CN115160091B - Energy-containing burning rate inhibitor for solid propellant and preparation method thereof - Google Patents
Energy-containing burning rate inhibitor for solid propellant and preparation method thereof Download PDFInfo
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- CN115160091B CN115160091B CN202210587304.7A CN202210587304A CN115160091B CN 115160091 B CN115160091 B CN 115160091B CN 202210587304 A CN202210587304 A CN 202210587304A CN 115160091 B CN115160091 B CN 115160091B
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B33/00—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
- C06B33/08—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide with a nitrated organic compound
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- C—CHEMISTRY; METALLURGY
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- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
- C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids
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Abstract
The invention relates to an energetic burning rate inhibitor for a solid propellant and a preparation method thereof, which are prepared by adopting a one-pot method and a two-step method. One-pot method: respectively dissolving triamino guanidine nitrate and metal salt in deionized water, regulating the pH value of the solution, and finally adding glyoxal aqueous solution to crosslink and polymerize the solution to form the energy-containing burning rate inhibitor. The two-step method comprises the following steps: firstly, dissolving triaminoguanidine nitrate in deionized water, adding glyoxal aqueous solution to make it undergo the process of cross-linking polymerization, then adding metal salt solution to make them undergo the process of complex reaction so as to obtain the invented energy-containing burning rate inhibitor. The energy-containing burning rate inhibitor prepared by the invention inhibits the thermal decomposition process of the AP and the nitramine explosive by coating the surface of the AP or the nitramine oxidizer in situ, thereby achieving the purpose of reducing the burning rate of the corresponding solid propellant. The preparation process is simple, and the content of each component in the formula can be accurately controlled. The process adopts deionized water as solvent, is cheap and environment-friendly, and is easy to realize industrial production.
Description
Technical Field
The invention belongs to the technical field of composite solid propellant burning rate catalyst manufacturing, and relates to an energetic burning rate inhibitor for a solid propellant and a preparation method thereof.
Background
The composite solid propellant is a composite energetic material capable of rapidly releasing energy and generating thrust by combustion, and generally consists of a binder system, a metal fuel, an oxidant, a catalyst and a process aid. The combustion performance of the propellant is an extremely important parameter, and has a key role in regulating the thrust of the engine and stabilizing the working process of the engine. Currently, the use of burn rate catalysts is one of the most effective methods for adjusting the combustion performance of propellants. The combustion performance of the propellant can be regulated and controlled by high combustion speed and low combustion speed according to different application requirements, most researchers focus on high-combustion speed regulating technology at present, and little research is carried out on low-combustion speed regulating technology (Miao Nan, tang Chengzhi, wu Shixi and the like; calcium salt speed reducer research for HTPB/AP/Al propellant adapting to high-pressure combustion [ J ]. Solid rocket technology, 2017,40 (4): 461-465.).
The existing method for reducing the burning rate of the solid composite propellant is to add solid speed reducing agents such as ammonium salts (ammonium oxalate, ammonium citrate, ammonium chloride and ammonium sulfate), metal halides (lithium fluoride, calcium fluoride and calcium hexafluorophosphate), carbonates (calcium carbonate and strontium carbonate) and the like into the propellant formula. (Jiangxi space longitude and latitude chemical industry Co., ltd., a low burning rate high energy butyl hydroxy propellant and its preparation method: CN201810467399.2[ P ] 2018-08-03.). These speed reducers reduce the combustion speed of the propellant by lowering the combustion temperature, inhibiting the chemical equilibrium of the combustion reaction, and the like. However, most of the speed reducers are inert substances, and the energy performance of the propellant is reduced by adding a large amount of solid speed reducers. Taking ammonium oxalate as an example, although it can greatly reduce the burn rate of the propellant, too high an ammonium oxalate content can reduce the energy level of the propellant and increase the burn rate pressure index.
The addition of inert speed reducers increases the content of condensed phase products in the propellant combustion products, thereby exacerbating the two-phase flow losses of the combustion products in the combustion chamber and ultimately reducing the combustion efficiency of the propellant (Hubei institute of aerospace chemistry. Application of low-combustion-speed high-energy butoxide propellant and cycloaliphatic diisocyanate: CN201711405412.3[ P ] 2018-06-05.). And the existing low-combustion-speed propellant technology and a way for reducing the combustion speed cannot meet the requirements of high-performance missile weapon models. Therefore, there is an urgent need to develop high energy low burn rate propellant formulations and process technology that primarily achieve high pressure stage low burn rates without reducing the propellant energy density.
