CN102161628A - Preparation method and application of 1-amino-1-hydrazino-2,2-dinitroethylene bismuth salt - Google Patents
Preparation method and application of 1-amino-1-hydrazino-2,2-dinitroethylene bismuth salt Download PDFInfo
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- CN102161628A CN102161628A CN2011100407550A CN201110040755A CN102161628A CN 102161628 A CN102161628 A CN 102161628A CN 2011100407550 A CN2011100407550 A CN 2011100407550A CN 201110040755 A CN201110040755 A CN 201110040755A CN 102161628 A CN102161628 A CN 102161628A
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Abstract
The invention relates to a preparation method of 1-amino-1-hydrazino-2,2-dinitroethylene bismuth salt. The method comprises the following steps: synthetizing 1-amino-1-hydrazino-2,2-dinitroethylene potassium salt by using 1,1-diamino-2,2-dinitroethylene, hydrazine hydrate and KOH as raw materials, then reacting with soluble metal salts such as bismuth nitrate to prepare 1-amino-1-hydrazino-2,2-dinitroethylene bismuth salt. The synthesis method is simple; the industrialized production is easy to operate; and the synthesized 1-amino-1-hydrazino-2,2-dinitroethylene bismuth salt is a new high-energy compound, is used as green and energetic combustion catalyst and can be used to greatly reduce the burning rate pressure exponents of the double-base propellant and the modified double-base propellant.
Description
Technical field
The invention belongs to the energetic material technical field, relating to a kind of double-basis and be solid propellant can fuel catalyst 1-amino-1-diazanyl-2 with novel containing, 2-dinitrobenzene ethene bismuth salt preparation method and application thereof.
Background technology
Solid propellant is the propulsion source of solid propellant rocket, and the range of its combustionproperty and energy characteristics and guided missile, speed of response, attack precision etc. are closely related.
At present, double-basis is oxide compound and organic salt, the inorganic salt etc. mostly combustioncatalysts commonly used in the solid propellant (double-base propellent and composite modified double base propellant) is lead, copper, it mainly acts on is the combustionproperty of regulating propelling agent, reduce the burning rate pressure exponent of propelling agent, to guarantee the job stability of propelling agent.But plumbous oxide compound and its esters are one of primary pollution source of physical environment, are easy to human body, environment are caused bigger harm, press for the combustioncatalysts of development green high-efficient.
Organo-bismuth salt pair human body is poisoned less, is commonly used for the broad-spectrum sterilant in medicine.Organo-bismuth salt also is the green combustioncatalysts in a kind of generally acknowledged propelling agent, and the organic lead-salt combustioncatalysts that it replaces in solid propellant helps obtaining lowly poisoning, the environmentally friendly green propelling agent of low residue.The double-basis of being studied at present be the used organo-bismuth salt of propelling agent combustioncatalysts exist catalytic efficiency low, do not contain problem such as energy, it is joined in the propelling agent system, can not effectively reduce the burning rate pressure exponent that double-basis is a propelling agent, also reduce the energy level of propelling agent to a certain extent.Song Xiuduo etc. are published in " SCI " the 27th the 1st phase of volume 125～128 pages (in January, 2006) " Thermal Decomposition Mechanism of bismuth citrate, non-isothermal Kinetics and to Combustion of Double-base Propellant "; the bismuth citrate of being reported that does not contain energy only can make the burning rate pressure exponent of double-base propellent (comparing with blank formula) between 2MPa～22MPa drop to 0.42 from 0.75 as combustioncatalysts; can not satisfy low burning rate pressure exponential double-basis is the growth requirement of propelling agent, has influenced its practical value.
Summary of the invention
Technical problem to be solved by this invention is to overcome the shortcoming that above-mentioned double-basis is a solid propellant, and it is solid propellant combustion rate pressure exponential 1-amino-1-diazanyl-2 that a kind of effective reduction double-basis is provided, the preparation method of 2-dinitrobenzene ethene bismuth salt.
