A kind of copper azotetrazolyl, composition containing copper azotetrazolyl, preparation method and application thereof

Abstract

The invention discloses a copper azotetrazolyl, a composition containing the copper azotetrazolyl, a preparation method and an application thereof. The preparation method of the copper azotetrazolyl creatively adopts solid mixed raw materials and directly generates the composition containing the copper azotetrazolyl in situ by controlling the temperature, relative humidity and other conditions of the reaction environment.

Description

Technical Field

[0001] The invention relates to azotetrazolyl copper or a composition containing the azotetrazolyl copper, and also provides a corresponding preparation method and application. Background Art

[0002] The firing charge is the basic charge of various impact ignition devices. It is a mixed agent that causes deflagration after being stimulated by the initial impulse energy. It is mainly composed of explosives, combustibles and oxidants, and may also contain desensitizers, sensitizers or adhesives. After the firing charge is triggered by the outside world, a hot spot is generated, and the decomposition of the explosive causes the combustion reaction of the combustibles and the oxidants. The flame formed is used to ignite the pyrotechnics. The firing charge needs to meet the requirements of suitable mechanical sensitivity, good ignition ability, reliable action, and safe manufacturing and use. The explosives commonly used for firing charges include lead nitride, tetrazene and lead styphnate. The firing charges widely used at present contain a large amount of lead, barium and titanium. The oxides of these heavy metals are all toxic. In order to meet the requirements of environmental protection, lead-free and barium-free firing charges have been sought for nearly two decades.

[0003] Based on this, azotetrazole energetic compounds have become a research hotspot. Some azotetrazole energetic compounds do not contain oxygen in their molecular structure, but have high energy and high bombardment velocity. Compared with aminotetrazole energetic compounds, azotetrazole energetic compounds are relatively sensitive and more environmentally friendly than the currently widely used detonators, and are expected to become new green detonators. However, with the application of azotetrazole energetic compounds in high explosives and pyrotechnic agents, it was found that due to their high sensitivity, azotetrazole complexes still exist when used as detonators for firing agents, etc., but due to the impact and friction during the mixing and pressing process, explosions or combustion may occur, resulting in accidents. Based on this, the friction sensitivity and impact sensitivity of azotetrazole energetic compounds as detonators have gradually become research hotspots for their improvement.

[0004] In order to solve the above safety issues, it is necessary to seek new ways to achieve a harmonious unity between the energy and stability of the complex. Based on the high-energy nitrogen-containing azotetrazole compounds, domestic and foreign researchers have appropriately reduced the nitrogen content of the azotetrazole complex by introducing auxiliary ligands to achieve the unity of high energy and insensitivity. Through systematic research, the structure and performance of the complex have been optimized. Tao Guo-hong et al. (non-patent literature 1) have made a new approach to achieve a harmonious unity between the energy and stability of the complex by introducing auxiliary ligands based on the high-energy nitrogen-containing azotetrazole compounds. 2- The auxiliary ligands o-phenanthroline (o-phen) and 2,2'-bipyridyl (2,2'-bipyridyl) were introduced to enhance the stability of the complex by moderately reducing the nitrogen content; Zhang Tonglai et al. (Non-patent Literature 2) studied the Mn 2+ 、Cd 2+ 、Ni 2+The coordination compound is a coordination compound with DAT, C1OT, N, etc. as the central ion and DAT, C1OT, N, etc. as the ligands. The energy and insensitivity of energetic complexes are unified by introducing auxiliary ligands to synthesize mixed complexes. In addition, Xie Xingbing, Zhu Shunguan, et al. (non-patent document three) disclosed a relatively complex preparation method, in which the target compound [Cu(NH3)4]ATZ-2H20 is synthesized in two steps. First, 5-aminotetrazole is used as the raw material, and it is oxidized to generate 5,5-azotetrazole sodium (NaATZ) by Thiele alkaline oxidation method; the second step is to use NaATZ aqueous solution as the base liquid, add ammonia water and soluble copper salt to carry out coordination reaction to generate the target product crystal. On the basis of the high-energy nitrogen compound of azotetrazole, the nitrogen content of the azotetrazole complex is appropriately reduced by introducing auxiliary ligands to achieve the unity of high energy and insensitivity. Through systematic research, the structure and performance of the complex are optimized, and it is hoped that it will have practical application value in the field of pyrotechnics.

[0005] However, the lone pair of electrons on the ring-forming N atom in the 5,5'-azotetrazolyl ion structure provides the necessary conditions for its coordination with metal ions, making it a very excellent high-nitrogen energetic ligand. The research on azotetrazolyl energetic compounds has been carried out for many years, but most of them involve the synthesis of new compounds, process optimization, and performance modification. Regarding the research on azotetrazolyl metal salts, current reports generally involve alkaline earth metals, alkali metals, and some trivalent metal complexes, mainly manganese, cobalt, nickel, zinc, lead and other metal salts of azotetrazolyl.

[0006] In 2009, Yan Zhijun et al. (non-patent document 4) synthesized a dihydrate of copper azotetrazolyl, which has better explosive properties than other metal salts of azotetrazolyl, but is extremely sensitive to impact, friction, and static stimulation, especially after the copper azotetrazolyl loses its crystal water, which is a great potential safety hazard in the preparation, storage, and use process, making it difficult to use. If the safety problem of copper azotetrazolyl in the preparation and use process can be solved, and its excellent explosive properties and green and environmentally friendly characteristics can be used, it will replace traditional explosive agents containing toxic and harmful elements such as lead, cadmium, and chlorine, and provide research ideas for the miniaturization of weapon systems.

