer as linking compound,an energetic thermoplastic elastomer(ETPE) of number average molecular weight about 25000 was prepared by one-step solution polymerization.ETPE that prepared was meltable and soluble.Its tensile strength and elogation at room temperature were about 5MPa and 400%,respectively.

32. Synthesis and Characterization of Bis(1,3-diazido-2-propyl) formal(BDPF)
JI Yue-ping,WANG Wei,DING Feng,CHEN Bin,YU Tao,LIU Wei-xiao
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: The intermediate bis(1,3-dichloro-2-propyl)formal(BCPF) was prepared by condensation reaction in the presence of a catalyst with 1,3-dichloro-2-propanol and polyformaldehyde as primary materials.The title compounds bis(1,3-diazide-2-propyl)formal(BDPF) was obtained by BCDF reacted with a metal azide in a solvent with the yield of 98% and purity of 98%.Their structures were characterized by IR,NMR and elemental analysis.The effect of catalyst,solvent and reaction temperature on above mentioned reactions was studied.The optimum reaction conditions are: for condensation reaction,reaction temperature 0-5℃,4mL sulfuric acid as catalyst,ethylene dichloride as dissolvent;for hydrazoate reaction,reaction temperature 95-99℃,dimethyl sulfoxide as dissolvent,reaction time 4h.

33. Synthesis and Characterization of 3-Bromonomethyl3-Methyloxetane Homopolymer
DONG Jun,GAN Xiao-xian
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: Using 1,4-butanediol(BDO) as initiator,boron-trifluoride etherate as catalyst,3-bromomethyl-3-methyloxetane(BrMMO) as monomer,CH2Cl2 as solvent,an organic binder,3-bromomethyl-3-methyloxetane homopolymer(PBrMMO),was synthesized by cationic ring-opening polymerization mechanism.The monomer conversion rate changes with time under low-temperature conditions was studied,and the BrMMO conversion rate-time curve was obtained.The effect of catalyst concentration and temperature of reaction system on polymerization were studied.The results show that the optimum conditions of the controlled polymerization are: n(BF3•Et2O)∶n(BDO)=0.5∶1.0,add the BrMMO in reaction system at 0℃ and keep reacting for three days.The structure and characterization of the final product were characterized by IR,1HNMR,DSC and TGA.

34. Study Progress of Several High Energy Density Materials(HEDM)
ZHANG Zhi-zhong,WANG Bo-zhou,JI Yue-ping,ZHOU Yan-shui,ZHOU Cheng,LIU Qian,ZHU Chun-hua
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: The current situation of investigating five HEDMs(DNTF,ADN,TNAZ,FOX-12 and FOX-7)in China were summarized.Their synthesis methods,physicochemical and explosive properties,compatibility and applications in the formulation of explosive and propellant were introduced.DNTF shows an outstanding performance in composite explosives and explode network and is used as oxidant in propellant.ADN can be used as high energetic oxidant of the low specific signal propellant.TNAZ can be used in casting explosive and gun propellant.FOX-12 and FOX-7 are potential compositions of insensitive explosives,with 24 references.

35. Synthesis and Characterization of 1H,4H-3,6-Dinitropyrazolo[4,3-c]pyrazole Amine Salts
LUO Yi-fen,GE Zhong-xue,WANG Bo-zhou,ZHANG Hai-hao,XIONG Cun-liang
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: Taking 1H,4H-6-nitropyrazolo[4,3-c]pyrazole-3-carboxy as primary material,1H,4H-3,6-dinitropyrazolo[4,3-c]pyrazole(DNPP) was synthesized by one step reaction of decarboxylation and nitration.By using DNPP as primary material,two DNPP amine salts,TAG-DNPP and GUDNPP,were synthesized with solid triaminoguanidinium(TAG) nitrate and solid guanidylurea(GU) hydrochloride,respectively.Their structures were confirmed by IR,1 H NMR,13C NMR and elemental analysis.The reaction mechanism of decarboxylation and nitration was investigated.Some reasons was analyzed for triaminoguanidinium 3,6-dinitropyrazolo[4,3-c]pyrazole as the gun propellant additive.The results show that the pyrolysis residue of TAG-DNPP can form new melon compounds.These novel compounds make flame temperature suppress and burning rate of the gun propellants improve.

36. Synthesis and Characterization of 3-Nitropyrazole and its Salts
LI Hong-li,XIONG Bin,JIANG Jun, ZHENG Xiao-dong,LI Zhi-peng,MA Yu-xia
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: In order to synthesize the salts of 3-nitropyrazole,N-nitropyrazole was synthesized with pyrazole as raw material,and HNO3-Ac2O-HAc system as nitration agent.N-nitropyrazole at high temperature was rearranged as 3-nitropyrazole.Its organic copper and lead salts were synthesized by the reaction of 3-nitropyrazole with some inorganic copper and lead salts.The structure of products were characterized by melting point,IR,NMR and elemental analysis,showing that the products were target products.The optimum reaction yield were 85.5% for nitration,92.8% for rearrangement reaction and 79.3% for total yield.

37. Synthesis and Properties of Azido Terminated Glycidyl Azide Polymer
LI Na,GAN Xiao-xian,XING Ying, MO Hong-chang,ZHANG Zhi-gang,HAN Tao
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: Using 1,4-butanediol as initiator,boron-trifluoride etherate as catalyst,polyepichlorohydrin(PECH) was synthesized by the opening-ring polymerization of epichlorohydrin.Using the method of tosylation,tosylate terminated epichlorohydrin polymer as intermediate was synthesized by PECH and 4-toluenesulfonylzchloride in pyridine,azido terminated glycidyl azide polymer(ATGAP) was obtained by the reaction of intermediate and sodium azide.The structure of ATGAP was characterized by IR,1 HNMR and 13 CNMR,showing that the final product was target product.The glass transition temperature of ATGAP was-73 ℃.Its thermal decomposition temperature was 252.7 ℃.ATGAP has small viscosity and can be used as an energetic plasticizer.

38. Nitration of Halobenzens with Fluorous Biphasic System
YI Wen-bin,CAI Chun
Chemical Engineering College, Nanjing University of Science & Technology,Nanjing 210094,China)

Abstract: Halobenzens can be nitrated effectively in fluorous phase in the presence of ytterbium(Ⅲ) perfluorooctanesulfonate(Yb(OSO_2C_8F_(17))_3) catalyst. Perfluorodecalin(C_(10)F_(18)) was used as a fluorous solvent for this reaction. The fluorous phase after separating catalyst can be reused many times, and P/O ratio of p-isomer to o-isomer in the products of mononitration of flurobenzene,chlorobenzene and iodobenzene can be increased to (7.20),2.45,4.01 and 0.91 respectively. Partition coefficients involving organic and fluorous phase under different temperatures have been measured. Effects of reaction temperature, the ratio of fluorous phase/organic phase and the water content in the reaction system on the nitration were investigated. It was observed that the optimum temperature for fluorous biphasic nitrations of flurobenzene, chlorobenzene, bromobenzene and iodobenzene were 60℃,60℃,80℃ and 80℃ respectively. Reducing the ratio of fluorous phase/organic phase and the water content in the reaction system can increase P/O ratio.

39. Synthesis of Ammonium Dinitramide from Ethyl Carbamate
WANG Bo-zhou,LIU Qian,ZHANG Zhi-zhong,LIAN Peng,ZHU Chun-hua
Xi′an Modern Chemistry Research Institute,Xi′an 710065, China)

Abstract: In HNO_3-H_2SO_4,ammonium N-nitro carbamate ethyl ester was synthesized from ethyl carbamate,then taking N_2O_5 as nitrating agent, ammonium dinitramide(ADN) was prepared.its yield reached to 70%. It was recrystallized to yield a white hygroscopic powder with a melting point of 90～92℃. Its structure was identified by elemental analysis,infrared spectrum and ultraviolet spectroscopy. The main factors such as reaction medium, stuff ratio, reaction temperature were also briefly discussed, its optimum condition was obtained.

40. Synthesis and Characterization of High-Nitrogen Energetic Compounds Derived from Azotetrazolate
XU Song-Lin,YANG Shi-qing,YUE Shou-ti
College of Aerospace and Material Engineering, National University of Defense Technology, Changsha 410073, China)

Abstract: Three new high-nitrogen energetic compounds bis-(ammonium)-5,5′-Azotetrazolate, bis-(guan-idinium)-5,5′-Azotetrazolate and bis-(triaminoguani-dinium)-5,5′-Azotetrazolate have been synthesized from 5-aminotetrazole as a starting materials. Their structures were identified by IR, NMR, DSC, melting point test and elemental analysis. Their explosive performances were also introduced. It shows that these azotetrazolate compounds are possessed of positive enthalpy of formation, high gas generating ability with little or no smoke or residue produced, nonhygroscopic and excellent explosive performances. They are the important ingredients of gas generants, low signature propellants, pyrotechnics and high performance explosives.

41. Synthesis and Characterization of Diacetyltetrabenzylhexaazaisowurtzitane
CHEN Fei~1,PANG Si-ping~2,YU Yong-zhong~1, ZHAO Xin-qi~1
1.School of Material Science & Technology, Beijing Institute of Technology, Beijing 100081, China;
2.School of Life Science & Technology, Beijing Institute of Technology, Beijing 100081, China)

Abstract: The oxidation of hexabenzylhexaazaisowurtzitane (HBIW) by cerium(Ⅳ) ammonium nitrate has been studied. Diacetyltetrabenzylhexaazaisowurtzitane (DATBIW) was obtained and its structure was characterized by FT-IR,MS and ~1HNMR. The mechanism of the oxidation-debenzylation process of HBIW was deduced.

42. Synthesis of 3-Azidomethyl-3-Methyloxetane
LI Na, GAN Xiao-xian
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: 3-Hydroxymethyl-3-methyl oxetane (HMMO) was prepared by the cyclization of raw materials 1,1,1-tri(hydroxylmethyl) ethane and diethyl carbonate.Under lower temperature,3-methoxytosyl-3-methyl oxetane(MTMO) was synthesized by the reaction of HMMO with 4-toluenesulfonylchloride.3-Azidomethyl-3-methyl oxetane was synthesized by the reaction of MTMO and sodium azide.The yields of the three steps were 76%,96%,85%, respectively .The structure and properties of AMMO were identified by ~1HNMR,FTIR,elemental analysis and DSC .The results show that final product was target compound.AMMO was an important energetic oxetane monomer .It can conduct steady cationic polymerization.

43. Synthesis and Thermal Decomposition of 1,4-Dinitromidazole
CAO Duan-lin~1,LIU Hui-jun~(1,2),LI Yong-xiang~1
1.Department of Chemical and Engineering, North University of China, Taiyuan 030051,China
2.Department of Chemistry, Education University of Yanbei,Datong 037009, China)

Abstract: 1,4-Dinitroimidazole (1,4-DNI) is synthesized by following the reactions: 4-dinitroimidazole was N_3-acetylated by acetic anhydride in acidic solution to obtain acylate and acylate thus obtained was nitrated by the mixture of concentrated sulfuric acid, acetic anhydride and sodium nitrate to obtain 1,4-DNI. The synthestic condition is optimized by the orthogonal experiment. The optimum parameters are as follows: n (4-nitr-oimidazole)/n (sulfuric acid)/n (sodium nitrate)/n (acetic anhydride)=2/3/8/15,reaction temperature 30～40℃ and reaction time 3h. Thermal decomposition of 1,4-DNI is studied by DSC.

44. Homogeneous Synthesis of Azidodeoxycellulose
SHAO Zi-qiang~1,WANG Fei-jun~1,WANG Wen-jun~1,LIAO Bing~2
1.School of Materials Science and Engineering,Beijing Institute of Technology,Beijing 100081,China
2.GuangZhou Institute of Chemistry. Academia Sinca, Guangzhou 510650, China)

Abstract: A new high energetic bonder intermediate azidodeoxycellulose for solid propellant was synthesized from the raw material cotton linters under homogeneous conditions. The process of preparing azidodeoxycellulose includes two steps. The first is the tosylation of cellulose with tosylchloride using triethylamine as catalyst and the dimethylacetamide/LiCl system as solvent to obtain cellulose tosylate with certain ester number. The second is nucleophilic substitution reaction of the cellulose tosylate with NaN_3 in DMSO to obtain azidodeoxycellulose with the degree of substitution (DS) of 0.6～1.0. The effects of cellulose tosylate/DMSO ratio, reaction temperature and reaction time on the value of DS of azidodeoxycellulose were discussed. The samples were characterized by elemental analysis, FT-IR and X-ray diffraction.

45. Nitrolysis with Nitrogen Peroxide for Synthesis of 1,4,5,8-Tetranitro-1,4,5,8- tetraazabicyclo[4.4.0]decalin
CAI Chun,Lü Chun-xu
Chemical Engineering School, Nanjing University of Science & Technology, Nanjing 210094,China)

Abstract: 1,4,5,8-Tetranitro-1,4,5,8-tetraazabicyclo[4.4.0]decalin (TNAD) is used as an explosive and has several superior physical properties, such as heat-resistance and insensitivity to impact. This compound could be prepared from the raw material 1,4,5,8-tetraazabicyclo [4.4.0]decalin via nitrosation with sodium nitrite in hydrochloric acid, and followed nitrolysis with N_2O_5in mixed acid. In nitrolysis step, the effect of reaction medium and the reaction temperature on the yield have been investigated . The structure of compound was characterized by IR and elemental analysis.The total yield could reach as high as 85%.

46. Synthesis and Properties of 1,1-Diamino-2,2-Dinitroethylene

ZHOU Cheng,ZHOU Yan-shui,HUANG Xin-ping,WANG Xi-jie
Xi′an Modern Chemistry Research Institute, Xi′an 710065, China)

Abstract: 1,1-Diamino-2,2-dinitroethylene (DADE) was synthesized with 2-methylimidazole as primary substance by nitration and hydrolysis steps in turn and the yield of DADE is 13.4%. Its structure was char-acterized by elemental analysis, IR, MS and NMR. The effects of concentration of sulfuric acid, reaction temperature, reaction time on the yield were investigated. Some important properties of DADE were determined as :density ,1.885g/cm~3 , detonation velocity, 8047m/s(ρ=1.696g/cm~3); friction sensitivity ,10% (3.92MPa ,90°); impact sensitivity , 6%(10kg,25cm); H_(50), 89.1cm(5kg); vacuum stability test,0.14ml/5g(100℃,48h), explosion temperature, 285℃(5s delay).

47. Synthesis and Characterization of 1,1,1-Trimethylolpropane Trinitrate
CUI Jian-lan~1,GUO Wen-long,CAO Duan-lin,XU Chun-yan
1.Department of Chemical Engineering,North University of China,Taiyuan030051,China
2.The College of Pharmaceuticals and Biotechnology of Tianjin University,Tianjin 300072,China)

Abstract: 1,1,1-Trimethylolpropane trinitrate was synthesized from the raw material trimethylolpropane via nitration reaction.The effect of nitriting agent on the yield of nitration reaction was studied and the proper additive and nitriting agent was found. The experimental results showed under the following reaction conditions: 98% nitric acid as nitriting reagent, the molar ratio of trimethylolpropane to nitric acid, 10∶1; reaction time, 2h; reaction temperature,0～20℃,the yield of the title compound was up to 99.7% , providing a new highest yield method of synthesising 1,1,1-Trimethylolproane trinitrate.The product was characterized by IR,nuclear magnetic resonance and elemental analysis.

48. Synthesis of Poly(ether glycol)s Containing Isocyanurate Segments
CHANG Hai,FAN Xiao-dong,WANG Sheng-jie
Department of Applied Chemistry,School of Science,Northwestern Polytechnical University,Xi′an 710072,China)

Abstract: The cationic ring-opening polymerizations of epoxide based monomers were studied using tris(2-hydrooxyethyl) isocyanurate(THEIC) as initiator and trifluoroboron plus ether complex system as catalyst. It was found that the ring opening polymerizations of epoxide based monomers with THEIC can be carried out in a heterogeneous medium smoothly.However,using THEIC initiator,the reaction rate for epichlorohydrin is faster than that of propylene oxide and 2-butoxyxirane,respectively.By simply adjusting the monomer feeding sequence,the block poly(ether glycol) copolymers containing isocyanurate segments can be prepared successfully.

49. Synthesis of LLM-116 by VNS Reaction
WANG Ying-lei,ZHANG Zhi-zhong,WANG Bo-zhou,LUO Yi-fen
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: 3,5-Dinitropyrazole ammonium salt was synthesized by rearranging 1,3-dinitropyrazole as initial material and bubbling ammonia,and acidified to 3,5-dinitropyrazole.1,1,1-Trimethyhydrazinium iodide(TMHI) as a VNS agent was reacted with 3,5-dinitropyrazole in the presence of t-Buok as catalyst to get 4-amino-3,5-dinitropyrazole(LLM-116) through the VNS reaction.Their structures were confirmed by IR,NMR,MS and elemental analyses.The VNS reaction mechanism and factors of influencing the reaction were discussed.The results show that under optimal condition of TMHI as VNS reation reagent and the reaction at 25 ℃ for 4 h,the yield of LLM-116 was 60%.

50. Preparation and Crystal Structure of [Cu(DNI)_2(H_2O)_2]•3H_2O
CUI Rong1,ZHENG Xiao-dong1,MAO Zhi-hua2,ZHANG Zhi-zhong1 FENG Li-min1,YAO Yi-lun1,LI Hong-li1,JIANG Jun1
1.Xi′an Modern Chemistry Research Institute,Xi′an 710065,China
2.Analytical and Testing Centre of Sichuan University,Chengdu 610041,China)

Abstract: [Cu(DNI)2(H2O)2]•3H2O was prepared by the reaction of the aqueous solution of sodium 2,4-dinitroimidazolate and copper sulfate.The single crystal of [Cu(DNI)2(H2O)2]•3H2O suitable for X-ray determination was obtained by slow evaporation method.The single crystal structure of [Cu(DNI)2(H2O)2]•3H2O has been determined by single crystal X-ray diffraction analysis.The crystal is triclinic,space group P-1 with crystal parameters of a=7.2560(10)×10-1 nm,b=7.762(2)×10-1 nm,c=16.685(3)×10-1 nm,α=87.13(3)°,β=83.81(3)°,γ=62.25(3)°,V=826.8(3)×10-3 nm3,Z=2,Dc=1.871 g•cm-3,μ=1.411 mm-1,F(000)=470.The final deviation factor R is 0.0388.According to the analytical results of IR,the elemental analyses and X-ray diffraction,the chemical component of the 2,4-DNI copper complex is C6H10CuN8O13 and its formula is [Cu(DNI)2(H2O)2]•3H2O.

51. Synthesis of 3-Bromonomethyl-3-Methyloxetane
DONG Jun,GAN Xiao-xian
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: The 3-bromomethyl-3-methyloxetane(BrMMO) was synthesized by the closed-ring reaction between 2,2-dibromomethyl propanol(BBMP) as primary substance and alkali.The effect of kinds of alkali and its amount on the closed-ring yield of BBMP was discussed.The effect of the base concentration,reaction temperature and the reaction time on the yield of BrMMO in the closed-ring reaction was discussed.Under the reaction conditions of n(BBMP)∶n(NaOH)=1.0∶1.1,NaOH mass fraction 12%,reaction temperature 78℃,reaction time 4h,the yield of BrMMO was 65%.The structure of BrMMO was identified by elemental analysis,IR and 1 HNMR.The results showed that it was the target compound BrMMO.This experiment process was easy to do,raw material was liable to attain,and the solvent can be retrieved,so the pollution was small.

52. Synthesis of 2-Nitroimino-5-nitrohexahydro-1,3,5-triazine(NNHT)
ZHANG Hai-hao,WANG Bo-zhou,LIU Qian,XIONG Cun-liang,JIA Si-yuan
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: Taking formaldehyde,tert-butyl amine and nitroguanidine as primary materials,2-nitroimino-5-nitrohexahydro-1,3,5triazine(NNHT) was obtained by the process of nitration and Mannich reaction.Its structure was identified by NMR,IR and elemental analysis.The effect of temperature on Mannich reaction was investigated,the yield reached 89% while the temperature was 80 ℃.The conditions of nitration were further optimized,the yield rose to 94% while the reaction was controlled under the room temperature.Instead of 100% nitric acid,industrial nitric acid was used in the nitration under the room temperature,and the yield was 88%.

53. Synthesis of BBMO and BAMO by Phase Transfer Catalysis Method
ZHANG Zhi-gang,LU Xian-ming,GAN Xiao-xian,HAN Tao,XING Ying
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: Using water and toluene as solvent,quaternary ammonium salt as phase transfer catalyst,under the effect of NaOH,3,3-dibromomethyl oxetane(BBMO) was synthesized by the cylization of 1,1,1-tribromomethyl-1-hydroxymethyl methane.Using water as solvent,quaternary ammonium salt as phase transfer catalyst,3,3-diazidomethyl oxetane(BAMO) was obtained by the substitution of BBMO with NaN3.The structure of BBMO and BAMO was identified by HNMR and FTIR.The yield and purity are 81% and 97.2% for BBMO,and 80.9% and 98.37% for BAMO.The results show that the synthesis of BBMO and BAMO by phase transfer catalysis possesses advantages of safety,high yield and high purity.