Another technical problem to be solved by this invention is to be 1-amino-1-diazanyl-2, and 2-dinitrobenzene ethene bismuth salt provides a kind of new purposes.
Solving the problems of the technologies described above the technical scheme that is adopted is made up of following step:
1, preparation 1-amino-1-diazanyl-2,2-dinitrobenzene ethene potassium
With 1,1-diamino-2,2-dinitrobenzene ethene is scattered in the deionized water, drips hydrazine hydrate, 1 with 1～2 droplet/second speed, 1-diamino-2,2-dinitrobenzene ethene and hydrazine hydrate, the mol ratio of deionized water is 1: 1.6: 167, and 85 ℃ are stirred to the solution clarification, continue to stir 1 hour, be cooled to room temperature, with massfraction is that 10% aqueous hydrochloric acid is regulated pH value to 3～4, adding KOH, 1,1-diamino-2, the mol ratio of 2-dinitrobenzene ethene and KOH is 1: 1～3, and room temperature continues to stir 1 hour, concentrates, crystallisation by cooling, be prepared into 1-amino-1-diazanyl-2,2-dinitrobenzene ethene potassium.
2, preparation 1-amino-1-diazanyl-2,2-dinitrobenzene ethene bismuth salt
1-amino-1-diazanyl-2 with step 1 preparation, 2-dinitrobenzene ethene potassium adds in the deionized water, dripping massfraction with 1～2 droplet/second speed is 24.11% soluble bismuth salt brine solution, soluble bismuth salt and 1-amino-1-diazanyl-2, the mol ratio of 2-dinitrobenzene ethene potassium, deionized water is 1: 1～3: 167, drip while stirring, dripping the back continues to stir 1 hour, suction filtration, washing, precipitation placed 35 ℃ of dryings of vacuum drying oven 1 hour, be prepared into 1-amino-1-diazanyl-2,2-dinitrobenzene ethene bismuth salt.
Above-mentioned soluble bismuth salt is Bi (CH
3CO
2)
3Or Bi (NO
3)
35H
2O.
1-amino-1-the diazanyl-2 of the present invention's preparation, the purposes of 2-dinitrobenzene ethene bismuth salt in double-base propellent, its concrete using method is as follows:
With double-base propellent and 1-amino-1-diazanyl-2,2-dinitrobenzene ethene bismuth salt, carbon black are to mix at 100: 3: 0.4 by mass ratio, and the mass percent of double-base propellent consists of in its proportioning: the nitro-cotton 59% of nitrogen content 12%, nitroglycerine 30%, diethyl phthalate 8.5%, No. two centralite dimethyl sym-diphenylurea 2%, Vaseline 0.5%.
1-amino-1-the diazanyl-2 of above-mentioned preparation, the purposes of 2-dinitrobenzene ethene bismuth salt in composite modified double base propellant, its concrete using method is as follows:
With composite modified double base propellant and 1-amino-1-diazanyl-2,2-dinitrobenzene ethene bismuth salt, 2,4-resorcylic acid copper, carbon black are 100: 2.5: 1.0 by mass ratio: 0.5 mixes, and the mass percent of composite modified double base propellant consists of in its proportioning: the nitro-cotton 37% of nitrogen content 12%, nitroglycerine 29%, Cyclotrimethylene trinitramine 26%, No. two centralite dimethyl sym-diphenylurea 2.5%, Jis receive 5.0%, Vaseline 0.5%.
Synthetic method of the present invention is simple, be easy to suitability for industrialized production, the synthetic 1-amino-1-diazanyl-2 that obtains, 2-dinitrobenzene ethene bismuth salt is a kind of novel high-energy compound, can be used as double-basis is the green high-efficient combustioncatalysts of solid propellant, not only reduce the burning rate pressure exponent of propelling agent significantly, also improved the energy level of propelling agent to a certain extent.
