CN108558957B - N-ferrocenylmethyl-3-amino-1, 2, 4-triazole energy-containing transition metal complex and preparation method thereof - Google Patents
N-ferrocenylmethyl-3-amino-1, 2, 4-triazole energy-containing transition metal complex and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an N-ferrocenyl methyl-3-amino-1, 2, 4-triazole energetic transition metal complex and a preparation method thereof, wherein the complex has the structural formula:
the complex has the advantages of simple preparation method, low cost and high yield, and has better combustion catalysis effect on main components of ammonium perchlorate and hexogen of the composite solid propellant, wherein N-ferrocenyl methyl-3-amino-1, 2, 4-triazole ligand has high nitrogen content and higher positive formation enthalpy, and has synergistic catalysis effect with transition metal ions, and the introduction of the energy-containing compound 1,1 '-dihydroxy-5, 5' -bitetrazole disodium salt tetrahydrate can not only reduce the sensitivity of the combustion rate catalyst, but also contribute energy to the solid propellant, and the decomposed and released nitrogen is environment-friendly.
Description
Technical Field
The invention belongs to the technical field of solid propellants, and particularly relates to an N-ferrocenyl methyl-3-amino-1, 2, 4-triazole energetic transition metal complex and a preparation method of the complex.
Background
With the development of modern defense technology, many countries have shown increasing interest in improving the performance of tactical missiles, including improving the range, maneuverability, and flight speed of the missiles, which places increasing demands on engine and propellant energies. The solid propellant research must be developed to the direction of improving the energy density of the propellant, improving the comprehensive performance and reducing the cost no matter from the miniaturization, maneuvering launching, hiding, low cost and low-level maintenance requirements of strategic missiles, or from the signal and penetration, environment, maneuverability (thrust regulation), range increasing and vulnerability requirements of tactical missiles and the requirements of high energy, cleanness and the like in the aerospace field.
Ferrocene, also known as dicyclopentadienyl iron, is a metal organic compound with a sandwich structure. Ferrocene and its derivatives are widely used due to their own characteristics, such as hydrophobicity, bio-oxidizability, aromaticity, stability, low toxicity, bioactivity, etc. Ferrocene and its derivatives are more effective as burning rate catalysts for hydroxyl-terminated polybutadiene (HTPB) and carboxyl-terminated polybutadiene (CTPB) propellants than inorganic catalysts such as iron oxide and iron ferricyanide. Certain ferrocene derivatives not only can improve the mechanical property and the process property of the propellant, but also have the effect of reducing the pressure index. The method reduces the volatility and the mobility of the ferrocene burning rate catalyst, increases the iron content of the ferrocene burning rate catalyst, and improves the burning rate catalytic effect of the ferrocene burning rate catalyst, and is an important research topic of domestic and foreign scholars.
High-efficiency burning-rate catalysts of composite solid propellants, namely binuclear ferrocene derivatives, namely captoxin (Catocene, 2,2' -bis- (ethylferrocene) propane), BBFPr (2,2' -bis- (butylferrocene) propane) and BBFPe (1,1' -bis- (butylferrocene) pentane), are produced by Deland Weiba oil Co., Ltd. French explosives have developed a functional group-containing ferrocene polymer, Badyne (Butacene), which is a burn rate catalyst for linking ferrocene to hydroxyl-terminated polybutadiene prepolymers via chemical bonds, without volatility and migration. Catocene, BBFPr, BBFPe and Butacene are four recognized high-efficiency ferrocene derivatives. Bohn et al evaluated their behavior in regulating the burning rate of propellants and showed that they all had a significant effect in increasing the burning rate of propellants.
