CN102836733A - Preparation method of energetic bimetallic nitro complex - Google Patents
Preparation method of energetic bimetallic nitro complex Download PDFInfo
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- CN102836733A CN102836733A CN2012103266756A CN201210326675A CN102836733A CN 102836733 A CN102836733 A CN 102836733A CN 2012103266756 A CN2012103266756 A CN 2012103266756A CN 201210326675 A CN201210326675 A CN 201210326675A CN 102836733 A CN102836733 A CN 102836733A
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Abstract
The invention discloses a preparation method of an energetic bimetallic nitro complex. The preparation method comprises the following steps of: preparing KNO2 aqueous solution; preparing aqueous solution containing Pb<2+> and Cu<2+>; preparing a reverse micro-emulsion system; mixing two parts of reverse micro-emulsion systems; aging and then centrifuging; washing a product; drying and the like, wherein the product is K2Pb[Cu(NO2)6]. The product has the advantages of cubic and rod-like appearance, high dispersibility, superior various parameters, low price of used raw materials and concise preparation flow.
Description
Technical field
The invention belongs to the energetic material technical field, particularly a kind of preparation method who contains ability bimetallic nitro complex.
Background technology
At present; It is compound as combustion catalyst that double-basis and modified double base propellant are used lead salt, mantoquita and material with carbon element always; Because it can be inert catalyst that this type catalyst does not contain; Generally can reduce the energy characteristics of propellant, and activity is also lower, thus research, development of new to contain catalyst to be the important directions of solid propellant research.Theoretical Calculation and MOLECULE DESIGN research shows, will have containing of reproducibility can material and metallic ion coordination, and combines to form complex with Coulomb attraction with the anion with oxidisability, is to contain the up-and-coming developing direction of ability catalyst.As contain can complex part must satisfy 2 conditions: the one, it is few and nitrogen content is high to contain hydrocarbon amount; So just has the high positive enthalpy of formation; Make the product energy high, high nitrogen, low-carbon (LC) hydrogen content not only make it have higher density, and reach oxygen balance more easily simultaneously; The 2nd, contain a coordination atom that lone pair electrons can be provided at least, like N, O, S etc.According to above-mentioned condition, can be used as contain can part material molecule in contain the enthalpy of formation for just or approach positive-NO
2, C-NO
2And N-NO
2Deng contain can group.Thereby developed at present contain rich nitrogen heterocyclic such as triazolinones, tetrazolium class can catalyst be arranged, and rich nitrogen straight chain compound such as carbohydrazide (CHZ) and derivative thereof etc.Like document 1 Singh G, Kapoor P S, Prem F S; Et al.Studies on energetic compounds part 23:Preparation thermal and explosive charcteristics of transitionmetal salts of 5-nitro-2; 4-dihydro-3H-1,2,4-triazole-3-one (NTO) [J] .Propellant Explosive Pyrotech; 2002,27 (1): 16-22 has reported that NTO salt contains the ability catalyst; Document 2 She Jiang ripple .3; 5-dinitro pyridone contains synthesizing, characterizing of ability catalyst and heat analysis and research one. Shaanxi Normal University's Master's thesis; Reported that the pyrazoles salt contains the ability catalyst, but can exist problems such as sensitivity height, poor safety performance by catalyst above-mentioned containing.Going up does not both at home and abroad also have research to the ability catalyst that contains to metal ion and nitro formation complex.
Summary of the invention
The object of the present invention is to provide a kind of product pattern is cubic and bar-shaped, good dispersion, and various parameters are superior, and the cost of material that uses is cheap, the preparation method who contains ability bimetallic nitro complex that preparation flow is succinct.