Description of drawings
Fig. 1 is the 1-amino-1-diazanyl-2 of embodiment 1 preparation, the infrared spectrogram of 2-dinitrobenzene ethene bismuth salt.
Embodiment
Below in conjunction with drawings and Examples the present invention is further elaborated, but the invention is not restricted to these embodiment.
Embodiment 1
1, preparation 1-amino-1-diazanyl-2,2-dinitrobenzene ethene potassium
Get 1,1-diamino-2,2-dinitrobenzene ethene 4.4400g is scattered in the flask that fills the 30mL deionized water, drips hydrazine hydrate 2mL, 1 with 1～2 droplet/second speed in flask, 1-diamino-2,2-dinitrobenzene ethene and hydrazine hydrate, the mol ratio of deionized water is 1: 1.6: 167, places 85 ℃ constant temperature oil bath, is stirred to the solution clarification, continue to stir 1 hour, being cooled to room temperature, is that 10% aqueous hydrochloric acid is regulated pH value to 3～4 with massfraction, adding KOH 3.3600g, 1,1-diamino-2, the mol ratio of 2-dinitrobenzene ethene and KOH are 1: 2, and room temperature continues to stir 1 hour, 60 ℃ have been concentrated into solid and have separated out, place ice bath to cool off, suction filtration obtains the solid of orange, prepares 1-amino-1-diazanyl-2,2-dinitrobenzene ethene potassium 3.2803g, its productive rate is 80%.
2, preparation 1-amino-1-diazanyl-2,2-dinitrobenzene ethene bismuth salt
With the 1-amino-1-diazanyl-2 of above-mentioned preparation, 2-dinitrobenzene ethene potassium 3.0150g joins in the beaker that fills the 30mL deionized water, with constant temperature blender with magnetic force with 5 revolutions per seconds of stirrings under, with solubility Bi (NO
3)
35H
2It is 24.11% Bi (NO that O is mixed with massfraction
3)
3The aqueous solution, dripping the 4mL massfraction with 1～2 droplet/second speed in beaker is 24.11% Bi (NO
3)
3The aqueous solution, solubility Bi (NO
3)
35H
2O and 1-amino-1-diazanyl-2, the mol ratio of 2-dinitrobenzene ethene potassium, deionized water is 1: 3: 167, drips while stirring, in the dropping process, have the yellow solid precipitation in the solution and occur, after dripping, continue to stir 1 hour, suction filtration, with deionized water wash yellow solid precipitation three times, put yellow solid and be deposited in the vacuum drying oven 35 ℃ of dryings 1 hour, be prepared into catalyzer 1-amino-1-diazanyl-2,2-dinitrobenzene ethene bismuth salt 3.7206g, its productive rate is 93.6%.
Products therefrom characterizes with Avatar 360E.S.P.FTIR type Fourier transformation infrared spectrometer, the results are shown in Figure 1.As seen from Figure 1,3436,3338 and 3254cm
-1The absorption peak at place can be classified as NH
2With symmetry and the antisymmetric stretching vibration of NH, product is 3436 and 3254cm
-1The absorption peak and the initial feed 1-amino-1-diazanyl-2 at place, the corresponding absorption peak of 2-dinitrobenzene ethene (3430 and 3226cm
-1) relatively, the blue shift phenomenon has taken place, illustrate to have generated new compound.1701cm
-1Can belong to NH
2The scissors stretching vibration of group, the 1629th, the stretching vibration of the two keys of C=C, 1531cm
-1Should be NO
2Peculiar stretching vibration, 1143cm
-1Stretching vibration for the C-N key.
Show that by infrared analysis this yellow powder is exactly a prepared product on claims.