54. Synthesis and Application of the Heat-resistant Explosive PCS
DENG Ming-zhe,YE Zhi-hu,ZHAO Sheng-xiang,TIAN Zhan-huai
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: The heat-resistant explosive 2,2′,4,4′,6,6′-hexanitro-diphenyl sulfone(PCS) was synthesized by oxidation with CrO3 as oxidant in HNO3 medium of a intermidiate,2,2′,4,4′,6,6′-hexanitro-diphenyl sulfide(DPS),which was prepared by condensation reaction using 2,4,6-trinitrochlorobenzene and sodium thiosulfate as starting materials.The total yield was over 85%.The DSC exothermic peak temperature of the product was 360.1 ℃,and its purity was 98.3%.In heat-resistant test under the condition of 200 ℃ and 48 h,the mass loss of PCS was only 0.62%.The vacuum stability test result under the condition of 120 ℃ and 48 h was 0.35 ml/5 g.The impact and friction sensitivity were 100% and 94%,respectively.The charge density of the mixed heat-resistant explosive JF1 that mainly based on PCS was prepared.The application test results show that JF1 can completely replace ordinary explosive to use in oil explosive materials.

55. Development of Hexanitrohexaazaisowurtaitane at abroad
WANG Xin,PENG Cui-zhi
CNGC North Insititute for Scientific and Technical Information,Beijing 100089,China)

Abstract: The current situation about the synthesis method and industrialization production ability of CL-20 at abroad are overviewed,and the application of CL-20 in propellant and explosive formulations,including CL-20 based explosive formulations LX-19,PAX-12,PAX-11,PAX-29,DLEC038 and PBXW-16,is introduced with 21 references.

56. Synthesis of Polyurethane Thermoplastic Elastomer for Gun Propellants
LI Yu,JIAN Xiao-xia,ZHOU Wei-liang,XU Fu-ming
Department of Chemical Engineering,Nanjing University of Science and Technology,Nanjing 210094)

Abstract: A thermoplastic polyurethane elastomer is synthesized for the need of the binder in a novel gun propellant with polyethylene glycol(PEG) as soft segments,which has good miscibility with nitrate ester,4′4-methylenetis(phenyl isocyanate) and ethylene glycol as hard segments.The principle of molecular designation of the elastomers is analyzed and discussed.DSC,FTIR and DMA are applied to characterize the elastomers.Results show that the elastomers have structure characteristic of polyurethane structure and good microphase segregation in accordance with the molecular designation.Soft segment′s Tg show that the elastomers have good low temperature mechanical properties.

57. Synthesis and Theoritical Analysis of 2-(3-nitrophenyl)Fullerenopyrrolidine
PENG Ru-fang1,2,JIN Bo1, TAN Bi-sheng1,CHU Shi-jin1
1.College of Material Science and Engineering,Southwest University of Science and Technology,Mianyang Sichuan 621010,China
2.China Academy of Engineering Physics,Mianyang Sichuan 621900,China)

Abstract: A new fullerene derivative 2-(3-nitrophenyl)fullerenopyrrolidine(mNPF) containing energy-producing groups was prepared with glycine,m-nitrobenzaldehyde and fullerene as primary materials,and the reaction conditions were investigated by orthogonal test.The optimum reaction conditions with 82.1% yield(based on consumed C60) are: molar ratio of C60,m-nitrobenzaldehyde and glycine 1∶4∶6,reaction temperature 100℃,reaction time 24h,volume of toluene solvent 80mL.The structure of mNPF was characterized by UV-vis,FT-IR,1 HNMR,13 CNMR and MS.The feasibility of reaction was studied by semiempirical calculations PM3 method.The thermal stability of mNPF was studied by DTA,showing that mNPF has good thermal stability.

58. Synthesis of 2-(2-Nitrophenyl)fullerenopyrrolidine
PENG Ru-fang1,2,JIN Bo1,MA Dong-mei1,CHU Shi-jin1
1.College of Material Science and Engineering,Southwest University of Science and Technology, Mianyang Sichuan 621010,China
2.Graduate School,CAEP,Mianyang Sichuan 621900,China)

Abstract: A new nitrofulleropyrrolidine derivative 2-(2-nitrophenyl)fullerenopyrrolidine(NPF) was synthesized with fullerene,glycine and o-nitrobenzaldehyde as primary materials by 1,3-dipolar cycloaddition reaction.Its structure was characterized by UV-Vis,FT-IR,1HNMR,13CNMR and MS.Effects of the ratios of raw materials,temperature,reaction time and the volume of toluene on the reaction were investigated by orthogonal method.The results show that the reaction conditions of synthesizing NPF with the yield of 81.2%(based on consumed C60) are: molar ratio of C60,o-nitrobenzaldehyde and glycine 1∶4∶6,reaction temperature 80℃,reaction time 48h,volume of toluene solvent 70 mL.

59. Synthesis and Application of Geminal Dinitro Energetic Plasticizers
CHEN Bin,ZHANG Zhi-zhong,JI Yue-ping
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: According to the structure and synthesis character of the geminal dinitro energetic plasticizers,the current situation about the synthesis,the property and application of geminal dinitro aldehyde acetals,esters and ether energetic plasticizers is summarized with 21 references.The preparation technique of aldehyde acetals energetic plasticizers BDNPF and BDNPA is introduced.Their physico-chemical properties,energy characteristics,thermol performance and application in the formulations of explosives and propellants are reviewed,considering that synthesis and application of geminal dinitro energetic plasticizers are the key point in energetic plasticizer study.

60. The Green Synthesis of 1,2-Propylene Glycol Dinitrate
SHI Fei,WANG Qing-fa,ZHANG Xiang-wen,WANG Li,MI Zhen-tao
Key Laboratory for Green Chemical Technology of State Education Ministry,School of Chemical Engineering and Technology,Tianjin University,Tianjin 300072,China)

Abstract: In order to solve the environmental pollution of synthesizing 1,2-propylene glycol dinitrate(PGDN) with propylene oxide(PO) as raw material and the mixture of nitric acid and sulfuric acid as nitrating agent,a new method for preparation of PGDN by nitrating PO with dinitrogen pentoxide(N2O5) as a clean nitrating agent was presented.This reaction is environmental friendly with high atomic economy.Effects of the drip order,molar ratio of N2O5 to PO,reaction temperature and solvents on the yield and selectivity of PGDN were studied.The results show that the optimum reaction conditions are: dropping the PO into the solution of N2O5/organic solvent,the molar ratio of N2O5 to PO above 1.1∶1.0,the reaction temperature 15℃ and dichloromethane as solvent.Under the above optimum conditions,the yield of PGDN is about 96.3%,and the selectivity is nearly 100%.

61. Synthesis and Properties of 3,4-Bis(4′-aminofurazano-3′)furoxan
ZHOU Yan-shui,LI Jian-kang,HUANG Xin-Ping,ZHOU Cheng,ZHENG Wei,ZHANG Zhi-zhong
Xi′an Modern Chemistry Research Instritute,Xi′an 710065,China)

Abstract: 3,4-bis(4′-aminofurazano-3′)furoxan was synthesized using dicyanopropane as starting material by nitrosation,diazotization and condensation steps in turn,with overall yield 50%.Some physical and detonation properties were also measured,with density 1.795g/cm3,melt point 170-171℃,detonation velocity 7177m/s(1.530g/cm3),temperature of decomposition 260℃,friction sensitivity 8%(90°),impact sensitivity 60%(10kg,25cm),and vacuum stability test 0.4-0.7mL(5g,100℃,48h).The thermal stability and compatibility of DATF were investigated by DSC.The results show that DATF has better thermal stability,lower sensitivity and good compatibility with energetic materials of RDX,HMX,NC and NC/NG system.

62. Crystal Structure and Thermal Decomposition of FOX-7
ZHOU Cheng,HUANG Xin-ping,ZHOU Yanshui,WANG Xi-jie,FU Xia-yun
Xi′an Modern Chemistry Research Institute,Xi′an 710065, China)

Abstract: 1,1-Diamino-2,2-dinitroethylene(FOX-7) was synthesized with 2-methylpyrimidine-4,6-dione as primary substance by nitration and hydrolysis steps in turn.The yield is 85.1%.The structure of the obtained compound has been identified by elemental analysis,IR,MS and NMR.The single crystal of FOX-7 was cul-tivated from acetonitrile.Its crystal structure was determined by a X-ray single crystal diffractometer.The results show that the crystal is belong to monoclinic system,space group P21/n,with crystal parameters of a=0.6930(14)nm,b=0.6630(13)nm,c=1.1360(2)nm,β=90.43(3)°,V=0.5219(18)nm3,Z=4,Dc=1.885g•cm-3,μ=0.179mm-1,F(000)=304.Its thermal decomposition mechanism was studied by DSC and TG-DTG techniques.The thermal decomposition of FOX-7 consists of one endothermic and two exothermic decomposition processes continuously.The TG curve consists of two stage mass loss processes.The endothermic peak is attributed to the crystal transformation and the exothermic peaks are due to the decomposition reaction of FOX-7 and its decomposition products.Higher decomposition temperature shows that FOX-7 has better thermal stability.

63. A Review on 3-Nitro-1,2,4-Triazol-5-One and its Salts
MA Hai-xia~(1,2),SONG Ji-rong~2,HU Rong-zu~2
1.School of Chemical Engineering,Nanjing University of Science and Technology,Nanjing 210094,China
2.College of Chemical Engineering/Shaanxi Key Laboratory of Physico-InorganicChemistry,Northwest University,Xi′an 710069,China)

Abstract: The synthesis and properties of a new energetic material 3-nitro-1,2,4-triazol-5-one(NTO),including synthesis methods,crystal structure,quantum chemistry,thermal behaviors and toxicity were reviewed in details.The molecule structure and thermodynamic properties of twenty-one kinds of NTO complexes of alkali,alkaline earth,transition metals and rare earth metals were introduced emphatically and the thermal decomposition products of NTO alkali complexes were concluded as carbonate with Li,Na and K, and those of Rb and Cs complexes of NTO were carbonate,metal oxide and polymers.The relationship between the enthalpy of activation(ΔH~≠) and the value(T_(pdo)) of the peak temperature among NTO alkali metal complexes was obtained with 73 references.

64. Synthesis and Properties of 2,4-Dinitroimidazole Lead Salt
ZHENG Xiao-dong,CUI Rong,LI Hong-li,WANG Min-tao,WANG Jiang-ning, ZHONG Lei,JIANG Jun,ZHANG Zhi-Zhong
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: For solving the problem of energy decrease of solid propellant caused by adding inert catalyst into propellant,a novel energetic combustion catalyst,2,4-dinitroimidazole lead salt(PDNI)was synthesized by two steps of nitration,thermal rearrangement and ion exchange reactions using imidazole as starting material.The mechanical sensitivity and compatibility of PDNI were determined and compared with those of PNTO.The result shows that PDNI has fair compatibility with NC/NG system.In comparison with PNTO,PDNI has the lower mechanical sensitivity and better thermal stability.The effects of PDNI as an energetic combustion catalyst on the combustion performance of the modified double base propellant were investigated.The results show that PDNI has catalytic effect level approaching that of Pb(Ⅱ)-β-resorcylic acid complex.

65. Amination of Nitrotoluenes via Vicarious Nucleophilic Substitution(VNS) of Hydrogen
LI Jia-rong~1,ZHAO Jian-min~1,WEI Xiao-jie~1,ZHAO Xiao-fan~1,DONG Hai-shan~2
1.School of Chemical Engineering and Environment,Beijing Institute of Technology,Beijing 100081,China
2.Institute of Chemical Engineering and Material,CAEP,Mianyang Sichuan 621900,China)

Abstract: The VNS amination reaction of nitrotoluene with ATA in DMSO in the presence of MeONa via vicarious nucleophilic substitution(VNS) of hydrogen was studied.The results indicated that 3-amino-2,4-dinitrotoluene was obtained by VNS amination of DNT in the yield of 10.5%,and 3,5-diamino-2,4,6-trinitrotoluene was obtained via VNS amination of 2,4,6-trinitrotoluene in the yield of 27.6%.The yields were lower under microwave radiation than that at room temperature.The amination of TNT in hydroxylamine gave DATNT in poor yield.The products were characterized by IR,nuclear magnetic resonance,elemental analyses and MS.

66. Preparation and Performance of Double Base Propellant Modified by NGEC
WANG Fei-jun~1,YANG Fei-fei~1,WANG Jiang-ning~2,SHAO Zi-qiang~1
1.School of Materials Science and Engineering,Beijing Institute of Technology,Beijing 100081,China
2.Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: In order to enhance the mechanical performance of double-base propellant at low temperature,the cellulose was converted to cellulose glycidyl via basification and etherization reactions.A novel energetic binder named nitric acid ester of cellulose glycidyl ether(NGEC)with different esterification and etherification degree was synthesized by nitrating cellulose glycidyl.The mechanical performance and the section appearance of the two double base propellants based on NGEC and NC were surveyed and analyzed.The detonation heat and specific volume of the two propellants were tested and contrasted.The results show that the double-base propellant based on NGEC has better mechanical performance,detonation heat and specific volume level overaging those of double base propellant based on NC and its inner-structure turns more uniform.Its compressive strength σ_m(+50℃),elongation ε_m(25℃) and specific impulse are no less than 11.0MPa and 40% and 2218N•s•kg~(-1),respectively.

67. Synthesis and Characterization of 3-Nitatomethyl-3-Methyl Oxetane
MO Hong-chang,GAN Xiao-xian
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: In order to develop nitratopolyether binders,an energetic monomer,3-nitatomethyl-3-methyloxetane(NIMMO) was synthesized with 3-hydroxymethyl-3-methyloxetane(HMMO)as primary substance and nitrogen peroxide as nitrating agent.The effect of reaction temperature and N_2O_5/HMMO molar ratio on selective nitration was discussed.The optimum reaction conditions are as follows:n(N_2O_5):n(HMMO)=(1.1-1.0)∶1.0,reaction temperature-15——10℃ and the reaction was quenched after addition was over when temperature began to descend.The structure of the product was characterized by IR,NMR and elemental analyses,showing that final product was target compound.DSC experiment shows that NIMMO has better thermal stability.

68. HZSM-5 Assisted Clean Nitration of Toluene with Dinitrogen Pentoxide
QIAN Hua,YE Zhi-wen,Lü Chun-xu
School of Chemical and Engineering,Nanjing University of Science and Technology,Nanjing 210094,China

Abstract: In order to solve the problem of synthesizing p-mononitrotoluene involving the concentrated mineral acids as the catalysts,produces huge amounts of wastes along with a large amount of undesired o-MNT due to the nonselective nitration of toluene,the nitration of toluene by N_2O_5 has been investigated with solid acids catalysts HZSM-5.By the use of new nitrating agent,the reaction eliminated the use of concentrated sulfuric acid and was environmental friendly with high atom economy.The excellent selectivity of HZSM-5 makes the ratio of p-mononitrotoluene increase greatly.Effects of reaction temperature,reaction time,amount of catalyst and the ratio of Si/Al on the nitration were investigated,showing that under optimum conditions,the yield of nitration of toluene was 42%,and para-selectivity was 78.9%.

69. Research on Coating HNIW with Water-borne Branched Polyurethane
LIAO Su-ran~(1,2),LUO Yun-jun~1,YANG Yin~1,SUN Jie~3,TAN Hui-min~1
1.School of Material Science and Engineering,Beijing Institute of Technology,Beijing 100081,China
2.Textile and Chemical Engineering Department,Henan Textile College,Zhengzhou 450007,China
3.Institute of Chemical Materials,CAEP,Mianyang Sichuan 621900,China)

Abstract: The waterborne branched polyurethane(WBPU) was synthesized from toluene diisocyanates(TDI),TDB-2000,TMN-450,dimethylolpropionic acid(DMPA) and 1,4-butanediol(BDO) as raw materials under acetone reflux.The cast films obtained were characterized by FT-IR,~1HNMR and DSC.The DSC curve presented an endothermic decomposition bimodal profile,showing that water-borne branched polyurethane resin degraded obviously at about 299℃ and 380℃.The SEM photographs and FT-Raman spectra revealed that hexanitr-ohexaazaisowurtzitane(HNIW) was coated with water-borne branched polyurethane by means of latex deposition.The impact sensitivity results show that the characteristic height H_(50) of HNIW coated by water-borne branched polyurethane increases from 25.1cm to 31.6cm,indicating that the water-borne branched polyurethane can dec-rease the impact sensitivity of HNIW.

70. Synthesis and Properties of a Novel Azido Energetic Curing Agent
ZHENG Xiao-dong~1,MA Xiao-dong~2,QIU Shao-jun~3,LI Hong-li~1,JIANG Jun~1,GAN Xiao-xian~1
1.Xi′an Modern Chemistry Research Institute,Xi′an 710065,China
2.Military Office,Xi′an North Huian Chemical Industrial Co.Ltd,Xi′an 710302,China
3.School of Materials Scienceand Engineering,Northwestern Polytechnical University,Xi′an 710072,China)

Abstract: To improve the mechanical properties of the binder system,a novel azido poly-isocyanate energetic curing agent(EC) was synthesized via additional reaction of azido polyether polyol and hexamethylene diisocyanate(HDI).The material ratio,reaction temperature and post processing steps on the reaction were studied.The DSC results show that for EC,there was an exothermic peak at 252.89℃ and the glass transition temperature(T_g) was found at-47.13℃;for the EC/GAP system,thermal decomposition peak was at 254.56℃ and the glass transition temperature(T_g) was found at-45.78℃.And the EC/GAP/50%TEGDN system have good physical and chemical compatibility,there were two peaks at 213.05℃ and 250.89℃,and the glass transition temperature(T_g) was found at-69.08℃.The tensile strength and break elongation value of GAP/EC system is 0.67MPa and 129%,respectively,which is better than that of 0.5MPa and 56.5% of GAP/N100 system at 20℃.

71. Synthesis and Properties of 3-Azidomethyl-3-Ethyloxetane and its Homopolymer
HAN Tao,GAN Xiao-xian,XING Ying,LI Na,LU Xian-ming,ZHANG Zhi-gang,MO Hong-chang
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: To develop new energetic binder,a new azide oxetane monomer,3-azidomethyl-3-ethyloxetane(AMEO) was synthesized by 1,1,1-tri(hydroxylmethyl) propane,diethylcarbonate,4-toluenesulfonyl chloride and sodium azide as raw materials.Its structure and properties were identified by ~1HNMR,FTIR,elemental analyses and DSC.At the present of catalyst boron-trifluoride etherate,a solid energetic polymer,homopolymer of 3-azidomethyl-3-ethyloxetane PAMEO was prepared by the cationic polymerization of monomer AMEO with(1,4)-butanediol as initiator and dichlorometane as solvent.The structure of the polymer was identified by IR,(~1HNMR) and elemental analyses.The properties of the polymer were characterized by TGA,DSC,hydroxyl equivalent and number-average molecular weight.

72. Synthesis and Characterization of Ultrafine Cupric 2,4-Dihydroxy-benzoate(β-Cu)
LI Yu,GUO Yu,LIU You-zhi,,SHI Guo-liang,XIE Wu-xi
Research Center of Shanxi Province for High Gravity Chemical Engineering and Technology,Taiyuan 030051,China)

Abstract: Using impinging steam-rotating packed bed(IS-RPB),ultrafineβ-Cu powder was synthesized from CuSO_4•5H_2O and β-H as primary substances by high gravity reactive precipitation method.The TEM,laser size analysis(LSA),BET and TG-DTG techniques were used to characterize the product.Effects of the operation conditions of rotational speed,impact velocity and post-treatment conditions on the average particle size of β-Cu were also studied systematically.The results show that the operation conditions are optimized as: rotational speed,1000r/min,impact velocity,28m/s and vacuum desiccation temperature,100℃.Under the above-mentioned conditions the sheet β-Cu particles with size of 0.12μm to 0.363μm,an average particle size of 610nm and a specific surface area of 11.6265m~2/g are obtained.

73. Researches and Applications of Borate Surfactants
WANG Hai-ying,LI Bin-dong,Lü Chun-xu,ZOU Qi
School of Chemical Engineering,Nanjing University of Science & Technology,Nanjing 210094,China)

Abstract: The structures of the borate surfactant and its improved methods of properties are briefly introduced.The progress in synthesis of borate surfactant and their applications in the fields of antistatic,antiwear,flame retardancy were introduced.The antistatic researches of polymeric borate surfactant are described,and their application prospect in the industrial area such as the energetic material area is reviewed with 27 references.

74. Synthesis of CL-20 by Clean Nitration
QIAN hua,Lü Chun-xu,YE Zhi-wen
Chemical Engineering School,Nanjing University of Science and Technology,Nanjing 210094,China)

Abstract: CL-20 was synthesized via nitrotion in nitric acid with 2,6,8,12-tetraacetylhexaazatetracyclo [5.5.0.0~(3,11).0~(5,9)] dodecane(TAIW) and clean nitrating agent dinitrogen pentoxide.By the use of new nitrating agent,the reaction eliminated the use of concentrated sulfuric acid and was environmental friendly with high atom economy.The structure of the compound was characterized by elemental analysis,IR,NMR and MS.The effects of reaction temperature and reaction time on the yield were also investigated,showing that under the conditions of reaction temperature,0℃ and reaction time,1h,the optimum yield of CL-20 was up to 62%.