At present, the high-nitrogen two-dimensional material TAGP becomes a research hot spot due to the characteristics of high nitrogen content and low sensitivity. The nitrogen content of TAGP reaches 48.04 percent, and the nitrogen-carbon ratio is 4:3; its theoretical explosion speed is 6657 m.s -1 The impact initiation energy is 71.7J, the friction sensitivity is greater than 352.8N, and the material is a novel insensitive high-nitrogen two-dimensional energetic material. TAGP is an excellent chelating agent for binding various transition metal ions, and TAGP-Cu, TAGP-Co and TAGP-Ni have good thermal stability and feelLow in the degree of freedom, can be used as a novel high-energy binder and catalyst (Yan Q L, cohen A, chinnam A K, et al A layed 2D-triaminoguidine-glyoxal polymer and its transition metal complexes as novel insensitive energetic nanomaterials [ J)]Journal of Materials Chemistry A,2016,4 (47): 18401-1848. Ammonium Perchlorate (AP) and nitrate explosives (RDX, HMX and CL-20) are used as main components of the solid propellant, and the thermal decomposition performance of the solid propellant is closely related to the combustion performance of the solid propellant. The mass fraction of the AP accounts for 60-90% in the propellant formulation, the lower the high-temperature and low-temperature decomposition temperature is, the higher the burning rate of the solid propellant is (leaf flatness, lu Yuewen, xu Pengfei and the like is, nano CoFe is adopted 2 O 4 Preparation of @ C composite catalyst and catalytic Performance of the catalyst on AP [ J ]]Explosives and powders, school, 2019, volume 42 (4): 358-362.). Alkaline earth metal ions such as calcium ion, potassium ion and barium ion have good speed reducing effect, for example, calcium salt can be produced by forming a specific HClO 4 Or NH 4 ClO 4 Compounds with higher stability to inhibit AP decomposition reactions to reduce propellant burn rate (Ran Xiulun, yang Rongjie. HTPB/AP/Al composite propellant burn rate-reducing agent research [ J)]Explosive and powder journal 2006,29 (2): 41-43.).
According to the invention, the high-nitrogen two-dimensional material TAGP is matched with alkaline earth metal ions in situ to prepare the two-dimensional energetic complex burning rate inhibitor, and the two-dimensional energetic complex burning rate inhibitor is coated on the surface of the AP or the nitramine explosive, so that the decomposition of the AP and the nitramine explosive is inhibited in situ, the high-temperature decomposition peak temperature of the AP and the nitramine explosive is increased, the decomposition reaction rate is reduced, and the purpose of reducing the burning rate of the corresponding solid propellant is achieved.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides an energetic burning rate inhibitor for a solid propellant and a preparation method thereof, and the purpose of reducing the burning rate of the solid propellant is achieved by inhibiting the thermal decomposition process of nitramine explosive and AP in the solid propellant.
Technical proposal
The energetic burning rate inhibitor for solid propellant features its two-dimensional netted structure formed by self-polymerizing and cross-linking of triamino guanidine nitrate and glyoxal and has the following structural formula:
wherein: the carbon-nitrogen ratio is 3:4, the nitrogen content is more than 45%, and M is coordinated alkaline earth metal or transition metal element.
The coordination metal M is alkaline earth metal calcium, potassium, barium or transition metal copper.
A method for preparing an energetic burning rate inhibitor for a solid propellant by adopting a one-pot method is characterized by comprising the following operation steps:
step 1: adding the triaminoguanidine nitrate into deionized water, heating to 50-80 ℃, and stirring until the triaminoguanidine nitrate is completely dissolved;
step 2: adding the coordination metal salt into the solution prepared in the step 1, and stirring at 50-80 ℃ until the coordination metal salt is completely dissolved;
step 3: dropwise adding ammonia water into the solution in the step 2, and adjusting the pH value of the solution to 7;
step 4: finally, adding glyoxal aqueous solution, continuously stirring for 30-60min at 50-80 ℃ to separate out solid products;
step 5: filtering and drying the solid product obtained in the step 4 to obtain an energetic burning rate inhibitor;
the molar ratio of the triaminoguanidine nitrate, the glyoxal aqueous solution and the coordinated metal salt is controlled between 1:1:1 and 2:1:1.