A series of mono-substituted and di-substituted acyl ferrocene is obtained by ferrocene acylation reaction in 2002 by Wang British science and the like, corresponding alkyl ferrocene is obtained by a Clemmenson reduction method, and the electrochemical properties of the alkyl ferrocene and the burning rate catalytic property of the alkyl ferrocene in a composite solid propellant are researched. Experimental results show that the electrochemical properties of the alkyl ferrocene are similar, the combustion rate catalytic performance is not obviously affected, and the combustion rate catalytic performance only has a positive correlation trend with the mass fraction of the iron element in the compound. In 2004, after hydroxyl ferrocene derivatives (RF), ferrocene ester derivatives (FBB), polynuclear ferrocene derivatives (GFP) and carborane high burning rate regulators (NHC) are respectively added into a propellant formula by Thalictrum aquilegifolium et al, the burning rate can be regulated at 10-100 mm/s (6.86-9.8 MPa), and the propellant has good comprehensive performance. Compared with tert-butyl ferrocene (TBF), the volatility is GFP < FBB < RF < TBF, and the mobility is GFP < FBB < RF < TBF.
International britain in 2006 used ferrocene as a raw material, and synthesized a series of ferrocene derivatives such as dicyclopentadienyl iron propane, formaldehyde-based dicyclopentadienyl iron propane, monohydric hydroxymethyl dicyclopentadienyl iron propane (HBP) and the like through condensation reaction, Vilsmeier formylation reaction, reduction reaction and the like. The mobility and volatility of the catalyst as a burning rate catalyst are reduced on the basis of ensuring the iron content. In 2008, the acylation reaction of ferrocene is carried out by the Tangxiaoming to obtain the chloroacetyl ferrocene derivative, and the differential scanning calorimeter is used for researching that after 5 percent chloroacetyl ferrocene is added into ammonium perchlorate, the peak temperature of the maximum weight loss rate of Ammonium Perchlorate (AP) is advanced by 103.57 ℃.
The progress of research on binuclear ferrocene and its derivatives was reviewed in Tangxiaoming in 2012 for the last decade. If hetero atoms containing lone pair electrons are connected on the cyclopentadienyl rings of the ferrocene and the derivatives thereof to form potential electron donors, the potential electron donors can be chelated with metal atoms such as rubidium, cesium, ruthenium, platinum and the like to form compounds with catalytic activity. Designing, synthesizing and researching the ferrocene complex and providing the catalytic effect with the synergistic catalytic action are hot spots in the future research field of ferrocene derivatives.
In 2015, cinnabar, Bianxi and the like synthesize phenyl-containing ferrocene β -diketone and Cu and Ni complexes thereof, and ferrocene β -diketone or Cu (II) or Ni (II) complexes thereof are added into AP, so that sublimation of AP in a high-temperature thermal degradation stage is inhibited to a certain extent, and the thermal degradation temperature of AP is advanced2·6H2The ferrocene pyrrole-imine chelating Ni complex is synthesized by O coordination, and has obvious thermal decomposition catalysis effect on the main component AP of the solid propellant. In 2015, Wangchun swallow and other people take ferrocene tetrazole as a main ligand, 2, 2-bipyridine and 1, 10-phenanthroline as auxiliary ligands, and form a series of ferrocene tetrazole metal complexes with transition metals. In 2017, W.H.Mahmoud et al prepared a novel ferrocene Schiff base ligand from 2-acetylferrocene and 2-aminophenol through an aldehyde-amine condensation reaction, and reacted with transition metal ions and 1, 10-phenanthroline to generate a series of transition metal complexes.
The development of a novel ferrocene burning-rate catalyst with low migration and volatility and excellent comprehensive performance and combustion regulation performance is still a hotspot in the research field.
Disclosure of Invention
The invention aims to overcome the defects of easy migration, easy volatilization and low energy of the existing ferrocene burning-rate catalyst, provide an N-ferrocenyl methyl-3-amino-1, 2, 4-triazole energetic transition metal complex which has good thermal stability under natural conditions, higher generated heat and combustion heat and adjustable catalytic performance, and provide a preparation method which is simple and convenient to operate and low in cost for the complex.