75. Synthesis Mechanism of Tetranitrodiazidopropionylhexaazaisowurtzitane
MENG Zheng,OU Yu-xiang,LIU Jin-quan,WANG Yan-fei
College of Materials Science and Engineering,Beijing Institute of Technology,Beijing 100081,China)

Abstract: TAIW was formed from hydrogenolysis debenzylation of TADBIW using Pt as catalyst.TADCPIW was synthesized by α-chloropropionylation of TAIW.A mixture contained TNDCPIW was obtained by nitration of TADCPIW, then azido groups were introduced into product.Tetranitrodiazidopropionylhexaazaisowurtzitane(TNDAPIW) with high nitrogen content and high enthalpy of formation can be obtained by the product separation using column chromatography.The structures of TNDAPIW and the intermediate compounds were identified by IR,~1HNMR and elemental analysis.The related conditions and mechanisms of reactions such as hydrogenolysis,α-chloropropionylation,nitration and azidation were discussed.The results show that because of the caged structure of TAIW and the electrophilic effect in the-acyl radical,it is necessary for the actively reacting composite such as α-chloropropionyl chloride used in the chloropropionylation reaction;the nitration reagent should be appropriately used in the nitration,if not TADCPIW will be nitrated into HNIW;as the diazo-reaction is S_N2 reaction,it is advantageous for the reaction to choose the dipolar protophilic solvent like DMF or DMSO.

76. Synthesis of Trinitropyridine and its N-Oxide
ZHAO Jian-min~1,LI Jia-rong~1,WEI Xiao-jie~1,LI Wen-ting~1,DONG Hai-shan~2
1.School of Chemical Engineering and Environment,Beijing Institute of Technology,Beijing 100081,China
2.Institute of Chemical Engineering and Material,China Academy of Engineering Physics,Mianyang 621900,China)

Abstract: 2,2-Dinitropropane-1,3-diol was synthesized from nitromethane in low temperature by oxidative nitration method.Silver was successfully recycled with a yield upon 93% and reused in the synthesis of 2,2-dinitropropane-1,3-diol.Potassium 2,2-dinitroethanol,the key intermediatecompound for synthesis of trinitropyridine(TNPy),was prepared through one-pot method with a yield upon 62%,which is 10% higher than conventional method.Controlling the pH value in the range of 1-2,trinitropyridine N-oxide(TNPyO) was synthesized by the cyclization of potassium 2,2-dinitroethanol in 68% nitric acid at 50-60℃.Maintaining the temperature between 80-90 ℃,TNPyO can be further reduced to produce TNPy by refluxing for 1 h;The yields of TNPyO and TNPy are 50% and 15%,respectively.TNPyO can also be prepared from potassium 2,2dinitroethanol under phosphoric acid and sulfuric acid.The products were characterized by IR,nuclear magnetic resonance,elemental analysis and EI-MS.

77. Synthesis of Rich-Nitrogen Compound of 3,3′-Azobis(6-Amino-1,2,4,5-Tetrazine)
WANG Bo-zhou,LIAN Peng,LIU Qian, WANG Xi-jie,ZHANG Zhi-zhong,HUANG Xin-ping
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: 3,3′-Azobis(6-amino-1,2,4,5-tetrazine)(DAAT) was synthesized with triaminoguanidine nitrate and 2,4-pentanedione as primary substances by condensation,oxidation,hydrazinolysis,oxidation-bromation, aminolysis and hydrolysis in turn.DAAT is a new rich-nitrogen energy material with remarkable thermal stability and insensitivity against friction and impact.DAAT decomposes at relatively high temperatures(250℃) measured by DSC.The details of each reaction process and yields were described;the results are according with the references.The overall yield of DAAT is 19%.Its structure was confirmed by IR,HNM and DSC.The mechanisms of the condensation and oxidation-bromation reactions were presented.

78. Study on the Synthesis of TEX
XU Rong,ZHOU Xiao-qing,ZENG Gui-yu,LIU Chun
The Institute of Chemical Materials,CAEP,Mianyang Sichuan 621900,China)

Abstract: 1,4-Diformyl-2,3,5,6-tetrahydroxypiperazine (THDFP) was synthesized with glyoxal and amides as primary substance.The cage explosive 4,10-dinitro-2,6,8-12-tetraoxa-4,10-diazatetracyclo-[5.5.0.0~(5,9)0~(3,11)]-dodecane(TEX) was prepared using the method that taking THDFP into 98% H_2SO_4 and fuming HNO_3 at lower temperature,producing enough the cage compound,then carrying out nitration in higher tempreture.The purity and overall yield of TEX are 99.5% and 34.8%,respectivety.The effect of THDFP dry time,the temperature of adding material and reaction tempreture on the synthesis of TEX were studied.Results show that THDFP of full dried for synthesis is favored,should controll the temperature of adding material in the range 45～50℃ and the reaction tempreture in the range of 75～80℃.

79. Experimental Studies on the 2,4,6-Trinitro-m-Xylene Crystal
GUO Jin-Yu,ZHANG Tong-Lai,ZHANG Jian-Guo,LIU Yan-Hong
State Key Laboratory of Explosion Science and Technology,Beijing Instituteof Technology,Beijing 100081,China)

Abstract: The crystal of 2,4,6-trinitro-m-xylene (TNMX) has been synthesized,cultured and characterized by X-ray single crystal diffraction,~1HNMR,MS and FT-IR techniques.TNMX is crystallized into orthorhombic,Pbcn space group,a=(5.749(2))×10~(-10)m,b=15.043(3)×10~(-10)m,c=11.415(2)×10~(-10)m,α=β=γ=90.00°,V=987.2(3)×10~(-30)m~3,Z=4,D_c=1.623g/cm~3(calculated density),final R indices[I2σ(I)],R_1=0.0359,wR_2=0.1006,R indices for all data,R_1=0.0459,wR_2=0.1045.By means of weak interactions among the nitro O atoms from different TNMX molecules,two-dimensional frameworks come into being in this complex.The DSC and TG-DTG thermal analyses have also carried to predict its thermal decomposition mechanism.Based on thermal analyses,the crystal was predicted to decompose completely in one step.

80. Optimization of the Synthetical Craft of 2,6-Diamino-3,5-Dinitropyrazine-1-Oxide
GUO Feng-bo, LIU Yu-cun,LIU Dengcheng,YU Yan-wu
Department of Environmental and Safety Engineering,North University of China,Taiyuan 030051,China)

Abstract: LLM-105 was synthesized with 2,6-dichloropyrazine as primary substance by substitution,nitration,ammoniation and oxidation steps in turn and the overall yield of LLM-105 is greater than 36%.The purity of LLM-105 is more than 98%.Its structure was characterized by elemental analysis,IR,MS and NMR.Effects of the consumption of CH_3ONa,the volume proportion of HNO_3 and H_2SO_4,the consumption of NH_3•H_2O and the volume proportion of trifluoroacetic acid and H_2O_2 on the overall yield of LLM-105 were investigated.The optimal conditions of synthesizing LLM105 were ascertained as: for the substitution reaction,under the conditions of reflux,reaction time,2h;the consumption of CH_3ONa is 120% for the nitration reaction,reaction time 4h;reaction temperature 60～70℃,the volume proportion of HNO_3 and H_2SO_4,0.83;for the ammoniation reaction,under the conditions of 2h and 60℃,the consumption of NH_3•H_2O,200%;for the oxidation reaction,under the conditions of 24h and room temperature,the volume proportion of trifluoroacetic acid and H_2O_2,1∶10.

81. Progress in the Synthesis of TATB Free from Chloride
ZHOU Xin-li
School of Chemical Engineering,Nanjing University of Science & Technology,Nanjing 210094,China)

Abstract: Based on references,synthesis methods of insensitive explosive TATB are summarized.Modified synthesis methods of TATB containing chloride compounds are simply introduced.The progresses in the synthesis of TATB free from chloride by different raw materials and synthesis process are mainly introduced,especially direct amination synthesis principle and process of TATB according to vicarious nucleophilic substitution of hydrogen(VNS) are emphasized,including influences of raw materials,mole specific,amination agent and its addition methods,methods of quenching reaction on yield,particle size, purity and physical appearance.It is shown that VNS is a new method for preparation of energetic materials containing multi nitro and amino aromatic compounds.

82. Synthesis and Properties of N-guanylurea Dinitramide
LIU Qian,WANG Bo-zhou,ZHANG Zhi-zhong,ZHU Chun-hua,LIAN Peng
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: N-guanylurea dinitramide(GUDN) was synthesized with N-guanylurea hydrochloride as primary substance by hydrolysis and double decomposition reaction in turn and the overall yield of GUDN is 79%.The structure of GUDN was identified by elemental analysis,IR and UV.Some properties of GUDN were determined as:density,1.755g/cm~3;friction senstivity,0(2.45MPa,20mg,66°);H_(50)197cm(2kg) etc.And its properties were compared with properties of ADN.GUDN has low sensitivity,good thermal stability and unhygroscopicity.The results obtained by DSC show that GUDN is compatible with common energetic materials such as HMX and RDX.Application tests indicate that GUDN can be used in double base propellant.

83. A Review of Recent Advances of Energetic Plasticizers
JI Yue-Ping,LI Pu-rui,WANG Wei,LAN Ying,DING Feng
Xi′an Modern Chemistry Research Insititute,Xi′an 710065,China)

Abstract: The current situation about the synthesis and application of energetic plasticisers based on the kinds of energetic group is summarized.The primary role of energetic plasticisers in energetic material formulation is considered to modify the mechanical properties of charge to improve safety characteristics.The nitrate ester plasticisers is a sensitive explosive easily initiated by fricition and impact.The value of HD for most of the energetic nitrate esters is 1.1.The novel energetic compounds or oligomeric containing azido geminal dinitro and nitramine group with excellent properties are considered as primary research subject of energetic plasticisers.The shortcoming in the synthesis technology,variety and application of energetic plasticizer in domestics is analysed.The suggestions in the synthesis and application of novel energetic plasticizers are presented.

84. Synthesis of Polyurethane Elastomer Used in the Coating of Some Propellant and its Application
ZHU Kai-jin,XIAO Zhong-liang
Department of Chemical Engineering,North University of China,Taiyuan 030051,China)

Abstract: By utilizing toluene diisocyanate(TDI) and liquefied diphenylmethane diisocyanate(MDI) to synthesize polyisocyanate,and then to synthesize the adhesive of polyurethane as main component of certain propellant coating,a coating with good mechanical property and low smoke fog property is obtained.The results show that it is fit to choose the ratio 7∶3 of TDI to MDI,the reaction temperature 80℃,the reaction time(30min) and the solidified time 4～5d.The originality of the study rests on that TDI and liquefied MDI are simultaneously used as the synthetic material of polyisocyanate to make the coating of some propellant.

85. Progress of the High Density Hydrocarbon Fuel of Exo-tetrahydrodicyclopentadiene
DU Yong-mei,LI Chun-ying,Lü Jian
Xi′an Modern Chemistry Research Institute,Xi′an 710065,China)

Abstract: The current situation of synthetic methods of exo-tetrahydrodicyclopentadiene including hydrogenation of dicyclopentadiene and isomerization from endo-tetrahydrodicyclopentadiene to exo form is summarized.Different hydrogenation catalysts and process are generalized and several hydrogenation catalysts are compared.Continuous and intermittent process are recapitulated.Isomerization catalysts and machanism of isomerization with Lewis acid catalysts are introduced.Development direction of hydrogenation catalysts and isomerization catalysts is presented.New synthetic methods of exo-tetrahydrodicyclopentadiene is suggested.

86. Kinetics of Synthesis of TADF by Hydrogenolysis Debenzylation of TADB
MA Ai-ling,SUN Cheng-hui,FANG Tao,ZHAO Xin-qi
Beijing Institute of Technology, Beijing100081, China)

Abstract: The reaction kinetics of synthesis of tetraacetyldiformylhexaazaisowurtzitane(TADF) by hydrogenolysis debenzylation of tetraacetyldibenzylhexaazaisowurtzitane (TADB) has been studied over Pd(OH)_2/C catalyst in formic acid. The experiment was investigated in an atmosphere of hydrogen. The effects of both internal and external diffusions were eliminated by stirring adequately. The effects of catalyst and solvent were eliminated by the experiments without adding substrate. The changes of the absorption amount of hydrogen with reaction time were measured. The absorption amount of hydrogen was used to stand for the reaction extent. Kinetics calculations of the experimental data at various temperatures were carried out, according to the integrate reaction rate equation. Experimental results indicate that the reaction is the first-order with respect to TADB under the experimental conditions. The apparent activation energy (E_a) of the reaction is 50.41 kJ/mol and preexponential factor (A) (4.5326×106 min~(-1)). It showed that the reaction of hydrogenolysis debenzylation of tetraacetyldibenzylhexaa-zaisowurtzitane in formic acid can undergo easily.

87. A New Technique for Preparation of Pentaerythritol Diazido Dinitrate
SU Tian-duo ,ZHANG Li-jie ,LIU Heng, ZHANG Hong-yu,CUI Rong
Xi′an Mordern Chemistry Research Institute, Xi′an 710065,China)

Abstract: A new technique of preparing pentaerythritol diazido dinitrate (PDADN) via bromization reaction of pentaerythritol as starting material, azidonation reaction of 2,2-bromomethyl-1,3-propandiol and nitration reaction of 2,2-azido-1,3-propandiol was presented . The structure of PDADN was characterized by IR, ~(1)HNMR and elemental analysis
.
88. An Improved Synthetic Method of DADE with High Yield
WANG Xi-jie, ZHOU Cheng, WANG Bo-zhou, ZHANG Zhi-zhong, FU Xia-yun
Xi′an Modern Chemistry Research Institute,Xi′an710065, China)

Abstract: An improved synthetic route for DADE was investigated by the nitration of 2-methyl-4,6-pyrimidindione in nitric acid/sulphuric acid and hydrolysis of the intermediate 2-dinitromethylene-5,5-dinitro-dihydro-pyrimidine-4,6-dione based on the perfect detonation properties of DADE and a comparison of its reported preparation methods.Its total yield is over 83%. The structure of DADE was characterized by IR,MS,NMR and elemental analysis.

89. Synthesis and Properties of 3-azidomethyl-3-cyanoethoxylmethyloxetane Polymer
GAN Xiao-xian, XING Ying, LI Na, ZHANG Zhi-Gang, LU Xian-Ming
Xi′an Modern Chemistry Research Institute, Xi′an 710065, China)

Abstract: With indirect method, a new liquid hydroxyl-terminated azider polyether binder, 3-azidomethyl-3-cyanoethoxylmethyloxetane homopolymer (PAMCMO) was synthesized by 3-bromomethyl-3-cyanoethoxylme- thyloxetane homopolymer(PBMCMO) and sodium azide in DMF. PAMCMO had the following properties:number average molecular weights 2 500; glass transition temperature -38.75 ℃, decomposition temperature of azido group 257.35 ℃. PAMCMO had good compatibility with nitrate ester plasticizers because the introduce of cyanoethoxyl group could increase its solubility parameter to 23.45(J/cm~3)~(0.5).

90. Synthesis and Characterization of C/N Heterocyclic Vinyl Ester Resin
YANG Shi-shan, WANG Ji-gui, LI Dong-lin, GAN Xiao-xian
Xi′an Modern Chemistry Research Institute, Xi′an710065, China)

Abstract: C/N heterocyclic vinyl ester resin (CNVER) was synthesized by the reaction of ISEP and methacrylic acid. The technological conditions of synthesizing CNVER were optimized. Influence of the molar ratio of epoxy group and carboxy group, the amount of catalyzer and the reaction temperature on the reaction were discussed.The structure of CNVER was confirmed by IR spectrum. Styrene was chosen as a cross-linking agent of CNVER. The properties of CNVER was studied. Its elongation is 7.2% and tensile strength 74.7 MPa, indicating that the mechanical properties of CNVER are good.

91. Preparation of Polyurethane-acrylate Core-shell Latex and its Coating of RDX
LU Ming~1, SUN Jie~2, CHEN Yu~1, LUO Yun-jun~1, TAN Hui-min~1
1. School of Material Science and Engineering, Beijing Institute of Technology, Beijing100081, China
2. Institute of Chemical Materials, CAEP, Mianyang 621900, China)

Abstract: Waterborne polyurethane(WPU) was prepared with TDI,DL-400(M_n=340),DMPA and BDO as main materials, whose structure was characterized by FTIR .Polyurethane-acrylate(PUA) latex was synthesized through the method of the seed-latex polymerization with WPU, water and butyl acrylate as starting materials, two kinds of initiator, AIBN and (NH_4)_2S_2O_8-NaHSO_3. Latex particles shape of PUA were determined through TEM, and the results indicated that PUA latex with core-shell structure was synthesized with AIBN as initiator, whose shell were black polyurethane particles and core white polyacrylate ones. PUA latex initiated by (NH_4)_2S_2O_8-NaHSO_3 has no core-shell structure. The method was used for the first time to deposit core-shell latex to coat RDX with 10% KAl (SO_4)_2•12H_2O solution. distilled water,40℃. Through SEM, the surface of RDX was observed to have been covered with a layer of even film after being coated with PUA, and the particles among RDX were perfectly dispersed.

92. Synthesis and Properties of 3,3-diazidomethyloxetane and its Polymer
LU Xian-ming, GAN Xiao-xian
Xi′an Modern Chemistry Research Institute, Xi′an 710065, China)

Abstract: Using absolute alcohol as solvent,under the effect of NaOH,the 3,3-dibromomethyl oxetane (BBMO) was synthesized by the cyclization of 1,1,1-tribromomethly-1-hydroxymethyl methane. 3,3-Diazidomethyloxetane(BAMO) was obtain by the substitutation of BBMO with NaN_3 using 1,4-butylene-glycol as initiator and CH_2Cl_2 as solvent, a solid energetic binder(PBAMO) was synthesized by the cationic polymerization of the monomer BAMO. The structure of the polymer was identified by H NMR, FTIR, DSC and GPC. The physical chemistry properties of PBAMO are determined. The results show that PBAMO is an energetic binder with lower sensitivity, suitable melting point and lower melt viscosity and can be used as the hard segmer composition of energetic thrmaolastic elastomer.

93. Macro-kinetics Study of Ozone-mediated Nitration Reaction of Aromatic Compounds with Nitrogen Tetroxides
Lü Zao-sheng~1, WANG Xiao-yan~1, Lü Chun-xu~2
1. Wuhan University of Science and Technology, Hubei430081, China
2. Nanjing University of Science & Technology , Nanjing210094, China)

Abstract: The kinetics character in ozone-mediated nitration aromatic compound reaction with nitrogen tetroxide has been studied. Kinetics model has been constructed with the aid of stable state treatment method. Raman spectrum shows no nitronium ion in N_2O_4/O_3, which demonstrates N_2O_4/O_3 nitration aromatics is not a affinitive electronic substitution process. Experiment results show that the reaction rate of N_2O_4/O_3 nitration benzene and toluene is zero order in benzene and toluene, half order in N_2O_4, the reaction rate of N_2O_4/O_3 nitration fluorobenzene is first order in fluorobenzene, zero order in N_2O_4. By competing reaction, Hamett's equation of N_2O_4-O_3 nitrating substituted aromatics is obtained with logf~R_H=-7.26σ~+_p-0.125. The reaction constant (ρ=-7.26) is approaching to the result of mixture acid nitrating substituted aromatics, which shows the transition state that decides isomer distribution during two kinds of nitrating reaction has similar structure.

94. Hydrogenolysis Debenzylation of TADBIW in Propionic Acid and n-Butyric Acid
LIU Jin-quan,OU Yu-xiang, HAN Wei-rong, CHEN Bo-ren
School of Science of Materials and Engineering,Beijing Institute of Technology, Beijing100081, China)

Abstract: Tetraacetyldibenzylhexaazaisowurtzitane(TADBIW)is a product of hydrogenolysis debenzylation of hexabenzylhexaazaisowurtzitane(HBIW). Various products can be formed from hydrogenolysis debenzylation of TADBIW in different media using Pd catalyst prepared at the lab. Tetraacetylhexaazaisowurtzitane(TAIW)is obtained by hydrogenolysis of TADBIW in propionic acid and n-butyric acid. The related reaction mechanism is also discussed.

95. Development of High Strained Caged Hydrocarbons Used as High Density Fuels
XING En-hui, MI Zhen-tao, ZHANG Xiang-wen
Technology, Tianjin University, Tianjin300072, China)

Abstract: This paper introduces the recent development of a new class of high energy hydrocarbon fuels. These caged hydrocarbons with high energy and high density have been synthesized to be used as high energy fuels or fuel additives, with the expectation that their inclusion in the fuel mixture will result in a net increase in volumetric combustion value of the current generation of power-plants. These caged hydrocarbons exhibit high density and contain a moderate amount of strain energy, which contributes to the energy output during combustion. Research and development direction of caged hydrocarbon fuels are presented.

96. The Synthesis of Hexanitrohexaazaisowutzitane by Oxidation
PANG Si-ping~1, YU Yong-zhong~2, ZHAO Xin-qi~2
1. School of Life Science & Technology Beijing Institete of Technology Beijing 100081, China
2. School of Material Science & Technology, Beijing Institute of Technology, Beijing100081, China)

Abstract: The way of synthesising hexanitrohexaazaisowutzitane(HNIW) by oxidation was studied. HNIW was prepared by hydrolysis and nitration of the oxidation products of hexabenzylhexaazaisowurtzitane in 70% HNO3/AN system with the yield being 21%. The reaction mechanism of the nitration of N-benzoyl group on hexaazaisowutzitane as the parent ring of HNIW was discussed.

