三维无溶剂含能Ag-MOF的制备、热分解动力学及爆炸性能（英文）

溶剂分子的存在会严重降低能量金属-有机框架(EMOFs)材料的爆热和稳定性,开发无溶剂的EMOFs已成为制备高能量密度材料的有效策略。本文将高能的2,3-二(5~(-1)H-四唑基)吡嗪(H2DTPZ)配体与银离子作用在水热条件下制备了一例无溶剂的EMOF [Ag_2(DTPZ)]_n(1)(含氮量:32.58%),并借助元素分析、红外光谱、X射线衍射以及热分析等技术对其组成和结构进行了表征。化合物1中,DTPZ~(2-)配体构型高度扭转并以八齿配位模式桥联Ag+离子形成三维框架结构(ρ=2.812 g·cm~(-3)),配体大的位阻效应和强的配位能力有效阻止了溶剂分子与金属配位或占据框架空腔;同时,不同配体四唑环间强的π–π堆积作用(质心-质心距离为0.34461(1) nm),使得化合物1呈现高的热稳定性(T_e=619.1 K, T_p=658.7K)。热分析研究表明化合物1分解主要发生一步快速失重并伴有剧烈的放热,呈现出潜在的含能特质。通过差示扫描量热(DSC)技术对化合物1的热分解过程进行了非等温热动力学分析(基于Kissinger和Ozawa-Doyle方法)并获得了相应热动力学参数(活化能E_a=272.1 k J·mol~(-1),E_o=268.9 k J·mol~(-1);lgA=19.67 s~(-1))。进一步基于升温速率趋于0时的分解峰温和外延起始温度,计算得到了相关热力学参数(活化焓?H≠=266.9 k J·mol~(-1),活化熵?S≠=125.4 J·mol~(-1)·K~(-1),活化自由能?G~≠=188.3 k J·mol~(-1))以及热爆炸临界温度(T_b=607.1 K)和自加速分解温度(T_(SADT)=595.8 K),结果表明该化合物具有良好的热安全性,其分解属非自发的熵驱动过程。借助精密转动弹热量计测定了化合物1的恒容燃烧能(Q_v)并计算得其标准摩尔生成焓为(2165.99±0.81) k J·mol~(-1)。爆轰和安全性能测试表明,化合物1对撞击和摩擦均不敏感,爆热值达10.15 k J·g~(-1),远高于常见硝铵类炸药奥克托金(HMX)、黑索金(RDX)和2,4,6-三硝基甲苯(TNT),是一例有前景的高能钝感含能材料。     

含能配合物2，6-二氨基-3，5-二硝基吡啶-1-氧化物合钴(Ⅲ)的合成、晶体结构及催化性能

培养了含能配合物2,6-二氨基-3,5-二硝基吡啶-1-氧化物(ANPyO)合钴(Ⅲ)晶体,用X射线单晶衍射法测定了其分子结构。该配合物的分子式为[Co(ANPyO)3]。用DSC,TG-DTG技术对该配合物的热分解进行了研究,结果表明,该配合物的热分解由1个缓慢吸热峰和2个剧烈的放热峰组成,剩余残渣量为3.7277%。感度测试结果表明,该配合物感度较ANPyO有一定程度的降低,是一种不敏感含能材料。同时研究了配合物对高氯酸铵(AP)热分解的影响,结果表明,[Co(ANPyO)3]可以使AP的高温分解峰温提前65.15℃,使分解速度加快,对AP热分解具有良好的催化效果。     

硝基修饰MOF-5材料的制备及催化氨基甲酸酯热分解!

采用直接混合法在室温下制备了含硝基的金属-有机骨架材料MOF-5-NO2,并采用X射线衍射分析,红外光谱,N2等温吸附和扫描电子显微镜对其进行了表征.结果表明,MOF-5-NO2具有与MOF-5相似的晶体结构和表面形貌,二者都具有高比表面积及微孔特性,但由于硝基的吸电子效应,MOF-5-NO2比MOF-5具有更强的Lewis酸性,因而对氨基甲酸酯热分解制备异氰酸酯的反应具有良好的催化活性.在无溶剂条件下,MOF-5-NO2使苯氨基甲酸甲酯热分解的反应速度显著提高,催化剂转化频率达到ZnO的7倍以上;二苯甲烷二氨基甲酸苯酯热分解的中间产物减少,二苯甲烷二异氰酸酯的收率达到81.6%.     