The technical solution that realizes the object of the invention is:
A kind of preparation method who contains ability bimetallic nitro complex of the present invention may further comprise the steps:
Step 1: preparation KNO
2The aqueous solution;
Step 2: preparation contains Pb
2+And Cu
2+The aqueous solution, Pb wherein
2+And Cu
2+Mol ratio 1:1;
Step 3: two parts of the reverse microemulsion liquid system that dose volume equates; Cyclohexane in the reverse microemulsion liquid system: triton x-100: salting liquid: the cosurfactant volume ratio is 30:3:1:1; Wherein, the salting liquid in first part of reverse microemulsion liquid system is the KNO in the step 1
2Salting liquid in the aqueous solution, second part of reverse microemulsion liquid system is the Pb that contains in the step 2
2+And Cu
2+The aqueous solution;
Step 4: below 30 ℃, first part of reverse microemulsion liquid system mixed with second part of reverse microemulsion liquid system, wherein, K
+And Pb
2+Molar concentration rate more than or equal to 6; And gentle agitation is still aging under the room temperature then more than 0.5 hour;
Step 5: centrifugalize mother liquor after the ageing, washed product is also dry, promptly obtains K
2Pb [Cu (NO
2)
6] powder.
The present invention compared with prior art, its remarkable advantage:
The present invention utilizes reverse microemulsion process successfully to prepare nanometer K
2Pb [Cu (NO
2)
6] particle, pattern is a cubic and bar-shaped, good dispersion is surveyed quick-fried hot Q
VBe 514KJ/Kg, friction sensitivity is 0%, impact sensitivity H
50＞60cm.The present invention prepares nanometer K
2Pb [Cu (NO
2)
6] employed cost of material is cheap, preparation flow is succinct; And the K of the present invention's preparation
2Pb [Cu (NO
2)
6] product has good catalytic effect aspect the catalysis AP thermal decomposition, the pyrolytic peak of being not only AP shifts to an earlier date greatly, and makes sharp-pointed that the thermal decomposition peak of AP becomes, and has improved the thermal decomposition thermal discharge of AP to a great extent.
Below in conjunction with accompanying drawing the present invention is described in further detail.
Description of drawings
Fig. 1 is the K that is obtained by instance 1 method provided by the invention
2Pb [Cu (NO
2)
6] ESEM (SEM) photo; Wherein (a) is the product that the inventive method obtains, and pattern is a cube, and the average length of side is about 1 μ m, (b) is the bar-shaped product of the only a few that is mingled with in the product, and diameter is 200nm, and length is 2 ~ 3 μ m.
Fig. 2 is the K that is obtained by instance 5 methods provided by the invention
2Pb [Cu (NO
2)
6] ESEM (SEM) photo; Wherein (a) is the product of the inventive method acquisition, and pattern is cube and clava, (b) is the clava in the product, and diameter is 200 ~ 300nm, and length is 3 ~ 4 μ m.
Fig. 3 is the K that is obtained by instance 6 methods provided by the invention
2Pb [Cu (NO
2)
6] ESEM (SEM) photo.
Fig. 4 is for being the K that is obtained by instance 7 methods provided by the invention
2Pb [Cu (NO
2)
6] ESEM (SEM) photo; Wherein (a) is the product of the inventive method acquisition, and pattern is a hexagon, and the elongated 2 μ m that are about have dispersiveness preferably, (b) are the enlarged drawing of (a).
Fig. 5 is the K that is obtained by instance 1 method provided by the invention
2Pb [Cu (NO
2)
6] particle diameter distribute.
Fig. 6 is the K that is obtained by instance 1, instance 5 and instance 6 methods provided by the invention
2Pb [Cu (NO
2)
6] the XRD figure spectrum.
Fig. 7 is the K that is obtained by instance 1 method provided by the invention
2Pb [Cu (NO
2)
6] the DSC-TG collection of illustrative plates.
Fig. 8 is pure AP, the K that is obtained by instance 8 methods provided by the invention
2Pb [Cu (NO
2)
6The DSC curve of]/AP compound particle.
Fig. 9 is a method flow diagram of the present invention.