97. Synthesis of Keto-RDX Using Dinitrogen Pentoxide as the Nitrating Agent
Cao Duan-lin, Cao Ming-bao, Li Yong-xiang
Dept.of Chemical Engineering, North China University of Technology, Taiyuan030051, China)

Abstract: The synthesis of Keto-RDX with Urotropine, Urea as raw materials, the mixture of nitric acide and dinitrogen pentoxide as nitrating agent was studied. The best process conditions was concluded. Under the conditions the yield of Keto-RDX can be more than 120%. By contrast,with the mixture of nitric acide and dinitrogen pentoxide as nitrating agent, mild reaction condition,higher yield and less contamination are the major advantages.

98. Synthesis and Characterization of Nitrocellulose Azidonitrate Glycidyl Ether
SHAO Zi-qiang, WANG Wen-jun,WANG Fei-jun,CHEN Fan-geng, TAN Hui-ming
School of Materials Science and Engineering,Beijing Institute of Technology,Beijing100081, China)

Abstract: A kind of new high energetic bonder—nitrocellulose azidonitrate glycidyl ether (NCAGE) for solid propellant was synthesized based on cotton cellulose pretreated by steam explosion. The process of preparing NCAGE included the following steps: (a) alkalization of the treated cellulose; (b) etherification of the alkali cellulose; (c) nitration of the water-soluble cellulose ether; and (d) azidation of nitrocellulose glycidol ether. The nitrogen content, structure and properties of NCAGE were measured and characterized by elementary analysis, DSC, FTIR and X ray Diffraction. The results indicate that the nitrogen content of NCAGE can arrive at 15%～21% duo to the presence of - ONO2 and -N3, and the product can absolutely dissolve in solvents such as acetone, decompose at the temperature of 204℃ and has lower degree of crystallinity compared to original cellulose.

99. Nitrosolysis-debenzylation to Tetraacetyldibenzylhexaazaisowurtzitane
L(U••) Lian-ying, OU Yu-xiang, WANG Jian-long
Beijing Institute of Technology, Beijing100081, China)

Abstract: Two benzyls were removed at wild conditions (at room temperature or at 30℃) from tetraacetyldibenzylhexaazaisowurtzitane (TADBIW) molecule through three methods by using inorganic materials as the nitrosolysis reagent to convert tetraacetyldinitrosohexaazaisowurtzitane (TADNSIW), the precursor for synthesis of hexanitrohexaazaisowurtzitane (HNIW). The structure of TADNSIW was determined by FT-IR, MS, (~1H)NMR and element analysis. The mechanism of debenzylation to TADBIW was put forward. The enaminecation is the intermediate of the nitrosolysis-debenzylation to TADBIW, which was approved by benzaldehyde being the by-product of the reaction.

100. The Synthesis of Large Particle Size TATB
HUANG Ming, LUO Shun-huo, TIAN Ye
Insititute of Chemical Materials,CAEP,Mianyang621900, China)

Abstract: The influence factors on synthesis of TATB were described. The parameters affecting particle size of TATB, such as reaction temperature, ammonia flow rate, TCTNB concentration, stirring rate were optimized. The large particle size TATB was produced by the replicate experiment according to the optimized parameters and its average diameter of the particle exceeded 70 μm.

101. Study on HTPB Based PU/PIMA Interpenetrating Polymer Networks
GAO Tong zhai,TAN Hui min
Beijing Institute of Technology,Beijing 100081, China)

Abstract: A new kind of interpenetrating polymer network (IPN) was synthesized by introducing IMA monomer into polyurethane (PU) based on hydroxy terminated polybutadiene in this paper. FTIR results demonstrated that the two monomers reacted completely. Tensile test indicated that the mechanical properties of IPNs were evidently enhanced with the introduction of PIMA. The microstructure of IPN was also investigated by TEM. The results revealed that the two phases interpenetrated proportionally and possessed preferable compatibility.

102. Synthesis and Properties of 3-Azidomethyl-3-nitratomethyloxetane and Its Polymer
GAN Xiaoxian, QIU Shaojun, LU Xianming
Xi′an Modern Chemistry Research Institute, Xi′an 710065, China)

Abstract: 3Azidomethyl3nitratomethyloxetane(AMNMO) was obtained by the cyclization, substitutation and nitration of 2,2dibromomethyl1,3propanediol. Through the cationic polymerization of the monomer AMNMO, a liquid high energetic binder(PAMNMO) was synthesized. The possibility of PAMNMO used as a plasticizer or binder in solid propellants was studied.

103. The Inhibitor of Epoxy Resin with Isocyanurate Group
GAO Chao, GAN Xiaoxian, QIU Shaojun
Xi′an Jiaotong University, Xi′an710049,China)

Abstract: A novel epoxy resin containing isocyanurate group (ISEP) and a novel flexible curing agent (TPA) are synthesized. The mechanical properties of the composite by using biurea as filler are studied. Its tensile strength and elongation are 6.44 MPa and 124.15% at 20℃, 2.68 MPa and 85.24% at 50℃, 7.38 MPa and 24.09% at -40℃, respectively. A propellant is inhibited by this composite. The threeway smoke signature results of the inhibitor show that the transmit ratio of visible light and laser exceeds 80 percent, while 90.4% for IR. The thermal stability of the inhibitor is also studied by TGA.

104. Advance in Hydrazinium Nitroformate(HNF) and HNF Based Propellant
DING Li, LU Dianlin
Xi′an Modern Chemistry Research Institute,Xi′an710065, China)

Abstract: This paper reviews the developments of hydrazinium nitroformate (HNF) and the HNF based propellant. The synthesis,physicochemical properties, crystal structure and sensitivity aspects of HNF are introduced. The potential of HNF based propellants as propulsive force to missiles and space vehicles is also discussed in this paper.

105. A New Way to Synthesize Spherical KDNBF
LI Yufeng, ZHANG Tonglai, MIAO Yanling, ZHANG Jianguo
logy, Beijing100081, China)

Abstract: A new way was introduced to synthesize spherical crystal of potassium 4,6dinitrobenzofuroxanate (KDNBF). Crystal modifiers, such as PVA, Tween 80, Span, NaCMC, Dextrin and Triton X were used to control the shape of KDNBF. Of all the crystal modifiers, Tween 80 behaved most satisfying. The product was characterized by using FTIR, DSC and elemental analysis techniques.

106. Nitrosation of the Oxidation Products of Hexabenzylhexaazaisowurtzitane
LIU Jiangqiang, CHEN Shusen, YU Yongzhong, ZHAO Xinqi
Beijing Institute of Technology, Beijing100081, China)

Abstract: With the nitrosation of the oxidation products of hexabenzylhexaazaisowurtzitane—tetrabenzoyldibenzylhexaazaisowurtzitane (1) and pentabenzoylmonobenzylhexaazaisowurtzitane (2) by 65% HNO3/NaNO2, the remained benzyl groups were removed successfully, and the corresponding nitrosamine products—tetrabenzoyldinitrosohexaazaisowurtzitane (3) and pentabenzoylmononitrosohexaazaisowutzitane (4) were obtained.

107. Hydrolysis of Nitriles with Microwave Irradiation
ZHANG Qingshan, LU Baoping, GUO Bingnan
Beijing Institute of Technology, Beijing100081, China)

Abstract: The hydrolysis of nitriles (benzyl cyanide(1),4hydroxybenzonitrile(2) and 5cyanoindole(3)) to give the corresponding acids (phenylacetic acid(4), 4hydroxybenzoic acid(5) and 1Hindole5carboxylic acid(6)) in the present of alkalis in water coupled with microwave irradiation was investgated. The optimum reaction conditions were determined through the test results. The optimum power of the microwave is 530 W and the optimum time of the reaction is 4 min for 1, 4.5 min for 2 and 7 min for 3, respectively. The yield is 87.9% for 4, 85.8% for 5 and 89.6% for 6 respectively.

108. Nitration of Toluene with NO_2-O_2 System
CAI Chun,LU Chunxu
Nanjing University of Science & Technology,Nanjing210094, China)

Abstract: Toluene can be nitrated effectively with the system consisted of nitrogen dioxide and pressurized oxygen in the presence of inorganic oxides as catalysts, the partial pressure of oxygen has considerable effect on reaction results.The ratio of pMNT in the product could be increased when the pore size of catalyst is similar to the diameter of benzene ring.

109. Synthesis and Properties of 1,7-diazido-2,4,6-trinitro-2,4,6-triazoheptane
ZHANG Zhizhong, WANG Bozhou, SHI Zunchang
Xi'an Modern Chemistry Research Institute, Xi'an 710065, China)

Abstract: 1,7diazido2,4,6trinitro2,4,6triazoheptane was synthesized with urotuopine as primary substance by nitration, chlorization and azido substitution steps in turn, the yield is 75.3%. the properties of DATH have been experimentally studied, its density 1.71 g/cm3, melt point 135～137 ℃, detonation velocity 8300 m/s(1.64), heat of combustion 1.08×104 kJ/kg, temperature of decomposition 192 ℃, friction sensitivity 12%(25 kg/cm2, 66°) impact sensitivity 95%(2 kg, 25 cm).

110. Synthesis of Poly(aminotrinitropolyphenylene)
YU Zhanlong,WU Xiaoqing
North China Institute of Technology, Taiyuan 030051, China)

Abstract: Using polytrinitropolyphenylene(PNP) as initial materials, poly(aminotrinitroPhenylene) (PATNP) has been synthesized. The structure and nature of prepared PATNP has been characterized by FTIR, DTA. The stability of PATNP is better than that of PNP and the sensitivity of PATNP is less than that of PNP. PATNP has potential applications in heat resistant explosives.

111. Oxidation of Derivatives of Hexaazaisowurtzitane
LIU Jiangqiang, CHEN Shusen, YU Yongzhong, ZHAO Xinqi
Beijing Institute of Technology, Beijing100081, China)

Abstract: The oxidative debenzylation of tetraacetyldibenzylhexaazaisowurtzitane in the system of ammonium peroxydisulfate/cerium(Ⅳ) ammonium nitrate/acetic anhydride has been studied. The benzyl group of hexabenzylhexaazaisowurtzitane is removed and tetraacetyldibenzylhexaazaisowurtzitane is successfully synthesized by this method.

112. Synthesis of Nanocomposite Bi_2O_3•SnO_2 and Its Effect on Thermal Decomposition of RDX
HONG Weiliang, ZHAO Fengqi, LIU Jianhong
Shenzhen University, Shenzhen518060, China;)

Abstract: Nanocomposite oxide Bi2O3•SnO2 was synthesized by coprecipitation method using BiCl3 and SnCl4•5H2O as the reactant. The particle size, crystal form and phase were determined with XRD and TEM. Average particle size of samples were about 5 nm. The effect of nanocomposite oxide Bi2O3•SnO2 on the thermal decomposition characteristics of RDX was investigated by DSC. The results show that due to the effect of nanocomposite oxide Bi2O3•SnO2, the peak temperature of thermal decomposition of RDX shifts 13.7℃ downward, the decomposite enthalpy ΔH of RDX increases 665 J/g(about 59.9%), and the apparent activation energy of the thermal decomposition of RDX decreases 48.42 kJ/mol.

113. Characterization of the Structure of Large Particle TATB
HUANG Ming, LUO Shun huo, TIAN Ye
Institute of Chemical Material, CAEP, Mianyang 621900, China)

Abstract: TATB is synthesized in the enclosed high pressure reactor. Anhydrous gaseous ammonia with a feed pressure of 0.42 MPa is allowed to enter the reactor at 155℃. Trichlrotrinitrobenzene is gained in toluene on the liquid vapor interface after 8 hours. The average particle size of the production is above 40 μm,and sixty percent of the particles surpassed 40 μm. The production is proved to be TATB with FT IR, MS, elementary analysis and items defined in GJB3292 98. Its SEM photograph indicates obviously edges, corners and layers structure.

114. Nitrosation of the Oxidation Products of Hexabenzylhexaazaisowurtzitane
PANG Si ping, YU Yong zhong, ZHAO Xin qi
Beijing Institute of Technology, Beijing 100081, China)

Abstract: Nitrosation of the oxidation products of hexabenzylhexaazaisowurtzitane monoacetyltribenzoyldibenzylh exaazaisowutzitane(3),diacetyldibenzoyldibenzylhexaazaisowu tzitane(4) and triacetylmonobenzoyldibenzylhexaazai sowutzitane (5) by 65% HNO3/NaNO2, the remained benzy1 groups were removed successfully and gave the corresponding nitrosamine products monoacetyltribenzoyldinitrosohexaazaisowutzitane(6),diacetyldibenzoyldinitroso hexaazaisowutzitane(7) and triacetylmonobenzoyldinitrosohexaazaisowutzitane(8).

115. Synthesis of TNAZ via Nitromethane
BI Wei yu, LIU Qian, ZHANG Zhi zhong
Xi′an Modern Chemistry Research Institute, Xi′an 710065, China)

Abstract: The title compound, a known melt castable high performance explosive, was synthesized starting with commercially available nitromethane and formaldehyde via a 5 step process. The overall yield was above 40%. Also, the mechanisms of ring closing/dehydration and oxidative nitration were elucidated in light of literatures.

116. Novel Development of Syntheses and Properties of 1,3,3- Trinitroazetidine (TNAZ)
DING Li, LI Ying bo
Xi′an Modern Chemistry Research Institute, Xi′an 710065, China)

Abstract: Review of routes for TNAZ synthesis since 1990 is presented. Properties of TNAZ such as physico chemical properties are introduced also. It is stated that TNAZ is highly energetic material more powerful than RDX, and which is suitable for application as a castable explosive as well as a plasticizer.

117. Synthesis of Lead(Ⅱ) and Copper(Ⅱ) Salts of 4-Hydroxy-3,5- dinitropyridine Oxide
ZHENG Yu mei, DENG Min zhi, ZHAO Feng qi, YUAN Chao
Shanghai Institute of Organic Chemistry Chinese Academy of Sciences,Shanghai 200032, China)

Abstract: The paper describes that synthesis of lead(Ⅱ) and copper(Ⅱ) salts of 4 hydroxy 3,5 dinitropyridine oxide in good yields from pyridine via the multiple steps. The salts were characterized by M.S and microanalysis. DSC and TG experimental results of the salts showed that the salts could effectively catalyze the thermal decomposition of RDX, AP and NC+NG. Meanwhile, the decomposition heats of mixtures containing different salts were larger than those of the corresponding pure RDX, AP and NC+NG. The all facts suggested the salts might be better energetic burning catalysts.

118. Effect of Synthesis Method on Crystal Phase of Iron Oxide Nanocrystalline Powders
LIU Xiang xuan, WANG Xuan jun, LIU Zhen yu, ZHU Ming, LI You
Xi'an Institute of high technology, Xi'an 710025, China)

Abstract: Iron oxide Nanocrystalline Powders were prepared respectively by precipitation, stearic acid gel, polyethylene glycol gel, citrate gel and iron citrate combustion. The influence of synthesis method on the final product, such as the crystal structure, crystalline grain size, dispersivity were studied. XRD results show that the pure α Fe 2O 3, Fe 3O 4 were synthesized respectively by precipitation, ironic citrate combustion, and mixture of α Fe 2O 3 γ Fe 2O 3 were gained by Sol gol method.

119. Fluorodenitration Using Tetramethylammonium Fluoride for Synthesis of Aromatic Fluorine Compounds
CAI Chun, L U•• Chun xu
Nanjing University of Science and Technology, Nanjing 210094, China)

Abstract: Tetramethylammonium fluoride (TMAF) could be used as fluorodenitration reagent in synthesis of aromatic fluorine compounds from nitroaromatics. This process has the advantages of mild reaction condition, high yield and little by reaction.

120. Synthesis and Droperties of 3,3'-dinitroxazafurazan
SHI Yan shan, LI Zhan xiong, OU Yu xiang
Beijing Institute of Technology, Beijing 100081, China)

Abstract: dinitroxazafurazan(DNOAF)was synthesized from 3,4 dinaminofurazan as a non hydrogen energetic compound. Its structure has been identified by IR, NMR, MS and elemental analysis .The standard formation enthalpy, detonation velocity and detonation pressure of DNOAF were calculated to be 640 kJ/mol, 9390 m/s and 40.5 GPa respectively. Calculation shows that the specific impulse is 269.2 s -1 of NEPE propellant by substituting 20% of HMX with the title compound (if HNIW was substituted for HMX , the specific impulse is 268.7 s -1 ).

121. Synthesis of O,O-Bis ( β-azidoethyl)-α-(p-toluenesulfonamido)-Substituted-benzyl Phosphite Esters
YE Ling, ZHOU Yu lan, XU Rui xing
Capital University of Medical Science, Beijing 100054, China)

Abstract: A serial of Mannich compounds,including O,O Bis( β azidoethyl) α (P toluenesultonamido) substituted benzyl phosphite esters and O,O Bis( β,β′ diazidoispropyl) α (p toluenesulfonamido) m nitrobenzy1 phosphite ester,were firstly synthesized and their structures were verified by IR, 1H NMR and element analysis respectively. In addition, the thermostabilities of Mannich bases were analyzed by DTA.

122. Study on the Synthesis of Ultrafine Powder of Lead Carbonate
MA Feng guo, ZHOU Gui zhong, LIAO Shuang quan
Beijing Institute of Technology, Beijing 100081, China)

Abstract: Study on the synthesis of ultrafine powder of lead carbonate. The Ultrafine powder of lead carbonate crystallites was Synthesized by chemical precipitation method. The influences of reaction temperature, reaction time and the ratio of reactants on the formation of lead carbonate crystallites were investigate. The TEM was used to characterize the samples. The graphs TEM shows the product was hexaganal crystal and the size ranges from 1 to 15 micron. The results of show that with chemical precipitation method ,ultrafine powders of lead carbonate can be achieved.

123. Study on the Lab. Synthesis of HMX Using Dinitrogen Pentoxide as the Nitrating Agent
GE Zhong xue, LI Gao ming, HONG Feng, SONG Xin chao
Xi′an Modern Chemistry Research Institute, Xi′an 710065, China)

Abstract: The method of synthesizing HMX is presented in this paper. Using DADN(1,5 diacetyl 3,7-dinitro 1,3,5,7 tetranitrotetrazacycloctane) as reactant, the HMX was synthesized in the nitrating agent of the mixture of dinitrogen pentoxide and nitric acid. The yield of HMX was more than 96%, mp 272.0~272.8℃. In addation, factors that affecting the yield of HMX were discussed preliminely.

124. Study on the Preparation Technique of M-cresol From M-toluidine
HAO Yan xia, CHEN Shu sen
Nanjing University of Science and Technology, Nanjing 210094, China)

Abstract: A new thought for preparing m cresol from m nitrotoluene via reduction, diazotiation and hydrolsis is proposed in this paper. The procedure of synthesizing m cresol from m nitrotoluene is researched mainly and the better reaction condition was acquired by the orthogonal. The yield of m cresol is above 77% under this reaction condition. Moreover, the effect of copper salt on the hydrolysis procedure of diazonium salt is discussed.

125. New Synthesis of TATB in USA
WANG Zhen-yu, GUO Hui-li
Xi′an Modern Chemistry Research Institute, Xi′an 710065, China)

Abstract: Two kinds of new synthesis method of TATB are introduced. Picramide was used as reactant in one method, sonochemically-aminated TATB was synthesised in the other method.

126. Synthesis of Nanometer PbO,Bi_2O_3 and Their Effect on Burning Properties of Solid Propellants
HONG Wei liang, ZHAO Feng qi, LIU Jian hong, TIAN De yu
Department of Chemistry and Biology, Normal College, Shenzhen University, Shenzhen 518060, China)

Abstract: Nanometer PbO and Nanometer Bi 2O 3 were synthesized by solid state reaction using Pb(NO 3) 2, Bi(NO 3) 3 with NaOH at room temperature. The crystal form, particle size and morphology of nanometer PbO and Bi 2O 3 were characterized by XRD and TEM. The effect of two nanometer catalysts on burning Properties of RDX CMDB propellant were investigated. The results show that nanometer Bi 2O 3 can increase the burning rates of the propellant and lower burning rate pressure exponent.

127. Study on Nitrolysis of TADCIW
LIU Li hua, OU Yu xiang, WANG Jian quan, CHENG Bo ren, LEI Xiang yang
Beijing Institute of Technology, Beijing 100081, China)

Abstract: The effects of nitrolysis agents and reaction conditions on the purity and yield of nitrolysis product of tetraacetyldichloroacetylhexaazaisowurtzitane (TADCIW) were investigated, and the related reaction mechanism was discussed. Tetranitrodichloroacetylhezaazaisowurtzitane (TNDCIW) with high purity could be obtained in high yield (94%～98%) by nitrolysis of TADCIW using a mixture of fuming nitric acid and concentrated sulfuric acid or a mixture of alkali metal nitrate and concerntrated sulfuric acid as nitrolysis agents. Besides, the mixture acid from fuming acid and concentrated sulfuric acid could be reused. In the case of nitrolysis agent of a mixture of fuming nitric acid and phosphorus pentoxide or a mixture of concentrated nitric acid and concentrated sulfuric acid, the yield of TNDCIW was quite low(13%～40%).

128. Study on Preparation of Dinitropentmethylenetetramin with Sulfuric Acid Process
BAI Jing rui
Beijing Institute of Technology, Beijing 100081, China)

Abstract: Sulfuric acid and HADN are used as raw materials and formalin as agent for preparation of DPT. Normal design for researching factors (for example, different ratio way to put into, reaction temperature and so on) to affect product yield was applied and a good process conditions are determined. The yield of crude product is advanced from 30% (literature value) to 60%. The purity of product is more than 98%.

