CN102267982A - BTATz (3,6-bis(1-H-1,2,3,4-tetrazole-5-amino)-1,2,4,5-tetrazine) metal energetic complex and preparation method thereof - Google Patents
BTATz (3,6-bis(1-H-1,2,3,4-tetrazole-5-amino)-1,2,4,5-tetrazine) metal energetic complex and preparation method thereof Download PDFInfo
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- CN102267982A CN102267982A CN2011101494202A CN201110149420A CN102267982A CN 102267982 A CN102267982 A CN 102267982A CN 2011101494202 A CN2011101494202 A CN 2011101494202A CN 201110149420 A CN201110149420 A CN 201110149420A CN 102267982 A CN102267982 A CN 102267982A
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Abstract
The invention discloses a 3,6-bis(1-H-1,2,3,4-tetrazole-5-amino)-1,2,4,5-tetrazine (BTATz) metal energetic complex and a preparation method thereof. The chemical formula of the energetic complex is [(C4H4N14)2ML2].mH2O, wherein M is the Pb<2+> or Cu<2+>; C4H4N14 is ligand BTATz; L is acetate or nitrate; and mH2O is coordinated water and/or crystal water in the complex and m is an integer or decimal number from 0 to 2. The preparation method of the energetic complex comprises the following steps of: dissolving BTATz in a solvent to prepare a solution, adding a soluble metal salt solution, mixing uniformly, heating and stirring, and then carrying out standing, washing, filtering and other processes to prepare a product. As a combustion catalyst, the BTATz metal energetic complex prepared by the preparation method disclosed by the invention has significant catalysis effect and excellent capability of reducing the pressure index for the medium and low pressure combustion of a double-base propellant, and is an efficient medium and low pressure combustion catalyst.
Description
Technical field
The present invention relates to 3, two (the 1-hydrogen-pyrrotriazole-5-amino)-1,2,4 of 6-, 5-tetrazine (BTATz) metal contains energy title complex and preparation method thereof, and this contains the combustioncatalysts that the energy title complex can be used as solid rocket propellant.
Background technology
The combustionproperty of solid propellant directly affects ballisticperformances, flight velocity and the job stability etc. of rocket engine.Oneself becomes one of effective means of present adjusting propellant burning property to use combustioncatalysts.People are through secular effort, developed polytype combustioncatalysts, for example: metal oxide catalyst, inorganic salt catalyst, ferrocene class catalyzer, organic salt catalyzer, organic coordination compound catalyzer, containing can catalyzer and nanocatalyst etc., existing unit catalyzer also has polynary composite catalyst.Yet along with the continuous development of missilery, the combustioncatalysts that uses can not satisfy the demand for development of novel solid propelling agent well at present, and people are being devoted to Development of New Generation high-performance combustioncatalysts.
Double-basis is that propelling agent is rocket and a guided missile class high energy fuels commonly used.But double-basis is the shortcoming of propelling agent is that combustion speed is lower, the pressure index is higher, needs to add combustioncatalysts and regulates.
Summary of the invention
The purpose of this invention is to provide a kind of BTATz metal and contain the energy title complex, this contains and can be used as the combustioncatalysts that double-basis is a propelling agent by title complex.
Another object of the present invention provides the preparation method that the BTATz metal contains the energy title complex.
Implementation procedure of the present invention is as follows:
Shown in the formula I 3, two (the 1-hydrogen-pyrrotriazole-5-amino)-1,2,4 of 6-, 5-tetrazine (BTATz) contains the energy metal complexes,
[(C
4H
4N
14)
2ML
2]·mH
2O (Ⅰ)
Wherein, M is Pb
2+Or Cu
2+, M is preferably Pb
2+, C
4H
4N
14Be part BTATz, L is acetate or nitrate radical, mH
2O is coordinated water and/or the crystal water in the title complex, and m is 0~2 integer or decimal.At a certain temperature, [(C
4H
4N
14)
2ML
2] mH
2O can lose all or part of coordinated water and/or crystal water.