Embodiment 2
1, preparation 1-amino-1-diazanyl-2,2-dinitrobenzene ethene potassium
Get 1,1-diamino-2,2-dinitrobenzene ethene 4.4400g is scattered in the beaker that fills the 30mL deionized water, drips hydrazine hydrate 2mL, 1 with 1～2 droplet/second speed in beaker, 1-diamino-2,2-dinitrobenzene ethene and hydrazine hydrate, the mol ratio of deionized water is 1: 1.6: 167, places 85 ℃ constant temperature oil bath, is stirred to the solution clarification, continue to stir 1 hour, being cooled to room temperature, is that 10% aqueous hydrochloric acid is regulated pH value to 3～4 with massfraction, adding KOH 1.68g, 1,1-diamino-2, the mol ratio of 2-dinitrobenzene ethene and KOH are 1: 1, and room temperature continues to stir 1 hour, 60 ℃ have been concentrated into solid and have separated out, place ice bath to cool off, suction filtration obtains the solid of orange, prepares 1-amino-1-diazanyl-2,2-dinitrobenzene ethene potassium 2.4890g, its productive rate is 60.7%.
2, preparation 1-amino-1-diazanyl-2,2-dinitrobenzene ethene bismuth salt
With the 1-amino-1-diazanyl-2 of above-mentioned preparation, 2-dinitrobenzene ethene potassium 1.0050g joins in the beaker that fills the 30mL deionized water, with constant temperature blender with magnetic force with 5 revolutions per seconds of stirrings under, with solubility Bi (NO
3)
35H
2It is 24.11% Bi (NO that O is mixed with massfraction
3)
3The aqueous solution, dripping the 4mL massfraction with 1～2 droplet/second speed in beaker is 24.11% Bi (NO
3)
3The aqueous solution, solubility Bi (NO
3)
35H
2O and 1-amino-1-diazanyl-2, the mol ratio of 2-dinitrobenzene ethene potassium, deionized water is 1: 1: 167, drips while stirring, in the dropping process, have the yellow solid precipitation in the solution and occur, after dripping, continue to stir 1 hour, suction filtration, with deionized water wash yellow solid precipitation three times, put yellow solid and be deposited in the vacuum drying oven 35 ℃ of dryings 1 hour, be prepared into catalyzer 1-amino-1-diazanyl-2,2-dinitrobenzene ethene bismuth salt 1.2345g, its productive rate is 93.2%.
Embodiment 3
1, preparation 1-amino-1-diazanyl-2,2-dinitrobenzene ethene potassium
Get 1,1-diamino-2,2-dinitrobenzene ethene 4.4400g is scattered in the beaker that fills the 30mL deionized water, drips hydrazine hydrate 2mL, 1 with 1～2 droplet/second speed, 1-diamino-2,2-dinitrobenzene ethene and hydrazine hydrate, the mol ratio of deionized water is 1: 1.6: 167, places 85 ℃ constant temperature oil bath, is stirred to the solution clarification, continue to stir 1 hour, being cooled to room temperature, is that 10% aqueous hydrochloric acid is regulated pH value to 3～4 with massfraction, adding KOH 5.04g, 1,1-diamino-2, the mol ratio of 2-dinitrobenzene ethene and KOH are 1: 3, and room temperature continues to stir 1 hour, 60 ℃ have been concentrated into solid and have separated out, place ice bath to cool off, suction filtration obtains the solid of orange, prepares 1-amino-1-diazanyl-2,2-dinitrobenzene ethene potassium 3.2586g, its productive rate is 79.5%.
2, preparation 1-amino-1-diazanyl-2,2-dinitrobenzene ethene bismuth salt
With the 1-amino-1-diazanyl-2 of above-mentioned preparation, 2-dinitrobenzene ethene potassium 2.0100g joins in the beaker that fills the 30mL deionized water, with constant temperature blender with magnetic force with 5 revolutions per seconds of stirrings under, with solubility Bi (NO
3)
35H
2It is 24.11% Bi (NO that O is mixed with massfraction
3)
3The aqueous solution, the massfraction that drips 4mL with 1～2 droplet/second speed are 24.11% Bi (NO
3)
3The aqueous solution, solubility Bi (NO
3)
35H
2O and 1-amino-1-diazanyl-2, the mol ratio of 2-dinitrobenzene ethene potassium, deionized water is 1: 2: 167, drips while stirring, in the dropping process, have the yellow solid precipitation in the solution and occur, after dripping, continue to stir 1 hour, suction filtration, with deionized water wash yellow solid precipitation three times, put yellow solid and be deposited in the vacuum drying oven 35 ℃ of dryings 1 hour, be prepared into catalyzer 1-amino-1-diazanyl-2,2-dinitrobenzene ethene bismuth salt 2.1201g, its productive rate is 92.3%.