The method for preparing the energetic burning rate inhibitor for the solid propellant by adopting a two-step method is characterized by comprising the following steps:
step 1): adding the triaminoguanidine nitrate into deionized water, heating to 50-80 ℃, and stirring until the triaminoguanidine nitrate is completely dissolved;
step 2): adding glyoxal aqueous solution into the solution obtained in the step 1, and continuously stirring for 30-60min at 50-80 ℃ to obtain TAGP dispersion;
step 3): adding nitrate, perchlorate or chloride of coordinated metal into deionized water, stirring at 50-80 ℃ to dissolve completely;
step 4): dropwise adding ammonia water into the solution obtained in the step 3, and adjusting the pH value of the solution to 7;
step 5): dropwise adding the solution obtained in the step 4 into the TAGP dispersion liquid obtained in the step 2, and continuously stirring for 30-60min at 50-80 ℃ to separate out a solid product;
step 6): vacuum drying or suction filtering and drying the solid product obtained in the step 5 to obtain the energetic burning rate inhibitor;
the molar ratio of the triaminoguanidine nitrate, the glyoxal aqueous solution and the coordinated metal salt is controlled between 1:1:1 and 2:1:1.
The coordination metal salt is Cu (NO) 3 ) 2 ·3H 2 O、KNO 3 、Ba(NO 3 ) 2 、Ba(Cl) 2 Or Ca (NO) 3 ) 2 ·4H 2 O。
The stirring rate during the reaction in said step is 700 to 800rpm.
The drying in the final preparation step is drying in an oven at a temperature of 70 to 80 ℃ for 3 to 6 days.
Advantageous effects
The invention provides an energetic burning rate inhibitor for a solid propellant and a preparation method thereof, which are prepared by adopting a one-pot method and a two-step method. One-pot method: respectively dissolving triamino guanidine nitrate and metal salt in deionized water, regulating the pH value of the solution, and finally adding glyoxal aqueous solution to crosslink and polymerize the solution to form the energy-containing burning rate inhibitor. The two-step method comprises the following steps: firstly, dissolving triaminoguanidine nitrate in deionized water, adding glyoxal aqueous solution to make it undergo the process of cross-linking polymerization, then adding metal salt solution to make them undergo the process of complex reaction so as to obtain the invented energy-containing burning rate inhibitor. The energy-containing burning rate inhibitor prepared by the invention inhibits the thermal decomposition process of the AP and the nitramine explosive by coating the surface of the AP or the nitramine oxidizer in situ, thereby achieving the purpose of reducing the burning rate of the corresponding solid propellant. The preparation process is simple, and the content of each component in the formula can be accurately controlled. The process adopts deionized water as solvent, is cheap and environment-friendly, and is easy to realize industrial production.
The present invention obtains two-dimensional high nitrogen copolymer (TAGP) by reacting aqueous solution of triaminoguanidine glyoxal, and uses the copolymer as energy-containing ligand and alkaline earth metal ion such as K + 、Ba 2+ And Ca 2+ And (3) carrying out a complexation reaction to prepare the series of energetic complex burning rate inhibitors. And the burning rate inhibitor is coated on the surfaces of the AP and the nitramine explosive in situ by adopting a spray granulation method, so that the thermal decomposition process of the AP and the nitramine explosive is accurately inhibited, and the purpose of reducing the burning rate of the corresponding solid propellant is achieved. Wherein example 2 is most significant in AP seeding inhibition, example 2 can be achieved by combining with HClO 4 And combines to inhibit the thermal decomposition of the AP. 10wt% of example 2 is added to increase the peak temperature of the crystal transformation endothermic peak of the AP by 5.9 ℃ and the peak temperature of the low-temperature decomposition by 28.7 ℃; the maximum thermal decomposition rate of the AP is reduced by 58%, but the heat release quantity is increased by more than 50% compared with that of the pure AP, and the energy release efficiency is improved while the decomposition of the AP is restrained, so that the purposes of ensuring the energy density and reducing the burning rate of the solid propellant containing the AP are achieved.
