Integrated oil-phase emulsion explosive and preparation method thereof

Abstract

This application discloses an integrated oil-phase emulsion explosive and its preparation method. The raw materials of this emulsion explosive include an aqueous phase component, an oil phase component, and an emulsifier for emulsifying the aqueous and oil phase components. The aqueous phase component contains a modified oxidant formed by loading a nitrate-based oxidant component onto p-aminophenyl POSS. The preparation process of the modified oxidant includes: A) fully dispersing the nitrate-based oxidant component and p-aminophenyl POSS in an aqueous solution to ensure the nitrate-based oxidant component is fully attached to the p-aminophenyl POSS; B) separating the solid phase component from the solution system obtained in step B, which is the modified oxidant. The integrated oil-phase emulsion explosive and its preparation method provided in this application can effectively balance sensitivity and explosive power.

Description

Technical Field

[0001] This application relates to the technical field of emulsion explosives, and more particularly to emulsion explosives with an integrated oil phase and their preparation methods. Background Technology

[0002] Emulsion explosives are a new type of industrial explosive developed from the 1970s to the late 1980s. Due to their unique physical structure, these explosives have excellent water resistance, more complete explosive reactions, and are safe to manufacture, transport, and use, as well as being effective in mining blasting.

[0003] In related technologies, for emulsion explosives, it is often difficult to achieve a good balance between sensitivity and power. That is, emulsion explosives with high sensitivity often have insufficient power, and vice versa. See the following related technical literature:

[0004] Related technical document 1: CN 109369314A;

[0005] Related technical document 2: CN 106748589 A;

[0006] Related technical document 3: CN 111333473 A. Summary of the Invention

[0007] The issues to be addressed

[0008] This application aims to address at least one of the technical problems existing in the prior art. Therefore, one objective of this application is to provide an emulsion explosive that can better balance sensitivity and power.

[0009] [Methods for Solving the Problem]

[0010] In related technologies, to attempt to solve the balance between sensitivity and power of emulsion explosives, porous materials are often used as sensitizing additives. Examples include porous graphene (as described in reference 3), high-energy metal powder coated with porous silica hollow microspheres (as described in reference 2), and aerogels (as described in reference 1). Although these porous materials can enhance sensitivity by creating pores and providing gas transport channels for the explosive flow, the energy generated by the explosion is often greatly released through these channels, reducing its power. Therefore, it is evident that these related technologies struggle to achieve a balance between sensitivity and power in emulsion explosives.

[0011] To solve the aforementioned problems, the inventors conducted repeated and in-depth research and realized that, based on this realization, they creatively discovered that by loading nitrate oxidants onto p-aminophenyl POSS, the cage-like silica-oxygen framework of p-aminophenyl POSS can, through the adsorption force of its microcavities, encapsulate a considerable portion of the nitrate oxidant within the cage-like silica-oxygen framework, expanding the dispersion space of the oxidant and enhancing its sensitivity. Simultaneously, the rigidity of the cage-like silica-oxygen framework may create a temporary confinement space around the nitrate oxidant when it reacts with the energy generated by fuel combustion, accumulating explosive energy and enhancing its power. This led to the creation of this invention.

[0012] This application provides, on the one hand, a raw material comprising an aqueous phase component, an oil phase component, and an emulsifier for causing the aqueous phase component and the oil phase component to form an emulsion:

[0013] The aqueous phase component contains a modified oxidant formed by loading a nitrate-based oxidant component onto p-aminophenyl POSS;

[0014] The preparation process of the modified oxidant includes the following steps:

[0015] A. Ensure that the nitrate oxidant component and p-aminophenyl POSS are fully dispersed in the aqueous solution so that the nitrate oxidant component is fully attached to the p-aminophenyl POSS;

[0016] B. The solid phase component separated from the solution system obtained in step B is the modified oxidant.