Embodiment 4
1, preparation 1-amino-1-diazanyl-2,2-dinitrobenzene ethene potassium
Get 1,1-diamino-2,2-dinitrobenzene ethene 4.4400g is scattered in the 30mL deionized water, drips hydrazine hydrate 2mL, 1 with 1～2 droplet/second speed, 1-diamino-2,2-dinitrobenzene ethene and hydrazine hydrate, the mol ratio of deionized water is 1: 1.6: 167, places 85 ℃ constant temperature oil bath, is stirred to the solution clarification, continue to stir 1 hour, being cooled to room temperature, is that 10% aqueous hydrochloric acid is regulated pH value to 3～4 with massfraction, adding KOH 3.3600g, 1,1-diamino-2, the mol ratio of 2-dinitrobenzene ethene and KOH are 1: 2, and room temperature continues to stir 1 hour, 60 ℃ have been concentrated into solid and have separated out, place ice bath to cool off, suction filtration obtains the solid of orange, prepares 1-amino-1-diazanyl-2,2-dinitrobenzene ethene potassium 3.2803g, its productive rate is 80.0%.
2, preparation 1-amino-1-diazanyl-2,2-dinitrobenzene ethene bismuth salt
With the 1-amino-1-diazanyl-2 of above-mentioned preparation, 2-dinitrobenzene ethene potassium 3.0150g is added in the beaker that fills the 30mL deionized water, with constant temperature blender with magnetic force with 5 revolutions per seconds of stirrings under, with solubility Bi (CH
3CO
2)
3Be mixed with massfraction and be 24.11% Bi (CH
3CO
2)
3The aqueous solution, dripping the 6mL massfraction with 1～2 droplet/second speed is 24.11% Bi (CH
3CO
2)
3The aqueous solution, solubility Bi (CH
3CO
2)
3With 1-amino-1-diazanyl-2, the mol ratio of 2-dinitrobenzene ethene potassium, deionized water is 1: 3: 167, drips while stirring, in the dropping process, having the yellow solid precipitation in the solution occurs, after dripping, continue to stir suction filtration 1 hour, precipitate three times with the deionized water wash yellow solid, put yellow solid and be deposited in the vacuum drying oven 35 ℃ of dryings 1 hour, be prepared into catalyzer 1-amino-1-diazanyl-2,2-dinitrobenzene ethene bismuth salt.
Embodiment 5
1, preparation 1-amino-1-diazanyl-2,2-dinitrobenzene ethene potassium
Get 1,1-diamino-2,2-dinitrobenzene ethene 4.4400g is scattered in the 30mL deionized water, drips hydrazine hydrate 2mL, 1 with 1～2 droplet/second speed, 1-diamino-2,2-dinitrobenzene ethene and hydrazine hydrate, the mol ratio of deionized water is 1: 1.6: 167, places 85 ℃ constant temperature oil bath, is stirred to the solution clarification, continue to stir 1 hour, being cooled to room temperature, is that 10% aqueous hydrochloric acid is regulated pH value to 3～4 with massfraction, adding KOH 1.6800g, 1,1-diamino-2, the mol ratio of 2-dinitrobenzene ethene and KOH are 1: 1, and room temperature continues to stir 1 hour, 60 ℃ have been concentrated into solid and have separated out, place ice bath to cool off, suction filtration obtains the solid of orange, prepares 1-amino-1-diazanyl-2,2-dinitrobenzene ethene potassium 2.4890g, its productive rate is 60.7%.