The N-ferrocenyl methyl-3-amino-1, 2, 4-triazole energy-containing transition metal complex used for solving the technical problems has the following structural formula:
wherein M represents Cu, Zn, Mn, Ni, Co, Cd or Fe, L is 1H,1' H- (5,5' -bitetrazole) -1,1' -diol dianion, and x is an integer of 0-3.
The preparation method of the N-ferrocenyl methyl-3-amino-1, 2, 4-triazole energy-containing transition metal complex comprises the following steps: dissolving divalent metal salt in distilled water, simultaneously dropwise adding an absolute ethanol solution of N-ferrocenylmethyl-3-amino-1, 2, 4-triazole and an aqueous solution of 1,1 '-dihydroxy-5, 5' -bitetrazole disodium salt tetrahydrate at the temperature of 60-70 ℃, stirring at constant temperature for reacting for 3-5 hours after dropwise adding, filtering, washing with absolute ethanol and distilled water, and drying in vacuum to obtain the N-ferrocenylmethyl-3-amino-1, 2, 4-triazole energetic transition metal complex.
The divalent metal salt is perchlorate or ferrous chloride of metal copper, zinc, manganese, nickel, cobalt and cadmium.
The molar ratio of the divalent metal salt to the N-ferrocenyl methyl-3-amino-1, 2, 4-triazole ligand and the 1,1 '-dihydroxy-5, 5' -bistetrazole disodium salt tetrahydrate is 1 (2-2.5): 1, wherein the structure of the N-ferrocenyl methyl-3-amino-1, 2, 4-triazole is as follows:
the preparation method comprises the following steps: dissolving ferrocene carboxaldehyde and 3-amino-1, 2, 4-triazole in a molar ratio of 1:1.25 in absolute ethyl alcohol, refluxing for 8 hours, reacting to reach equilibrium, evaporating to remove the solvent, performing silica gel column chromatography on the obtained red oily substance, wherein an eluent is a mixed solution of absolute ethyl alcohol and petroleum ether in a volume ratio of 1:5, and removing the solvent to obtain the ferrocene triazole Schiff base ligand. Dissolving the obtained ferrocene triazole Schiff base ligand in absolute methanol, adding 1.2 times of equivalent of sodium borohydride solid under an ice salt bath, heating to room temperature for reaction for 2 hours, adding a small amount of water to remove the residual sodium borohydride after the reaction is finished, concentrating under reduced pressure, extracting with dichloromethane and water, separating an organic layer, concentrating under reduced pressure to the volume of a precipitate, adding N-hexane to precipitate a product, filtering, and drying under vacuum to obtain the N-ferrocenyl methyl-3-amino-1, 2, 4-triazole ligand, wherein the yield is 73.3%.
The N-ferrocenylmethyl-3-amino-1, 2, 4-triazole energy-containing transition metal complex takes N-ferrocenylmethyl-3-amino-1, 2, 4-triazole as a neutral ligand and 1,1 '-dihydroxy-5, 5' -bitetrazole disodium salt tetrahydrate as an anionic ligand, and has the following advantages:
1. the complex is a transition metal complex, is not easy to volatilize under natural conditions, has good thermal stability, higher generated heat and combustion heat and extremely low mobility and volatility, and is favorable for solving the problems of easy migration and easy volatilization of ferrocene combustion regulators in propellants.
2. Compared with the traditional Schiff base ligand, the N-ferrocenyl methyl-3-amino-1, 2, 4-triazole ligand used by the complex has stable chemical property and can be stably stored; the anionic ligand 1,1 '-dihydroxy-5, 5' -bitetrazole disodium salt tetrahydrate has high nitrogen content, can reduce the sensitivity of a burning rate catalyst, and can contribute energy to a solid propellant.
3. The complex can regulate and control the catalytic performance of the main components ammonium perchlorate and hexogen of the composite solid propellant, reduce the sensitivity of the propellant on the combustion rate influenced by temperature and pressure, improve the combustion stability of the propellant and regulate the combustion rate of the propellant, thereby realizing different thrust schemes required by the propellant design.