Above-mentioned BTATz metal contains the preparation method of energy title complex, may further comprise the steps:
(1) acetate or the nitrate with lead or copper is dissolved in water;
(2) BTATz is dissolved in DMF or DMSO, under 60 ℃ ~ 90 ℃ stirrings, mixes with metal salt solution;
(3) at 50 ℃ ~ 80 ℃ constant temperature stirring reaction 1 h ~ 2 h, cool off, leave standstill;
(4) washing of precipitate, filtration, drying can be made the BTATz metal and contain the energy title complex.
Advantage of the present invention and positively effect: but have a plurality of coordination nitrogen-atoms in the BTATz molecule, can form title complex with metal, title complex of the present invention has following characteristics as combustioncatalysts: contain tetrazine and tetrazolium aromatic ring structure in (1) BTATz molecule, tetrazine ring has the π bond structure of class benzene, and the N of band H provides two P electronics to form big π system on the tetrazole ring.This structure make BTATz and metal complexes thereof have thermally-stabilised, to the character of static, friction and bump insensitiveness; (2) BTATz is a kind of novel nitrogen-enriched compounds, has very high positive Enthalpies of Formation, and the high nitrogen low-carbon (LC) hydrogen richness in the molecular structure makes it have higher density.The BTATz metal contains the energy of energy title complex itself, can solve because the problem that the propellant formulation energy that uses inert catalyst to bring reduces; (3) lead of BTATz, copper complex can improve the combustionproperty of composite modified double base propellant.BTATz metal of the present invention contain can title complex be that the burning of solid propellant has good catalytic effect as combustioncatalysts to double-basis, can significantly improve the combustion speed of propelling agent, reduce the pressure index.
Description of drawings
Fig. 1 contains the infrared spectrogram of energy title complex for BTATz lead (II);
Fig. 2 contains the structural representation of energy title complex for BTATz lead (II);
Fig. 3 contains the infrared spectrogram of energy title complex for BTATz copper (II);
Fig. 4 contains the structural representation of energy title complex for BTATz copper (II);
Fig. 5 is the burningrate curve of double-base propellent;
Fig. 6 is the burningrate curve of composite modified double base propellant.
Embodiment
BTATz lead of the present invention (II), copper (II) contain the concrete preparation method of energy title complex combustioncatalysts and the katalysis performance of BTATz lead (II) is provided in detail by following examples.
(1) takes by weighing 2.5 g BTATz, under 70 ℃, it is dissolved in the 200 ml dimethyl sulfoxide (DMSO); Take by weighing 1.9 g Pb (CH
3COO)
23H
2O is configured to solution with deionized water dissolving, joins in the BTATz solution, mixes;
(2) at 70 ℃ of constant temperature stirring reaction 1 h, cool off then, leave standstill;
(3) precipitate with deionized water and dehydrated alcohol are repeatedly washed, filtration, drying can make BTATz lead (II) and contain energy title complex, yield 83.3%.
BTATz lead (II) contains the C and the elemental analyser analysis of H content of energy title complex, and Pb content is measured with X-ray fluorescence spectra.Ultimate analysis (%): C 17.20, and H 1.81, and N 47.32, and Pb 23.63, infer the PbC that consists of that this title complex thus
12H
16N
28O
5, calculated value (%): C 17.2, and H 1.91, and N 46.7, and Pb 24.7.Contain a plurality of constructional features of participating in the coordinate group according to BTATz, infer that this title complex is made up of the part of 1 Pb (II) and 4 molecules, part is the BTATz of 2 molecules and the carboxylate radical of 2 molecules, and its chemical formula is: [(C
4H
4N
14)
2Pb (CH
3COO)
2] H
2O.
BTATz lead (II) contains the infrared spectrum of energy title complex and sees Fig. 1.By part (
a) and title complex (
b) the infrared spectra comparative analysis as can be known, after title complex forms, on the part tetrazine ring
υ N-NBy 1345.47 cm
-1Move to 1322.87 cm
-1, show that the N atom on the part tetrazine ring participates in coordination Cheng Jian.New discovery 1506.48 cm in title complex
-1The absorption peak at place can belong to the asymmetrical stretching vibration of carboxylate radical, shows that carboxylic acid ion has also participated in coordination in title complex.At 1042.58 cm
-1The absorption peak at place can belong to the in-plane bending vibration for tetrazine ring.Can tentatively infer N atom and carboxylic acid ion and lead (II) coordination on the part tetrazine ring in conjunction with above-mentioned analysis.Complex structure as shown in Figure 2.