129. The Improvement of Synthetical Technics of Tetranitrodibenzo-1,3a,4,6a-Tetrazapentalene
LI Zhan xiong, OU Yu xiang, CHEN Bo ren
Beijing Institute of Technology, Beijing 100081, China)

Abstract: TACOT was synthesized by the improved technics, the time of reaction was shortened to a half, and the operation was predigested. Moreover, the total yields have been increased from 26.7% to 52.0%. This methods reduced the cost of TACOT greatly.

130. Synthetic Principle and Application of Lubricant G for Glass Fiber
REN Chuan rong,LI Tao qi,YAO Yi lun
Xi'an Modern Chemistry Research Institute,xi'an 710065,China)

Abstract: This paper describes a new idea on condenstion reaction principle of dicyanodiamide and formal dehyde according to manufacture of lubricant G for glass fiber, and the synthetic technology and the application are discussed.

131. Synthesis of 2,4,6-Trinitro 2,4,6-triazacyclo-hexanone (Keto RDX)
ZHANG Yue jun
Nanjing University of Science and Technology, Nanjing 210094, China)

Abstract: This paper reports the method of synthesizing 2,4,6 trinitro 2,4,6 triazacyclohexanone (Keto RDX) from DPT (or PHX) and urea (or nitrourea) in several kinds of nitrating agents. There are primary investigations on reaction forms of nitrolysis fragments of DPT, PHX and BSX, and on the mechanism of forming by products. Experimental results showed that the nitrolysis fragments N,N dihydroxymethylamines that were not directly substituted by nitro groups condensed with urea or nitrourea to form Keto RDX, while N, N dihydroxymethylnitroamine did not. Using DPT as a reactant, the yield of Keto RDX was 69% (one mole Keto RDX per mol reactant), and by products were HMX, RDX and small molecule fragments. Using PHX, the yield was 36%, and by products were HMX and small molecule fragments. While using BSX, no Keto RDX product and no cyclonitroamine by products were obtained.

132. Synthesis of Mononitrochlorobenzene by Green Nitration Technology
L U•• Zao sheng, L U•• Chun xu
Nanjing University of Science and Technology, Nanjing 210094, China)

Abstract: Application research of green nitration technology in synthesis of mononitrochlorobenzene is reported in this paper. Reporter find out that the yield of mononitrochlorobenzene in the same reaction time is relevant to preliminary concentration of chlorobenzene and nitrogen dioxide and velocity of oxygen stream, the research results show that the reaction has a evident reaction induction period, yield decrease as reaction time is prolonged, which may result from oxidation of ozone.

133. Synthesis and Nitrolysis of Substituted 2,4,6,8-Tetraazabicyclo[3.3.0]octanes
CAI Chun, L U•• Chun xn
Nanjing University of Science Technohgy, Nanjing 210094, China)

Abstract: Two substituted 2,4,6,8 tetraazabicyclo[3.3.0] octanes have been synthesized from the condensation of formaldehyde, glyoxal, benzylamine and the addition between glyoxal and N,N′ methylenebisacetamide. Bicyclo HMX couldn't be obtained by nitrolysis of these compounds under the normal condition. One probable method for the synthesis of bicyclo HMX has been suggested.

134. The Synthesis of Polynitropolyphenylene
GAN Xiao xian,CUI Yan jun, QIU Shao jun
Xi′an Modern Chemistry Research Institute, Xi′an 710065,China)

Abstract: Using 1,3 dichloro 2,4,6 trinitrobenzene as monomers, polynitropolyphenypene(PNP) were prepared in nitrobenzene by the condensation polymerization. PNP is distiguished by very good thermal stability, non crystallzation and energetic behaviors. It may be used as energetic binding agent of high temperature resistant explosive and propellent.

135. Preparation of Standard Substance of Diphenylamine and its Nitro derivatives
LEI Ming,ZHOU Ji hua,CHEN Shen kun
Xian Modern Chemistry Research Institute,Xian 710065,China)

Abstract: Standard substance of diphenylamine and three kind of nitro derivatives were prepared.Diphenylamine(DPA) was purified from analytical reagent (AR) DPA. 2 Nitrodiphenylamine(2 NDPA) was directly purified from its industrial product.4 Nitrodiphenylamine (4 NDPA) and N nitrosodiphenylamine (NNDPA) were synthesised and then purified. Their pureness deterimined in methods of two different priciples and conformed to the technical norm of first grade military standard substance.

136. A New Method for the Synthesis of 1,4,6,9 Tetranitro 1,4,6,9 tetraazabicyclodecane
Cai Chun Lu Chunxu
Nanjing University of Science and Technology,Nanjing 210094)

Abstract: Tetranitro 1,4,6,9 tetraazabicylo decane has been synthesized by addition, esterfication and condensation from ethylenedinitramine with the yield over 76%。

137. Synthesis and Characterization of Potassium Dinitramide
Lei Ming Zhang Zhizhong Zhu Chunhua
Xi′an Modern Chemistry Research Institute, Xi′an 710065)

Abstract: Potassium Dinitramide (KDN) was synthesized via decyanothylation reaction of N, N dinitro β aminopropionitrile.The pure sample was prepared by recrystalization. The structure of KDN was confirmed by elemental analysis,IR,UV,atom absorption spectrum. The thermal behaviour (DSC) and density of KDN were determined.

138. Study on Nitrolysis of Tetraacetyldinitrohexaazaisowurtzitane(TADN)
Li Li Zhao Xingqi Bai Junhong
Fifth Design & Research Institute,China North Industries Group,Beijing 100053)

Abstract: Seven kinds of nitrating agents,100% HNO 3、P 2O 5/HNO 3、N 2O 5/HNO 3、N 2O 5/HCCl 3、N 2O 5/CH 3NO 2、HNO 3/PPA and HNO 3/HClO 4 were used to nitrolyze TADN,the result shows that none of these nitrating agents is suitable to nitrolyzing TADN to HNIW,and the solube medium was found in the nitrating agents system of HNO 3.

139. A New Method of Synthesizing 1,3,3-Trinitroazetidine
Zhang Jiaoqiang Zhu Chunhua Ma Lan
Xi′an Modern Chemistry Research Institute, Xi′an 710065)

Abstract: A new method is discribed for synthesizing 1,3,3 trinitroazetidine, and the mechanism of nitration reactione of 1 p toluenesulfonylazetidine 3 oxime is discussed.

140. Synthesis and Properties of 2,14-dioxo-5,5,11,11-tetranitro-3,7,9,13-tetraoxapentadecane
Wang Cai Ou Yuxiang Chen Boren Chen Jing
Beijing Institute of Technology, Beijing 100081)

Abstract: The title compound, a polynitro carboxylic ester was synthesized starting with bis(2,2,2 trinitroethyl) formal via a 3 step reaction:denitration, Henry reaction and esterifiction. The structure of the obtained ester was identified by mp, IR, 1 HNMR,MS and elemental analysis. After experiencing a quite number of runs, the synthetic procedure has been improved and discussed. In addition, some important performances of the target compound were measured and are as follows: density 1.57g/cm 3 (suspension method), sensitivity to impact (explosion probability) 0%(drop hammer of 10kg,drop height of 250mm, 25 runs, charge 50±1mg), endothermic peak temperature of thermal decompersition 266.3℃(DTA method).

141. Synthesis of 1-Oxo-4-(p-nitro-benzoyl)methylene-2,6,7-trioxa-1-phosphabicyclooctane
Ye Ling Zhou Zhiming Ou Yuxiang Chen Boren
Beijing Institute of Technology, Beijing 100081)

Abstract: A energetic additive 1 oxo 4 (p nitro benzoyl) methylene 2,6,7 trioxa 1 phosphabicyclo octane(Ⅲ) was synthesized.The molecular structure of the title compound has been confimed by IR, MS and elemental analysis.

142. Preparation of Standard Substance N-Methyl-4-nitroaniline
Zhou Jihua Chen Shenkun
Xi′an Modern Chemistry Research Institute, Xi′an 710065)

Abstract: The standard substance N methyl 4 nitronailine was synthesised from 1 chloro 4 nitrobenzene and puridfied using recrystallization method. The structure and purity were determined by department of analysis of MCRI.

143. Synthesis of 4-Alkyl-4′-bromobiphenyls
Ding Li Shen Ning An Zhongwei Li Zhibin Gao Aiai
Xi′an Modern chemistry Research Institute, Xi′an 710065)

Abstract: Alkyl 4′ bromobiphenyls are useful as liquid crystal intermediate. It was synthesized starting with biphenyl via a 3 step reactin, Friedel Crafts acylation, bromination and Huang Min Lon reduction. The total yeild was 48.6%. The structure of the obtained compound was identified by IR, 1 HNMR and elemental analysis.

144. The Syntheses BAMO/THF Azido Copolymer
Qu Hongxiang Feng Zengguo Yu Yongzhong
Beijing Institute of Technology, Beijing 100081)

Abstract: Bis(azidomethyl)oxetane(BAMO) was prepared by the process of chlorination, ring closing and azido substitution from pentaerythritol. The azido copolymers based on 3,3 bis(azidomethyl)oxetane and tetrahydrofuran(THF) have been synthesized by cationic ring opening polymerization with a Lewis initiator,boron trifluoride etherate(BF 3•Et 2O)and the molecular structure was characterized by IR and 1HNMR. The molecular mass and end group properties were analyzed with GPC and 13 CNMR.

145. Synthesis, Characteristics and Application of DPT with 15 N labelled Atoms
Zhang Yuejun
Nanjing University of Science and Technology, Nanjing 210094)

Abstract: The method that three kinds of nitrogen atoms in different positions of DPT molecule are labelled respectively by 15 N tracer was reported in this paper. DPT with 15 N atoms were characterized through 15 N NMR spectra and Mass spectra. On the basis of these, the forming mechanism of DPT in small molecular method without using acetic anhydrid and of keto RDX in direct method using DPT as a reactant was verified. The obtained results is of a high value in the application of the mechanism researches of DPT nitrolysis and nitrolysis fragments'condensation.

146. Synthesis of 1 Oxo 4 azido methylene 2,6,7 trioxa 1 phosphabilyclooctane
Ye Ling Zhou Zhiming Ou Yuxiang Chen Boren
Beijing Institute of Technology, Beijing 100081)

Abstract: A energetic additive 1 Oxo 4 azido methylene 2,6,7 trioxa 1 phosphabilyclooctane(4) was synthesized. The molecular structure of the title compound has been confirmed by IR, 1 H NMR , MS elemental analysis. Some physical properties of compound(4) including density and thermal decomposition are reported.

147. Hydrolysis of Tetranitro hemi Glycoluril and the Stability of the Product
Dong Shuan Zhang Guozhen
Shandong Teacher's University, Jinan 250014)

Abstract: Hydrolysis of tctranitro hcmi glycoluril(TNHG)was studied under different conditions, it's the first time to find that TNHG could hydrolysis to produce methylene dinitramine, and 1,3 dinitro 4,5 dinitroamino imidazolidine, another hydrolysis product of TNHG, could further hydrolysis to yield methylenedinitramine also.

148. The Method of Choice for Ring Cleavage of 2-(Dinitroethylene)- 4,5-Imidazolidinedione.
Li, Y. [College of Chemical Engineering and Environment, North University of China, Taiyuan 030051, Shanxi (China)], Cao, D. [College of Chemical Engineering and Environment, North University of China, Taiyuan 030051, Shanxi (China)], Fude, R. [College of Chemical Engineering and Environment, North University of China, Taiyuan 030051, Shanxi (China)] and Zheng, L. (2009) [College of Chemical Engineering and Environment, North University of China, Taiyuan 030051, Shanxi (China)], Propellants, Explosives, Pyrotechnics, 34: 480–483.

Abstract: 2-(dinitroethylene)-4,5-imidazolidinedione, which is the intermediate in preparing FOX-7, was synthesized by acetamidine hydrochloride and diethyl oxalate. Ring cleavage reaction could be carried out more quickly, when methanol, water, and formic acid were used as ring cleavage reagents; the disadvantages from using ammonia as ring cleavage reagent could be overcome with yields of up to 65.5%. When water is used as ring cleavage reagent, the reaction rate will be high and the reaction conditions will be milder. So this method is more suitable for further up-scaling research.

149. Combustion Synthesis and Catalytic Activity of LaCoO3 for HMX Thermal Decomposition.
Zhi-Xian Wei [Department of Chemistry and the Institute for Chemical Physics, Beijing Institute of Technology, Beijing, 100081 (P. R. China)], Ying-Nan Chi [Department of Chemistry and the Institute for Chemical Physics, Beijing Institute of Technology, Beijing, 100081 (P. R. China)], Chang-Wen Hu [State Key Laboratory of Explosion Science and Technology Beijing Institute of Technology, Beijing 100081 (P. R. China)], Hai-Yan Liu [Department of Chemistry, Science Institute, North China University, Taiyuan, Shanxi 030051 (P. R. China)], Propellants, Explosives, Pyrotechnics, 34: 394–399.

Abstract: Perovskite-type LaCoO3 was prepared by stearic acid solution combustion method and characterized by XRD, DSC-TG, and XPS techniques. The catalytic activities of LaCoO3 for HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) thermal decomposition were investigated. The as-prepared LaCoO3 shows higher activity than the calcined one. This could be due to higher concentration of surface-adsorbed oxygen and hydroxyl species as well as higher BET surface area of the as-prepared LaCoO3.

150. Synthesis, Thermal Decomposition, and Properties of [Mn(CHZ)3][C(NO2)3]2
Jin Zhang, Tonglai Zhang, Li Yang, Jianguo Zhang [State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing 100081 (P. R. China)], Yan Cui, Xiaochun Hu, Zhenhua Liu [State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing 100081 (P. R. China)], Propellants, Explosives, Pyrotechnics, 34: 24–31.

Abstract: A new coordination compound, [Mn(CHZ)3][C(NO2)3]2, was synthesized and characterized by elemental analysis, IR and UV spectra, and its crystal structure was determined by X-ray single crystal diffraction. The crystal belongs to the triclinic system and space group with a=0.88737(18) nm, b=1.1804(2) nm, c=1.1936(2) nm, β=83.73(3)°, V=1.1121(4) nm3, Z=2, Dc=1.867 g cm−3. Every Mn(II) ion is six-coordinated to three CHZ molecules through three carbonyl oxygen atoms and three terminal nitrogen atoms to form a distorted octahedral structure. Mn(II) ions, carbohydrazide ligand molecules, and trinitromethanide anions are jointed to a complicated three-dimensional netted structure through coordination bonds, electrostatic forces, and extensive hydrogen bonds. The thermal decomposition character and mechanism was studied by DSC, TG-DTG, and FTIR techniques. The non-isothermal kinetics has also been studied on the exothermic decomposition by using Kissinger's method and Ozawa–Doyle's method. In addition, the impact, friction, and flame sensitivity data were determined. All properties data observed show that the title complex has high energy, good thermal stability, and moderately friction sensitivity.

151. A Novel Insensitive High Explosive 3,4-Bis (Aminofurazano) Furoxan
Jun Wang, Jinshan Li, Qinqin Liang, Yigang Huang, Haishan Dong [Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang, Sichuan 621900 (China)], Propellants, Explosives, Pyrotechnics, 33: 347–352.

Abstract: A novel insensitive high explosive 3,4-bis (aminofurazano) furoxan (BAFF) was prepared using 3-amino-4-acylchloroximinofurazan (ACOF) as a precursor. The molecular and crystal structures of BAFF were characterized by IR, MS, 1H NMR, 13C NMR, elemental analysis, and single crystal X-ray diffraction. The single crystal structure of BAFF recrystallized from water is monoclinic, space group P 21/c, and ρc=1.745 g cm−3, and that recrystallized from ethanol is triclinic, space group P 1, and ρc=1.737 g cm−3. BAFF has multiple crystal forms. The calculated detonation velocity by BKW code is 8100 m s−1 (ρ=1.795 g cm−3, theoretical density calculated by quantum chemistry) and the experimental value is 7177 m s−1 (ρ=1.530 g cm−3, charge density). The tested values of impact, friction, and electrostatic spark sensitivity show that BAFF is insensitive.

152. Preparation of ε-HNIW by a One-Pot Method in Concentrated Nitric Acid from Tetraacetyldiformylhexaazaisowurtzitane
Shaohua Jin, Qinghai Shu, Shusen Chen, Yanshan Shi [School of Material Science and Technology, Beijing Institute of Technology, Beijing 100081 (P. R. China)], Propellants, Explosives, Pyrotechnics, 32: 468–471.

Abstract: ε-HNIW was prepared by a one-pot method in concentrated nitric acid from tetraacetyldiformylhexaazaisowurtzitane (TADFIW). γ-HNIW was firstly obtained, then γ-HNIW was directly transformed to ε-HNIW in the solution in which nitration reaction occurred. The acid number of ε-HNIW prepared by the method mentioned above is less than 0.2‰, yield of ε-HNIW is up to 91%, and the purity of ε-HNIW is up to 99.5%. Because steps of filtration and drying of γ-HNIW were omitted, the process by which ε-HNIW was prepared simplified greatly.

153. Synthesis, Thermal Decomposition and Sensitivity Study of CsDNBF
Shaozong Wang, Tonglai Zhang, Li Yang, Jianguo Zhang, Yuanhua Sun [State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Beijing 100081 (P. R. China)], Propellants, Explosives, Pyrotechnics, 32: 16–19.

Abstract: CsDNBF (cesium 7-hydroxy-4,6-dinitro-5,7-dihydrobenzofuroxanide) was synthesized from the sodium salt of DNBF and cesium nitrate. The thermal decomposition process has been investigated and the results show that the solid residues at 240 °C are RCOOCs, CsNCO, RNO2 and CsNO3. The sensitivity results demonstrate that CsDNBF has better properties than KDNBF, which has been widely used.

154. A Novel Synthetic Route to Hexanitrohexaazaisowurtzitane
Si-Ping Pang , Yong-Zhong Yu, Xin-Qi Zhao [School of Material Science and Technology, Beijing Institute of Technology, Beijing 100081, PR China], Propellants, Explosives, Pyrotechnics, 30: 442–444.

Abstract: A new, non-hydrogenolytic synthesis of hexanitrohexaazaisowurtzitane (HNIW, 1) has been investigated. The treatment of hexabenzylhexaazaisowurtzitane (HBIW, 2) with potassium permanganate in acetic anhydride resulted in oxidative debenzylation and acetylation to give tetraacetyldibenzylhexaazaisowurtzitane (TADB, 3a) and other intermediates from the oxidation. Subsequent nitrosolysis and nitrolysis of these intermediates with 65% HNO3/NaNO2 and 70% HNO3/AN produced HNIW in fair yield.

155. Synthesis, Crystal Structure and Theoretical Study of Tetranitrodiazidoacetylhexaazaisowurtzitane (TNDAIW)
Wu Yukai, Ou Yuxiang, Liu Jinquan, Liu Lihua, Chen Boren , Liu Zhiguo [School of Material Science and Engineering, Beijing Institute of Technology, Beijing 100081 (P. R. China). School of Chemistry and Chemical Engineering, Henan University, Kaifeng 475001 (P. R. China)], Propellants, Explosives, Pyrotechnics, 29: 155–159.

Abstract: A novel polycyclic caged compound, tetranitrodiazidoacetylhexaazaisowurtzitane (TNDAIW), has been synthesized by a six-step reaction. The molecular structures of two key intermediates and TNDAIW were identified. The crystal structure of the titled compound was established by X-ray crystallography. Semi-empirical MO calculations were performed with AM1 and PM3 methods based on the crystal structure. The corresponding data of β-CL-20 are also given for comparison.

156. Preparation and Molecular Structure of {[Ca(CHZ)2(H2O)](NTO)2⋅3.5H2O}n
Zhang Tonglai, Lu Chunhua, Zhang Jianguo [State Key Lab of Prevention and Control of Explosion, Beijing Institute of Technology, Beijing 100081, P.R. China], Yu Kaibei [Chengdu Branch, Chinese Science Academy, Chengdu 610064, P.R. China], Propellants, Explosives, Pyrotechnics, 28: 271–276.

Abstract: The title compound {[Ca(CHZ)2(H2O)](NTO)2⋅3.5H2O}n was synthesized by using an aqueous solution of calcium 3-nitro-1,2,4-triazol-5-onate and carbohydrazide (CHZ, NH2NHCONHNH2). Its molecular structure was determined by X-ray diffraction and its crystals have monoclinic form, with space group C2/c, where a=2.4483(4) nm, b=1.2581(2) nm, c =1.6269(3) nm, β=121.168(12)°, V=4.2879(13) nm3, Z=8, dc=1.727 g⋅cm−3, μ (Mo Kα)=3.9 cm−1, M=557.47, F(000)=2312. The coordination polyhedron is a tricapped trigonal prism in a tetradecahedron with a coordination number of nine. The whole molecule has many long chains formed through the carbohydrazide bridges, and every long chain is unlimited along the c axis. The long chains are linked by hydrogen bonds to form the crystal structure.

157. Review on the Nitration of [60]Fullerene
Nai-Xing Wang [Institute of Photographic Chemistry, Chinese Academy of Sciences, Beijing 100080, (PR China)], Propellants, Explosives, Pyrotechnics, 26: 109–111.