4. The complex of the invention has simple preparation method, lower cost and higher yield, and overcomes the defects of complex synthesis process, high cost, long synthesis period and the like of the existing ferrocene burning-rate catalyst.
Drawings
FIG. 1 is a differential scanning calorimetry analysis of ammonium perchlorate with 5% of the complexes of examples 1 to 7 added thereto.
FIG. 2 is a differential scanning calorimetry analysis of hexogen with 5% of the complexes of examples 1-7 added.
FIG. 3 is a thermogravimetric analysis curve of the complexes of examples 1-4.
FIG. 4 is a thermogravimetric analysis curve of the complexes of examples 5-7.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
Example 1
0.09g (0.25mmol) of Cu (ClO)4)2·6H2Dissolving O in a 100m L round-bottom flask containing 10m L distilled water, when the temperature is raised to 60 ℃, simultaneously dropwise adding an absolute ethanol solution dissolved in 20m L and 0.14g (0.5mmol) of N-ferrocenylmethyl-3-amino-1, 2, 4-triazole and an aqueous solution dissolved in 10m L and 0.05g (0.25mmol) of 1,1 '-dihydroxy-5, 5' -bitetrazole disodium salt tetrahydrate, stirring at constant temperature for reaction for 2 hours after dropwise adding, generating a precipitate, filtering, washing a filter cake with absolute ethanol and distilled water, and drying in vacuum at normal temperature to obtain the N-ferrocenylmethyl-3-amino-1, 2, 4-triazole energetic Cu complex with the structural formula as follows:
the yield was 59.9%, and the structural characterization data were: IR (KBr, cm)-1):3391(s,br),3107(m),2362(w),1626(s),1590(s),1439(vs),1253(vs),1182(s),1102(m),1005(m),836(w),748(s),491(m)cm-1Elemental analysis (theoretical calculations in parentheses) C% 38.47(38.66), H% 4.39(4.59), N% 24.75(24.87).
Example 2
In this example, equimolar Zn (ClO) was used4)2·6H2Replacement of Cu (ClO) in example 1 by O4)2·6H2And O, prolonging the reaction time to 3 hours, and obtaining the N-ferrocenylmethyl-3-amino-1, 2, 4-triazole energy-containing Zn complex with the structural formula as follows by the same steps as in the example 1:
the yield is 32.21%The structural characterization data is: IR (KBr, cm)-1):3391(vs,br),1617(s),1563(m),1439(vs),1253(vs),1182(s),1013(m),836(w),748(s),491(m)cm–1Elemental analysis (theoretical calculations in parentheses) C% 39.80(39.37), H% 4.78(4.44), N% 25.75(25.33).
Example 3
In this example, equimolar Mn (ClO) was used4)2·6H2Replacement of Cu (ClO) in example 1 by O4)2·6H2And O, prolonging the reaction time to 5 hours, and obtaining the N-ferrocenylmethyl-3-amino-1, 2, 4-triazole energy-containing Mn complex with the structural formula shown in the specification by the same steps as in the example 1:
the yield was 50.86%, and the structural characterization data are: IR (KBr, cm)-1):3374(vs,br),1617(s),1546(m),1439(vs),1253(vs),1182(s),1013(m),836(w),748(m),491(m)cm–1Elemental analysis (theoretical calculations in parentheses) C% 41.80(41.55), H% 4.57(4.21), N% 26.46(26.73).
Example 4
In this example, equimolar Ni (ClO) was used4)2·6H2Replacement of Cu (ClO) in example 1 by O4)2·6H2And O, prolonging the reaction time to 5 hours, and obtaining the N-ferrocenylmethyl-3-amino-1, 2, 4-triazole energy-containing Ni complex with the structural formula shown in the specification by the same steps as in the example 1:
the yield was 73.92%, and the structural characterization data were: IR (KBr, cm)-1):3383(s,br),2362(m),1617(vs),1546(m),1439(s),1253(s),1182(m),1102(m),1013(m),819(m),739(m),491(s)cm–1Elemental analysis (theoretical calculations in parentheses) C% 39.80(39.67), H% 4.82(4.48), N% 25.73(25.52).