金属卟啉的热稳定性及热分解动力学研究

热重分析;金属卟啉的热稳定性及热分解动力学研究     

环丙沙星-钨硅多金属氧酸盐的制备及热分解动力学

A new polyoxometalate （CPFX·HCl）3H4SiW12O40·10H2O was prepared from ciprofloxacin hydrochloride and H4SiW12O40·nH2O in aqueous solution, and characterized by elemental analysis, IR spectra and DTA-TG-DTG techniques. The IR spectrum confirmed the presence of Keggin structure and the characteristic functional group for ciprofloxacin in the compound. The TG-DTA-DTG curves showed that its thermal decomposition was a four-step process consisting of simultaneous collapse of Keggin type structure. The residue of decomposition was the mixture of WO3 and SiO2, confirmed by X-ray diffraction and IR spectroscopy. The decomposition mechanism and nonisothermal kinetic parameters of the polyoxometalate were obtained from an analysis to the TG-DTG curves by the single scanning methods （the Achar method and Coats-Redfern method） and the multiple scanning methods （the Kissinger method, Flynn-Wall-Ozawa method and Starink method）. The results indicate that the kinetic equationswith parameters describing the thermal decomposition reaction are dα/dt=6.65×10^6[3（1-α）^2/3]e^-10495.5/T with E=87.26 kJ/mol and A=6.65×10^6 s^-1 for the second step,dα/dt=7.01×10^9（1-α）e^-18770.7/T with E=156.06 kJ/mol and A=7.01×10^9 s^-1 for the third step,dα/dt=9.77×10^43[（1-α）^2]e^-88980.0/T with E=739.78 kJ/mol and A=9.77×10^43 s^-1 for the fourth step.     

1,2,3-三唑类含能化合物的合成研究进展

1,2,3-三唑类含能化合物具有密度高、生成焓高及热稳定性好等特点,近年来受到科研人员的广泛研究和报道.较全面地综述了单环1,2,3-三唑、多环1,2,3-三唑和稠环1,2,3-三唑类含能化合物的研究成果,对其合成方法、感度和爆轰性能进行了总结.结果表明,1,2,3-三唑含能化合物具有良好的爆轰性能和热稳定性,在含能材料领域具有重要的研究价值和应用潜力.最后,对1,2,3-三唑含能化合物的发展现状进行总结与展望,提出了各类1,2,3-三唑含能化合物未来可能的应用方向,以期为从事含能化合物研究的科研人员提供一定的参考.     

水合硼酸锶的制备及脱水热分解动力学

以氯化锶和硼酸氢铵为原料,采用液相沉淀法制备了片状水合硼酸锶（SrB6O10•5H2O）粉体,并用XRD、FT-IR及SEM进行了表征。利用热重分析法对片状纳米硼酸锶粉体的脱水热分解动力学进行了研究,分别采用 Coats- Redfern 方程和 Flynn-Wall-Ozawa（FWO）法对热重分析数据进行了处理和拟合,初步确定了水合硼酸锶的四步脱水过程及相应的热分解反应机理,得到各步反应的表观活化能和指前因子。     

基于3,6-二肼基-1,2,4,5-四嗪的两种高氮含能离子盐

本文通过3,6-二肼基-1,2,4,5-四嗪(DHT)分别与高氯酸和硝酸反应得到2种高氮含能离子盐,并通过X-射线单晶衍射技术对它们的结构进行了表征。(DHT)(NO₃)₂(1)属于单斜晶系,C2/c空间群,晶胞参数：a=1.300 0(6) nm,b=0.834 9(3) nm,c=1.018 7(5) nm,β=118.89(5)°,Z=4;(DHT)(ClO₄)₂(2)属于正交晶系,P2₁2₁2空间群,晶胞参数：a=0.980 4(4) nm,b=1.074 7(4) nm,c=0.532 5(2) nm,Z=2。采用DSC和TG-DTG技术研究了这两种含能离子盐的热分解机理,并对这两种含能离子盐的非等温动力学、爆热及感度进行了测试分析。研究表明这两种含能离子盐在敏感型含能材料领域具有潜在的应用前景。     