Abstract: [60]Fullerenes continued to attract the interest of a broad scientific community since the method of macroscopic synthesis of fullerenes was discovered in 1990. Studies on the nitration of fullerenes have been carried out under different conditions and nitration reagents. The radical (˙NO2) is an excellent reactivity group to make direct multiplet additions with [60]fullerene to get polynitrofullerenes. Radical (˙NO2) can be obtained by many different methods.

158. Modified Preparation and Purification of 3-(2′,4′,6′-Trinitrobenzenyl) Amino-1,2,4-Triazole
Jiarong Li, Boren Chen, Yuxiang Ou [College of Chemical Engineering and Material Science, Beijing Institute of Technology, Beijing 100081 (P.R. China)], Propellants, Explosives, Pyrotechnics, 24: 95.

No abstract is available for this article.

159. Study on the Nitrolysis of Hexamethylenetetramine by NMR-Spectrometry, Part IV: A Novel Mechanism of the Formation of RDX from HA
Zhijie Fang [Nanjing University of Science and Technology, Institute of Chemical Engineering, Jiangsu(P. R. China)], Shaofang Wang, Fuping Li [Xian Modern Chemistry Research Institute, Xian, Shanxi(P. R. China)], Propellants, Explosives, Pyrotechnics, 23: 317–319.

Abstract: The mechanisms of the nitrolysis of hexamethylenetetramine(hexamine or HA) with nitric acid, and with the mixture of nitric acid and ammonium nitrate to form 1,3,5-trinitro-1,3,5-triazacyclohexane(hexogen or RDX) were studied by NMR tracing. It was found that HA immediately disappeared, while RDX was formed gradually, which indicates the formation of some intermediates in the HA nitrolysis to give RDX. The chemical shifts of the peaks in the 1H- and 13C-NMR tracing spectra disagreed with the possible cyclic-structure intermediates proposed by Wright and co-workers. Comparison of the 13C-NMR spectra showed that the nitrolysis fragments in K process can be used to form RDX. Based on the results, structures of intermediates were proposed. All the evidences mentioned above suggested a novel mechanism of the formation of RDX from HA, i.e., the nitrolysis of HA first gives some open-chain methylenenitramine intermediates, and the condensation of the latter gives RDX under certain conditions.

160. Synthesis of 2-Methyl-2-Nitro-1-Azidopropane
Naixing Wang, Jisheng Li [Institute of Chemistry, Academia Sinica, Beijing, 100080(P. R. China)], Boren Chen, Yuxiang Ou [Department of Chemical Engineering, Beijing Institute of Technology, Beijing 100081(P. R. China)], Propellants, Explosives, Pyrotechnics, 23: 46–47.

Abstract: 2-Methyl-2-nitro-1-azidopropane was synthesized through a condensation reaction, substitution reaction and azideation. The molecular structure of the product has been determined by MS, IR and 1H-NMR spectrometries.

161. A Study of β-Azidoethylamino-3-Nitro-1,2,4-Triazole-5-Onate
Dong Shuan, Chen Boren, Ou Yuxiang, Pan Zelin [Department of Chemical Engineering, Beijing Institute of Technology, Beijing 100081(P. R. China)], Propellants, Explosives, Pyrotechnics, 23: 48–49.

Abstract: The title compound(AANTO) has been first synthesized, and its molecular structure and crystal structure have been determined. The preliminary applications in hydroxy-terminated polybutadiene propellant(HTPB) and composite modified double base propellant(CMDB) showed that replacement of part of ammonium perchlorate(AP) or HMX by AANTO could reduce the combustion temperature greatly and improve the specific impulse to some extent.

162. Relationships Between Electron Structures of Substitutive Ureas and their reactivity in Mannich reaction
Yuejun Zhang, Mahong Yu, Weimin Li [School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing, 21 0094 (P.R. China)], Propellants, Explosives, Pyrotechnics, 22: 279–283.

Abstract: The electron structures of urea, substitutive ureas and N-methylolamine with special structure and its imine cation were studied by SCF-MO AM1 computation. The influence of different electronegative substituents on the reactivity of substitutive ureas acting as acid components to react with Mannich reaction intermediates and on the requirement of their reaction conditions were discussed according to the charge density of reaction-centre atoms. The reactivity of imine cations was also discussed on the basis of Frontier Orbital Theory and Bonding Principle. These results showed that the electronegativity of substituents make effects not only obviously on the nucleophilicity of acid components but also on the requirement of media acidity. As the electron-withdrawing ability of substituents increases, the nucleophilicity of nitrogen atom which acts as a reaction-centre in substitutive ureas increases so that they can exist stably in strong acidic media and can condense further with the Mannich intermediate imine cation. These conclusions were confirmed by experimental facts.

163. Synthesis of Trinitrophenyl C60 Derivative
Naixing Wang, Jisheng Li, Gaijiao Ji [Institute of Chemistry, Academia Sinica, Beijing 100 080 (P.R. China)], Propellants, Explosives, Pyrotechnics, 21: 317–318.

Abstract: Trinitrophenyl C60 derivative was synthesized by allowing C60 to react with trinitrochlorobenzene and sodium azide. This fullerene derivative would first provide a brillant prospect in the energetic materials. The product structure was identified by FD-MS, UV-VIS, IR and 13C-NMR.

164. Synthesis of a New Organic Azide: 1,9-Diazido-2,2,8,8-tetranitro-4,6-dioxanonane
Yan Hong,* [Centre of Chemistry and Bioengineering of Cancer, Beijing Polytechnic University, Beijing 100022 (P.R. China)], Guan Xiaopei, Chen Boren [College of Chemical Engineering and Materials Science, Beijing Institute of Technology, Beijing 100081 (P.R. China)], Propellants, Explosives, Pyrotechnics, 21: 231–232.

Abstract: The title compound has been synthesized from its appropriate bis(trinitroethyl)formal. For this compound the molecular structure has been determined, and some of the properties are also reported.

165. Synthesis of 2-Nitro-1,3-Diazidopropane Derivatives
Wang Naixing [Institute of Chemistry, Academia Sinica, Beijing 100080 (P.R. China)], Chen Boren, Ou Yuxiang [Department of Chemical Engineering, Beijing Institute of Technology, Beijing 100081 (P.R. China)], Propellants, Explosives, Pyrotechnics, 21: 233–234.

Abstract: 2-Nitro-1,3-diazidopropane derivatives were synthesized through a condensation reaction, substitution reaction and azideation. The molecular structure of the products have been determined by MS, IR, 1H-NMR.

166. Synthesis of N, N′ -Bis(2, 4-Dinitrobenzofuroxanyl)-3, 5-Dinitro-2, 6-Diaminopyridine
Wang Naixing, Chen Boren, Ou Yuxiang [Department of Chemical Engineering, Beijing Institute of Technology, Beijing 100081 (China)], Propellants, Explosives, Pyrotechnics, 19: 300–301.

Abstract: N,N′-Bis(2,4-dinitrobenzofuroxanyl) -3,5-dinitro-2,6-diaminopyridine has been synthesized from 2,6-diaminopyridine and trinitrodichlorobenzene. For this compound, the structure has been determined by elemental analysis, IR,1HNMR and MS spectroscopies.

167. Synthesis of N,N′-Bis(2-Nitro-Benzodifuroxanyl)-1,3,5-Trinitro-2,6-Diaminobenzene
Wang Naixing, Chen Boren, Ou Yuxiang [Department of Chemical Engineering, Beijing Institute of Technology, Beijing, 100081 (P.R. China)], Propellants, Explosives, Pyrotechnics, 19: 255–256.

Abstract: N,N′-Bis(2-nitro-benzodifuroxanyl)-1,3,5-trinitro-2,6-diaminobenzene has been synthesized from 1,3-diaminobenzene and trinitrotrichlorobenzene. The molecular structure of this compound has been determined by elemental analysis, IR, 1HNMR, and MS spectroscopies.

168. Synthesis of N-2,4,6-trinitrophenyl-N'-2,4-dinitrobenzofuroxano-3,5-dinitro-2,6-diaminopyridine
Wang Naixing, Chen Boren, Ou Yuxiang [Department of Chemical Engineerinf, Beijing Institute of Technolgy, Beijing 100081 (P.R.China)], Propellants, Explosives, Pyrotechnics, 17: 265–266.

Abstract: N-2,4,6-trinitrophenyl-N' -2,4-dinitrobenzofuroxano-3,5-dinitro2,6-diaminopyridine has been synthesied from 2,6-diaminopyridine and dinitrodichlorobenzene as well as 2,4,6-trinitrochlorobenzene. For this compound, the structure has been determined by elemental analysis, IR 1HNMR, and MS spectroscopies.

169. Syntheses of 3,3′ -Disubstituted Polynitrostilbenes
Feng Zeng-guo, Chen Boren [Chemical Engineering and Material Science College, Beijing Institute of Technology, Beijing 100081 (P.R.China)], Propellants, Explosives, Pyrotechnics, 17: 237–240.

Abstract: This paper describes the syntheses of 3,3′-disubstituted tetranitrostilbenes with increasing the electron-donting ability of substituting groups (MeNH > MeO > Cl) on the benzene rings. Two of them are nitrated to form 3,3′ -disubstituted methylnitroamino hexanitrostilbenes. Also observed is that the methylnitroamino group is not converted into the amino group and only the methoxy group can be substituted by the amino group in 3-methoxy-3′-methylnitroamino-2,2′, 4,4′, 6,6′-hexanitrostibene is obtained.

170. Synthesis of 3,3′-Bis(2,2′,4,4′,6,6′-Hexanitortilbene)
Feng Zeng-Gno, Chen Boren [Department of Chemical Engineering, Beijing Institute of Technology. Beijing 100 081 (P. R. China)], Propellants, Explosives, Pyrotechnics, 16: 12–15.

Abstract: This paper describes the synthesis of 3,3′bis(2,2′,4,4′,6,6′-hexanitrostilbene) (5). Based on the Ullmann reaction we prepared the title compound in nitrobenzene by using 3-chloro 2,2′,4,4′,6,6′-hexanitroztilbene (4) as the starting material and copper powder as the catalyst. (4) was reacted with hydrazine, not to yield a desired product, azo-3,3′bist(2,2′,4,4′,6,6′-hexanitrostilbene.) but to form a well-known explosive, 2,2′,4,4′,6,6′-hexanitrostibene (6). Differential scanning calorimetrical analysis has shown that (5) begins to decompose at the temperature of 298°C.

171. Synthesis of 6-Nitro-Tetrafuroxano[b,d,b',d']Biphenyl
Chen Boren, Liao Zhiyuan [Department of Chemical Engineering, Beijing Institute of Technology, Beijing 100 081 (P. R. China); *Correspondence: Chen Boren, Department of Chemical Engineering, Beijing Institute of Technology, Beijing 100 081 (P. R. China)], Propellants, Explosives, Pyrotechnics, 15: 97–98.

Abstract: 6-Nitro-tetrafuroxano[b,d,b',d']biphenyl has been synthesized from 3,5,3′,5′-tetrahalogenobiphenyl (halogeno = chloro, bromo). For this compound the molecular structure has been determined by elemental analysis, I.R., 'H-N.M.R., and Mass spectroscopies, some of the properties, including density ((ϱ = 1.80 g/cm3)), are also reported.

172. Synthesis of Polynitrocompounds from Nitroguanidine†
Yu Yongzhong, Su Zhuang [Department of Chemical Engineering, Beijing Institute of Technology, Beijing, 100081 (P. R. China)], Duan Baoru, Chen Fubo [Gansu Institute of Chemical Engineering, Lanzhou (P. R. China)
†This paper was read at the International Symposium of Pyrotechnics and Explosives, Beijing, China, 1987.], Propellants, Explosives, Pyrotechnics, 14: 150–152.

Abstract: The reactions of nitroguanidine (NG) with urotropine or formaldehyde have been studied. The following compounds are synthesized from NG:
(a) 6-nitroimino-1,3,5-trinitro-1,3,5-triazacyclohexane [2] and a number of itsderivatives;
(b) bis(nitroguanidino)methane [9], a valuable intermediate for preparing some high explosives;
(c) 1,5-dinitro-2,4-dinitroimino-1,3,5triazacyclohexane [10] and some of its derivatives via intramolecular cyclization of [9];
(d) 2-nitroimino-1,3-diaza-5-oxacyclohexane [15], 1-(nitroguanidinomethyl)-2-nitroimino-1,3-diaza-5-oxacyclohexyl [14], and bis(2-nitroimino-1,3-diaza-5-oxacyclohexyl)methane [16] by reactions of [9] with formaldehyde.
Some detonation data of the above compounds are reported. Campounds [2] and [10] are powerful explosives but very unstable thermally and easily hydrolized. However, compounds [14], [15], and [16] possess a better stability than triazacyclic polynitrocompounds containing nitroimino groups, such as [2] and [10].

173. Use of NMR spectrometry for studying the acetolysis of hexamethylenetetramine III. The reaction between hexamethylenetetramine and acetic anhydride to form TRAT†
Wang Shaofang, Chen Ju, Li Fuping [Xian Modern Chemistry Research Institute, Xian, Shaanxi (PRC)], Propellants, Explosives, Pyrotechnics, 12: 41–45.
†Projects supported by the Science Fund of the Chinese Academy of Sciences.

Abstract: The acetolysis of hexamethylenetetramine (HA) to form 1,3,5-triacetyl-1,3,5-triazacyclohexane (TRAT) has studied by NMR. It was found that this reaction experienced two different courses. HA turned to TRAT through the intermediate 3,7-diacetyl-1,3,5,7-tetraaza-[3.3.1]-bicyclononace (DAPT), and HA converted at first to an intermediate M1, which gave TRAT through another intermediate M2 in the presence of water. Based on the 1H and 13C spectra, the change in the spectra with reaction and the possibility of reaction, we assumed both the structure of M2 and its reaction mechanism.

174. Use of NMR Spectometry for studying the acetolysis of hexamethylenetetramine. I. The reaction of TAT formation from DAPT
Chen Ju, Wang Shao-Fang [Xian No. 3 Chemical Industrial Institute, Shan Xi, Xian (PRC)], Propellants, Explosives, Pyrotechnics, 9: 58–63.

Abstract: The reaction of forming TAT from DAPT was followed by 1H NMR spectroscopy. This investigation shows that water or ammonium acetate quickens the reaction and they do take part in the reaction. Reaction intermediates were detected and according to the information obtained by NMR, their structures were postulated to be X or X1 in the absence or presence of water respectively.
The kinetic study further indicated that acetylation of X1 to TAT is first order in X1 and in acetic anhydride. In other words, it is a bimolecular reaction. The rate constant k was found to be 1.46 × 10−4 mol−1 • s−1.

175. Novel Nitrocellulose Made from Bacterial Cellulose.
Dong-Ping Sun, Bo Ma, Chun-Lin Zhu, Chang-Sheng Liu, Jia-Zhi Yang[Bioengineering Department, Institute of Chemical Engineering, Nanjing University of Science and Technology, Nanjing, China], Journal of Energetic Materials; Apr-Jun2010, Vol. 28 Issue 2, p85-97

Abstract: Nitrocellulose (NC) is useful in several industrial segments, especially in the production of gun, rocket, and missile propellants. The conventional way to prepare NC is done through the nitration of plant cellulose with nitric acid. In this work, bacterial cellulose nitrate (NBC) is synthesized by bacterial cellulose (BC) and nitro-sulfric acid under heterogeneous conditions. NBC with the degree of substitution (DS) of 1-2.85 was obtained, and the effects of sulfuric to nitric ratio, reaction temperature, and reaction time on the value of DS of NBC are discussed. The samples are also characterized by elemental analysis, thermal analysis, Fourier transform infrared (FT-IR) spectroscopy, and X-ray diffraction.

176. Synthesis of RDX Catalyzed by Brønsted Acidic Ionic Liquids.
Cheng, G., Li, X., Qi, X., Lu, C. [School of Chemical Engineering, Nanjing University of Science & Technology, Nanjing, Jiangsu, People's Republic of China.], Journal of Energetic Materials; Jan-Mar2010, Vol. 28 Issue 1, p35-44

Abstract: The experimental study was carried out on the direct nitrolysis of hexamethylenetetramine (HA) to synthesize hexahydro-1,3,5-trinitro 1,3,5-triazine (RDX) with nitric acid (95%) catalyzed by Brønsted acidic ionic liquids. Various ionic liquids, such as [HMim]X, [(CH2)4SO3HMim]X, and [(CH2)4SO3HPy]X (X- = pTSO-, [image omitted], CF3COO-), and various parameters, such as equivalents of ionic liquid, mass ratio of nitric acid (95%) to the starting material, and reaction time, were investigated. Ionic liquid [(CH2)4SO3HPyr]NO3 showed good catalytic activity. In the presence of 3.0% mol ratio [(CH2)4SO3HPyr]NO3 ionic liquid to HA, the yield of RDX was improved by 10.5% compared to the system without ionic liquid.

177. Synthesis of 1-oxo-4-hydroxymethyl-2,6,7-trioxa-1-phosphabicyclo[2,2,2] octane derivatives
Ye Ling, Zhou Zhiming, Ou Yuxiang, Chen Boren [College of Chemical Engineering and Materials Science, Beijing Institute of Technology, Beijing, (P. R. China)], Journal of Energetic Materials, Volume 17, Issue 2 & 3 June 1999 , pages 297 - 300

Abstract: Three 1-oxo-4-hydrorymethyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2] octanc energetic derivatives were synthesized. The molecular structure of the products has been confirmed by MS, IR, 1H NMR and elemental analysis. Some physical properties of these products including density and thermal decomposition are reported.

178. Synthesis of new azide: 1,3,5,-tris[(azidomethyl) dinitromethyl]benzene
Yan Hong [Centre of Chemistry & Bioengineering of Cancer, Beijing Polytechnic University, Beijing, (P. R. China) ], Guan Ziaopei [College of Chemical Engineering and Materials Science, Beijing Institute of Technology, Beijing, (P. R. China) ], Chen Boren [College of Chemical Engineering and Materials Science, Beijing Institute of Technology, Beijing, (P. R. China) ], Journal of Energetic Materials, Volume 16, Issue 1 March 1998 , pages 23 - 29

Abstract: 1,3,5-Tris[(azidomethyl)dinitromethyl] benzene has been synthesized from tripotassium salt of 1,3,5-tris(dinitromethyl)benzene in three steps. It's structure has been established with the help of elemental analysis, IR, 1H-NMR, and Mass spectroscopies. Thermal decomposition of the title compound has been studied by DTA, and some other properties are also reported.

179. Synthesis of polynitro and azido diesters of pentacyclo[4.3.0.02,5.03,8.04,7]nonane-2,4-dicarboxylic acid
Xiao-Pei Guan, Zhuang Su [School of Chemical Engineering and Materials Science Beijing Institute of Technology, Beijing, P. R. China], Jian-Wei Du [School of Chemical Engineering and Materials Science Beijing Institute of Technology, Beijing, P. R. China], Jian-Guang Sun [School of Chemical Engineering and Materials Science Beijing Institute of Technology, Beijing, P. R. China], Yong-Zhong Yu[School of Chemical Engineering and Materials Science Beijing Institute of Technology, Beijing, P. R. China], Journal of Energetic Materials, Volume 15, Issue 2 & 3 June 1997 , pages 139 – 149

Abstract: Homocubane-2,4-dicarboxylic acid (6) was synthesized starting from cyclopentadiene and 2,5-dibromobenzoquinone (3). Six polynitro and azido diesters of 6 were also synthesized as advanced energetic plasticizers. The results of DTA indicated that these compounds (8a—8f) are quite thermally stable.

180. Studies on reactions of polynitrostilbenes with sodium azide
Feng Zengguo; Chen Boren [Department of Chemical Engineering Beijing, Institute of Technology, Beijing, People's Republic of China], Journal of Energetic Materials, Volume 12, Issue 4 December 1994 , pages 237 - 247

Abstract: Three polyazidonitrostilbenes were prepared via the reaction of polynitrostilbenes with sodium azide. Addition of 2 mole of this nucleophile to a solution of 3-chloro-2,2', 4,4',6,6'-hexanitrostilbene in DMF results in the substitution of azido groups for one nitro group and the chlorine in the same benzene ring. The reactions of 2,2',4,4',-6,6'-hexanitrostilbene with 2 and 4 mole of NaN3 exhibit a different reactivity and selectivity and produce symmetrically substituted azido polynitrostilbenes.

181. Synthesis OF N,N1-BIS(2-nitro-benzodifuroxanyl) -3,5-dinitro-2,6-diaminopyridine
Wang Naixing, Chen Boren; Ou Yuxiang [Department of Chemical Engineering, Beijing Institute of Technology, Beijing, China], Journal of Energetic Materials, Volume 11, Issue 1 March 1993 , pages 47 - 50

Abstract: N,N1-bis(2-nitro-benzodifuroxanyl)-3,5-dinitro-2,6-diaminopyridine has been synthesized from 2,6-diaminopyridine and trinitrotrichlorobenzene, Yields of 80 - 90% were obtained under extremely mild reaction conditions. For this end compound,The structure has been determined by elemental analysis,IR, 1HNMR, and MS spectroscopies.