Compared with the prior art, the invention has the advantages and beneficial effects that:
the preparation method of the novel energy-containing burning rate inhibitor for the solid propellant provided by the invention has the advantages of simple preparation flow and environment-friendly catalyst without heavy metal. The invention designs the quaternary ammonium with the reducing effect and aldehyde structure TAGP molecule precisely, and the quaternary ammonium with the reducing effect and alkaline earth metal ion K + 、Ba 2+ And Ca 2+ The complex reaction occurs, the latter has stronger inhibition effect on flame, and the energy of the propellant is ensured while the characteristic signal is reduced. In addition, the process is simpler and more convenient than the traditional catalyst preparation method, mainly adopts deionized water as a solvent, is low in cost and environment-friendly, and is easy to realize industrial production. According to the complexing characteristics of alkaline earth metal ions, two preparation processes of a one-step method and a two-step method are designed, so that metal ions and TAGP are successfully complexed. The obtained energetic two-dimensional complex burning rate inhibitor can obviously reduce the thermal decomposition rate of the AP and the nitrate explosive, thereby reducing the burning rate of the corresponding solid propellant.
Drawings
FIG. 1 is an SEM and EDS images of the energetic burn rate depressants of examples 1-4;
FIG. 2 is a DSC/TG plot of the energetic flame retardant agent of examples 1-4 of the present invention;
FIG. 3 is a DSC/TG/DTG plot of HMX/10wt% energetic flame retardant system;
FIG. 4 is a DSC/TG/DTG plot of HMX/5wt% energetic flame retardant system;
FIG. 5 is a DSC curve of an AP and AP/10wt% of an energetic flame retardant agent;
FIG. 6 is a graph of the TG/DTG profiles of AP and AP/10wt% of the energetic burn rate inhibitor.
Detailed Description
The invention will now be further described with reference to examples, figures:
example 1: the preparation process of new type energy-containing burning rate inhibitor for solid propellant includes the following steps:
dissolution of the triaminoguanidine nitrate: 0.835g of triaminoguanidine nitrate was dissolved in 10mL of deionized water;
dissolution of alkali metal salt: 1.208g Cu (NO) 3 ) 2 ·3H 2 Adding O into the dissolved triaminoguanidine nitrate solution, and stirring until the O is completely dissolved;
adjusting the pH value of the solution: dropwise adding ammonia water into the solution to adjust the pH value to 7;
formation of energetic flame retardant (copper salt): adding 0.71ml glyoxal water solution, and continuously stirring at 70 ℃ for reaction for 30min;
and (3) collecting products: the product was washed with deionized water, filtered and dried to give example 1.
Example 1 was subjected to Scanning Electron Microscope (SEM) analysis and its crystal morphology is shown in fig. 1. Example 1 was tightly packed with nanomicrospheres and the samples were relatively compact. The DSC/TG curve of example 1 is shown in FIG. 2, the example 1 has only one exothermic peak, the yield is high, the thermal stability is good, and the density is as high as 2.02g/cm 3 The combustion heat is 6593.19J/g, and the formation enthalpy is-2258J/g.
To study the effect of example 1 on the HMX and AP thermal decomposition process, example 1 was mechanically groundGrinding method to coat the HMX surface with the example 1, wherein the ratio of the example 1 in the mixed system is 10wt% and 5wt% respectively; DSC/TG curves of the mixed systems of example 1 with the addition of 10wt% and 5wt% are shown in FIGS. 3 and 4, DSC parameters are shown in Table 3, and TG/DTG parameters are shown in Table 4. As is clear from Table 2, when 10wt% of example 1 was added, the exothermic peak was substantially the same as that of pure HMX, and the exothermic amount was reduced to 1189.0 J.g -1 And example 1 can effectively reduce the maximum thermal decomposition rate of HMX.