基于3,6-二肼基-1,2,4,5-四嗪的两种高氮含能离子盐

本文通过3,6-二肼基-1,2,4,5-四嗪(DHT)分别与高氯酸和硝酸反应得到2种高氮含能离子盐,并通过X-射线单晶衍射技术对它们的结构进行了表征。(DHT)(NO₃)₂(1)属于单斜晶系,C2/c空间群,晶胞参数:a=1.3000(6)nm,b=0.8349(3)nm,c=1.0187(5)nm,β=118.89(5)°,Z=4;(DHT)(ClO₄)₂(2)属于正交晶系,P2₁2₁2空间群,晶胞参数:a=0.9804(4)nm,b=1.0747(4)nm,c=0.5325(2)nm,Z=2。采用DSC和TG-DTG技术研究了这两种含能离子盐的热分解机理,并对这两种含能离子盐的非等温动力学、爆热及感度进行了测试分析。研究表明这两种含能离子盐在敏感型含能材料领域具有潜在的应用前景。     

DABT含能化合物的合成,结构及性质研究

利用水热法制备了一个单核含能配合物[Ni(DABT)(H₂O)₄] SO₄·H₂O(1)(DABT=3,3’-二氨基-5,5’-二(1H-1,2,4-三唑))和一个含能离子盐DABT·SO₄(2)。结构分析表明,1和2均通过三唑环的π-π堆积作用及其氢键相互作用形成了三维超分子结构。研究了1和2的红外光谱,紫外可见光谱;运用TG-DSC热分析仪研究了1的热分解行为,结果表明1在失去水分子后可以稳定到350℃才放热分解;探究了2对推进剂主要组分的热分解行为,结果表明2对AP具有一定的燃烧催化作用。     

聚碳酸亚丙酯马来酸酐的热分解动力学(英文)

通过热重分析研究了新型三元共聚物聚碳酸亚丙酯马来酸酐(PPCMA)在不同升温速率下的热分解动力学.设计并引入一种新的计算方法,非线性约化法(NLA),对共聚物热分解过程中的表观活化能进行了计算.研究发现,虽然用非线性约化法计算的表观活化能相对误差值稍大于用传统计算方法Flynn-Wall-Ozawa(FWO),Tang和Kissinger-Akahira-Sunose(KAS)计算的相对误差值,但其分析合理且计算过程更为简便.此外,固态反应模型拟合方法计算结果表明,共聚物的热分解过程对应多个反应机理.整个热分解过程,表观活化能值处于70-135kJ·mol-1之间,指前因子处于5.24×104-9.89×107min-1之间.同时,通过对表观活化能值的比较,初步解释了聚碳酸亚丙酯(PPC)与PPCMA热解温度差异的原因.     

双核Cu(I)配合物的热分解非等温动力学

Thermal decomposition process of four benzimidazolyl-containing dicopper(Ⅰ) complexes: [Cu2(OCTB)](ClO4)2•1.5H2O(1), [Cu2 (NMOCTB)](ClO4)2•H2O(2), [Cu2(NBUOCTB)](ClO4)2(3), [Cu2(NBOCTB)](ClO4)2•H2O(4) and their kinetics were studied under the non-isothermal conditions by TG-DTG techniques. The non-isothermal kinetic data were analyzed by means of Achar and Coats-Redfern method respectively. The kinetic equation for the second step of the decomposition of complex (1) can be expressed as: dα/dt=A•exp(-E/RT) •(1-α), the mechanism of this reaction corresponds to "Coring and Growth" with n=1; while for the first step of complex (3) decomposition, dα/dt=A•exp(-E/RT)• (1-α)2, which corresponds to the mechanism of "the second-order chemical reaction".     