[0017] In any embodiment, the amount of the nitrate oxidant component fed is such that the concentration of the nitrate oxidant in the aqueous solution is 1-5 mol / L.

[0018] In any embodiment, the nitrate oxidant component includes:

[0019] Nitrate oxidizing agents, selected from at least one of sodium nitrate and ammonium nitrate;

[0020] The first accelerator is selected from at least one of sodium perchlorate and ammonium chloride;

[0021] The second accelerator is selected from at least one of sodium nitrite, calcium nitrate, and zinc nitrate.

[0022] In any embodiment, the ratio of the amount of metal ions fed to the amount of nitrate oxidant contained in the nitrate oxidant component, based on molar number, is 1:2 to 1:5.

[0023] In any embodiment, in step A, dispersion is performed under ultrasonic dispersion.

[0024] In any implementation, the dispersion temperature in step A is 50-70°C.

[0025] In any implementation, the dispersion time in step A is 2-4 hours.

[0026] In any embodiment, the pH of the dispersion is 5-7.

[0027] In any embodiment, in step A, the aqueous solution further includes a dispersant selected from at least one of C1-4 alcohol, DMF, and DMSO.

[0028] In any embodiment, the amount of the modified oxidant fed is 56-74 wt% based on the weight of the aqueous phase component.

[0029] This application also provides a method for preparing an integrated oil-phase emulsion explosive, comprising the following steps:

[0030] An aqueous phase component is provided, the aqueous phase component containing a modified oxidant formed by loading a nitrate oxidant component onto p-aminophenyl POSS; the preparation process of the modified oxidant includes: A) fully dispersing the nitrate oxidant component and p-aminophenyl POSS in an aqueous solution, so that the nitrate oxidant component is fully attached to the p-aminophenyl POSS; B) separating the solid phase component from the solution system obtained in step B, which is the modified oxidant;

[0031] Provide oil phase components;

[0032] The oil phase component is continuously added to the aqueous phase component and fully dispersed until a homogeneous emulsion is formed.

[0033] [Invention Effects]

[0034] The integrated oil-phase emulsion explosive and its preparation method provided in this application can better balance sensitivity and power. Detailed Implementation

[0035] The following detailed description discloses specific embodiments of this application. However, unnecessary detailed descriptions may be omitted. For example, detailed descriptions of well-known matters and repetitive descriptions of actually identical structures may be omitted. This is to avoid making the following description unnecessarily lengthy and to facilitate understanding by those skilled in the art. Furthermore, the following description is provided to enable those skilled in the art to fully understand this application and is not intended to limit the subject matter recorded in the claims. The "scope" disclosed in this application is defined in the form of a lower limit and an upper limit. A given scope is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular scope. Scopes defined in this way may include or exclude end values ​​and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a scope. For example, if a scope of 60-120 and 80-110 is listed for a specific parameter, it is expected that the scopes of 60-110 and 80-120 are also included. Furthermore, if the minimum range values ​​1 and 2 are listed, and if the maximum range values ​​3, 4, and 5 are listed, then the following ranges can all be expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this application, unless otherwise stated, the numerical range “ab” represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range “0-5” means that all real numbers between “0-5” have been listed herein, and “0-5” is merely a shortened representation of these numerical combinations. Additionally, when a parameter is stated as an integer ≥ 2, it is equivalent to disclosing that the parameter is, for example, an integer 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0036] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0037] Unless otherwise specified, all technical features and optional technical features of this application may be combined to form new technical solutions.

[0038] Unless otherwise specified, all steps in this application may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the mention that the method may also include step (c) indicates that step (c) may be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0039] Unless otherwise specified, the terms "comprising" and "including" as used in this application can be open-ended or closed-ended. For example, "comprising" and "including" can mean that other components not listed may also be included, or that only the listed components may be included.

