1-甲基-4,5-二硝基咪唑的晶体结构和热分解

采用溶剂缓慢挥发法在室温下培养出1-甲基-4,5-二硝基咪唑(4,5-MDNI)的单晶,并用X射线四圆衍射仪测定了其单晶结构,晶胞参数为a=8.4123(A),b=12.646(A),c=6.5627(A),V=698.2(A)3,Z=4,D=1.637g/cm3,F(000)=352,属斜方晶系,空间群Pna2(1)...     

5-(3-氨基呋咱-4-基)-1-羟基四唑胍盐的合成及性能研究

以丙二腈为原料,高收率合成了5-(3-氨基呋咱-4-基)-1-羟基四唑(1)的胍盐(2)、二氨基胍(3)以及联胍盐(4).采用红外光谱、核磁共振、元素分析、热分析等对其结构进行了表征;培养了2和3的单晶,并采用X射线单晶衍射测试了其晶体结构;通过落锤法和摩擦感度仪测试了3种胍盐的撞击感度和摩擦感度;采用DSC研究了3种胍盐的热分解过程.结果表明,3种胍盐的撞击感度均大于24J,摩擦感度均大于360N,分解点介于266~277℃,显示出良好的热稳定性.     

硝化纤维素/增塑剂共混体系相结构的介观动力学模拟

采用介观动力学(MesoDyn)模拟方法对比研究了增塑剂硝化甘油(NG)、1,5-二叠氮-3-硝基氮杂环戊烷(DIANP)、N-丁基硝氧乙基硝胺(Bu-NENA)、双(2,2-二硝基丙醇)缩甲醛(BDNPF)/双(2,2-二硝基丙醇)缩乙醛(BDNPA)(BDNPF/A,两者质量比为1∶1)与硝化纤维素(NC)共混体系的相结构及其演变过程和影响因素,用扫描电子显微镜对比研究了质量配比为50/50的4种NC/增塑剂共混体系混溶产物的微观形貌。结果表明,与NG相比,DIANP、Bu-NENA和BDNPF/A与NC的混溶性更好,且显微形貌特征与介观动力学模拟结果一致性较好;20℃下,质量配比为30/70的NC/BDNPA/F共混体系和质量配比为70/30、60/40、50/50、40/60和30/70的NC/NG共混体系产生相分离;质量配比为50/50的NC/NG共混体系,NG与NC的混溶性随温度的升高而改善,40℃以上时体系的相分离现象消失。     

1-甲基-3,4-二硝基吡唑的合成、性能及晶体结构

以3,4-二硝基吡唑(DNP)为原料,通过甲基化制备了1-甲基-3,4-二硝基吡唑(MDNP),采用熔点测定、红外光谱、核磁共振等对目标产物结构进行了表征。室温下培养了MDNP的单晶,用X-射线四圆衍射仪测定了其单晶结构,用DSC法研究了MDNP的热性能,用Kamlet公式计算了MDNP的爆速和爆压。结果表明,该晶体属单斜晶系,空间群P 2 1/n,晶胞参数为a=0.726 3nm,b=1.514 3nm,c=1.036 8nm,V=1.123 4nm3,Z=4,D=1.480g/cm3,F(000)=520。MDNP有良好的热稳定性,爆速和爆压分别为6.14km/s、17.0GPa,是具有潜在应用价值的含能材料。     

3,4-双(4′-氨基呋咱基-3′)氧化呋咱的合成及性能

以丙二腈为起始原料,经亚硝化、重氮化、缩合等反应合成出3,4-双(4′-氨基呋咱基-3′)氧化呋咱(DATF),总收率为50%。经测定,DATF的部分理化及爆轰性能为:密度1.795g/cm3,熔点170~171℃,爆速7177m/s(1.530g/cm3),热分解温度260℃,摩擦感度8%(90°摆角),撞击感度60%(10kg,25cm),真空安定性(5g样品,100℃,48h),放气量0.4~0.7mL。采用差热扫描(DSC)法,测定了DATF的热稳定性及DATF同NC,RDX,HMX和NC/NG体系的相容性。结果表明,DATF具有较好的热稳定性和较低的感度,与RDX,HMX,NC和NC/NG体系有较好的相容性。     

四水合5,5′-联四唑-1,1′-二氧锂盐的晶体结构与性能

制备了四水合5,5′-联四唑-1,1′-二氧锂盐[Li2(BTO)(H2O)4]n,培养了[Li2(BTO)(H2O)4]n的单晶。采用X-射线衍射仪测定了单晶结构。采用DTA/TG技术研究了[Li2(BTO)(H2O)4]n的热性能,并测试了其撞击感度和摩擦感度。结果表明,该晶体属于三斜晶系,空间群为P-1,晶体学参数为:a=0.534 5(17)nm,b=0.636 3(2)nm,c=0.830(3)nm,α=105.904(7),β=98.216(7),γ=111.516(7),V=2.430 2(13)nm3,z=2,D=1.736g/cm3。其热分解峰温为349.1℃,撞击感度为71.8cm,摩擦感度为0。     