Example 5
In this example, equimolar Co (ClO) was used4)2·6H2Replacement of Cu (ClO) in example 1 by O4)2·6H2And O, prolonging the reaction time to 5 hours, and obtaining the N-ferrocenylmethyl-3-amino-1, 2, 4-triazole energetic Co complex with the structural formula shown in the specification by the same steps as in the example 1:
the yield was 36.5%, and the structural characterization data were: IR (KBr, cm)-1):3400(vs,br),1617(s),1563(s),1439(vs),1253(vs),1182(s),1102(m),1013(m),739(s),482(m)cm–1Elemental analysis (theoretical calculations in parentheses) C% 39.80(39.66), H% 4.63(4.48), N% 25.70(25.51).
Example 6
In this example, equimolar amounts of Cd (ClO) were used4)2·6H2Replacement of Cu (ClO) in example 1 by O4)2·6H2And O, prolonging the reaction time to 5 hours, and obtaining the N-ferrocenylmethyl-3-amino-1, 2, 4-triazole energy-containing Cd complex with the structural formula shown in the specification by the same steps as in the example 1:
the yield was 62.5%, and the structural characterization data were: IR (KBr, cm)-1):3391(vs,br),1617(s),1581(s),1439(vs),1253(vs),1005(m),748(s),482(m)cm–1Elemental analysis (theoretical calculations in parentheses) C% 38.20(38.12), H% 4.80(4.08), N% 24.68(24.54).
Example 7
In this example, equimolar FeCl was used2·4H2Replacement of Cu (ClO) in example 1 by O4)2·6H2And O, prolonging the reaction time to 5 hours, and obtaining the N-ferrocenylmethyl-3-amino-1, 2, 4-triazole energy-containing Fe complex with the structural formula shown in the specification by the same steps as in the example 1:
the yield was 24.35%, and the structural characterization data were: IR (KBr, cm)-1):3347(vs,br),1652(s),1617(s),1439(vs),1253(vs),1182(s),1013(m),748(s),561(m)cm–1Elemental analysis (theoretical calculations in parentheses) C% 39.53(39.80), H% 4.80(4.49), N% 25.45(25.60).
In order to prove the beneficial effects of the invention, the inventors used Ammonium Perchlorate (AP) and hexogen (RDX) as examples to test the catalytic performance of the complexes prepared in examples 1 to 7, and the specific experimental conditions are as follows:
1. test for catalytic Performance
(1) Respectively taking 5mg of the complexes prepared in the embodiments 1-7 and 95mg of powdered AP, and grinding and uniformly mixing; taking 5mg of carbethoxyine and 95mg of powdery AP, grinding and uniformly mixing; the catalytic performance of the catalyst was measured by a differential scanning calorimeter, and the results are shown in FIG. 1. As can be seen from fig. 1, the thermal decomposition of AP can be divided into three stages: the first process is the phase transition endothermic process of AP, the peak temperature is 249.0 ℃, the peak temperature in the second stage is 284.4 ℃, the process is the low-temperature decomposition process of AP, the peak temperature in the third stage is 415.3 ℃, the process is called the pyrolysis stage, and the process from the low-temperature pyrolysis stage to the pyrolysis stage shows a downward endothermic peak due to the thermal decomposition of AP to form gas (HCl, NH) in the stage3) The absorbed heat is larger than the released heat by the decomposition of the AP, so the heat release of the AP by the thermal decomposition process is not obvious. When 5% of the complexes of examples 1 to 7 are added into AP, the termination temperature of the pyrolysis stage is advanced to 312.7 to 356.8 ℃, and the heat released is 964.71 to 1453.56J/g. Therefore, compared with pure AP, the high-temperature decomposition stage of the system after the complex is added shows a concentrated heat release phenomenon, the heat release peak temperature is advanced, and the released heat is obviously increased; wherein the combustion catalysis effect of the complexes prepared in the examples 1 and 3 on AP is more remarkable than that of the carbenicin. The complex of the invention has good combustion catalysis effect on the thermal decomposition of AP.