[0007] Therefore, it is very necessary to solve the safety issues of copper azotetrazolyl during its preparation, storage and use.

[0008] Non-patent literature 1: TAO Guo-hong, Twamley B, Shreeve J M. Energetic nitrogen rich Cu(II) and Cd(II)5,5'-azobis(tetrazolate) complexes[J]. Inorg.Chem.2009,48,20,9918–9923.

[0009] Non-patent literature 2: Huang Huisheng, Zhang Tonglai, Zhang Jianguo, et al. Theoretical study on the structure and properties of energetic complexes of cobalt, nickel and copper with nitric acid carbohydrazide [J]. Acta Chimica Sinica, 2010, 68(4): 289-293.

[0010] Non-patent literature 3: Xie Xingbing, Zhu Shunguan, Chen Pengyuan, Tang Xiangbin, Tao Peipei, Synthesis and properties of tetraamminecopper(II) dihydrate azotetrazolyl[J]. Journal of Explosives and Propellants, 2014, 37(6): 31-34.

[0011] Non-patent literature 4: Yan Zhijun, Jiao Baojuan, Gao Shengli. Synthesis of a novel energetic complex CuATZ·2H2O[J]. Applied Chemistry, 2009, 26(4): 483-485. Summary of the invention

[0012] 1. Problem to be solved

[0013] One of the purposes of the present invention is to provide a novel method for preparing copper azotetrazolyl, wherein the method creatively adopts solid mixed raw materials and directly generates a composition containing copper azotetrazolyl in situ by controlling the temperature, relative humidity and other conditions of the reaction environment;

[0014] Based on one of the purposes of the present invention, the present invention also provides copper azotetrazolyl, a composition containing copper azotetrazolyl, and a percussion cap or detonator containing copper azotetrazolyl.

[0015] 2. Technical solution

[0016] In order to solve the above problems, the technical solution adopted by the present invention is as follows:

[0017] According to one of the purposes of the present invention, the present invention provides a method for preparing azotetrazolyl copper, comprising the following steps:

[0018] 1) mixing solid component raw materials and filling the mixed solid component raw materials into a container;

[0019] Wherein, the component raw materials include sodium azotetrazolyl and a copper source;

[0020] 2) placing the container in an environment with a temperature of 20 to 80 degrees Celsius and a relative humidity of not less than 40% to form a product containing copper azotetrazole;

[0021] Wherein, the processing time is 0.5 to 72 hours.

[0022] According to the method for preparing copper azotetrazole according to any embodiment of the first aspect of the first object of the present invention, in step 1), the amount of sodium azotetrazole and the copper source added is calculated according to the molar ratio of azotetrazole anion to divalent copper ion of (1-2): (2-1);

[0023] Preferably, the molar ratio of the azotetrazolyl anion to the divalent cupric ion is 1:(2-1); or the molar ratio of the azotetrazolyl anion to the divalent cupric ion is 2:(2-1); or the molar ratio of the azotetrazolyl anion to the divalent cupric ion is (1-2):1; or the molar ratio of the azotetrazolyl anion to the divalent cupric ion is (1-2):2.

[0024] According to the method for preparing copper azotetrazole in any embodiment of the first aspect of the first object of the present invention, the sodium azotetrazole can pass through a sieve of not less than 40 meshes.

[0025] According to the method for preparing copper azotetrazole of any embodiment of the first aspect of the first object of the present invention, the mesh number of the sieve through which the sodium azotetrazole can pass can be any value taken from any of the following numerical ranges: 40-500 mesh, 40-300 mesh, 40-200 mesh, 40-100 mesh, 40-80 mesh, 80-500 mesh, 80-400 mesh, 80-300 mesh, 80-200 mesh, 80-100 mesh, 100-500 mesh, 100-400 mesh, 100-300 mesh, 100-200 mesh.

[0026] According to the method for preparing copper azotetrazole in any embodiment of the first aspect of the first object of the present invention, the copper source can pass through a sieve of not less than 40 meshes.

[0027] According to the method for preparing azotetrazole copper of any embodiment of the first aspect of the first object of the present invention, the mesh number of the sieve through which the copper source can pass can be any value taken from any of the following numerical ranges: 40-500 mesh, 40-300 mesh, 40-200 mesh, 40-100 mesh, 40-80 mesh, 80-500 mesh, 80-400 mesh, 80-300 mesh, 80-200 mesh, 80-100 mesh, 100-500 mesh, 100-400 mesh, 100-300 mesh, 100-200 mesh.

[0028] According to the method for preparing copper azotetrazole of any embodiment of the first aspect of the first object of the present invention, the particle size of the sodium azotetrazole is no more than 400 microns.

[0029] According to the method for preparing azotetrazole copper of any embodiment of the first aspect of the first object of the present invention, the particle size of the sodium azotetrazole can be any value taken from any one of the following numerical ranges: 400-10 microns, 400-50 microns, 400-100 microns, 400-150 microns, 400-200 microns, 400-250 microns, 400-300 microns, 400-350 microns, 300-10 microns, 300-50 microns, 300-100 microns, 300-150 microns, 300-200 microns, 300-250 microns, 200-10 microns, 200-50 microns, 200-100 microns, 200-150 microns.