3,5-二硝基-1-氧杂-3,5-二氮杂环己烷的分离、热分解及硝解机理分析

为掌握乌洛托品的硝解机理,研究了直接法硝解乌洛托品制备黑索今(RDX)的废水。实验通过乙酸乙酯萃取富集废水中的副产物,水洗至中性,浓缩,用薄层色谱法分析,展开系统为:丙酮/二氯甲烷/冰乙酸=1/6/0.1。采用硅胶柱柱层析法分离,丙酮/二氯甲烷梯度洗脱,分离得到两种物质,一种物质通过熔点、红外、核磁比对确认为1,3,5-三硝基-1,3,5-三氮杂环己烷(RDX);另一种物质采用红外光谱、核磁、质谱、元素分析及单晶衍射等分析方法进行结构表征,认定其为3,5-二硝基-1-氧杂-3,5-二氮杂环己烷。用DSC-TG技术研究了3,5-二硝基-1-氧杂-3,5-二氮杂环己烷热行为,结果表明该化合物是一种熔点低、热稳定性好的化合物,对主要副产物的分离和结构鉴定为直接法硝解反应机理提供了可靠的实验依据。     

1-(2,3-环氧丙基)-2-甲基-5-硝基咪唑的晶体结构及参数计算

采用相转移催化法,制得了1-(2,3-环氧丙基)-2-甲基-5-硝基咪唑(1),并使用单晶X-射线衍射法测定1的晶体结构,结果表明,1属于三斜晶系,P-1空间群,晶胞参数a=6.570(5)A,b=7.536(5)A,c=9.050(6)A,V=423.5(5)A3,Z=2,晶体密度为1.436 g/cm3,最终偏离因子R1=0.045 6,ωR2=0.132 4。采用密度泛函理论的B3LYP方法,在6-31G**基组水平上对1进行了结构优化,计算得到1的理论密度为1.465 g/cm3,固相生成焓为-123.76 k J/mol。     

3,3-二甲基-1-丁烯的合成工艺研究

以叔丁醇为原料,优化了其与浓盐酸氯代合成叔丁基氯的反应,采用CaCl₂ 氯化盐助催化体系使反应收率提高到95%,产品质量分数为99%;3,3-二甲基-1-丁烯合成的关键步骤是叔丁基氯与乙烯反应制备3,3-二甲基-1-氯丁烷,探讨了催化剂用量、反应温度对反应收率的影响.反应以无水三氯化铝为催化剂,用量为n(AlCl₃):n[(CH₃)₃CCl]=0.018:1,反应温度为-17~-20 ℃时,产物3,3-二甲基-1-氯丁烷的收率可达80%;最后由3,3-二甲基-1-氯丁烷脱氯化氢制备3,3-二甲基-1-丁烯.考察了不同溶剂对反应收率的影响,以聚乙二醇-400为溶剂,无需加入相转移催化剂,收率可达88.5%,3,3-二甲基-1-丁烯的质量分数为可达95%以上.     

(+)-1-苯基乙磺酸的合成

以乙基苯和溴为起始原料,光照条件下制得1-溴乙苯;与硫脲缩合得S-(1-苯乙基)异硫脲氢溴酸盐;在碱催化下分解得1-苯乙硫醇;经过氧化氢氧化、氢氧化钠成盐得(±)-1-苯基乙磺酸钠[(±)-1-PES-Na];再经D-对羟基苯甘氨酸(D-HPG)拆分及分离制得(+)-1-苯基乙磺酸[(+)-1-PES]。(±)-1-PES-Na的合成总收率为29.6%;拆分收率为69.6%[以(+)-PES理论量计]。结构经IR、1H NMR确证。     

2,4-二羟基苯甲酸铜纳米催化剂的合成及性能

以2,4-二羟基苯甲酸和硫酸铜制备纳米燃速催化剂，采用TEM、XRD、TG和IR等手段对催化剂样品进行表征，考察了反应终点和反应浓度对收率的影响，洗涤溶剂极性影响最终催化剂形貌，实验表明,纳米催化剂对双基推进剂NC/NG热分解有明显催化效果。     

纳米氧化铁的制备及其对吸收药热分解催化作用的研究

用室温湿固相反应制备了纳米氧化铁，并进行了表征，用BSC研究了纳米氧化铁对吸收药（耠化棉吸收硝化甘油的混合物，NC／NG）热分解反应的催化作用，并提出了该催化反应的机理，实验结果表明，纳米氧化铁能有效地催化吸收药的热分解。     

An Investigation on Thermal Decomposition of DNTF‐CMDB Propellants

The thermal decomposition of DNTF‐CMDB propellants was investigated by pressure differential scanning calorimetry (PDSC) and thermogravimetry (TG). The results show that there is only one decomposition peak on DSC curves, because the decomposition peak of DNTF cannot be separated from that of the NC/NG binder. The decomposition of DNTF can be obviously accelerated by the decomposition products of the NC/NG binder. The kinetic parameters of thermal decompositions for four DNTF‐CMDB propellants at 6 MPa were obtained by the Kissinger method. It is found that the reaction rate decreases with increasing content of DNTF.     