(2) Respectively taking 5mg of each of the complexes prepared in the embodiments 1-7 and 95mg of powdered hexogen (RDX), and uniformly grinding and mixing; taking 5mg of carbethoxy and 95mg of powdered RDX, grinding and uniformly mixing; the catalytic performance of the catalyst was measured by a differential scanning calorimeter, and the results are shown in FIG. 2. As can be seen from figure 2, RDX has a remarkable exothermic decomposition peak at 229.2 ℃, and the heat released is 827.9J/g; when 5% of the complexes of examples 1 to 7 are added to RDX, the exothermic amount of RDX is increased by the complexes except the complex of example 2, wherein the exothermic amount of RDX is maximum by the complex of example 4 and is 1230.14J/g. Experimental results show that the complex has a certain catalytic action on thermal decomposition of RDX.
2. Thermal stability test
The complexes 3mg and captoxin 3mg prepared in examples 1 to 7 were taken, and the thermal stability of the complexes and captoxin was measured by a thermogravimetric analyzer, and the results are shown in fig. 3 and 4.
As can be seen from FIGS. 3 and 4, the weight loss temperature of the complexes prepared in the embodiments 1 to 7 of the invention is above 200 ℃, and the complexes have good thermal stability.
Claims (3)
1. An N-ferrocenyl methyl-3-amino-1, 2, 4-triazole energy-containing transition metal complex is characterized in that the structure of the complex is as follows:
wherein M represents Cu, Zn, Mn, Ni, Co, Cd or Fe, L is 1H,1' H- (5,5' -bitetrazole) -1,1' -diol dianion, and x is an integer of 0-3.
2. A preparation method of the N-ferrocenylmethyl-3-amino-1, 2, 4-triazole energy-containing transition metal complex as claimed in claim 1, which is characterized by comprising the following steps: dissolving divalent metal salt in distilled water, simultaneously dropwise adding an absolute ethanol solution of N-ferrocenylmethyl-3-amino-1, 2, 4-triazole and an aqueous solution of 1,1 '-dihydroxy-5, 5' -bitetrazole disodium salt tetrahydrate at the temperature of 60-70 ℃, stirring at constant temperature for reacting for 3-5 hours after dropwise adding, filtering, washing with absolute ethanol and distilled water, and drying in vacuum to obtain an N-ferrocenylmethyl-3-amino-1, 2, 4-triazole energetic transition metal complex;
the divalent metal salt is perchlorate or ferrous chloride of any one of copper, zinc, manganese, nickel, cobalt and cadmium.
3. The preparation method of the N-ferrocenylmethyl-3-amino-1, 2, 4-triazole energetic transition metal complex as claimed in claim 2, which is characterized in that: the molar ratio of the divalent metal salt to N-ferrocenyl methyl-3-amino-1, 2, 4-triazole and 1,1 '-dihydroxy-5, 5' -bitetrazole disodium salt tetrahydrate is 1: 2-2.5: 1.
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| US3781179A (en) * | 1971-03-29 | 1973-12-25 | C Huskins | Compositie propellants with a difunctional ballistic modifier curing agent |
| EP0794192A1 (en) * | 1996-03-06 | 1997-09-10 | Chemische Betriebe Pluto GmbH | Ferrocene derivatives |
| CN106831888A (en) * | 2017-03-28 | 2017-06-13 | 陕西师范大学 | Ferricinum ion type nitrogen metal complex high and preparation method thereof |
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| Ionic Ferrocenyl Coordination Compounds Derived from Imidazole and 1,2,4-Triazole Ligands and Their Catalytic Effects During Combustion;Na Zhang等，;《Journal of Inorganic and General Chemistry》;20180220;全文 * |
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