[0040] Unless otherwise specified, the term "or" is inclusive in this application. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, the condition "A or B" is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0041] [Emulsion Explosives]

[0042] The raw materials of the emulsion explosive include an aqueous phase component, an oil phase component, and an emulsifier for forming an emulsion between the aqueous phase component and the oil phase component; wherein the aqueous phase component contains a modified oxidant formed by loading a nitrate oxidant component onto p-aminophenyl POSS.

[0043] The specific proportions of the aqueous phase component, oil phase component, and emulsifier can be adjusted according to performance requirements based on the conventional proportions of emulsion explosives. As a widely used but non-limiting demonstration form, the weight ratio of the aqueous phase component, oil phase component, and emulsifier is 100 parts by weight of aqueous phase component, 5-8 parts by weight of oil phase component, and 20-32 parts by weight of emulsifier.

[0044] The role of the aqueous phase component is to disperse the hydrophilic oxidant (sensitizer). The amount of dispersion medium (such as water, and a small amount of ethanol can also be added to promote dispersion) in the aqueous phase component can be 56-74 wt% of the weight of the modified oxidant in the aqueous phase component.

[0045] Here, the term "nitrate oxidant component" refers to a component primarily composed of nitrate oxidants. Suitable, but not limiting, specific examples include:

[0046] Nitrate oxidizing agents, selected from at least one of sodium nitrate and ammonium nitrate;

[0047] The first accelerator is selected from at least one of sodium perchlorate and ammonium chloride;

[0048] The second accelerator is selected from at least one of sodium nitrite, calcium nitrate, and zinc nitrate.

[0049] The role of the oil phase component is twofold: firstly, to provide the fuel required for the explosive detonation, and secondly, to disperse the lipophilic components. The oil phase component can be in the form commonly used in emulsion explosives, which is a widely used but non-limiting exemplary form. The oil phase component contains 8-12 parts of composite wax, 8-12 parts of fully refined paraffin wax, 15-25 parts of microcrystalline wax, and 15-25 parts of base oil (which acts as fuel).

[0050] Here, base oils include vegetable oils, mineral oils, and synthetic oils.

[0051] In addition to the above components, stabilizers such as borax and zinc stearate can also be added to the oil phase.

[0052] The emulsifier can be in conventional forms, such as S-80 emulsifier, succinimide emulsifier, sodium dodecyl sulfonate, and acetylenol, etc., but is not limited to these. The emulsifier can be added to the oil phase component, the aqueous phase component, or a combination of both.

[0053] Modified oxidizing agent

[0054] The preparation process of the modified oxidant includes the following steps:

[0055] A. Ensure that the nitrate oxidant component and p-aminophenyl POSS are fully dispersed in the aqueous solution so that the nitrate oxidant component is fully attached to the p-aminophenyl POSS;

[0056] B. The solid phase component separated from the solution system obtained in step B is the modified oxidant.

[0057] The aforementioned p-aminophenyl POSS, also known as octa(aminophenyltrioxosilane) or octa(aminophenyltrioxosilane) polyhedral oligomeric silsesquioxane, has the CAS number 518359-82-5. Given that its physicochemical properties are well-known in the art, they will not be described further here. p-Aminophenyl POSS can be prepared using methods known to those skilled in the art, or it can be obtained through established commercial channels, as specified in the following examples.

[0058] Understandably, in step A, the nitrate oxidant component adheres fully to the p-aminophenyl POSS, relying on both the physical adsorption force generated by the micropores of the silicon-oxygen framework of the p-aminophenyl POSS and, more importantly, the molecular hydrogen bonds formed between the phenylamino group and the nitrate ion on the p-aminophenyl POSS. The reason for the molecular hydrogen bonds between the phenylamino group and the nitrate ion is that the oxygen atom on the nitrate ion has strong electronegativity; for the phenylamino group, the N atom, after withdrawing electrons from the H atom, allows its electron orbitals to be better dispersed through the delocalized space provided by the benzene ring, thus making the phenylamine anion formed by the phenylamino group more stable, which is more conducive to forming molecular hydrogen bonds with the nitrate ion. In other words, the benzene ring on the phenylamino group, compared to molecules without a similar benzene ring structure, increases the likelihood of forming molecular hydrogen bonds with the nitrate ion.