To investigate the effect of example 1 on the AP thermal decomposition process, 10wt% of example 1 was coated on the AP surface by mechanical grinding. DSC/TG curves of the AP mixture of example 1 at 10wt% added are shown in FIGS. 5 and 6, DSC parameters are shown in Table 5, and TG/DTG parameters are shown in Table 6. Example 1 reduced the endothermic peak heating value of AP from 79.4J/g to 8.3J/g (Table 5). Meanwhile, example 1 allows the pyrolysis process and the low-temperature decomposition process of the AP to be combined and the pyrolysis to be finished at 316.4 ℃ earlier than the pure AP by 106.7 ℃.
Example 2: the preparation process of new energy-containing burning rate inhibitor for solid propellant includes the following steps:
dissolution of the triaminoguanidine nitrate: 0.835g of triaminoguanidine nitrate was added to 5mL of deionized water;
dissolution of alkali metal salt: will be 0.50g KNO 3 Adding into 5mL of deionized water;
adjusting the pH value of the solution: at KNO 3 Dropwise adding ammonia water into the aqueous solution to adjust the pH value to 7;
preparation of TAGP dispersion: adding glyoxal water solution into the dissolved triaminoguanidine nitrate solution, and stirring and reacting for 30min at 70 ℃ to form TAGP dispersion;
formation of energetic flame retardant (potassium salt): dropwise adding KNO into TAGP dispersion liquid 3 Stirring the aqueous solution at 800rpm for 30min;
and (3) collecting products: the product was washed with deionized water, filtered and dried to give example 2.
SEM analysis was performed for example 2, the morphology of which is shown in fig. 1. As can be seen from FIG. 1, example 2 is in the form of a block, but has a rough surface, a large number of small crystals of different sizes are embedded, and a large number of crystals exist in example 2Holes. Example 2 has a density of 1.72g/cm 3 The combustion heat is up to 10289.3J/g, and the enthalpy of formation is-1054J/g.
Example 2 the thermal decomposition performance is shown in FIG. 2, and there is only one exothermic peak, the exothermic peak temperature is 201.5 ℃, and the exothermic amount is 1512.0J/g. Example 2 the higher energy density, as an energetic deceleration catalyst added to a solid propellant formulation, can maximize the energy level of the propellant while reducing the burn rate.
The heat analysis test is carried out by coating the HMX surface of the example 2 by a grinding method, and the result shows that the crystal transformation peak of the HMX is reduced by about 10 ℃ and the exothermic peak-to-peak temperature of the HMX is reduced by 1.1 ℃.
Example 2 was coated on the surface of AP by grinding and subjected to thermal analysis test. As shown in FIG. 5, after 10wt% of example 2 was added, the endothermic peak to peak temperature of AP was delayed by 5.9℃and the endothermic amount was increased from 79.4J/g to 100.3J/g. The peak temperature of the low-temperature decomposition of the example 2/AP mixed system is delayed from 283.8 ℃ to 312.5 ℃, the peak temperature of the high-temperature decomposition is delayed from 365.7 ℃ to 382.4 ℃, and the heat release amount is reduced from 866.7J/g to 363.5J/g.
Example 3: the preparation process of new type energy-containing burning rate inhibitor for solid propellant includes the following steps:
dissolution of the triaminoguanidine nitrate: 0.835g of triaminoguanidine nitrate was dissolved in 8mL of deionized water;
dissolution of alkali metal salt: 1.36g of Ba (NO) 3 ) 2 Adding the mixture into the dissolved triaminoguanidine nitrate solution, and stirring until the mixture is completely dissolved;
adjusting the pH value of the solution: dropwise adding ammonia water into the solution to adjust the pH value to 7;
formation of energetic flame retardant (barium salt): adding 0.71ml glyoxal water solution, and continuously stirring at 70 ℃ for reaction for 30min;
and (3) collecting products: the product was washed with deionized water, filtered and dried to give example 3.
SEM testing was performed on example 3, and the results are shown in fig. 1. Example 3 is a microcrystal formed from a large number of nanocrystals randomly stacked. Example 3 was subjected to a thermal analysis test, the results of which are shown in figure 2,example 3 had only one exotherm peak with an exotherm of 427.2J/g. Example 2 has a density of 1.20g/cm 3 The heat of combustion was 4614.69J/g and the enthalpy of formation was-2746J/g.