纳米氧化镧对吸收药热分解的催化作用

研究了纳米氧化镧对吸收药(硝化棉吸收硝化甘油的混合物，NC／NG)热分解反应的催化作用，并提出了形成过渡态配合物的反应机理。实验结果表明，纳米氧化镧能有效地催化吸收药的热分解。     

静态与动态高压对含能材料热分解的影响

利用常压和高压差示扫描量热仪（DSC、PDSC）在动态和静态状下研究了CL-20、HMX、RDX、NC、NG、NG NC等几种含能材料的热分解,探讨了常压与高压条件下,静态与动态对这些含能材料热分解的影响。结果显示含能材料热分解受压力和动态气氛的影响有三种情况：1、热分解同时受到压力和动态气氛的影响;2、热分解既不受压力也不受动态气氛的影响;3、热分解只受压力的影响而不受动态气氛的影响。     

Dissociation equilibria of 1-1 electrolytes in acetylacetone

The dissociation equilibria of tetraalkylammonium and alkali metal salts have been studied by conductometry in acetylacetone as a new electrochemical solvent. The limiting molar conductivities and ion association constants of these 1-1 electrolytes have been calculated by the Shedlovsky method, and the dependence of ion association constants on cation and anion sizes has been discussed in connection with the properties of acetylacetone. In acetylacetone, as well as in acetone, alkali metal ions are not strongly solvated, and alkali metal salts form contact ion-pairs predominantly. On the other hand, the small anions such as chloride and bromide are solvated in this solvent to a considerable extent based on the enol form of the solvent, and the ion-pairs of tetraalkylammonium halides are solvent-separated as in alcohols.     

Research progress of microbial decomposition of nitroglycerine and nitrocellulose

硝酸酯类物质（如硝化甘油和硝化棉等）是有机羟基基团与硝酸缩合的产物,在军事工业上有非常广泛的用途。由于它们并非天然存在的物质,且有爆炸等潜在危害,故不能直接排放到环境中。作为地球生物化学循环中分解者的微生物对硝酸酯类物质的生物降解起着很大的作用,本文将对硝化甘油和硝化棉的生物降解研究进展进行综述。     

Investigation of the Decomposition Mechanism and Thermal Stability of Nitrocellulose/Nitroglycerine Based Propellants by Electron Spin Resonance

Nitrocellulose based (NC) and nitroglycerin based (NG) propellants often have a fixed acid and water content during the manufacturing time. After manufacture, the quantity and ratio of acid/water will continue to vary depending upon the conditions of storage and operation. The level of variation depends on many factors such as loading density, temperature, volume of ullage and sealing condition of the containing cartridge, just to name a few. As described in this paper and other literature, the degradation mechanisms and aging processes of NC/NG based propellants are extremely complicated. This paper describes the details of the application of Electron Spin Resonance (ESR) to study if the free‐radical mechanism is involved in the decomposition of nitrocellulose and nitroglycerin. Due to the high free‐radical intensity possessed by the propellant composition, we believe that a π complex intermediate may be formed between DPA and NG and/or NC. The formation of a π complex intermediate is not preferred because it may enhance the rate of decomposition of nitrate esters.     

Synthesis,Characterization, and Combustion Catalytic Activities of Copper(II) and Lead(II) Salts of p‐Nitrocalix[n]arenes (n=4, 6, 8)

Six copper(II) and lead(II) salts of p‐nitrocalix[n]arene (n=4, 6, 8) were synthsized and characterized. The DSC curves of all salts showed exothermic decomposition. Sensitivity studies revealed that all the salts with the exception of the lead salt of p‐nitrocalix[6]arene (NCPb6) are relatively insensitive materials. Investigations of the catalytic activities showed that most of the salts displayed high activities in thermal decomposition of NC‐NG and RDX. As evaluated in this work, the salts enhanced the burning rates of both double base (DB) and RDX‐component modified double base propellants. The best catalytic effect was obtained with NCPb6, which increased the burning rate of the DB propellant to the order of about 200 % (2–6 MPa) and 103–198 % (8–20 MPa) while decreasing the pressure index (n) to 0.22 (20–22 MPa).     

熔盐高效分解含钛高炉渣制备纳米二氧化钛

采用熔盐法对含钛高炉渣进行高效分解并提取含钛组分,利用含钛滤液为原料制备了纳米二氧化钛粉体。对熔盐分解含钛高炉渣进行了热力学分析,并研究了碱渣比、熔盐反应温度及熔盐反应时间对钛组分浸出率的影响和pH及水解温度对二氧化钛产品纯度的影响。实验结果表明高炉钛渣在氢氧化钠熔盐中反应生成钛酸钠在热力学上是可行的。确定了最佳的碱渣比为3:1,最佳熔盐反应温度为500℃,最佳反应时间为3 h,在此条件下钛元素的浸出率为99.8%。得出较佳的水解pH范围为0.1～0.2,最佳水解温度为100℃。实验中制备的纳米二氧化钛粒子球形度好,粒度大小均匀且分散性好,颗粒直径为100 nm左右。