[0030] According to the method for preparing azotetrazole copper of any embodiment of the first aspect of the first object of the present invention, the particle size of the copper source does not exceed 400 microns.

[0031] According to the method for preparing azotetrazole copper of any embodiment of the first aspect of the first object of the present invention, the particle size of the copper source can be any value taken from any one of the following numerical ranges: 400-10 microns, 400-50 microns, 400-100 microns, 400-150 microns, 400-200 microns, 400-250 microns, 400-300 microns, 400-350 microns, 300-10 microns, 300-50 microns, 300-100 microns, 300-150 microns, 300-200 microns, 300-250 microns, 200-10 microns, 200-50 microns, 200-100 microns, 200-150 microns.

[0032] According to the method for preparing copper azotetrazole of any embodiment of the first aspect of the first object of the present invention, in step 1), the mixed component raw materials are compacted;

[0033] and / or

[0034] The mixed component raw materials are processed by a vibration compaction method.

[0035] According to the method for preparing copper azotetrazole of any embodiment of the first aspect of the first object of the present invention,

[0036] The mixed component raw materials are compacted at a pressure of not less than 50 MPa;

[0037] Preferably, the mixed component raw materials are compacted using a pressure of 50 to 150 MPa.

[0038] According to the method for preparing azotetrazole copper of any embodiment of the first aspect of the first object of the present invention, the pressure can be any value taken from any one of the following numerical ranges: 50-200MPa, 50-175MPa, 50-150MPa, 50-125MPa, 50-100MPa, 50-75MPa, 80-200MPa, 80-175MPa, 80-150MPa, 80-125MPa, 80-100MPa.

[0039] According to the method for preparing copper azotetrazole of any embodiment of the first aspect of the first object of the present invention, the copper source includes one or more of copper sulfate, copper nitrate, copper chloride and hydrates thereof.

[0040] According to the method for preparing copper azotetrazole according to any embodiment of the first aspect of the first object of the present invention, in step 2), the container is placed in an environment with a temperature of 20 to 80 degrees Celsius and a relative humidity of not less than 40% to form a product containing copper azotetrazole;

[0041] Wherein, the processing time is 0.5 to 72 hours;

[0042] According to the method for preparing copper azotetrazole according to any embodiment of the first aspect of the first object of the present invention, the temperature at which the container is placed can be any value within any of the following numerical ranges: 20 to 80 degrees Celsius, 20 to 75 degrees Celsius, 20 to 70 degrees Celsius, 20 to 65 degrees Celsius, 20 to 60 degrees Celsius, 20 to 55 degrees Celsius, 20 to 50 degrees Celsius, 20 to 45 degrees Celsius, 20 to 40 degrees Celsius, 20 to 35 degrees Celsius , 25-30 degrees Celsius, 25-35 degrees Celsius, 25-40 degrees Celsius, 25-45 degrees Celsius, 25-50 degrees Celsius, 25-55 degrees Celsius, 25-60 degrees Celsius, 25-65 degrees Celsius, 25-70 degrees Celsius; the preferred range is 20-45 degrees Celsius, 20-40 degrees Celsius, 20-35 degrees Celsius, 25-30 degrees Celsius, 25-35 degrees Celsius, 25-40 degrees Celsius, 25-45 degrees Celsius.

[0043] According to the method for preparing azotetrazole copper of any embodiment of the first aspect of the first object of the present invention, the relative humidity can be any value taken from any of the following numerical ranges: 40-100, 40-95, 40-90, 40-85, 40-80, 40-75, 40-70, 40-65, 40-60, 40-55, 40-50, 50-100, 50-95, 50-90, 50-85, 50-80, 50-75, 50-70, 50-65, 50-60, 50-55, 60-100, 60-95, 60-90, 60-85, 60-80, 60-75, 60-70, 60-65, 70-100, 70-95, 70-90, 70-85, 70-80, 70-75, 80-100, 80-95, 80-90, 80-85; a more preferred range is 70-100, 70-95, 70-90, 70-85, 70-80, 70-75, 80-100, 80-95, 80-90, 80-85; the most preferred range is 80-100, 80-95, 80-90, 80-85.

[0044] According to the method for preparing copper azotetrazole of any embodiment of the first aspect of the first object of the present invention, the treatment time can be any value taken from any one of the following numerical ranges: 0.5-72h, 0.5-36h, 0.5-18h, 0.5-9h, 1-72h, 1-36h, 1-18h, 1-9h, 2-72h, 2-36h, 2-18h, 2-9h, 3-72h, 3-36h, 3-18h, 3-9h, 4-72h, 4-36h, 4-18h, 4-9h, 6-72h, 6-36h, 6-18h, 6-9h, 8-72h, 8-36h, 8-18h, 8-9h.

[0045] Based on the first object of the present invention and any of the above technical solutions, the second object of the present invention is to provide azotetrazolyl copper.

[0046] Based on the first object of the present invention and any of the above technical solutions, the third object of the present invention is to provide a composition containing copper azotetrazole;

[0047] The composition containing copper azotetrazolyl comprises copper azotetrazolyl and sodium azotetrazolyl and / or a copper source with a total concentration of no more than 50 wt %.

[0048] Furthermore, the composition containing copper azotetrazolyl comprises copper azotetrazolyl and sodium salt.