The thermal decomposition performance of the example 3/HMX blend system is shown in fig. 3, and the addition of 5wt% of example 3 reduced the maximum thermal decomposition rate of HMX from 115.2%/min to 99.3%/min. The thermal decomposition performance of the mixed system of example 3/AP is shown in FIG. 5, and the endothermic peak, the low-temperature decomposition peak and the high-temperature decomposition peak of the mixed system of example 3/AP are respectively delayed by 2.1 ℃, 16.2 ℃ and 5.0 ℃ compared with pure AP by adding 10wt% of example 3.
Example 4: the preparation process of new energy-containing burning rate inhibitor for solid propellant includes the following steps:
dissolution of the triaminoguanidine nitrate: 0.418g of the triaminoguanidine nitrate was dissolved in 4mL of deionized water;
dissolution of alkali metal salt: 0.59g of Ca (NO 3 ) 2 ·4H 2 O was added to 4mL deionized water;
adjusting the pH value of the solution: in Ca (NO) 3 ) 2 ·4H 2 Dropwise adding ammonia water into the O aqueous solution to adjust the PH value to 7;
preparation of TAGP dispersion: adding 0.36ml of glyoxal water solution into the dissolved triaminoguanidine nitrate solution, and stirring and reacting for 30min at 70 ℃ to form TAGP dispersion liquid;
formation of energetic flame retardant (calcium salt): ca (NO) was added dropwise to the TAGP dispersion 3 ) 2 ·4H 2 The O aqueous solution is stirred for 30min at 800 rpm;
and (3) collecting products: the product was washed with deionized water, filtered and dried to give example 4.
Example 4SEM image as shown in fig. 1, example 4 has a graphene-like structure formed by stacking a plurality of thin film crystals, which have a rough surface and nano-scale protrusions. Thermal analysis test was conducted on example 4, and the result is shown in FIG. 2, and example 4 has two exothermic peaks, the exothermic amounts of which were 281.4J/g and 26.1J/g, respectively. Example 4 has a density of 1.72g/cm 3 The combustion heat is up to 9583.55J/g, and the enthalpy of formation is-858J/g.
The thermal decomposition performance of the example 4/HMX mixed system is shown in FIG. 3 and FIG. 4, and as can be seen from Table 3, after 5wt% of example 4 is added, the HMX exotherm is reduced to 1448.0J/g; however, the content of example 4 was increased to 10% by weight, and the heat release amount of the whole system was increased to 1589.0J/g.
The thermal decomposition performance of the example 4/AP mixed system is shown in FIGS. 5 and 6, 10wt% of example 4 is added, so that the endothermic peak-to-peak temperature of AP is increased by 0.9 ℃, the pyrolysis peak is delayed from 365.7 ℃ to 386.3 ℃, but the heat release amount of the example 4/AP system is increased from 866.7J/g of pure AP to 1313.0J/g.
TABLE 1 preparation of energetic flame speed inhibitor of examples 1-4 and Performance Table
TABLE 2 Performance parameters of the energetic burn rate inhibitor of examples 1-4
TABLE 3 DSC thermal decomposition parameters of Industrial grade HMX, HMX/5wt% energy-containing burn rate inhibitor and HMX/10wt% energy-containing burn rate inhibitor Mixed System
Injection T i Initial decomposition temperature/°c; t (T) o The initial temperature of the decomposition peak, DEG C; t (T) p Decomposing peak temperature, and controlling the temperature; t (T) e The end temperature of the decomposition peak, DEG C; ΔH 1 Endothermic peak heat value J.g -1 ；ΔH 2 Exothermic peak calorific value J.g -1 .
TABLE 4 thermal decomposition parameters of HMX, HMX/5wt% energetic burn rate inhibitor and HMX/10wt% energetic burn rate inhibitor Mixed System TG/DTG
Injection T o Uncontrollable decomposition reaction initiation temperature; t (T) e The end temperature of the uncontrollable decomposition reaction; t (T) p The temperature at which the decomposition reaction rate is maximum; MS, percent mass loss at the uncontrolled decomposition reaction stage; rs, residual amount of decomposition reaction residue; l (L) max Maximum thermal decomposition rate%/min.