Preparation,Crystal Structure,and Thermal Decomposition of the Energetic Compound [Co(IMI)4(PA)](PA) (IMI = Imidazole and PA = Picrate)

The novel multi‐ligand coordination compound [Co(IMI)₄(PA)](PA) ( 1 ) was synthesized by using imidazole (IMI) and picrate (PA) and characterized by elemental analysis and FT‐IR spectroscopy. The crystal structure was determined by X‐ray single crystal diffraction and the crystallographic data showed that the compound crystallizes in the triclinic space group P$\bar{1}$ (α = 8.839(2) Å, b = 13.550(3) Å, c = 13.840(3) Å, α = 68.386(6)°, β = 88.349(9)°, and γ = 87.494(9)°). Furthermore, the Co^II ion is six‐coordinated by four nitrogen atoms from four imidazole ligands and two oxygen atoms from a PA group. Its thermal decomposition mechanism was determined based on differential scanning calorimetry (DSC) and thermogravimetry‐derivative thermogravimetry (TG‐DTG) analysis. The kinetic parameters of the first exothermic process were studied by using Kissinger's and Ozawa's method, respectively. The energy of combustion and the enthalpy of formation were measured and calculated. They showed good combustion performance of the compound. Additionally, the sensitivity properties were determined with standard methods. The results of all these studies showed that [Co(IMI)₄(PA)](PA) has potential application as ignition composition.     

Synthesis,Crystal Structure,Thermal Decomposition and Sensitive Properties of a New Complex [Cu(IMI)4](PA)2

A new coordination complex [Cu(IMI)₄](PA)₂ had been synthesized with imidazole(IMI) as ligands and picrate(PA^-) groups as outer anions, and characterized by Fourier transform infrared(FTIR) spectrum and elemental analysis. Its crystal structure was determined by single crystal X-ray diffraction(XRD) analysis. The crystallographic data show that the crystal belongs to monoclinic, C2/c space group, a=2.542(5) nm, b=0.91773(18) nm, c=1.3778(3) nm, β=107.854(3)° and Z=4. Furthermore, the central copper(II) ion is coordinated by four N atoms from four imi- dazole ligands. All the molecular units are linked into a zigzag pattern along a-axis by the hydrogen bonds, and extended to the distance regularly. Thermal decomposition mechanisms were determined based on differential scanning calorimetry(DSC) and thermogravimetry-differential thermogravimetry(TG-DTG) analysis, and kinetic parameters of the first exothermic process were studied using Kissinger’s and Ozawa-Doyle’s method, respectively. Sensitivity tests show that the title complex has low sensitivity to external stimulus, but it has a higher energy of combustion of 14.2 kJ/g due to which it may be used as the additives of energetic materials to improve the explosive performance.     

一种新型含能材料s-四嗪钴盐的合成、热分解动力学及热安全性

四嗪类含能化合物因其高能、钝感、高燃速、低压力指数、良好的热安定性等特点被广泛应用于含能材料领域。然而却存在低密度、低热稳定性的问题,为提高四嗪类化合物的这一性能,制备的一系列金属衍生物得到了广泛关注。3,6-双(1-氢-1,2,3,4-四唑-5-氨基)-1,2,4,5-四嗪(BTATz)作为四嗪类高氮含能化合物一种,具有良好的催化性能及应用前景。本文以BTATz钾与硝酸钴在水溶液中反应合成了1,2,4,5-四嗪(s-四嗪)的钴盐。采用元素分析(EA)、傅里叶变换红外光谱分析(FTIR)及电感耦合等离子体质谱(ICP-MS)对其进行了结构表征,推测其化学式为Co(C_4H_2N_(14))·4H_2O。采用差示扫描量热仪(DSC)和热重分析仪(TG/DTG)研究了其热分解行为及主放热反应的动力学方程。计算了自加速分解温度(T_(SADT))、热爆炸临界温度(T_b)、热点火温度(T_(TIT))和绝热至爆时间(t_(TIAD)),其值分别为509.69 K、556.31 K、524.93 K和88.40 s,并以此来评价化合物的热安全性。该金属盐的绝热至爆时间大于相应的Ca盐、Mg盐和Sr盐,放热量高于配体BTATz,有望成为良好的燃烧催化剂。     

二水草酸亚铁热分解反应动力学

用原位XRD技术和热重法分析了二水草酸亚铁的热分解过程, 并进行了动力学研究. 通过结合主曲线法和统计方法判定了热分解过程的动力学模型函数, 并求算了动力学参数. 在静态自产气氛下, 二水草酸亚铁脱水反应遵循随机成核与核增长模型, 草酸亚铁热分解生成氧化铁遵循相界面控制动力学模型. 结果表明, 该方法可以准确、可靠地判定非等温热分解反应的动力学模型函数,并求算动力学参数.     