[0049] Furthermore, the composition containing copper azotetrazolyl oxide has a copper azotetrazolyl oxide content of 10 to 70 wt %.

[0050] Based on the first object of the present invention and its technical solution, or based on the second object of the present invention and its technical solution, or based on the third object of the present invention and its technical solution, the third object of the present invention is to provide a primer or detonator containing azotetrazole copper.

[0051] Based on the first object of the present invention and its technical solution, or based on the second object of the present invention and its technical solution, or based on the third object of the present invention and its technical solution, the fourth object of the present invention is to provide a percussion cap or detonator comprising a composition containing copper azotetrazole. DETAILED DESCRIPTION

[0052] The present disclosure may be more easily understood by reference to the following description in conjunction with examples, all of which constitute a part of the present disclosure. It should be understood that the present disclosure is not limited to the specific products, methods, conditions or parameters described and / or illustrated herein. Further, the terms used herein are only used for the purpose of describing specific embodiments by way of example and are not intended to be limiting unless otherwise indicated.

[0053] It should also be understood that, for the sake of clarity, certain features of the present disclosure may be described herein in the context of separate embodiments, but may also be provided in combination with each other in a single embodiment. That is, unless clearly incompatible or specifically not included, each separate embodiment is considered to be combinable with any other embodiment, and the combination is considered to represent another different embodiment. Conversely, for the sake of simplicity, the various features of the present disclosure described in the context of a single embodiment may also be provided individually or in any sub-combination. Finally, although a particular embodiment may be described as part of a series of steps or part of a more general structure, each step or substructure itself may also be considered to be an independent embodiment.

[0054] Unless otherwise indicated, it should be understood that each individual element in a list and each combination of individual elements in the list will be interpreted as a different embodiment. For example, a list of embodiments represented as "A, B, or C" should be interpreted to include embodiments "A", "B", "C", "A or B", "A or C", "B or C", or "A, B, or C".

[0055] In the present disclosure, the singular forms of the articles "a," "an," and "the" also include the corresponding plural references, and a reference to a specific value includes at least that specific value unless the context clearly indicates otherwise. Thus, for example, a reference to "a substance" is a reference to at least one of that substance and equivalents thereof.

[0056] The terms including ordinal numbers such as "first" and "second" can be used to explain various components or fluids, but these components and fluids are not limited by these terms. Therefore, without departing from the teachings of the present disclosure, these terms are only used to distinguish the component / fluid from another component / fluid.

[0057] When items are described by using the conjunction terms "... and / or...," etc., the description should be understood to include any one of the associated listed items and all combinations of one or more thereof.

[0058] In general, the use of the term "about" indicates an approximate value that may vary depending on the desired properties obtained by the disclosed subject matter, and will be interpreted in a context-dependent manner based on function. Therefore, one of ordinary skill in the art will be able to interpret a certain degree of difference on a case-by-case basis. In some cases, the number of significant figures used when expressing a particular value can be a representative technique for determining the difference allowed by the term "about". In other cases, a gradient in a range of values ​​can be used to determine the range of differences allowed by the term "about". Further, all ranges in this disclosure are inclusive and combinable, and reference to the values ​​stated in the range includes each value within the range.

[0059] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention belongs; the terms used herein and / or include any and all combinations of one or more of the associated listed items.

[0060] In order to demonstrate the technical solutions and advantages of the present invention, the technical solutions in the embodiments of the present invention will be fully described below.

[0061] [1] The preparation method of copper azotetrazole of the present invention comprises the following steps:

[0062] 1) mixing solid component raw materials, and filling the mixed solid component raw materials into a container;

[0063] The component raw materials include sodium azotetrazolyl and a copper source; further, the addition amount of the sodium azotetrazolyl and the copper source is calculated according to the molar ratio of the azotetrazolyl anion to the divalent copper ion of (1-2): (2-1); optionally, the molar ratio of the azotetrazolyl anion to the divalent copper ion is 1: (2-1); or the molar ratio of the azotetrazolyl anion to the divalent copper ion is 2: (2-1); or the molar ratio of the azotetrazolyl anion to the divalent copper ion is (1-2): 1; or the molar ratio of the azotetrazolyl anion to the divalent copper ion is (1-2): 2; or the molar ratio of the azotetrazolyl anion to the divalent copper ion is (1-2): 2; the ideal result is that the molar ratio of the azotetrazolyl anion to the divalent copper ion that actually participates in the reaction can be kept infinitely close to 1: 1.

[0064] As component raw materials, ideally, only sodium azotetrazolyl and a copper source may be included, but usually some unavoidable impurities may also be contained.

[0065] The sodium azotetrazolyl in the component raw material is used to provide anionic azotetrazolyl. Further, the particle size of the sodium azotetrazolyl needs to be micrometer level, preferably not more than 400 micrometers, more preferably not more than 420 micrometers, or, the sodium azotetrazolyl as the component raw material can be sieved through a sieve, and the sodium azotetrazolyl can at least pass through a sieve of 40 mesh.

[0066] The copper source in the component raw material is used to provide copper ions. Therefore, there is no particular limitation on the type of the copper source. For example, copper salts such as copper sulfate, copper nitrate, copper chloride and its hydrate can be cited. Further, the particle size of the copper source needs to be micron-level, preferably not more than 400 microns, more preferably not more than 420 microns, or, the copper source as the component raw material can be sieved through a sieve, and the copper source can at least pass through a 40-mesh sieve.