The specific embodiment
A kind of preparation method who contains ability bimetallic nitro complex of the present invention may further comprise the steps:
Step 1: preparation KNO
2The aqueous solution;
Step 2: preparation contains Pb
2+And Cu
2+The aqueous solution, Pb wherein
2+And Cu
2+Mol ratio 1:1;
Step 3: two parts of the reverse microemulsion liquid system that dose volume equates; Cyclohexane in the reverse microemulsion liquid system: triton x-100: salting liquid: the cosurfactant volume ratio is 30:3:1:1; Wherein, the salting liquid in first part of reverse microemulsion liquid system is the KNO in the step 1
2Salting liquid in the aqueous solution, second part of reverse microemulsion liquid system is the Pb that contains in the step 2
2+And Cu
2+The aqueous solution;
Step 4: below 30 ℃, first part of reverse microemulsion liquid system mixed with second part of reverse microemulsion liquid system, wherein, K
+And Pb
2+Molar concentration rate more than or equal to 6; And gentle agitation is still aging under the room temperature then more than 0.5 hour;
Step 5: centrifugalize mother liquor after the ageing, washed product is also dry, promptly obtains K
2Pb [Cu (NO
2)
6] powder.
Wherein, the washing in the step 5 is meant with absolute ethanol washing product 3-5 time until the free from admixture ion; Described drying is meant the product after the washing is placed baking oven dry 4-6h under 40 ℃-80 ℃.
Following embodiment can make those skilled in the art more fully understand the present invention, but does not limit the present invention in any way.
(1) preparation 2molL
-1KNO
2The aqueous solution: the KNO that takes by weighing 3.4g
2Be dissolved in the deionized water of 20ml.
(2) preparation 0.2molL
-1Pb (NO
3)
2And Cu (NO
3)
23H
2The mixed aqueous solution of O: the Pb (NO that takes by weighing 1.3248g
3)
2Cu (NO with 0.9664g
3)
23H
2O is dissolved in the deionized water of 20ml.
(3) preparation reverse microemulsion liquid system A1: the cyclohexane of measuring 60ml adds the surfactant triton x-100 of 6ml in the beaker of 200ml, under the magnetic agitation condition, drip 2molL
-1KNO
2Solution 1.8ml, this moment, solution became milky, under powerful stirring condition, dropwise dripped cosurfactant n-amyl alcohol 2.0ml, continued to stir 15 minutes, and solution becomes clarification.Its ω
0(mol ratio of water and surfactant) is 10, and P value (mol ratio of cosurfactant n-amyl alcohol and surfactant triton x-100) is 2.
(4) preparation reverse microemulsion liquid system B1: in the cyclohexane of measuring 60ml and the beaker of 200ml, the surfactant triton x-100 of adding 6ml drips 0.2molL under the magnetic agitation condition
-1Pb (NO
3)
2And Cu (NO
3)
23H
2O solution 1.8ml, this moment, solution became light blue emulsion, under powerful stirring condition, dropwise dripped cosurfactant n-amyl alcohol 2.0ml, continued to stir 15 minutes, and solution becomes clarification.
Under (5) 20 ℃, reverse micro emulsion B1 is mixed among the A1 gentle agitation 0.5h, still aging 24h under the room temperature then rapidly.
(6) the centrifugal product that makes separates with mother liquor, with absolute ethanol washing product 4 times until the free from admixture ion.
(7) product after will washing place baking oven 40 ℃ down dry 6h promptly obtain K
2Pb [Cu (NO
2)
6] powder.