(1) takes by weighing 2.0 g BTATz, under 70 ℃, it fully is dissolved among the 80 ml DMSO; Take by weighing 0.8 g Cu (CH
3COO)
2H
2The O deionized water dissolving joins in the BTATz solution, mixes;
(2) at 70 ℃ of constant temperature, stirring reaction 1.5 h cool off then, leave standstill;
(3) precipitate with deionized water and dehydrated alcohol are repeatedly washed, filtration, drying can make BTATz copper (II) and contain energy title complex, product yield 57.5%.
BTATz copper (II) contains the C and the elemental analyser analysis of H content of energy title complex, and Cu content is measured with X-ray fluorescence spectra; Ultimate analysis (%): C 20.18, and H 2.541, and N 54.93, and Cu 8.90, infer the CuC that consists of that this title complex thus
12H
18N
28O
6, calculated value (%): C 20.2, and H 2.52, and N 54.90, and Cu 8.96.Contain a plurality of constructional features that participate in the coordinate group according to BTATz, the deduction title complex is made up of the part of 1 Cu (II) and 4 molecules, and part is the BTATz of 2 molecules and the carboxylate radical of 2 molecules, and its chemical formula is: [(C
4H
4N
14)
2Cu (CH
3COO)
2] 2H
2O.
BTATz copper (II) contains the infrared spectrum of energy title complex and sees Fig. 3.By part (
a) and title complex (
b) the infrared spectra comparative analysis as can be known, after title complex formed, part was at 1345.47 cm
-1On the tetrazine ring at place the N-N stretching vibration peak a little less than, show that the N on the part tetrazine ring participates in coordination Cheng Jian.New discovery 1506.48 cm in title complex
-1The absorption peak at place can belong to the asymmetrical stretching vibration of carboxylate radical, shows that carboxylic acid ion has also participated in coordination in title complex.Can tentatively infer N atom and carboxylic acid ion and Cu (II) coordination on the part tetrazine ring in conjunction with above-mentioned analysis.Complex structure as shown in Figure 4.
Embodiment 3
The basic components that the BTATz lead (II) of embodiment 1 preparation contains the double-base propellent that adopted of katalysis performance test that can title complex is: nitro-cotton (NC, 12.0%N) 59%, nitroglycerine (NG) 30%, diethyl phthalate (DEP) 8.5%, other auxiliary agent 2.5%.Spice is by 500 g batching, and it can title complex be outer dosage that combustioncatalysts BTATz lead (II) contains, and add-on is 2.5%; The blank propelling agent sample of control group does not contain combustioncatalysts.
The propelling agent sample by absorption-expelling water-put ripe-the conventional solvent-free companding shaping technology of rolling-being cut into medicinal strip makes.The combustion speed of sample adopts the target collimation method to record.Φ 5 * 150 mm powder column sides of having handled are coated 6 times with the polyvinyl alcohol solution dipping and dry, fire and fire the speed test in the fast instrument filling nitrogen slow-action formula then.Test temperature is 20 ° of C, pressure range 2 MPa ~ 22 MPa.
As can be seen from Figure 5, after the BTATz lead (II) of adding 2.5% contains the energy title complex, double-base propellent significant hypervelocity combustion phenomena occurs at 2 MPa ~ 8 MPa propelling agents, propellant burning rate begins to descend after being higher than 8 MPa, " wheat is spread " effect occurs at 8 MPa ~ 12 MPa, continue to raise steadily at 14 MPa ~ 22 MPa propellant burning rates.This catalyzer is at the catalytic efficiency of 2 MPa ~ 8 MPa
Z(
,
Be the combustion speed of blank propelling agent,
For containing the propellant burning rate of catalyzer) be respectively 3.08,2.26,1.77,1.52.At 8 MPa ~ 12 MPa, the pressure index of propelling agent
nWei – 0.06.