[0067] As the "container", the basic requirement it meets is that it can accommodate the corresponding amount of component raw materials; under this premise, it can be further clarified that the better choice for the "container" is a "container" that is directly used to hold or contain the "gunpowder or firing powder" when the later copper azotetrazole is used as "gunpowder or firing powder", such as primer shells and detonators.

[0068] 2) placing the container in an environment with a certain temperature and humidity for treatment;

[0069] The temperature of the environment is 20 to 80 degrees Celsius, preferably 20 to 60 degrees Celsius, and may also be 25 to 35 degrees Celsius;

[0070] The humidity of the environment, measured by relative humidity, has a relative humidity of not less than 40%, and the "relative humidity" as mentioned herein specifically refers to the percentage of the water vapor pressure in the air to the saturated water vapor pressure at the same temperature; the calculation method is U = E / E ω , where U is the relative humidity, E is the water vapor pressure at that temperature (Pa), and E ω is the saturated water vapor pressure (Pa) at that temperature; its detection methods include dry-wet bulb method, telescopic method, electrolysis method, electronic humidity sensor, etc. In the present invention, an electronic humidity sensor is used for inspection. Regarding the selection of humidity, if it is to improve the preparation efficiency or reduce the ambient temperature, it is preferred that the environment has a relative humidity of not less than 60%, and it is most preferred that the environment has a relative humidity of not less than 80%.

[0071] The treatment time is 0.5 to 72 hours.

[0072] Further examples include:

[0073] The temperature of the environment can be 20 degrees Celsius, the relative humidity of the environment can be 60%, and the treatment time can be 72 hours;

[0074] The temperature of the environment can be 30 degrees Celsius, the relative humidity of the environment can be 60%, and the treatment time can be 60 hours;

[0075] The temperature of the environment can be 40 degrees Celsius, the relative humidity of the environment can be 60%, and the treatment time can be 48 hours;

[0076] The temperature of the environment can be 60 degrees Celsius, the relative humidity of the environment can be 60%, and the treatment time can be 24 hours;

[0077] The temperature of the environment can be 80 degrees Celsius, the relative humidity of the environment can be 60%, and the treatment time can be 12 hours;

[0078] The temperature of the environment can be 30 degrees Celsius, the relative humidity of the environment can be 80%, and the treatment time can be 12 hours;

[0079] The temperature of the environment may be 40 degrees Celsius, the relative humidity of the environment may be 90%, and the treatment time may be 8 hours.

[0080] In addition, it should be noted that, depending on the actual need to produce and use the target product "copper azotetrazole or a composition containing copper azotetrazole" in situ, a compaction treatment step can be selectively added between the aforementioned preparation steps 1) and 2) of the copper azotetrazole or the composition containing copper azotetrazole, as follows: the mixed solid component raw materials filled into the container need to have a certain density, and the density can be selected according to the actual application requirements or other factors. For example, when the copper azotetrazole is used as a detonator, the pressing step can be performed as required to achieve the density requirement.

[0081] There is no special requirement for the method of making the mixed solid component raw materials filled into the container have a certain density. For example, it can be compacted by rolling, tamping or vibration. The intensity of the compaction can be selected within the pressure range of 50 to 150 MPa, preferably 100 MPa.

[0082] Before the "compacting process", the "solid component raw materials" are preferably subjected to a "mixing" process. The "mixing" method is not particularly limited, and any known method that can help the materials to be mixed more evenly can be used, for example: mixing using a pharmaceutical mixer (also called a pharmaceutical mixer); or mixing using a high-speed mixer.

[0083] In addition, it should be noted that in order to improve certain aspects of the performance of the percussion cap or detonator, such as mechanical sensitivity, ignition ability, etc., ingredients such as combustibles, oxidants, desensitizers, sensitizers or adhesives may be added to the solid component raw materials in the preparation process of the aforementioned copper azotetrazole or a composition containing copper azotetrazole, especially in step 1) of the preparation process.

[0084] [2] Based on the preparation method provided by the present invention, the present invention can also provide azotetrazolyl copper.

[0085] [3] In addition, based on the preparation method provided by the present invention, the present invention can also provide a composition containing copper azotetrazolyl. The composition comprises copper azotetrazolyl, wherein the content of the copper azotetrazolyl is 10-70wt%, and in addition, the composition also comprises the corresponding sodium salt.

[0086] The content of copper azotetrazolyl in the composition depends on the particle size, dosage, ratio, and process parameters of the raw material components; the type of the metal sodium salt in the composition depends on the use of the raw material (copper source);

[0087] For example, if the copper source is copper sulfate, the content of the azotetrazolyl copper obtained can be controlled to be 10-61 wt %, and the corresponding sodium salt is sodium sulfate.

[0088] If the copper source is copper chloride, the content of the azotetrazolyl copper obtained can be controlled to be 10-66wt%, and the corresponding sodium salt is sodium chloride.

[0089] If the copper source is copper nitrate, the content of the azotetrazolyl copper obtained can be controlled to be 10-57wt%, and the corresponding sodium salt is sodium nitrate.