The K of this examples preparation
2Pb [Cu (NO
2)
6] the product pattern is cube, the average length of side is about 1 μ m (shown in Fig. 1 (a)); And the bar-shaped product that is mingled with only a few, diameter are 200nm, and length is 2 ~ 3 μ m (shown in Fig. 1 (b)).XRD shows that product is a cubic, and particle diameter distributes as shown in the table:
Table 1 K
2Pb [Cu (NO
2)
6] particle size distribution data
| Concentration | Spacing size distribution width | The uniformity distributing homogeneity | Measurement unit |
| 0.0001%Vol | 1.505 | 0.465 | Volume |
| Specific area | Press surface area weighted average D [3,2]: | Weighted average D [4,3] by volume: | ? |
| 4.13m 2/g | 1.454 um | 2.072um | ? |
| D(0.10):0.81μm | D(0.50):1.88μm | D(0.90):3.64μm | D(1.00):5.97μm |
(1) preparation 2molL
-1KNO
2The aqueous solution: the KNO that takes by weighing 3.4g
2Be dissolved in the deionized water of 20ml.
(2) preparation 0.2molL
-1Pb (CH
3COO)
23H
2O and Cu (CH
3COO)
2Mixed aqueous solution: the Pb (CH that takes by weighing 1.5174g
3COO)
23H
2Cu (the CH of O and 0.7266g
3COO)
2Be dissolved in the deionized water of 20ml.
(3) preparation reverse microemulsion liquid system A2: the cyclohexane of measuring 60ml adds the surfactant triton x-100 of 6ml in the beaker of 200ml, under the magnetic agitation condition, drip 2molL
-1KNO
2Solution 1.8ml, this moment, solution became milky, under powerful stirring condition, dropwise dripped cosurfactant n-hexyl alcohol 1.73ml, continued to stir 15 minutes, and solution becomes clarification.Its ω
0(mol ratio of water and surfactant) is 10, and P value (mol ratio of cosurfactant n-amyl alcohol and surfactant triton x-100) is 2.
(4) preparation reverse microemulsion liquid system B2: in the cyclohexane of measuring 60ml and the beaker of 200ml, the surfactant triton x-100 of adding 6ml drips 0.2molL under the magnetic agitation condition
-1Pb (CH
3COO)
23H
2O and Cu (CH
3COO)
2Mixed aqueous solution 1.8ml, under powerful stirring condition, dropwise drip cosurfactant n-hexyl alcohol 1.73ml, continue to stir 15 minutes, solution becomes clarification.
Under (5) 10 ℃, reverse micro emulsion B2 is mixed among the A2 gentle agitation 1h, still aging 24h under the room temperature then rapidly.
(6) the centrifugal product that makes separates with mother liquor, with absolute ethanol washing product 5 times until the free from admixture ion.
(7) product after will washing place baking oven 80 ℃ down dry 4h promptly obtain K
2Pb [Cu (NO
2)
6] powder.
Embodiment 3
(1) preparation 3molL
-1KNO
2The aqueous solution: the KNO that takes by weighing 5.1g
2Be dissolved in the deionized water of 20ml.
(2) preparation 0.3molL
-1Pb (NO
3)
2And Cu (CH
3COO)
2Mixed aqueous solution: the Pb (NO that takes by weighing 1.9872g
3)
2Cu (CH with 1.0899g
3COO)
2Be dissolved in the deionized water of 20ml.
(3) preparation reverse microemulsion liquid system A2: the cyclohexane of measuring 60ml adds the surfactant triton x-100 of 6ml in the beaker of 200ml, under the magnetic agitation condition, drip 3molL
-1KNO
2Solution 1.8ml, this moment, solution became milky, under powerful stirring condition, dropwise dripped cosurfactant n-hexyl alcohol 1.73ml, continued to stir 15 minutes, and solution becomes clarification.Its ω
0(mol ratio of water and surfactant) is 10, and P value (mol ratio of cosurfactant n-amyl alcohol and surfactant triton x-100) is 2.
(4) preparation reverse microemulsion liquid system B2: in the cyclohexane of measuring 60ml and the beaker of 200ml, the surfactant triton x-100 of adding 6ml drips 0.3molL under the magnetic agitation condition
-1Pb (NO
3)
2And Cu (CH
3COO)
2Solution 1.8ml dropwise drips cosurfactant n-hexyl alcohol 1.73ml under powerful stirring condition, continue to stir 15 minutes, and solution becomes clarification.