2, preparation 1-amino-1-diazanyl-2,2-dinitrobenzene ethene bismuth salt
With the 1-amino-1-diazanyl-2 of above-mentioned preparation, 2-dinitrobenzene ethene potassium 1.0050g is added in the beaker that fills the 30mL deionized water, with constant temperature blender with magnetic force with 5 revolutions per seconds of stirrings under, with solubility Bi (CH
3CO
2)
3Be mixed with massfraction and be 24.11% Bi (CH
3CO
2)
3The aqueous solution, dripping the 6mL massfraction with 1～2 droplet/second speed is 24.11% Bi (CH
3CO
2)
3The aqueous solution, solubility Bi (CH
3CO
2)
3With 1-amino-1-diazanyl-2, the mol ratio of 2-dinitrobenzene ethene potassium, deionized water is 1: 1: 167, drips while stirring, in the dropping process, having the yellow solid precipitation in the solution occurs, after dripping, continue to stir suction filtration 1 hour, precipitate three times with the deionized water wash yellow solid, put yellow solid and be deposited in the vacuum drying oven 35 ℃ of dryings 1 hour, be prepared into catalyzer 1-amino-1-diazanyl-2,2-dinitrobenzene ethene bismuth salt.
Embodiment 6
1, preparation 1-amino-1-diazanyl-2,2-dinitrobenzene ethene potassium
Get 1,1-diamino-2,2-dinitrobenzene ethene 4.4400g is scattered in the 30mL deionized water, drips hydrazine hydrate 2mL, 1 with 1～2 droplet/second speed, 1-diamino-2,2-dinitrobenzene ethene and hydrazine hydrate, the mol ratio of deionized water is 1: 1.6: 167, places 85 ℃ constant temperature oil bath, is stirred to the solution clarification, continue to stir 1 hour, being cooled to room temperature, is that 10% aqueous hydrochloric acid is regulated pH value to 3～4 with massfraction, adding KOH 5.0400g, 1,1-diamino-2, the mol ratio of 2-dinitrobenzene ethene and KOH are 1: 3, and room temperature continues to stir 1 hour, 60 ℃ have been concentrated into solid and have separated out, place ice bath to cool off, suction filtration obtains the solid of orange, prepares 1-amino-1-diazanyl-2,2-dinitrobenzene ethene potassium 3.2580g, its productive rate is 79.5%.
2, preparation 1-amino-1-diazanyl-2,2-dinitrobenzene ethene bismuth salt
With the 1-amino-1-diazanyl-2 of above-mentioned preparation, 2-dinitrobenzene ethene potassium 2.0100g is added in the beaker that fills the 30mL deionized water, with constant temperature blender with magnetic force with 5 revolutions per seconds of stirrings under, with solubility Bi (CH
3CO
2)
3Be mixed with massfraction and be 24.11% Bi (CH
3CO
2)
3The aqueous solution, dripping the 6mL massfraction with 1～2 droplet/second speed is 24.11% Bi (CH
3CO
2)
3The aqueous solution, solubility Bi (CH
3CO
2)
3With 1-amino-1-diazanyl-2, the mol ratio of 2-dinitrobenzene ethene potassium, deionized water is 1: 2: 167, drips while stirring, in the dropping process, having the yellow solid precipitation in the solution occurs, after adding, continue to stir suction filtration 1 hour, precipitate three times with the deionized water wash yellow solid, put yellow solid and be deposited in the vacuum drying oven 35 ℃ of dryings 1 hour, be prepared into catalyzer 1-amino-1-diazanyl-2,2-dinitrobenzene ethene bismuth salt.