[0090] However, the content of copper azotetrazolyl is usually less than 70wt%. For example, the amount and ratio of sodium azotetrazolyl and copper source used to prepare copper azotetrazolyl solid component raw materials, if the copper source is excessive, the sodium azotetrazolyl can be guaranteed to have a higher conversion rate, if the sodium azotetrazolyl is excessive, the copper salt can be guaranteed to have a higher conversion rate, and the sensitivity of the product can be adjusted by controlling the excess raw materials;

[0091] For example, the particle size of the sodium azotetrazolyl is below 60 mesh; the particle size of the copper source is below 60 mesh.

[0092] For example, in step 2), the ambient temperature, ambient humidity and treatment time for the reaction are:

[0093] The temperature of the environment is 20±2 degrees Celsius, the relative humidity of the environment is 40±2%, and the treatment time is 48 hours; the content of copper azotetrazole in the obtained product is not less than 10wt%;

[0094] The temperature of the environment is 30±2 degrees Celsius, the relative humidity of the environment is 80±2%, and the treatment is 12 hours; the content of copper azotetrazole in the obtained product is not less than 15wt%;

[0095] The temperature of the environment is 30±2 degrees Celsius, the relative humidity of the environment is 80±2%, and the treatment is 24 hours; the content of copper azotetrazole in the obtained product is not less than 20wt%;

[0096] The temperature of the environment is 40±2 degrees Celsius, the relative humidity of the environment is 90±2%, and the treatment is 12 hours; the content of copper azotetrazole in the obtained product is not less than 30wt%;

[0097] The content of copper azotetrazolyl in the product can be characterized by the following idea: the sample to be tested is fully dissolved with water, and the remaining insoluble part is copper azotetrazolyl.

[0098] [4] Based on the method for preparing copper azotetrazolyl or a composition containing copper azotetrazolyl provided by the present invention, the safe use of the copper azotetrazolyl or a composition containing copper azotetrazolyl as a detonator is achieved, and a method for further obtaining a percussion cap or a detonator is as follows:

[0099] According to the preparation step 1) of the copper azotetrazolyl compound or the composition containing copper azotetrazolyl compound, the solid component raw materials (sodium azotetrazolyl compound and copper source) are directly mixed and filled into a cap shell or a detonator;

[0100] According to the preparation step 2) of the copper azotetrazolyl compound or the composition containing copper azotetrazolyl compound, the cap shell or detonator is placed in a corresponding environment for reaction.

[0101] At this point, it is necessary to clarify that it is recommended to add a compaction treatment step between the aforementioned steps 1) and 2) of preparing the copper azotetrazole or the composition containing copper azotetrazole, as follows: the mixed solid component raw materials filled into the container need to have a certain density, and the density can be selected according to the actual application requirements or other factors. For example, when the copper azotetrazole is used as a detonator, the pressing step can be performed as required to achieve the density requirement.

[0102] There is no special requirement for the method of making the mixed solid component raw materials filled into the container have a certain density. For example, it can be compacted by rolling, tamping or vibration. The intensity of the compaction can be selected within the pressure range of 50 to 150 MPa, preferably 100 MPa.

[0103] Before the "compacting process", the "solid component raw materials" are preferably subjected to a "mixing" process. The "mixing" method is not particularly limited, and any known method that can help the materials to be mixed more evenly can be used, for example: mixing using a pharmaceutical mixer (also called a pharmaceutical mixer); or mixing using a high-speed mixer.

[0104] In addition, it should be noted that in order to improve certain aspects of the performance of the percussion cap or detonator, such as mechanical sensitivity, ignition ability, etc., ingredients such as combustibles, oxidants, desensitizers, sensitizers or adhesives may be added to the solid component raw materials in the preparation process of the aforementioned copper azotetrazole or a composition containing copper azotetrazole, especially in step 1) of the preparation process.

[0105] Example 1 (Preparation method example)

[0106] Weigh a certain proportion of the raw materials sodium azotetrazolyl and copper sulfate;

[0107] Add the mixture into the mixing tank, start the mixer and mix for 30 minutes before discharging;

[0108] Pressing the mixed component raw materials into a reaction container;

[0109] Place the reaction container in a constant temperature and humidity chamber for reaction;

[0110] After being taken out, the mixture is dried to obtain a product composition, wherein the product composition contains copper azotetrazole.

[0111] [Specific process parameters used in the preparation of sample 1]:

[0112] Sodium azotetrazolyl: copper sulfate (weight ratio) = 55:45; (anion azotetrazolyl: copper ion molar ratio is 1:1)

[0113] The sodium azotetrazolyl chloride is sieved through a 60-mesh sieve before use, and the sieve residue is taken;

[0114] The copper sulfate is sieved through a 60-mesh sieve before use, and the sieve residue is taken;

[0115] The pressure of the mixed raw materials into the reaction vessel is 100MPa;

[0116] The reaction container directly selects the cap shell;

[0117] The temperature of the thermostat is 30 degrees Celsius and the relative humidity is greater than 85%;

[0118] The reaction time is 12h.

[0119] [Specific process parameters used in the preparation of sample 2]:

[0120] Sodium azotetrazolyl: copper sulfate (weight ratio) = 55:45; (anion azotetrazolyl: copper ion molar ratio is 1:1)

[0121] The sodium azotetrazolyl chloride is sieved through a 40-mesh sieve before use, and the sieve residue is taken;

[0122] The copper sulfate is passed through a 40-mesh sieve before use, and the sieve residue is taken;

[0123] The pressure of the mixed raw materials into the reaction vessel is 100MPa;

[0124] The reaction container directly selects the cap shell;

[0125] The temperature of the thermostat is 30 degrees Celsius and the relative humidity is greater than 85%;

[0126] The reaction time is 12h.