[0059] Suitable, but not limiting, specific examples include the amount of the nitrate oxidant component added so that the concentration of the nitrate oxidant in the aqueous solution is 1-5 mol / L.

[0060] A suitable, but not limiting, specific example is that in step A, dispersion is carried out under ultrasonic dispersion.

[0061] As a suitable but not limiting specific example, in step A, the dispersion temperature is 50-70°C.

[0062] A suitable but non-restrictive specific example is that in step A, the dispersion time is 2-4 hours.

[0063] Suitable, but not limiting, examples show that the dispersion occurs at a pH of 5-7, particularly preferably 6. This slightly acidic environment facilitates the minimal protonation of aniline, thereby improving its dispersibility. Excessive acidity may cause the amino group of aniline to oxidize with the nitrate group.

[0064] As a suitable, but not limiting, specific example, in step A, the aqueous solution further includes a dispersant selected from at least one of C1-4 alcohols, DMF, and DMSO. Thus, the dispersant improves the dispersion of p-aminophenyl POSS in the aqueous solution.

[0065] Preparation methods of emulsion explosives

[0066] Regarding the preparation methods of emulsion explosives, one can combine the conventional feeding methods, oil phase raw materials, and other relevant information in the field.

[0067] [Implementation process of the examples and comparative examples]

[0068] The following describes embodiments of this application. The embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments used, unless otherwise specified, are all conventional products that can be obtained commercially.

[0069] 1. [Example of manufacturing modified oxidizing agents]

[0070] A round-bottom flask was filled with a mixture of water and ethanol (ethanol comprising 9 vol% of the water volume). Then, p-aminophenyl POSS (produced by Xi'an Qiyue Biotechnology Co., Ltd., with a molecular weight of 1153.63 and molecular formula C) was added to the flask. 48 H 48 N8O 12 The reaction mixture consisted of 23-40 parts by weight of Si8, 76-85 parts by weight of ammonium nitrate, 2-5 parts by weight of sodium nitrate, 0-4 parts by weight of sodium perchlorate, 0-4 parts by weight of ammonium chloride, 0-0.3 parts by weight of sodium nitrite, and 0-0.08 parts by weight of zinc nitrate, all placed in a water bath of an ultrasonic oscillating water bath (manufactured by Bandelin SONOSHAKE, Germany). The temperature of the reaction system in the water bath was controlled at 60°C, and the pH of the reaction system was controlled to a predetermined value using a pH meter mounted on the water bath. Ultrasonic dispersion was then initiated, and the ultrasonic power was controlled at 1000W. After reacting for 3 hours, the liquid in the water bath was transferred to a conical flask for vacuum filtration. The filter residue was washed with deionized water and then vacuum dried to obtain the modified oxidant.

[0071] Using the above operations described in "[Example of Manufacturing Modified Oxidants]" of this section and in conjunction with the process conditions in Table 1, a series of modified oxidants A1-A10 were prepared.

[0072] 2. [Example]

[0073] S1. Preparation of the aqueous phase component. The modified oxidants A1-A10 and sodium dodecyl sulfonate described above are added to a flask containing a mixture of water and ethanol (ethanol accounting for 9 vol% of the water volume) (the flask is equipped with a mechanical stirrer). The amount of modified oxidant added is 56-74 wt% of the weight of the water-ethanol mixture, and the amount of sodium dodecyl sulfonate added is 10 wt% of the weight of the water-ethanol mixture. The flask is placed in a water bath, the heating temperature is adjusted to 50 degrees Celsius, and the mechanical stirrer is turned on to ensure that the modified oxidant is fully dispersed in the water-ethanol mixture, thus obtaining the aqueous phase component.