Embodiment 7
1-amino-1-the diazanyl-2 of embodiment of the invention preparation, the purposes of 2-dinitrobenzene ethene bismuth salt in double-base propellent, its concrete using method is as follows:
Nitro-cotton 0.59g, nitroglycerine 0.30g, diethyl phthalate 0.085g, No. two centralite dimethyl sym-diphenylurea 0.02g, Vaseline 0.005g of nitrogen content 12% are mixed, obtain double-base propellent 1.0g, in double-base propellent, add 1-amino-1-diazanyl-2,2-dinitrobenzene ethene bismuth salt 0.03g, carbon black 0.004g.
Embodiment 8
1-amino-1-the diazanyl-2 of embodiment of the invention preparation, the purposes of 2-dinitrobenzene ethene bismuth salt salt in composite modified double base propellant, its concrete using method is as follows:
The nitro-cotton 0.37g of nitrogen content 12%, nitroglycerine 0.29g, Cyclotrimethylene trinitramine 0.26g, No. two centralite dimethyl sym-diphenylurea 0.025g, Jis are received 0.05g, Vaseline 0.005g to mix, obtain composite modified double base propellant 1.0g, in composite modified double base propellant, add 1-amino-1-diazanyl-2,2-dinitrobenzene ethene bismuth salt 0.025g, 2,4-resorcylic acid copper 0.01g, carbon black 0.005g.
In order to prove beneficial effect of the present invention, the contriver is with the catalyzer 1-amino-1-diazanyl-2 of the embodiment of the invention 1 preparation, 2-dinitrobenzene ethene bismuth salt is applied in double-base propellent and the composite modified double base propellant, investigates its influence to propellant burning property, and concrete test situation is as follows:
1,1-amino-1-diazanyl-2, the influence of 2-dinitrobenzene ethene bismuth salt pair Combustion Property of Double Base Propellant
Nitro-cotton 0.59g, nitroglycerine 0.30g, diethyl phthalate 0.085g, No. two centralite dimethyl sym-diphenylurea 0.02g, Vaseline 0.005g of nitrogen content 12% are mixed, obtain double-base propellent 1.0g.Make 2 parts of double-base propellents as stated above altogether.
The composition of control sample: double-base propellent 1.0g, bismuth citrate 0.03g, carbon black 0.004g.
Use 1-amino-1-diazanyl-2, the composition of 2-dinitrobenzene ethene bismuth salt: double-base propellent 1.0g, 1-amino-1-diazanyl-2,2-dinitrobenzene ethene bismuth salt 0.03g, carbon black 0.004g.
Combustion speed and burning rate pressure exponent testing method: it is that 5mm, length are the little medicinal strip of cylinder shape of 150mm that the propelling agent tablet is processed into diameter, and with reference to GJB-770A-97 method 706.1 test combustion speed, burning rate pressure exponent is according to formula u=aP
nCalculate, a is a burn rate coefficient in the formula, and u is combustion speed, the pressure when P is burning, and n is a burning rate pressure exponent.Test and calculation result see Table 1.
Table 1 1-amino-1-diazanyl-2, the combustionproperty of 2-dinitrobenzene ethene bismuth salt pair propelling agent
By table 1 as seen, 1-amino-1-diazanyl-2,2-dinitrobenzene ethene bismuth salt be introduced in the combustion speed that has improved double-base propellent to a certain extent, and can significantly reduce the burning rate pressure exponent of propelling agent, make propelling agent in 2～22MPa pressure range, produce platform incendiary effect (burning pressure index is 0.14), produce " wheat is spread effect " (burning pressure index is-0.05) in 16～22MPa pressure range.
2,1-amino-1-diazanyl-2, the influence of 2-dinitrobenzene ethene bismuth salt pair composite modified double base propellant combustionproperty
The nitro-cotton 0.37g of nitrogen content 12%, nitroglycerine 0.29g, Cyclotrimethylene trinitramine 0.26g, No. two centralite dimethyl sym-diphenylurea 0.025g, Jis are received 0.05g, Vaseline 0.005g to mix, obtain composite modified double base propellant 1.0g, make 2 parts of double-base propellents as stated above altogether.