182. Synthesis of 2, 4-Dinitroimidazole by Microwave Heating
Liu Hui-Jun, Fan Yue-qin, Feng Feng, Meng Shuang-ming, Guo Yong, Lu Zhen and Cao Duan-lin, Chinese journal of energetic materials,2010,18(1):1~3

Abstract: For synthesis of 2,4-dinitroimidazole(2,4-DNI) from the rearrangement of 1,4-dinitroimidazole(1,4-DNI),microwave heating instead of conventional heating can improve yield of the product and shorten the reaction time from 4~50 h to 10 min. The authors investigated the effects of microwave power for heating,reaction time,solvent type and concentration of 1,4-DNI in chlorobenzene on the yield of 2,4-DNI. Based on this investigation the optimal rearrangement conditions would be as follows: microwave power: 375 W, heating time: 10 min,solvent: chlorobenzene,concentration of 1,4-DNI: 10%. Under the conditions listed above,the yield of resulting 2,4-DNI can be up to 95% with a melting point of 265-268°C(decomposition).

183. Synthesis of Furoxano derivatives using Dimerization reaction
Li Ya-nan, Zhang Zhi-zhong, Zhou Yan-shui, Ji Yue-ping and Wang Ying lei, Chinese Journal of energetic materials, 2010, 18(1):7-10

Abstract: 3,4-Diphenylfuroxan and four no-reported compounds 3,4-bis(pyridine-2'-yl)furoxan, 3,4-bis(pyridine-3'-yl)furoxan, 3,4-bis(pyridine-4'-yl)furoxan and 3,4-bis(pyrazine-2'-yl)furoxan were self-designed and synthesized using chloride oxime-based compounds as starting materials and the synthetic method of dimerization reaction of cyanide oxidation. The structures of target compounds were characterized by IR, NMR, MS and elemental analysis. The effects of different substituents, different catalysts,reaction temperature on the synthesis of furoxan derivatives using dimerization reaction were preliminarily investigated. Results show that the electron withdrawing ability of substituents is stronger,the structure of cyanide oxidation is more easily generated,and the yields of target products are higher. The inorganic weak base(for example Na2CO3, KHCO3) is usually chosen as catalyst. The reaction temperature is usually controlled at 2-10 °C. Under the optimal conditions, the yields of target compounds are 64.7%, 71.3%, 70.0%, 71.1% and 75.6%, respectively.

184. Synthesis of 2-Methyl-2-nitro-1 ,3-diazido-propane
Wang Ying-lei, Ji Yue-ping, Li Pu-rui, Chen Bin and Lan Ying, Chinese Journal of energetic materials, 2010, 18(1): 11-14

Abstract: 2-Methyl-2-nitro-1 ,3-diazido-propane (NMPA) can be used as a low-molecular plasticizer of propellants and as an ingredient of gas generators. NMPA was mentioned in literatures, but its detailed synthesis procedures were not reported. The authors synthesized NMPA via a self designing process that consistes of three steps, i.e. condensation, sulfonation and azido-substituition, using nitroethane and formaldehyde as starting materials. Based on this investigation, the optimal reaction conditions were determined: temperature 93 ~ 95 °C, reaction time 30 h, medium DMSO, which made NMPA’s yield (based on nitroethane) upto 71.5% and 99% purity. Some of the properties of NMPA were measured are as follows: ρ = 1.28 g • cm ~ ( -3), T_g (DSC) =- 51.5 ?, T_p (DSC) = 234 ?, the impact sensitivity was 34 cm, friction sensitivity of 32%.

185. Clean Procedure for Synthesis of Substituted Diphenyl Ethers via Williamson Reaction in Ionic Liquid
FANG Dong1,2,JIAO Chang-mei1,ZHANG Hua-bin1,LIU Zu-liang2(1.Jiangsu Provincial Key Laboratory of Coastwetland Bioresources & Environment Protection,Yancheng 224002,China;2.School of Chemical Engineering,Nanjing University of Science & Technology,Nanjing 210094,China), Chinese journal of energetic materials, 2010, 18(1): 15-18

Abstract: Substituted diphenyl ethers(SDE) belong to an important fine chemical intermediates which can be synthesized via Williamson reactions.Room-temperature ionic liquid(RIL) as solvent could realize clean procedure of SDE's synthesis.The authors prepared a RIL of 1-butyl-3-methyl imidazolium hexafluorophosphate(BMIMPF6),and synthesized a series of SDEs from substituted nitrobenze and phenol via Williamson reaction by use of BMIMPF6 as green solvent and K2CO3 as catalyst.Some factors affecting the etherification,such as temperature,time and catalysts etc,were studied,and the relatively optimal reaction conditions were worked out:molar ratio of reaction material/catalyst=1/1(molar),T=100 °C,t=1 h.Under the above procedures the yield of resulting SDEs could be 70%-93%,and the structural confirmation was done by 1H NMR,13C NMR and MS.One additional point should be emphasized that the RIL could be reused at least 5 times without noticeably deteriorating SDE's yield and purity.This is beneficial to environmental protection.

186. Preparation of Nanosolid Superacid and Synthesis of 2,4,N-Trinitroanilinoacetic Acid Directly
Xi Li-min and Zhang Xin-xin, Chinese journal of energetic materials, 2010, 18(1):19-23

Abstract: The new nanosolid superacid catalyst TiO_2/SO_4~(2-) was prepared by sol-gel method,and samples were characterized by acid base titration,XRD and TEM. Results show that the superfine solid TiO_2/SO_4~(2-) is nanocrystal with good dispersibility and its average size is 27 nm. With the catalyst TiO_2/SO_4~(2-),2,4,N-trinitroanilinoacetic acid(TNAA) was synthesized from chlorobenzene and glycine with yield of 71.6%. The optimum conditions are 0.2 mol chlorobenzene,and 0.7 g catalyst,and 0.07 mol glycine,and 0.08 mol nitric acid,and reaction time of 3 hours,and reaction temperature of 45 °C. When calcined at 600 °C,the activity of regeneration catalyst is restored mostly after regenerated eight times.

187. Synthesis and Characterization of Polyepichlorohydrin with Terminal Hydroxyl
Sun Zhao-ren, Gu Yao and Sun Dong-dong, Chinese Journal of energetic materials, 2010, 18(1):24-28

Abstract: Using emulsion double metal cyanide(EDMC) complex instead of Lewis acids etc as catalyst the hydroxyl terminated polyepichlorohydrin(PECH) with high relative molecular mass(MW) and narrow distribution was synthesized by ring-opening polymerization of epichlorohydrin(ECH).The PECH obtained can be used to prepare energetic azide binders with top quality.The key factors influencing the ECH's polymerization were studied,including initiators,addition method of monomer,dosage of catalysts,and reaction time.Results show that the functionality of PECH varies as types of initiators.The increase of catalyst dosage and the rise of reaction temperature result in higher MW of PECH.To add the monomer droprise continuosly could be helpful to improve the polymerization.The yield of PECH reaches more than 95% on the conditions listed below:bisphenol A as initiator,catalyst dosage of 0.05%(based on resulting PECH mass),reaction temperature of 128 °C.The MW of PECH can be adjusted by varying the molar ratio of monomer to initiator.The functionality of the synthesized PECH was calculated based on f=(OH value/MW)/56100 and found to be of 2-3.The PECH structure was identified by FTIR,1H NMR,and GPC.

188. Synthesis and Characterization of 3-Amino(nitro)-5-nitro-1,2,4-triazole derivatives
ZHANG Hai-hao,JIA Si-yuan,WANG Bo-zhou,XIONG Cun-liang,WANG Xi-jie(Xi'an Modern Chemistry Research Institute,Xi'an 710065,China) , Chinese Journal of Energetic materials, 2010, 18(1):29-33

Abstract: Two new heat-resistant explosives of 1-picryl-3-amino-5-nitro-1,2,4-triazole(TNTA-TNB) and 4-picryl-3,5-dinitro-1,2,4-triazole(DNT-TNB) were synthesized via condensation of 3-amino-5-nitro-1,2,4-triazole(ANTA)(or ammonium 3,5-dinitro-1,2,4-triazole(ADNT)) with 2,4,6-trinitrochlorobenzene.The condensation mechanism was explored and discussed.The effects of some key reaction conditions,such as media,temperature,time and catalysts,on condensation were investigated.The explosive synthesis was carried out at 70 °C,8 h in DMF and NaF as catalyst.IR,NMR and elemental analysis confirmed the synthesized compound structures.In addition,we imroved the synthetic process of 2,4,6-tris(3-amino-5-nitro-1,2,4-triazole-1-yl)-1,3,5-triazine by means of direct reaction of ANTA with 2,4,6-trichloro-1,3,5-triazine omitting the preparation of ANTA-Na and without using phase transfer catalyst,lowering the production cost,simplifing the procedure,and improving the reaction safety.

189. Synthesis of Nitrate Ester Explosives in Micro Reactor
Han Jun-qi, Meng Zi-hui, Meng Wen-jun, Chen Guang-wen, Wang Bo-zhou and Ge Zhong-xue, Chinese Journal of Energetic Materials, 2010, 18(1):34-36

Abstract: Nitrate ester explosives were synthesized in chip based micro reactor. When alcohol and nitric-sulfuric mixed acid are mixed in the micro reactor, the yield of triethylene glycoldinitrate (TEGN) is 86.39%,and the yield of diethylene glycol dinitrate is 90.60%. The effects of the ratio between nitration agent and raw material, and the effect of liquid hourly space velocity (LHSV) on the reaction were studied. The results show that when the ratio of acid/alcohol is low, the yield of nitrate explosives decreases with the increase of LHSV, however, when the mole ratio of acid/alcohol increased for a certain, the yield of the product did not change significantly with the decrease of LHSV. And the optimal mole ratio of nitric acid/alcohol for diethyleneglycol is 5, and for triethylene glycol is 4.

190. Synthesis Technique of 2-Methyl-6-nitroaniline
QI Lei ,PANG Si-ping ,SUN Cheng-hui , chinese journal of energetic materials,2009,17(1):4~6 ,10

Abstract: The synthesis technique of 2-methyl-6-nitroaniline was studied. In previous method, acetylation and nitration of 2-methylaniline were completed in one pot, but the nitration reaction temperature was difficult to be controled. To improve the method, the acetylation and nitration were detached into two parts. The structure of the product, its by-product and its intermediate were characterized by IR,NMR and MS. The results show that the temperature of nitration process can be controlled easily,and the yield is 59.4% and the purity is up to 99.68%.

191. Synthesis and Crystal Structure of 2,2',5,5'-Tetrachloro-1,1'-azo-1,3,4-triazole
LI Sheng-hua ,SHI Hong-gang ,SUN Cheng-hui ,LI Xiao-tong ,PANG Si-ping ,YU Yong-zhong ,ZHAO Xin-qi ,Chinese journal of energetic materials,2009,17(1):7~10

Abstract: 2,2',5,5'-tetrachloro-1,1'-azo-1,3,4-triazole (1) was synthesized by reaction of 4-amino-1,2,4-triazole and sodium dichloroisocyanurate (SDCI). Its structure was determined by X-ray single crystal diffraction. It crystallizes in the triclinicspace groupP-1,with a=6.2824(13)?,b=7.7173(15)?,c=10.443(2)?,α =89.16(3)°, ß=88.20(3)°, γ=89.10(3)°, V=505.94(18) ?3,Z=2,Mr=301.92, DC =1.982 mg•m -3,F(000) =296 and µ (MoKα)=1.152 mm-1,the final R=0.0498 and wR =0.1139. X-ray analysis reveals that a stronger p interaction of the triazole units with the tetrazene moiety,

192. Synthesis and Characterization of 3-Allyl-5,5-dimethylhydantoin
ZHANG Li-na, YANG Rong-jie , chinese journal of energetic materials,2009,17(1):19~22

Abstract: Bonding agent is functional component to improve mechanical properties of solid propellant. A new bonding agent,3-allyl-5,5-dimethylhydantoin(ADMH) was synthesized by the Gabriel method. The condition of the reaction was n(DMH): n (allylbromine): n (methyl alcohol solvent of KOH)=1: 1: 1,and water was used as solvent. The yield of ADMH is 50% and its purity is 99.97%. Chemical structure of ADMH was identified by TG-DTA,UV,NMR,FT-IR and MS etc. Melting point of ADMH is 65-66 °C and its decomposition temperature is 168.3 °C.

193. Synthesis of Unsymmetrical Nitrofurazanyl Picryl Ether
QIU Shao-jun,GE Zhong-xue,JIANG Jun,WANG Xi-jie,LIAN Peng and GAN Xiao-xian, chinese journal of energetic materials,2009,17(1):124~

Abstract: An unsymmetrical nitrofurazanyl polynitrobenzene ether was synthesized via Williamson reaction and the structure was confirmed by NMR,FTIR and elemental analysis. Some properties of the compound,such as density,heat of formation,oxygen balance,detonation velocities and detonation pressures were calculated

194. Synthesis and Blending of High-density Hydrocarbon Fuels with Density Beyond 1.0 g•cm-3
WANG Lei,ZHANG Xiang-wen,ZOU Ji-jun,HAN Hong,WANG Li and MI Zhen-tao, chinese journal of energetic materials,2009,17(2):157~160

Abstract: Three high-density hydrocarbons with molecular structure of C10H16 (C10), C15H22 (C15) and C20H28 (C20) were synthesized using dicyclopentadiene as feedstocks. The density of the fuels increases in the order of C10,C15 and C20,whereas the low-temperature properties show the inverse tendency. To obtain higher density and acceptable low-temperature property,binary and ternary blendings of them were prepared. The dependence of density and viscosity on the composition of blends was analyzed,and an equation was established to predict the density of blendings. C10 can improve the low-temperature of blendings,whereas C20 can enhance the density. According to the density-viscosity-composition ternary diagrams,an optimized blending composition of C15=75wt%,C20=20wt% and C20=5wt% was determined. The resulting fuel has density larger than 1.0 g•cm-3 (15 °C),volume heat larger than 42.0 MJ•L-1,viscosity smaller than 500 mm2•s-1 (-40 °C),and pour point smaller than -70 °C, which is very promising for propulsion applications

195. Synthesis of 2,6-Diamino-3,5-dinitropyridine-1-oxide
CHENG Jian,YAO Qi-zheng and LIU Zu-liang, chinese journal of energetic materials,2009,17(2):166~168

Abstract: 2,6-Diamino-3,5-dinitropyridine-1-oxide (ANPyO) was synthesized with 2,6-diaminopyridine as a starting material by acetylation, N-oxidation, nitration and hydrolysis steps in turn, and the yield of ANPyO was up to 81%. The main factors affecting the acetylation, N-oxidation and nitration were investigated, and the structures of intermediates and ANPyO were characterized by 1H NMR,MS and IR spectra

196. Adsorption of TNT using Beaded Molecularly-imprinted Polymer
ZHANG Qiu-yue,MOU Jing-hai,MENG Zi-hui,HUANG Ying and WANG An, chinese journal of energetic materials,2009,17(2):249~250

Abstract: Molecular imprinting is a promising technology in molecular recognition. Beaded molecularly-imprinted polymers(MIPs) were synthesized by using suspension polymerization methods. MIPs were packed into a flash chromatograph column to simulate adsorptive reactor,performance parameters obtained can be applied for scale-up experiment.

197. Synthesis and Characterization of Nitro Fulleropyrrolidine Derivatives
JIN Bo,PENG Ru-fang,TAN Bi-sheng,HUANG Yi-min,SHU Yuan-jie,CHU Shi-jin and FU Yi-bei, chinese journal of energetic materials,2009,17(3):287~292

Abstract: Six nitro fulleropyrrolidine derivatives were synthesized by the 1,3-dipolar cycloaddition reactions of [60]fullerene and the nucleophilic substitution reaction of N-unsubstituted fulleropyrrolidine. The structures of the products were characterized by ultraviolet-visible spectroscopy(UV-Vis),Fourier transform infrared spectrometer(FT-IR),mass spectrometry(MS) and 1H,13C nuclear magnetic resonance(NMR) techniques. The effects of the different products on the impact sensitivity and friction sensitivity of HMX were tested. The friction and impact sensitivities of HMX reduces from 100% to 48% and to 50%,respectively when 1% N-methyl-2-(3-nitrophenyl)fulleropyrrolidine 2 added in HMX.

198. Synthesis and Characterization of 4-Amino-3,5-dinitropyrazole(LLM-116) Condensation Products
WANG Bo-zhou,WANG Ying-lei,ZHANG Zhi-zhong,XIONG Cun-liang and ZHANG Ye-gao, chinese journal of energetic materials,2009,17(3):293~295

Abstract: Taking 2,4,6-trinitrochorobenzene,2,4,6-trichoro-1,3,5-triazine and 4-amino-3,5-dinitropyrazole(LLM-116) as primary substances,1-(2,4,6-trinitrobenzene-1-yl)-4-amino-3,5-dinitro-pyrazole(I) and 2,4,6-tri(4-amino-3,5-dinitropyrazole-1-yl)-1,3,5-triazine(II) which have not been reported in the literature were synthesized by condensation reaction. Their structures were confirmed by IR,NMR and element analysis,and their melting point are 234-236 °C,296.5 °C(dec.),respectively. The condensation reaction mechanism was discussed,and the optimal reaction conditions synthesizing 2,4,6-trichoro-1,3,5-triazine are as follows: reaction medium is N-methyl-2-pyrrolidone(NMP),temperature is 70 °C and time is 16 h

199. Synthesis of Nitroglycerin with N2O5
WANG Qing-fa,SHI Fei,ZHANG Xiang-wen,WANG Li and MI Zhen-tao, chinese journal of energetic materials,2009,17(3):304~306

Abstract: The green synthesis of nitroglycerin from nitration of glycidol with dinitrogen pentoxide (N2O5) as the nitrating agent was studied by investigating the effects of different parameters on the nitration of glycidol. Results show that H-ZSM-5 has good catalytic activity,and the preferred catalyst concentration is 15 g•L-1,and the molar ratio of dinitrogen pentoxide to glycidol is 3:1 and the temperature is 15 °C. After reaction for 4 h under the above conditions,the selectivity of 100% and yield of 91.1% for nitroglycerin were obtained.

200. Progress in Imidazolium-based Energetic Compounds
YANG Li,GAO Fu-lei,FAN Qing-tao and ZHANG Tong-lai, chinese journal of energetic materials,2009,17(3):374~379

Abstract: The status and development of 2,4-dinitroimidazole,4,5- dinitroimidazole,2,4,5-trinitroimidazole,azidoimidazole and their derivatives were summarized,and the aspect of the development of energetic imidazole compounds was also prospected.

201. Synthesis and Crystal Structure of 3,3'-Dicyano-4,4'-azofurazan(DCAF)
FAN Yan-jie,WANG Bo-zhou,ZHOU Yan-shui,JIA Si-yuan and HUO Huan, chinese journal of energetic materials,2009,17(4):385~388

Abstract: 3,3'-Dicyano-4,4'-azofurazan (DCAF) was synthesized from 3-amino-4-aminoxim-idofurazan (AAOF) through two-step oxidization and the product was characterized by IR, NMR and elemental analysis. The crucial factors of KMnO4 oxidization reaction were studied and the optimal reaction conditions were confirmed. The single crystal of DCAF was cultivated for the first time and tested by single-crystal X-ray diffraction. The crystal is triclinic, space group P-1 with crystal parameters a=1.8297(11) nm, b=0.588(3) nm, c=0.9069(5) nm, V=0.8853(9) nm-3, Z=4,Dc=1.622 g•cm-3, F (000)=432, µ (Mo Ka )=0.131 mm-1, R1=0.1039, wR =0.2420.

202. Synthesis,Characterization and Performance of [Co(C2H6N6S)]ClO4•2H2O
Wang Yan-lan,SHENG Di-lun,ZHU Ya-hong,MA Feng-e,CHEN Li-kui and YANG Bin, chinese journal of energetic materials,2009,17(4):389~391

Abstract: Laser sensitive coordination compound 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole cobalt (II) perchlorate dihydrate(TACo) was synthesized with the yield of 71%. The structure of the obtained compound was identified by IR and elemental analysis. The laser sensitivity and part of the explosive performance were tested. The 50% fire energy density in 915 nm laser wavelength was 39.85 J•cm-2. Results show that the temperature and particle size of the samples have significant effects on the synthesis reaction.

203. Synthesis and Characterization of Glycidyl Nitrate
MO Hong-chang,GAN Xiao-xian,LU Xian-ming,QIU Shao-jun and LIU Qing, chinese journal of energetic materials,2009,17(4):396~398

Abstract: The synthetic route of glycidyl nitrate(GN) was improved. Glycidol was synthesized by the cyclization process from allyl alcohol and m-CPBA, then glycidyl nitrate was synthesized with glycidol as raw materials and HNO3/(AcO) 2O as nitrating agent. Results show that the yield of GN is 70.2%, and after vacuum distillation, the purity of GN is 98.9%. The product was characterized by IR, 1H NMR and elemental analysis. The optimal nitration conditions are as follows: the molar ratio of HNO3/GA is 1.5:1.0, reaction temperature is -10 °C, and reaction is quenched when addition is finished.