[0074] S2. Preparation of the oil phase component. The raw materials for the oil phase component are prepared according to the following weight proportions: 10 parts composite wax, 9 parts fully refined paraffin wax, 18 parts microcrystalline wax, 22 parts vegetable oil, 15 parts S-80 emulsifier, and 4 parts succinimide emulsifier. The above raw materials for the oil phase component are added to a flask equipped with a mechanical stirrer. The flask is placed in a water bath and the temperature is adjusted to 50 degrees Celsius. Mechanical stirring is then turned on to fully disperse the components, thus obtaining the oil phase component.

[0075] S3. Place the oil phase component into a dropping funnel and install the dropping funnel in the flask for preparing the aqueous phase component. Place the flask in a water bath and adjust the temperature to 50 degrees Celsius. Turn on the mechanical stirrer inside the flask, open the valve of the dropping funnel, and maintain a relatively constant dropping rate into the aqueous phase component. Control the mechanical stirring dispersion time to 40 minutes.

[0076] Using the above-described operations in this section, "[Example of Manufacturing Emulsion Explosives]", and in conjunction with the process conditions in Table 2, a series of examples were prepared.

[0077] 3. [Comparative Example]

[0078] Comparative Example 1

[0079] Based on the previous "[Example]", the modified oxidant was changed to "p-aminophenyl POSS and nitrate oxidant components (ammonium nitrate, sodium nitrate, sodium perchlorate, ammonium chloride, sodium nitrite, zinc nitrate)", and the amount of nitrate oxidant components and p-aminophenyl POSS was controlled to be the same as the amount of nitrate oxidant components and p-aminophenyl POSS used in the manufacture of modified oxidant A1.

[0080] Comparative Example 2

[0081] Based on the previous "[Example]", the p-aminophenyl POSS used in the manufacturing process of modified oxidant A1 was changed to octaphenyl POSS (produced by Xi'an Qiyue Biotechnology Co., Ltd., CAS No. 5256-79-1, C). 48 H 40 O 12 Si8 (molecular weight: 1033.51), and in order to better promote the dispersion of octaphenyl POSS, the ethanol-water mixture in the manufacturing process of modified oxidant A1 was replaced with an ethanol-tetrahydrofuran mixture (tetrahydrofuran: ethanol volume ratio of 1:5). The resulting modified oxidant was named B1, and all other conditions remained unchanged.

[0082] Table 1 Process conditions for modified oxidants

[0083]

[0084] Table 2 Process conditions for emulsion explosives

[0085]

[0086]

[0087]

evaluate

[0088] The emulsion explosives prepared according to the various examples and comparative examples in Table 1 were evaluated as follows:

[0089] [power]

[0090] The emulsion explosive was made into 35mm cartridges, and the detonation velocity was determined according to the standard "GB / T 13228-2015, Determination Method of Detonation Velocity of Industrial Explosives". The sympathetic detonation distance was determined according to the sand method in the standard "WJ / T 9055-2006, Test Method of Sympathetic Detonation Distance of Industrial Explosives". The saturation was determined according to the standard "GB / T 12440-1990, Explosives Saturation Test - Lead Column Compression Method".

[0091] [Mechanical Sensitivity]

[0092] Friction sensitivity shall be determined in accordance with the provisions of standard “WJ / T 9052.1-2006, Test Methods for Sensitivity of Industrial Explosives, Part 1: Friction Sensitivity”, and impact sensitivity shall be determined in accordance with the provisions of standard “WJ / T 9052.2-2006, Test Methods for Sensitivity of Industrial Explosives, Part 2: Impact Sensitivity”.

[0093] Table 3 Evaluation Results

[0094]

[0095] As can be seen from Table 3, the power and mechanical sensitivity of Example 1 are significantly better than those of Comparative Example 1. This indicates that the technical contribution brought about by loading the nitrate oxidant component onto p-aminophenyl POSS is that the nitrate oxidant component and p-aminophenyl POSS are simply added.