The composition of control sample: composite modified double base propellant 1.0g, bismuth citrate 0.025g, 2,4-resorcylic acid copper 0.01g, carbon black 0.005g.
Use 1-amino-1-diazanyl-2, the composition of 2-dinitrobenzene ethene bismuth salt: composite modified double base propellant 1.0g, 1-amino-1-diazanyl-2,2-dinitrobenzene ethene bismuth salt 0.025g, 2,4-resorcylic acid copper 0.01g, carbon black 0.005g.
The testing method of combustion speed is identical with test 1 with the method for calculation of burning rate pressure exponent, and test and calculation result see Table 2.
Table 21-amino-1-diazanyl-2, the combustionproperty of propelling agent after the modification of 2-dinitrobenzene ethene bismuth salt pair
By table 2 as seen, 1-amino-1-diazanyl-2, the adding of 2-dinitrobenzene ethene bismuth salt can improve the combustion speed under the composite modified double base propellant low pressure to a certain extent, and can significantly reduce the burning rate pressure exponent of propelling agent, burning rate pressure exponent in 2～22MPa pressure range reduces to 0.23, produce the platform incendiary effect in 4～18MPa pressure range, burning pressure index only is 0.14.
Claims (3)
1. 1-amino-1-diazanyl-2, the preparation method of 2-dinitrobenzene ethene bismuth salt is characterized in that being made up of following step:
(1) preparation 1-amino-1-diazanyl-2,2-dinitrobenzene ethene potassium
With 1,1-diamino-2,2-dinitrobenzene ethene is scattered in the deionized water, drips hydrazine hydrate, 1 with 1～2 droplet/second speed, 1-diamino-2,2-dinitrobenzene ethene and hydrazine hydrate, the mol ratio of deionized water is 1: 1.6: 167, and 85 ℃ are stirred to the solution clarification, continue to stir 1 hour, be cooled to room temperature, with massfraction is that 10% aqueous hydrochloric acid is regulated pH value to 3～4, adding KOH, 1,1-diamino-2, the mol ratio of 2-dinitrobenzene ethene and KOH is 1: 1～3, and room temperature continues to stir 1 hour, concentrates, crystallisation by cooling, be prepared into 1-amino-1-diazanyl-2,2-dinitrobenzene ethene potassium;
(2) preparation 1-amino-1-diazanyl-2,2-dinitrobenzene ethene bismuth salt
1-amino-1-diazanyl-2 with step (1) preparation, 2-dinitrobenzene ethene potassium adds in the deionized water, dripping massfraction with 1～2 droplet/second speed is 24.11% soluble bismuth salt brine solution, soluble bismuth salt and 1-amino-1-diazanyl-2, the mol ratio of 2-dinitrobenzene ethene potassium, deionized water is 1: 1～3: 167, drip while stirring, dripping the back continues to stir 1 hour, suction filtration, washing, precipitation placed 35 ℃ of dryings of vacuum drying oven 1 hour, be prepared into 1-amino-1-diazanyl-2,2-dinitrobenzene ethene bismuth salt;
Above-mentioned soluble bismuth salt is Bi (CH
3CO
2)
3Or Bi (NO
3)
35H
2O.
2. the 1-of claim 1 amino-1-diazanyl-2, the purposes of 2-dinitrobenzene ethene bismuth salt in double-base propellent.
3. the 1-of claim 1 amino-1-diazanyl-2, the purposes of 2-dinitrobenzene ethene bismuth salt in composite modified double base propellant.
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| CN106045929A (en) * | 2016-06-14 | 2016-10-26 | 太原理工大学 | Synthesis process of bistetrazole hydroxyl bismuth salt |
| CN106045929B (en) * | 2016-06-14 | 2018-08-24 | 太原理工大学 | A kind of synthesis technology of bistetrazole hydroxyl bismuth salt |
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