稀土配合物Sm2(CH3COO)4(NO3)2(phen)2 的合成、 结构及非等温热分解动力学研究

在水-乙醇混合体系中, 将浓硝酸硝化的Sm2O3与1,10-邻菲啰啉反应, 用冰醋酸调节pH≈4, 形成醋酸根桥联的双核钐配合物［Sm2(CH3COO)4(NO3)2(phen)2］(phen=1,10-邻菲啰啉), 用元素分析、红外光谱和核磁共振谱等进行了表征, 并用X射线衍射测定了配合物的晶体结构, 此外, 对配合物进行了非等温热分解动力学研究. 该晶体属于三斜晶系, P1空间 群, 晶胞参数a=0.979 6(3) nm, b=0.981 3(4) nm, c=1.127 3(4) nm, α=106.666(5)°, β=113.034(5)°, γ=102.656(5)°, V=0.885 4(5) nm3, Z=1, μ=3.361 mm-1, Dc=1.915 g/cm3, F(000)=498, R1=0.059 6, wR2=0.144 8. 该配合物是双核分子, 2个Sm(Ⅲ)离子通过4个醋酸根的羧基桥联, 每个中心离子分别与周围5个来自羧基的桥氧原子、 一个硝酸根的两个氧原子和一个邻菲啰啉分子中的两个氮原子配位, 形成九配位扭曲多面体. 非等温热分解动力学研究结果表明， 配合物第一步热分解反应可能为二级反应, 其动力学方程为dα/dT=A/［βe-E/RT(1-α)2］, 分解反应的表观活化能为344.84 kJ/mol, 指前因子lnA=66.52.     

Synthesis and thermal decomposition of GAP-Poly(BAMO) copolymer

An energetic copolymer of glycidyl azide polymer (GAP) and poly(bis(azidomethyl)oxetane (Poly(BAMO)) was synthesized using the Borontrifluoride-dimethyl ether complex/diol initiator system. The synthesized copolymer exhibited the characteristics of an energetic thermoplastic elastomer (ETPE). Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were used to study the thermal decomposition behavior and the results were compared with that of the constituent homopolymers. The main weight loss step in all the polymers coincides with the exothermic dissociation of the azido groups in the side chain. In contrast with the behavior of the homopolymers, the copolymer shows a broad exothermic shoulder peak at 298 °C after the main exothermic decomposition peak at 228 °C. Kinetic analysis was performed by Vyazovkin's model-free method, which suggests that the activation energy of the main decomposition step is around 145 kJ/mol and for the second shoulder it is around 220 kJ/mol. Fourier transform infra red (FTIR) spectra of the degradation residues show that the azido groups in the copolymer decompose in two stages at different temperatures which is responsible for the double decomposition behavior.     

地开石热分解过程及非等温动力学研究

Fourier-transform infrared emission spectroscopy was used to study the dehydroxylation behavior of the thermal decomposition of dickite from Chenxi, Hunan Province, China. Dehydroxylation of dickite was followed by a loss of intensity of the 3620.73, 3695.34 cm-1 OH-stretching bands and 916.06, 1009.33 cm-1 OH bending bands. The thermal decomposition was investigated by thermogravimetric analysis (TGA). A good agreement is found with TG curves of dickite and the mass loss is 13.7% (close to the theoretical value). The non-isothermal kinetics of the thermal decomposition of dickite was studied in TG-DTG curves over the temperature range from 298 K to 1123 K by thermogravimetry and differential thermal analysis in air. Mathematical analysis of TG-DTG data using the integral methods (Coats-Redfern equation, HM equation, MKN equation) and differential method (Achar equation) shows that the thermal decomposition of dickite accords F2 mechanism. The kinetic parameters such as the activation energy (E=131.62 kJ/mol), pre-exponential factor (A=108.30 s-1) and reaction order (n=2.1) are reported. The Ozawa method was used to analyse the activation energy of the same sample at different heating rate and gave 133.07 kJ/mol. The kinetic parameters calculated from different equation are rather close to each other.