[0096] The power and mechanical sensitivity of Example 1 are significantly better than those of Comparative Example 2, which shows that the coordination effect of water-soluble metal ions during the preparation of the modified oxidant of this application contributes to the power and mechanical sensitivity.

[0097] The potency and mechanical sensitivity of Example 1 are significantly better than those of Examples 8, 9, and 10, which indicates that pH 5-7 is a suitable value for the modified oxidant in this application.

[0098] The power and mechanical sensitivity of Example 1 are significantly better than those of Examples 8 and 9, which demonstrates the technical contribution of the addition of the first and second accelerators in this application.

[0099] The above embodiments are merely illustrative of the technical solutions of this application and are not intended to limit it. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. These modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application, and they should all be covered within the scope of the claims and specification of this application. In particular, as long as there is no structural conflict, the various technical features mentioned in the embodiments can be combined in any way. This application is not limited to the specific embodiments disclosed herein, but includes all technical solutions falling within the scope of the claims.

Claims

1. An integrated oil-phase emulsion explosive, characterized in that, Its raw materials include an aqueous phase component, an oil phase component, and an emulsifier for emulsifying the aqueous phase component and the oil phase component: The aqueous phase component contains a modified oxidant formed by loading a nitrate-based oxidant component onto p-aminophenyl POSS; The preparation process of the modified oxidant includes the following steps: A. Ensure that the nitrate oxidant component and p-aminophenyl POSS are fully dispersed in the aqueous solution so that the nitrate oxidant component is fully attached to the p-aminophenyl POSS; B. The solid phase component separated from the solution system obtained in step A is the modified oxidant.

2. The integrated oil-phase emulsion explosive according to claim 1, characterized in that, The amount of the nitrate oxidant component added is such that the concentration of the nitrate oxidant in the aqueous solution is 1-5 mol / L.

3. The integrated oil-phase emulsion explosive according to claim 1, characterized in that, The nitrate-based oxidant component includes: Nitrate oxidizing agents, selected from at least one of sodium nitrate and ammonium nitrate; The first accelerator is selected from at least one of sodium perchlorate and ammonium chloride; The second accelerator is selected from at least one of sodium nitrite, calcium nitrate, and zinc nitrate.

4. The integrated oil-phase emulsion explosive according to claim 3, characterized in that, In step A, dispersion is carried out under ultrasonic dispersion.

5. The integrated oil-phase emulsion explosive according to claim 1, characterized in that, In step A, the dispersion temperature is 50-70℃.

6. The integrated oil-phase emulsion explosive according to claim 1, characterized in that, In step A, the dispersion time is 2-4 hours.

7. The integrated oil-phase emulsion explosive according to claim 1, characterized in that, The dispersion has a pH of 5-7.

8. The integrated oil-phase emulsion explosive according to claim 1, characterized in that, In step A, the aqueous solution further includes a dispersant selected from at least one of C1-4 alcohol, DMF, and DMSO.

9. The integrated oil-phase emulsion explosive according to claim 1, characterized in that, The amount of the modified oxidant added is 56-74 wt% of the solvent weight based on the aqueous phase component.

10. A method for preparing an integrated oil-phase emulsion explosive, characterized in that, Includes the following steps: An aqueous phase component is provided, the aqueous phase component containing a modified oxidant formed by loading a nitrate oxidant component onto p-aminophenyl POSS; The preparation process of the modified oxidant includes: A) fully dispersing the nitrate oxidant component and p-aminophenyl POSS in an aqueous solution so that the nitrate oxidant component is fully attached to the p-aminophenyl POSS; B) separating the solid phase component from the solution system obtained in step A, which is the modified oxidant. Provide oil phase components; The oil phase component is continuously added to the aqueous phase component and fully dispersed until a homogeneous emulsion is formed.

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