[0127] [Specific process parameters used in the preparation of comparative sample 1]:

[0128] Basically the same as [Sample 2], the only difference is that the sodium azotetrazolyl oxide particles are larger, and are sieved through a 10-mesh sieve before use, and the sieve residue is taken;

[0129] The copper sulfate particles are relatively large and are sieved through a 10-mesh sieve before use to obtain the material under the sieve.

[0130] [Specific process parameters used in the preparation of sample 3]:

[0131] Sodium azotetrazolyl: copper sulfate (weight ratio) = 55:45; (anion azotetrazolyl: copper ion molar ratio is 1:1)

[0132] The sodium azotetrazolyl chloride is sieved through a 60-mesh sieve before use, and the sieve residue is taken;

[0133] The copper sulfate is sieved through a 60-mesh sieve before use, and the sieve residue is taken;

[0134] The pressure of the mixed raw materials into the reaction vessel is 80MPa;

[0135] The reaction container directly selects the cap shell;

[0136] The temperature of the thermostat is 30 degrees Celsius and the relative humidity is greater than 85%;

[0137] The reaction time is 12h.

[0138] [Specific process parameters used in the preparation of sample 4]:

[0139] Sodium azotetrazolyl: copper sulfate (weight ratio) = 55:45; (anion azotetrazolyl: copper ion molar ratio is 1:1)

[0140] The sodium azotetrazolyl chloride is sieved through a 60-mesh sieve before use, and the sieve residue is taken;

[0141] The copper sulfate is sieved through a 60-mesh sieve before use, and the sieve residue is taken;

[0142] The pressure of the mixed raw materials into the reaction vessel is 100MPa;

[0143] The reaction container directly selects the cap shell;

[0144] The temperature of the thermostat is 20 degrees Celsius and the relative humidity is greater than 85%;

[0145] The reaction time is 48h.

[0146] [Specific process parameters used in the preparation of comparative sample 2]:

[0147] Basically the same as [Sample 4], the only difference is that the temperature of the thermostatic box is 10 degrees Celsius, and the sieve is sieved with a 10-mesh sieve before use, and the sieve is taken;

[0148] The copper sulfate particles are relatively large and are sieved through a 10-mesh sieve before use to obtain the material under the sieve.

[0149] [Specific process parameters used in the preparation of comparative sample 3]:

[0150] Basically the same as [Sample 4], the only difference is that the reaction time is 12h.

[0151] [Specific process parameters used in the preparation of comparative sample 4]:

[0152] Basically the same as [Sample 4], the only difference is that the relative humidity does not exceed 50%.

[0153] [Specific process parameters used in the preparation of sample 5]:

[0154] Sodium azotetrazolyl: copper sulfate (weight ratio) = 55:45; (anion azotetrazolyl: copper ion molar ratio is 1:1)

[0155] The sodium azotetrazolyl chloride is sieved through a 60-mesh sieve before use, and the sieve residue is taken;

[0156] The copper sulfate is sieved through a 60-mesh sieve before use, and the sieve residue is taken;

[0157] The pressure of the mixed raw materials into the reaction vessel is 100MPa;

[0158] The reaction container directly selects the cap shell;

[0159] The temperature of the thermostat is 30 degrees Celsius and the relative humidity is greater than 75%;

[0160] The reaction time is 48h.

[0161] [Specific process parameters used in the preparation of sample 6]:

[0162] Sodium azotetrazolyl: copper sulfate (weight ratio) = 55:45; (anion azotetrazolyl: copper ion molar ratio is 1:1)

[0163] The sodium azotetrazolyl chloride is sieved through a 60-mesh sieve before use, and the sieve residue is taken;

[0164] The copper sulfate is sieved through a 60-mesh sieve before use, and the sieve residue is taken;

[0165] The pressure of the mixed raw materials into the reaction vessel is 100MPa;

[0166] The reaction container directly selects the cap shell;

[0167] The temperature of the thermostat is 30 degrees Celsius and the relative humidity is greater than 85%;

[0168] The reaction time is 4h.

[0169] [Specific process parameters used in the preparation of sample 7]:

[0170] Sodium azotetrazolyl: copper sulfate (weight ratio) = 55:45; (anion azotetrazolyl: copper ion molar ratio is 1:1)

[0171] The sodium azotetrazolyl chloride is sieved through a 60-mesh sieve before use, and the sieve residue is taken;

[0172] The copper sulfate is sieved through a 60-mesh sieve before use, and the sieve residue is taken;

[0173] The pressure of the mixed raw materials into the reaction vessel is 100MPa;

[0174] The reaction container directly selects the cap shell;

[0175] The temperature of the thermostat is 20 degrees Celsius and the relative humidity is greater than 40%;

[0176] The reaction time is 48h.

[0177] [Specific process parameters used in the preparation of sample 8]:

[0178] Sodium azotetrazolyl: copper sulfate (weight ratio) = 55:45; (anion azotetrazolyl: copper ion molar ratio is 1:1)

[0179] The sodium azotetrazolyl chloride is sieved through a 60-mesh sieve before use, and the sieve residue is taken;

[0180] The copper sulfate is sieved through a 60-mesh sieve before use, and the sieve residue is taken;

[0181] The pressure of the mixed raw materials into the reaction vessel is 50MPa;

[0182] The reaction container directly selects the cap shell;

[0183] The temperature of the thermostat is 30 degrees Celsius and the relative humidity is greater than 85%;

[0184] The reaction time is 12h.