Under (5) 10 ℃, reverse micro emulsion B2 is mixed among the A2 gentle agitation 1h, still aging 24h under the room temperature then rapidly.
(6) the centrifugal product that makes separates with mother liquor, with absolute ethanol washing product 5 times until the free from admixture ion.
(7) product after will washing place baking oven 80 ℃ down dry 4h promptly obtain K
2Pb [Cu (NO
2)
6] powder.
The K of this examples preparation
2Pb [Cu (NO
2)
6] the product pattern is cube, compares with instance 1, particle diameter is bigger.
Embodiment 4
(1) preparation 1molL
-1KNO
2The aqueous solution: the KNO that takes by weighing 1.7g
2Be dissolved in the deionized water of 20ml.
(2) preparation 0.1molL
-1Pb (CH
3COO)
23H
2O and Cu (NO
3)
23H
2O mixed aqueous solution: the Pb (CH that takes by weighing 0.7587g
3COO)
23H
2Copper nitrate Cu (the NO of O and 0.4832g
3)
23H
2O is dissolved in the deionized water of 20ml.
(3) preparation reverse microemulsion liquid system A3: the cyclohexane of measuring 60ml adds the surfactant triton x-100 of 6ml in the beaker of 200ml, under the magnetic agitation condition, drip 1molL
-1KNO
2Solution 1.8ml, this moment, solution became milky, under powerful stirring condition, dropwise dripped cosurfactant n-amyl alcohol 2.0ml, continued to stir 15 minutes, and solution becomes clarification.Its ω
0(mol ratio of water and surfactant) is 10, and P value (mol ratio of cosurfactant n-amyl alcohol and surfactant triton x-100) is 2.
(4) preparation reverse microemulsion liquid system B3: in the cyclohexane of measuring 60ml and the beaker of 200ml, the surfactant triton x-100 of adding 6ml drips 0.1molL under the magnetic agitation condition
-1Pb (CH
3COO)
23H
2O and Cu (NO
3)
23H
2O solution 1.8ml dropwise drips cosurfactant n-amyl alcohol 2.0ml under powerful stirring condition, continue to stir 15 minutes, and solution becomes clarification.
(5) under the room temperature condition, reverse micro emulsion B3 is mixed among the A3 gentle agitation 2h, still aging 24h under the room temperature then rapidly.
(6) the centrifugal product that makes separates with mother liquor, with absolute ethanol washing product 3 times until the free from admixture ion.
(7) product after will washing place baking oven 40 ℃ down dry 4h promptly obtain K
2Pb [Cu (NO
2)
6] powder.
Embodiment 5
Preparation method according in the instance 1 prepares K
2Pb [Cu (NO
2)
6], digestion time is increased to 48h by the 24h in the instance 1.
The K of this examples preparation
2Pb [Cu (NO
2)
6] the product pattern is cube and bar-shaped (shown in Fig. 2 (a)); Bar-shaped diameter is 200 ~ 300nm, and length is 3 ~ 4 μ m (shown in Fig. 2 (b)).Product has dispersed preferably.
Embodiment 6
Keep the P value constant, digestion time 24h, ω
0Value is reduced to 8 by 10 in the instance 1, and promptly the salting liquid addition among reverse micro emulsion A1, the B1 becomes 1.44ml.
The K of this examples preparation
2Pb [Cu (NO
2)
6] product is the cube pattern, size is about 0.8 μ m, and is better dispersed.
Embodiment 7
This instance uses the surfactant-dispersed precipitation method to prepare K
2Pb [Cu (NO
2)
6] product, concrete preparation flow is following:
(1) takes by weighing the Pb (NO of 0.6624g respectively
3)
2Cu (NO with 0.4832g
3)
23H
2O is dissolved in the ethylene glycol of 20ml, obtains solution A 4.
(2) (PVP K-30) is dissolved in the 40ml deionized water, adds the KNO of 1.702g to take by weighing the polyvinylpyrrolidone of 4.44g
2(PVP and KNO
2Mol ratio be 2) dissolving, obtain solution B 4.