The basic components that the BTATz lead (II) of embodiment 1 preparation contains the composite modified double base propellant that adopted of katalysis performance test that can title complex is: nitro-cotton (NC, 12.0%N) 38%, nitroglycerine (NG) 28%, Cyclotrimethylene trinitramine (RDX) 26%, Ji Na (DINA) 5%, other auxiliary agent 3.0%.Spice is by 500 g batching, and it can title complex be outer dosage that combustioncatalysts BTATz lead (II) contains, and add-on is 2.5%; The blank propelling agent sample of control group does not contain combustioncatalysts.The preparation of propelling agent sample is with embodiment 3.
As can be seen from Figure 6, after the BTATz lead (II) of adding 2.5% contained the energy title complex, composite modified double base propellant was in the significantly increase of mesolow district combustion speed, and this catalyzer is at the catalytic efficiency of 2 MPa ~ 8 MPa
ZBe respectively 2.59,1.85,1.44,1.11.At 4 MPa ~ 12 MPa, the pressure index of propelling agent
nBe 0.18.
As seen, BTATz lead (II) contain can title complex be that the mesolow burning of propelling agent has remarkable katalysis and good reduction pressure exponential ability for double-basis, illustrate that this contains can title complex be a kind of combustioncatalysts of mesolow efficiently.
Embodiment 5
The BTATz copper (II) of embodiment 2 preparations contains tests combustion speed and pressure index in energy title complex adding double-base propellent or the composite modified double base propellant, appearance and BTATz lead (II) contain the similar feature of energy title complex, in the remarkable increase of mesolow district combustion speed.
Claims (4)
1. 3 shown in the formula I, two (the 1-hydrogen-pyrrotriazole-5-amino)-1,2,4 of 6-, 5-tetrazine (BTATz) contain can metal complexes,
[(C
4H
4N
14)
2ML
2]·mH
2O (Ⅰ)
Wherein, M is Pb
2+Or Cu
2+, C
4H
4N
14Be part BTATz, L is acetate or nitrate radical, mH
2O is coordinated water and/or the crystal water in the title complex, and m is 0~2 integer or decimal.
2. the energy metal complexes that contains according to claim 1, it is characterized in that: M is Pb
2+
3. the described BTATz metal of claim 1 contains the preparation method of energy title complex, may further comprise the steps:
(1) acetate or the nitrate with lead or copper is dissolved in water;
(2) BTATz is dissolved in DMF or DMSO, under 60 ℃ ~ 90 ℃ stirrings, mixes with metal salt solution;
(3) at 50 ℃ ~ 80 ℃ constant temperature stirring reactions, cool off, leave standstill;
(4) washing of precipitate, filtration, drying can be made the BTATz metal and contain the energy title complex.
The described BTATz metal of claim 1 contain can title complex be as the purposes of mesolow combustioncatalysts in the propelling agent in double-basis.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105440070A (en) * | 2015-11-11 | 2016-03-30 | 西安近代化学研究所 | 1,1'-dihydro-5,5'-bistetrazole-lead coordination polymer and preparation method thereof |
CN111233900A (en) * | 2019-01-26 | 2020-06-05 | 南京理工大学 | Preparation method of high-oxygen-balance energetic metal complex |
CN115724705A (en) * | 2021-08-31 | 2023-03-03 | 南京理工大学 | Preparation method of transition metal particle coated pentaminotetrazole |
-
2011
- 2011-06-07 CN CN2011101494202A patent/CN102267982A/en active Pending
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105440070A (en) * | 2015-11-11 | 2016-03-30 | 西安近代化学研究所 | 1,1'-dihydro-5,5'-bistetrazole-lead coordination polymer and preparation method thereof |
CN105440070B (en) * | 2015-11-11 | 2017-11-24 | 西安近代化学研究所 | Bistetrazole lead coordination polymer of 1,1 ' dihydro 5,5 ' and preparation method thereof |
CN111233900A (en) * | 2019-01-26 | 2020-06-05 | 南京理工大学 | Preparation method of high-oxygen-balance energetic metal complex |
CN115724705A (en) * | 2021-08-31 | 2023-03-03 | 南京理工大学 | Preparation method of transition metal particle coated pentaminotetrazole |
CN115724705B (en) * | 2021-08-31 | 2024-04-12 | 南京理工大学 | Preparation method of transition metal particle coated pentaaminotetrazole |
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Application publication date: 20111207 |