204. Synthesis and Properties of Tetracyclo[7.4.0.02,7.13,6]tetradecane as a High Density Hydrocarbon Fuel
DU Yong-mei,LI Chun-ying,YANG Jian-ming,KANG Jian-pin,LIU Bo and Lü Jian, chinese journal of energetic materials,2009,17(4):399~403

Abstract: As a high density hydrocarbon fuel,tetracyclo[7.4.0.02,7.13,6]tetradecane was synthesized from dicyclopentadiene and indene by D-A reaction and hydrogenation. Under the optimal conditions, the yield of tetracyclo[7.4.0.02,7.13,6]tetradecane is 68.1%. Properties of tetracyclo[7.4.0.02,7.13,6]tetradecane were measured (i.e. density is 0.986 g•cm-3, volumetric combustion heat is 43.7 MJ•L-1, viscosity (-18 °C) is 97.44 mm2•s-1, flash point is 50 °C,freezing point is -45 °C). Thermal decomposition of tetracyclo[7.4.0.02,7.13,6]tetradecane was analyzed by DSC. Results show that tetracyclo[7.4.0.02,7.13,6]tetradecane has high thermal stability.

205. Mannich Reaction Catalyzed by Biodegradable Ionic Liquid
FANG Dong,CAO Shao-ting,FEI Zheng-hao and LIU Zu-liang, chinese journal of energetic materials,2009,17(4):404~407

Abstract: The novel task-specific room-temperature ionic liquid 3-(N, N-dimethyldodecyl ammonium)propanesulfonic acid hydrogen sulfate [DMDAPS]•[HSO4] was designed and synthesized as a biodegradable recyclable catalyst for one-pot three-component Mannich reaction in water. Twelve ß -amino carbonyl compounds were obtained with yield of 80%-91% under the mild conditions. The product can be simply separated from the catalyst/water, and the enviromentally benign catalyst can be reused at least 9 times without noticeably decreasing of the catalytic activity.

206. Synthesis of P (MMA/EA)/PEG-TPE Semi-Interpenetrating Polymer Networks
JIAN Xiao-xia,XIAO Le-qin,ZHOU Wei-liang and XU Fu-ming, chinese journal of energetic materials,2009,17(4):442~445

Abstract: P(MMA/EA)/PEG-TPE semi-interpenetrating polymer networks(S-IPN) were synthesized by PEG-TPE and copolymer of methyl methylacrylate and ethyl acrylate, P(MMA/EA),to improve the compatibility of semi-interpenetrating polymer networks (S-IPN) of polymethyl methyacrylate (PMMA) and polyethylene glycol thermoplastic elastomer (PEG-TPE). The acrylate was entirely converted to its polymer and the translation ratio of PEG-TPE can get to 89% by Fourier transform infrared spectrometer (FTIR) and nuclear magnetic resonance spectrometry(1H NMR). The transition peak in the P(MMA/EA)/PEG-TPE S-IPNs shifts inward compared with that of PMMA/PEG-TPE, even a single Tg was observed in the composition of 10/90,30/70 in DMA, the flexible morphology was observed from scanning electron micrograph(SEM), which indicates some compatibility and degree of interpenetrating between two polymers in the phases.

207. Progress in 1, 5-Diamino-1H-tetrazole and Its Derivatives
QI Shu-yuan,ZHANG Tong-lai,YANG Li,ZHANG Jian-guo,ZANG Yan and CUI Yan, chinese journal of energetic materials,2009,17(4):486~490

Abstract: The progress in the salts and complexes of 1, 5-diamino-1H-tetrazole (DAT) were described and reviewed. The optimized synthesis processes were emphasized with the precursor of diaminoguanidine chloride as raw materials. The DAT can easily forms salt resulting from reacting with strong acid, and easily forms six energetic complexes resulting from coordinating in six DAT molecules with perchlorate. All of these DAT compounds are sensitive to mechanic stimulus,and possess good explosive properties. Therefore, DAT compounds have potential applications in the high energy density materials

208. Synthesis of PDMH-GAP and Its Application
ZHANG Li-na and YANG Rong-jie, .chinese journal of energetic materials,2009,17(5):514~517

Abstract: GAP-PDMH was prepared by the chemical reaction between alkyne and azide in DMF,and the molar ratio was 6/7. The reaction temperature was 60 °C and reaction time was 48 h. The GAP-PDMH was identified by FT-IR and 1H NMR, and glass transition temperature of the GAP-PDMH was measured. Results show that PDMH is grafted into the branch of GAP chains by 1, 3-dipolar cycloaddition reaction between alkyne and azide. Mechanical properties of composite GAP propellant with GAP-PDMH were tested. Compared with the blank sample, GAP-PDMH can improve the mechanical properties of the composite propellant at room temperature. The maximum tensile strength is increased by 210% (to be 0.65 MPa); the maximum elongation is increased by 226% (to be 22.24%); the fracture elongation is increased by 207% (to be 25.87%).

209. A New Synthetic Route to 1,3-Diamino-5-methylamino-2,4,6-trinitrobenzene
ZHANG Xue-mei,DONG Hai-shan,ZHOU Zhi-ming and HE Xing, chinese journal of energetic materials,2009,17(5):523~526

Abstract: A new synthetic route for preparation of 1,3-diamino-5-methylamino-2,4,6-trinitrobenzene with chlorobenzene as the starting material was reported. Via the sequence nitration-nucleophilic substitution-vicarious nucleophilic substitution of hydrogen reaction, the title product was obtained with yield of 60.3%. The structure of the title product and its intermediate products were identified by IR, 1H NMR, and elemental analysis. DSC curve of the title product shows the peak temperature of thermal decomposition is 303 °C, which indicates its molecule is stable to heat.

210. Two Synthetic Methods of 3,4-Bis(3'-nitrophenyl-1'-yl)furoxan
YANG Jian-ming,XUE Yun-na,LI Chun-ying,GE Zhong-xue and Lü Jian, chinese journal of energetic materials,2009,17(5):527~530

Abstract: 3,4-Bis(3'-nitrophenyl-1'-yl)furoxan was synthesized by two methods (oxidative dehydrogenation reaction and dimerization reaction of nitrile oxide). The target compound was characterized by IR, NMR, elemental analysis and DSC. The target compound was obtained with yield of 32.4% by the oxidative dehydrogenation reaction which involved nitration of benzil, hydroamine addition,and oxidative cyclization,and the target compound was obtained with yield of 21.0% by the dimerization reaction of nitrile oxide which involved hydroamine addition of benzonitrile, diazotization,intermolecular cyclization and nitration of 3,4-bisphenyl furoxan. DSC curve shows that the exothermic peak of the opening-ring for 3,4-bis(3'-nitrophenyl-1'-yl)furoxan is 280.7 °C with releasing heat of 1142 J•g-1

211. Synthesis of 1,4-Dinitrofurazano[3,4-b]piperazine(DNFP)
BI Fu-qiang,WANG Bo-zhou,WANG Xi-jie,XIONG Cun-liang and JIA Si-yuan, chinese journal of energetic materials,2009,17(5):537~540

Abstract: The synthesis of 1,4-dinitrofurazano[3,4-b]piperazine (DNFP) with an overall yield of 32.6%,was described. The cyclizative condensation between N,N'-di-tert-butyl ethylenediamine and dichloroglyoxime at low temperature generated 1,4-di-tert-butyl piperazine-2,3-dioxime(PDO-tB), which underwent a base-promoted dehydration at high temperature to obtain 1,4-di-tert-butylfurazano[3,4-b]piperazine (FP-tB). Furthermore, nitrolysis of FP-tB provided an efficient access to the novel explosive compound DNFP. The structures of DNFP and its intermediates were characterized by IR, 1H NMR, 13C NMR and elemental analysis. Moreover, the effects of reaction conditions on the yield of PDO-tB were studied, and the optimum reaction condition is dropwise addition at -18 ?. Converting FP-tB to DNFP with several nitrolysis reagents were also studied, and the nitrolysis with the mixed acid of 98% HNO3 and H2SO4 provides a good yield of 61.7%.

212. Reaction Mechanism Studies on Synthesis of 3-Amino-4-amidoximinofurazan
WANG Bo-zhou,LUO Yi-fen,ZHOU Yan-shui,LAI Wei-peng and LIU Qian, chinese journal of energetic materials,2009,17(6):674~677

Abstract: The synthesis of 3-amino-4-amidoximinofurazan from malononitrile (MN) was proposed in the literature as four-step reaction: nitrosation, rearrangement, oximation and dehydration cyclization. In this paper the nitrosation was tracked via in situ IR, and 2-nitrosomalonitrile (NMN) and 2-oximinomalonitrile (OMN) (as a pair of isomer) were detected. In addition, the 3-demensional in situ IR spectra of —NO, NOH and —OH, and the intensity history of characteristic peaks for —NO,CN and —OH during the nitrosation process were recorded and derived, which gives an insight into the nitrosation. But OMN was not successfully separated. As a product of reaction of MN with NaNO2 and that of reaction of sodium salt of OMN (NaOMN) with NH2OH, both of NaOMN and 1,3-diamino-1,2,3-trioximinopropane were obtained and characterized by IR, NMR, MS and elemental analysis. Based on what described above, we propose the following five-step mechanism for the title reaction: nitrosation, rearrangement, salification, oximation, and dehydration cyclization.

213. Synthesis of 1-Methyl-4,5-dinitroimidazole
CAO Duan-lin,WANG Xiao-jun,YANG Cai-yun,SONG Lei,HAN Hao,ZHOU Jun-feng and CHANG Jun-fang, chinese journal of energetic materials,2009,17(6):678~680

Abstract: 1-Methyl-4,5-dinitroimidazole(4,5-MDNI) was synthesized from nitration of 1-methylimidazole. 4,5-Dinitroimidazole (4,5-DNI) displaying acidity was dissolved. The structure of 4,5-MDNI was characterized by IR,elemental analysis,1H NMR and MS. Effects of the temperature, reaction time and the ratios of fuming sulfuric acid to fuming nitric acid on its yield were studied by orthogonal test. The optimal reaction conditions for synthesizing 4,5-MDNI are obtained as follows: the yield of 4,5-MDNI is 60%, and reaction temperature is 105-115 °C, and reaction time is 2 h, and the ratios of sulfuric acid and nitric acid is 1:1. The thermolysis property of 4,5-MDNI was studied by differential scanning calorimetry(DSC). Results show that the melting point of 4,5-MDNI is 78 °C,and 4,5-MDNI has good thermal stability

214. Synthesis and Properties of Tri-arms Glycidyl Azide Polymer Azide
XU Ruo-qian,JI Yue-ping,DING Feng,WANG Wei,LAN Ying and LIU Ya-jing, chinese journal of energetic materials,2009,17(6):681~684

Abstract: Taking 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione as initiator,boron-trifluoride etherate as catalyst, and 2-chlorooxirane as monomer,two polymers(polyepichlorohydrin(PECH)) with different molecular weights were synthesized by the opening-ring polymerization of epichlorohydrin. And then two bran-new tri-arms glycidyl azide polymer azide(GAPA) were obtained by the reaction of nitration and azidonation. The structure of GAPA was characterized by IR and GPC. Results show that the glass transition temperature of GAPA is -52.86 °C,and its thermal decomposition temperature is 247.9 °C. The superior properties of GAPA show that it can be used as an energetic plasticizer.

215. Dimerization Reaction of Cyanide Oxide: Important Route for Synthesis of Furoxan Derivatives
LI Ya-nan,SHU Yuan-jie and ZHANG Zhi-zhong, chinese journal of energetic materials,2009,17(6):740~744

Abstract: Common methods of furoxan ring formation were analyzed. Main preparation reactions of cyanide oxide and their advantages and disadvantages were summarized, such as the reaction of hydroxamic chloride and weak base,the reaction of aldehyde oxime and nitric oxide, the reaction of hydrazide potassium salt and oxidants, et al. Dimerization reaction of cyanide oxide leads to formation the furoxan derivatives with symmetrical substituent groups. The properties of some symmetrical furoxan derivatives were listed.

216. Review on Synthesis of BAMO Homopolymer and Copolymers
GE Zhen,LUO Yun-jun,GUO Kai,Lü Yong and JIU Yong-bin, chinese journal of energetic materials,2009,17(6):745~750

Abstract: The polymers of 3, 3-diazidomethyloxetane (BAMO) are typical high-energy and high-density energetic polymers. The development of synthesizing BAMO monomer, BAMO homopoymer and copolymers was reviewed, and future study about them was also prospected in this paper. BAMO-AMMO and BAMO-GAP energetic thermoplastic elastomers are widely used. Cation livng polymerization is major synthesizing method of BAMO polymers.

217. Synthesis of Aromatic Alkyol and Fluorescence Quenching with TNT
LIU Yong,XIONG Ying,SHU Yuan-jie,LIU Xue-yong,ZHONG Fa-chun,ZHANG Yong and SUN Yi, .chinese journal of energetic materials,2009,17(6):751~752

Abstract: 9-Hydroxy-9-acetenylanthrone was synthesized and characterized, and its fluorescence quenching with TNT in chloroform was investigated.

218. Synthesis and Properties of 3-Amino-2,4,6-trinitroanisole
ZHANG Xue-mei,DONG Hai-shan,XIA Yun-xia and LIU Xiao-feng, chinese journal of energetic materials,2010,18(2):135~138

Abstract: To find suitable components for energetic eutectic mixtures, 3-amino-2,4,6-trinitroanisole with an overall yield of 76% was synthesized via the sequence methylation-VNS amination of commercial picric acid. And its properties were preliminarily studied by IR, 1H NMR and elemental analysis. The mechanism of methylation and VNS amination were discussed. DSC-TG curves show that the endothermic peak temperature is 133.77 ? and the exothermic peak temperature is 254.10 °C. The massloss is about 1.71% at 199.6 °C. H50 is 82.5 cm and the friction sensitivity is 0%. V50 is 11.42 kV and E50 is 1.99 J. The theoretical detonation velocity is 7.459 km•s-1 (ρ=1.709 g•cm -3), and the theoretical detonation pressure is 22.9 GPa (ρ=1.709 g•cm -3). Results show that 3-amino-2,4,6-trinitroanisole is stable to heat. The theoretical detonation velocity and pressure of 3-amino-2,4,6-trinitroanisole are larger than that of TNT.

219. Preparation of TNAZ from Nitrolysis of N-Tert-butyl-3,3-dinitroazetidinium Nitrate
XIONG Cun-liang,JIA Si-yuan,LIU Qian,WANG Bo-zhou and HUO Huan, .chinese journal of energetic materials,2010,18(2):139~142

Abstract: Taking N-tert-butyl-3,3-dinitroazetidinium nitrate (BDNAN) as precursor,1,3,3-trinitroazetidine(TNAZ) was synthesized by five different nitrolysis systems. The optimal nitrolysis system was NH4NO3/Ac2O. At the same time,the reaction conditions were optimized, and the optimal reaction conditions are as follows: n(Ac2O):n(BDNAN)=25:1, reaction temperature is 80 °C and yield is 83.1%. The thermal characteristics and the split mechanism of TNAZ were studied. Results show that TNAZ having a stable four-membered ring skeleton melts at 99.5 °C with decomposition at 264.68 °C.

220. Separation of TAT and TRAT using HPLC
LOU Zhong-liang,MENG Zi-hui,MENG Wen-jun and WANG Peng, chinese journal of energetic materials,2010,18(2):226~228.

Abstract: A high performance liquid chromatography (HPLC) method was developed for the separation of 1,3,5,7-tetraacetyl-1,3,5,7-tetraazacyclooctane (TAT) and 1,3,5-triacetyl-1,3,5-triazacyclohexane (TRAT), which are the intermediates for the synthetic reaction of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX). The chromatograms of TAT and TRAT were further confirmed by high performance liquid chromatography-mass spectrometry (HPLC-MS). The optimal separation conditions are: sillca column (4.6 mm×250 mm i.d., 5 µm), mobile phase: acetonitrile/water (75/25, V/V); the flow rate is 1.0 mL•min-1, the wavelength is 215 nm, the injection volume is 20 µL.

221. Synthesis of Exo-tetrahydrodicyclopentadiene in Ionic Liquids
LI Chun-ying,DU Yong-mei and Lü Jian, .chinese journal of energetic materials,2010,18(3):257~260

Abstract: Synthesis of exo-tetrahydrodicyclopentadiene (exo-THDCPD) in ionic liquids was studied. Ionic liquids were prepared by aluminum chloride and dialkylimidazolium halide or alkylpyridinium halide and were used in isomerization of endo-tetrahydrodicyclopentadiene (endo-THDCPD) as catalyst and solvent. Effects of reaction conditions such as reaction temperature,reaction time,and ionic liquid amount on the conversion of endo-THDCPD and yield of exo-THDCPD were studied. Results show that the conversion of endo-THDCPD is 100% in different ionic liquids. The yield of exo-THDCPD is 98.3% in 1,3-dialkylimidazolium chloride/aluminum chloride (n(AlCl3)⁪n( Cl=1.5) at 50 °C for 3 h. The yield of exo-THDCPD is 97.8% in 1-butylpyridinium chloride/aluminum chloride (n(AlCl3)⁪n( Cl=1.8) at 50 °C for 3 h. The product can be simply separated and ionic liquids can be reused at least five times without decreasing of the catalytic activity.

222. Synthesis of High Energy Thermoplastic Binder CE-PBAMO
LU Xian-ming,GAN Ning,XING Ying,HAN Tao,LIU Qing,ZHANG Zhi-gang and LI Lei, chinese journal of energetic materials,2010,18(3):261~265

Abstract: Using water and toluene as solvents,and quaternary ammonium salt as phase transfer catalyst,under the effect of NaOH,3,3-dibromomethyl oxetane (BBMO) was synthesized by the cylization of 1,1,1-tribromomethyl-1-hydroxymethyl methane. Using water as solvent,quaternary ammonium salt as phase transfer catalyst,3,3-diazido methyloxetane (BAMO) was obtained by the substitutation of BBMO with NaN3. The prepolymer of BAMO (PBAMO) was synthesized by the cationic polymerization of the monomer BAMO,and it had a number average molecular weight from 3000 to 4000. The chain-extended PBAMO (CE-PBAMO) was synthesized by the chain extended of the PBAMO with 2,4-toluene diisocyanate (2,4-TDI) and 1,4-butanediol (1,4-BDO). The structure and physical chemical properties of BBMO,BAMO,PBAMO and CE-PBAMO were identified by FTIR,1H NMR,HPLC,DSC and GPC. The results show that the yield and purity of BBMO are 81% and 97.2%,and the yield and purity of BAMO are 80.9% and 98.37%; the synthesis of BBMO and BAMO by phase transfer catalysis possesses advantages of safety,high yield and high purity; the synthesized CE-PBAMO which has a number average molecular weight of 38933,can melt and dissolve,and its tensile strength is 12.7 MPa at 20 °C,it can be used as high energy thermoplastic binder in the manufacture of the new type of combustible cartridge case which has concept of 3R(recycle,recover,reuse).

223. Synthesis and Property of Energetic Binder Poly(3,3-dinitrobutyl acrylate)
ZHANG Gong-zheng,LI Hai-hua and GUO Ling-hong, chinese journal of energetic materials,2010,18(3):266~269

Abstract: 3,3-Dinitrobutyl acrylate was prepared from 3,3-dinitro-1-butanol and acrylic acid through direct esterification,which was obtained by the reaction of the oxidative-nitration,Michael addition,hydrolyzation,decarboxylative-bromating,nucleophilic addition and alcoholysis using nitroethane as starting materials. The energetic binder poly(3,3-dinitrobutyl acrylate) was synthesized by the free radical polymerization of 3,3-dinitrobutyl acrylate in ethyl acetate by using azobisiosbutyronitrile as initiator. The structures and properties of poly(3,3-dinitrobutyl acrylate) were also characterized by FTIR,1H NMR,XRD,TG-DTA and DSC. Results show that poly(3,3-dinitrobutyl acrylate) is amorphous,and its glass state temperature is 38 °C,and its mass loss is 22% at 250 °C.

224. Synthesis and Properties of 2,4-Dinitroimidazole(2,4-DNI) Salts
YANG Wei,JI Yue-ping,WANG Wei,CHEN Bin and WANG Ying-lei, chinese journal of energetic materials,2010,18(3):270~272

Abstract: Using 2,4-dinitroimidazole(2,4-DNI) and organic amines as starting materials,four new salts,i.e.ADNI (A=guanidine,triaminoguanidine,gunanyl urea,and hydrazine ),were synthezised with yield of 87.2%,67.5%,67.7% and 96.6% respectively. The resulting salts structures were identified with FTIR,NMR and elemental analysis. The authors measured density,melting point,thermal stability,combustion heat,impact and friction sensitivity,and calculated formation enthalpy,detonation velocity and detonation pressure for all the salts(not including hydrazine). They exhibit relatively higher energy level,lower sensitivity,and better thermal stability. Among them,TAGDNI may be promising in applications to propellants with low signals,as a substitute for partial ammonium perchlorate(AP). Results show that TAGDNI has higher enthalpy of formation (623.36 kJ•mol-1),detonation velocity (8948.68 m•s-1),and detonation pressure (34.57 GPa),and its characteristic height (H50) is 125 cm (2 kg hammer).

225. Synthesis of Fluorescent Sensors Skeleton 9,10⁪Bis(trimethylsilylethynyl) Anthracene and Its Spectral Properties LUO Ya-jun,SHU Yuan-jie and HU Xiao-li, chinese journal of energetic materials,2010,18(3):356~357

Abstract: 9,10⁪Bis(trimethylsilylethynyl) anthracene was prepared by a coupling reaction of dibromoanthracene dibromobenzene and trimethylsilylethyne,using PdCl⁪2(PPh⁪3)⁪2 and CuI as catalysts. A mixed solvent of THF/diethylamide was used as the media of the coupling reaction. The product was obtained with desired yields and it was characterized by IR,UV,⁪⁪⁪1HNMR.