(3) under the situation of ultrasonic vigorous stirring, A4 solution slowly is added drop-wise to B4 solution, dropwises and continue ultrasonic agitation 30min, ageing 24h under the room temperature condition.
(4) with the centrifugation of the product that obtains, with absolute ethanol washing product 4 times until the free from admixture ion.
(5) product after will washing place baking oven 40 ℃ down dry 4h promptly obtain K
2Pb [Cu (NO
2)
6] powder.
The K of this examples preparation
2Pb [Cu (NO
2)
6] product is hexagon, the elongated 2 μ m that are about have dispersed (shown in Fig. 4 (a), (b) being its enlarged drawing) preferably.
(1) according to mass fraction is 5% ratio, takes by weighing K respectively by the 0.025g of embodiment 1 preparation
2Pb [Cu (NO
2)
6] and the AP of 0.475g mix.
(2) in stuff and other stuff, add an amount of ultrasonic 5min of absolute ethyl alcohol, ultrasonic scattered stuff and other stuff is put in the agate mortar, carefully grind 10min.
(3) the safe baking oven of putting into 60 ℃ after grinding finishes is dry.After treating its bone dry, continue to grind 5 min and obtain K with agate
2Pb [Cu (NO
2)
6] and the compound sample of AP.Composite sample and pure AP sample are carried out dsc analysis under nitrogen atmosphere.
Claims (3)
1. a preparation method who contains ability bimetallic nitro complex is characterized in that, may further comprise the steps:
Step 1: preparation KNO
2The aqueous solution;
Step 2: preparation contains Pb
2+And Cu
2+The aqueous solution, Pb wherein
2+And Cu
2+Mol ratio 1:1;
Step 3: two parts of the reverse microemulsion liquid system that dose volume equates; Cyclohexane in the reverse microemulsion liquid system: triton x-100: salting liquid: the cosurfactant volume ratio is 30:3:1:1; Wherein, the salting liquid in first part of reverse microemulsion liquid system is the KNO in the step 1
2Salting liquid in the aqueous solution, second part of reverse microemulsion liquid system is the Pb that contains in the step 2
2+And Cu
2+The aqueous solution;
Step 4: below 30 ℃, first part of reverse microemulsion liquid system mixed with second part of reverse microemulsion liquid system, wherein, K
+And Pb
2+Molar concentration rate more than or equal to 6; And gentle agitation is still aging under the room temperature then more than 0.5 hour;
Step 5: centrifugalize mother liquor after the ageing, washed product is also dry, promptly obtains K
2Pb [Cu (NO
2)
6] powder.
2. according to claim 1 a kind of contain can bimetallic the preparation method of nitro complex, it is characterized in that the washing in the step 5 is meant with absolute ethanol washing product 3-5 time until the free from admixture ion.
3. a kind of preparation method who contains ability bimetallic nitro complex according to claim 1 is characterized in that described drying is meant the product after the washing is placed baking oven dry 4-6h under 40 ℃-80 ℃.
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103433065A (en) * | 2013-09-04 | 2013-12-11 | 万华化学集团股份有限公司 | Preparation method and application of bi-metal cyanide catalyst |
| CN105566091A (en) * | 2015-12-16 | 2016-05-11 | 国药集团化学试剂有限公司 | Preparation method of copper lead salicylate complex |
-
2012
- 2012-09-06 CN CN2012103266756A patent/CN102836733A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 崔海勇: "新型硝基配合物粒子的制备及其对AP/RDX中的催化研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅱ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103433065A (en) * | 2013-09-04 | 2013-12-11 | 万华化学集团股份有限公司 | Preparation method and application of bi-metal cyanide catalyst |
| CN105566091A (en) * | 2015-12-16 | 2016-05-11 | 国药集团化学试剂有限公司 | Preparation method of copper lead salicylate complex |
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Application publication date: 20121226 |