TABLE 5 DSC thermal decomposition parameters of Industrial grade AP and AP/10wt% energy containing burn rate inhibitor Mixed System
Injection T i Initial decomposition temperature/°c; t (T) o The initial temperature of the decomposition peak, DEG C; t (T) p Decomposing peak temperature, and controlling the temperature; t (T) e The end temperature of the decomposition peak, DEG C; ΔH 1 Endothermic peak heat value J.g -1 ；ΔH 2 Exothermic peak calorific value J.g -1 .
TABLE 6 thermal decomposition parameters of Industrial grade AP and AP/10wt% energy-containing flame retardant Mixed System TG/DTG
Injection T o Uncontrollable decomposition reaction initiation temperature; t (T) e The end temperature of the uncontrollable decomposition reaction; t (T) p The temperature at which the decomposition reaction rate is maximum; MS, percent mass loss at the uncontrolled decomposition reaction stage; rs, residual amount of decomposition reaction residue; l (L) max Maximum thermal decomposition rate (%/min).
Claims (7)
1. An energetic burning rate inhibitor for a solid propellant is characterized in that the energetic burning rate inhibitor has a two-dimensional network structure formed by self-polymerization and cross-linking reaction of triaminoguanidine nitrate and glyoxal, and the structural formula is as follows:
wherein: the carbon-nitrogen ratio is 3:4, the nitrogen content is more than 45%, and M is coordinated alkaline earth metal or transition metal element.
2. An energetic flame retardant agent for a solid propellant according to claim 1 wherein: the coordination metal M is alkaline earth metal calcium, potassium, barium or transition metal copper.
3. A method for preparing the energetic burning rate inhibitor for the solid propellant as claimed in claim 1 or 2 by a one-pot method, which is characterized by comprising the following operation steps:
step 1: adding the triaminoguanidine nitrate into deionized water, heating to 50-80 ℃, and stirring until the triaminoguanidine nitrate is completely dissolved;
step 2: adding the coordination metal salt into the solution prepared in the step 1, and stirring at 50-80 ℃ until the coordination metal salt is completely dissolved;
step 3: dropwise adding ammonia water into the solution in the step 2, and adjusting the pH value of the solution to 7;
step 4: finally, adding glyoxal aqueous solution, continuously stirring for 30-60min at 50-80 ℃ to separate out solid products;
step 5: filtering and drying the solid product obtained in the step 4 to obtain an energetic burning rate inhibitor;
the molar ratio of the triaminoguanidine nitrate, the glyoxal aqueous solution and the coordinated metal salt is controlled between 1:1:1 and 2:1:1.
4. A process for the preparation of an energetic burn rate depressant for a solid propellant according to claim 1 or 2 by a two-stage process,
the method is characterized by comprising the following steps:
step 1): adding the triaminoguanidine nitrate into deionized water, heating to 50-80 ℃, and stirring until the triaminoguanidine nitrate is completely dissolved;
step 2): adding glyoxal aqueous solution into the solution obtained in the step 1, and continuously stirring for 30-60min at 50-80 ℃ to obtain TAGP dispersion;
step 3): adding nitrate, perchlorate or chloride of coordinated metal into deionized water, stirring at 50-80 ℃ to dissolve completely;
step 4): dropwise adding ammonia water into the solution obtained in the step 3, and adjusting the pH value of the solution to 7;
step 5): dropwise adding the solution obtained in the step 4 into the TAGP dispersion liquid obtained in the step 2, and continuously stirring for 30-60min at 50-80 ℃ to separate out a solid product;
step 6): vacuum drying or suction filtering and drying the solid product obtained in the step 5 to obtain the energetic burning rate inhibitor;
the molar ratio of the triaminoguanidine nitrate, the glyoxal aqueous solution and the coordinated metal salt is controlled between 1:1:1 and 2:1:1.
5. The method according to claim 3 or 4, characterized in that: the coordination metal salt is Cu (NO) 3 ) 2 ·3H 2 O、KNO 3 、Ba(NO 3 ) 2 、Ba(Cl) 2 Or Ca (NO) 3 ) 2 ·4H 2 O。
6. The method according to claim 3 or 4, characterized in that: the stirring rate during the reaction in said step is 700 to 800rpm.
7. The method according to claim 3 or 4, characterized in that: the drying in the final preparation step is drying in an oven at a temperature of 70 to 80 ℃ for 3 to 6 days.
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