[0185] Example 2

[0186] The ignition test adopts the explosion probability method. In this embodiment, referring to "GJB 3196.13A-2005 Gun and Bullet Test Method Part 13: Primer Impact Sensitivity Test", the ignition sensitivity test is carried out using an explosion probability method, and a falling ball weight of 55g is used.

[0187] The formulations of various embodiments and comparative examples and their product properties are shown in Table 1.

[0188] Table 1 Samples and comparative samples and their properties

[0189] Sodium azotetrazolyl / wt% Copper source / wt% Drop height / cm Firing rate Sample 1 55 45(Copper sulfate) 240 100 / 100 Sample 2 55 45(Copper sulfate) 280 100 / 100 Sample 3 55 45(Copper sulfate) 240 100 / 100 Sample 4 55 45(Copper sulfate) 240 100 / 100 Sample 5 55 45(Copper sulfate) 240 100 / 100 Sample 6 55 45(Copper sulfate) 280 72 / 100 Sample 7 55 45(Copper sulfate) 280 77 / 100 Sample 8 55 45(Copper sulfate) 280 100 / 100 Comparative sample 1 55 45(Copper sulfate) 280 21 / 100 Comparative sample 2 55 45(Copper sulfate) 280 6 / 100 Comparative sample 3 55 45(Copper sulfate) 280 19 / 100 Comparative sample 4 55 45(Copper sulfate) 280 9 / 100

[0190] Example 3

[0191] According to different proportions, sodium tetrazolyl chloride (under 60 mesh) and copper sulfate (under 60 mesh) were added to the mixing tank, and the mixer was started to mix for 30 minutes, and the material was discharged. The mixed material was pressed into the cap shell, and the cap shell was placed in a constant temperature and humidity chamber with a temperature of 30 degrees Celsius and a relative humidity greater than 85% for in-situ reaction for 12 hours. After being taken out, it was dried and assembled into products (samples 9 to 11, comparative samples 5 and 6) and then tested. The ignition test adopted the explosion probability method (refer to "GJB 3196.13A-2005 Bullet Test Method Part 13: Primer Impact Sensitivity Test"), and a falling ball weight of 55g was used.

[0192] The formulations of various embodiments and comparative examples and their product properties are shown in Table 2.

[0193] Table 2 Samples and comparative samples and their properties

[0194] Sodium azotetrazolyl / wt% Copper source / wt% Drop height / cm Firing rate Sample 9 40 60(Copper sulfate) 240 100 / 100 Sample 10 65 35(Copper sulfate) 280 100 / 100 Sample 11 55 45(Copper chloride) 280 100 / 100 Comparative sample 5 35 65(Copper sulfate) 280 46 / 100 Comparative sample 6 30 70(Copper sulfate) 280 17 / 100

[0195] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing copper azotetrazole, characterized in that: The following steps are involved: 1) Mixing solid component raw materials and filling the mixed solid component raw materials into a container; Wherein, the component raw materials include sodium azotetrazolyl and a copper source; 2) placing the container in an environment with a temperature of 20 to 80 degrees Celsius and a relative humidity of not less than 40% for 0.5 to 72 hours to form a product containing copper azotetrazole.

2. The method for preparing copper azotetrazole according to claim 1, characterized in that: In step 1), the added amounts of sodium azotetrazolyl and copper source are calculated according to the molar ratio of azotetrazolyl anion to divalent copper ion of (1-2):(2-1).

3. The method for preparing copper azotetrazole according to claim 2, characterized in that: The sodium azotetrazolyl can pass through a sieve of not less than 40 mesh; and / or, The copper source can pass through a sieve of not less than 40 mesh; and / or, The particle size of the sodium azotetrazolyl is no more than 400 microns; and / or, The particle size of the copper source does not exceed 400 microns.

4. The method for preparing copper azotetrazole according to claim 2, characterized in that: The copper source includes one or more of copper sulfate, copper nitrate, copper chloride and hydrates thereof.

5. The method for preparing copper azotetrazole according to any one of claims 1 to 4, characterized in that: In step 2), the container is placed at a temperature of 20 to 60 degrees Celsius; and / or, In step 2), the container is placed in an environment with a relative humidity of not less than 60%; and / or, In step 2), the treatment time is 8 to 72 hours.

6. The method for preparing copper azotetrazole according to claim 5, characterized in that: In step 2), the container is placed at a temperature of 20 to 40 degrees Celsius; and / or, In step 2), the container is placed in an environment with a relative humidity of not less than 70%; and / or, In step 2), the processing time is 12 to 48 hours.

7. The method for preparing copper azotetrazole according to claim 5, characterized in that: In step 1), the mixed component raw materials are compacted.

8. The method for preparing copper azotetrazole according to claim 6, characterized in that: In step 1), the mixed component raw materials are compacted.

9. The method for preparing copper azotetrazole according to claim 7 or 8, characterized in that: The mixed component raw materials are compacted using a pressure of not less than 50 MPa.

10. The method for preparing copper azotetrazole according to claim 7 or 8, characterized in that: The mixed component raw materials are compacted using a pressure of 50-150 MPa.