Integrated oil phase emulsion explosive and preparation method thereof

Abstract

The invention discloses an integrated oil phase emulsion explosive and a preparation method thereof. The emulsion explosive is prepared from the following raw materials: a water-phase component, an oil-phase component and an emulsifier for emulsifying the water-phase component and the oil-phase component, wherein the water-phase component contains a modified oxidant formed by loading a nitrate oxidant component on p-aminophenyl POSS (Polyhedral Oligomeric Silsesquioxane); the preparation process of the modified oxidizing agent comprises the following steps: A, fully dispersing a nitrate oxidizing agent component and p-aminophenyl POSS in an aqueous solution, so that the nitrate oxidizing agent component is fully attached to the p-aminophenyl POSS; and B, separating a solid-phase component, namely the modified oxidant, from the solution system obtained in the step B. According to the integrated oil phase emulsion explosive and the preparation method thereof provided by the invention, the sensitivity and the power can be well considered.

Description

Technical Field

[0001] This application relates to the technical field of emulsion explosives, and particularly to an emulsion explosive with an integrated oil phase and a preparation method thereof. Background Art

[0002] Emulsion explosives are a new variety of industrial explosives developed from the 1970s to the end of the 1980s. Due to its unique physical structure, this type of explosive has excellent water resistance, more complete explosion reactions, is very safe in manufacturing, transportation, and use, and has good blasting effects in mines, etc.

[0003] In related technologies, for emulsion explosives, it is often difficult to balance sensitivity and power well in many cases, that is, for emulsion explosives with higher sensitivity, in many cases, the power is insufficient; for emulsion explosives with higher power, in many cases, the sensitivity is insufficient. Such as the following related technical documents:

[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]

Problems to be Solved

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

[0009]

Means for Solving the Problems

[0010] In related technologies, in order to try to solve the balance problem between the sensitivity and power of emulsion explosives, some porous materials are usually used as sensitizing additives. For example, the porous graphene involved in Related Technical Document 3, the high-energy metal powder coated with porous silica hollow microspheres involved in Related Technical Document 2, and the aerogel involved in Related Technical Document 1. Although these porous materials can create pores to provide a transmission channel for the gas generated by the explosion airflow to promote sensitivity, the energy generated by the explosion is often greatly released through this gas transmission channel, reducing its power. It can be seen that it is really difficult for emulsion explosives in these related technologies to balance sensitivity and power.

[0011] The inventors of the present invention have conducted repeated and in-depth research to solve the above problems and realized that, based on this awareness, they have creatively discovered that nitrate oxidants are loaded on p-aminophenyl POSS. The cage-like silica-oxygen skeleton of p-aminophenyl POSS can, through the adsorption force of its microcavities, wrap a considerable part of the nitrate oxidants within the cage-like silica-oxygen skeleton, expanding the dispersion space of the oxidants and promoting sensitivity. At the same time, the rigidity of the cage-like silica-oxygen skeleton may form a transient confinement space around the nitrate oxidants and the fuel during energy generation from combustion, accumulating explosive energy and promoting its power. Thus, the present invention has been completed.

[0012] On the one hand, the present application provides a raw material comprising an aqueous phase component, an oil phase component, and an emulsifier for emulsifying the aqueous phase component and the oil phase component:

[0013] Among them, the aqueous phase component contains a modified oxidant formed by loading a nitrate oxidant component on p-aminophenyl POSS;

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

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

[0016] B. Separate the solid phase component from the solution system obtained in step B, which is the modified oxidant.

[0017] In any embodiment, the feeding amount of the nitrate oxidant component 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] A nitrate oxidant selected from at least one of sodium nitrate and ammonium nitrate;

[0020] A first promoter selected from at least one of sodium perchlorate and ammonium chloride;

[0021] A second promoter selected from at least one of sodium nitrite, calcium nitrate, and zinc nitrate.

[0022] In any embodiment, the feeding amount of the metal ions and the feeding amount of the nitrate oxidant contained in the nitrate oxidant component are based on a molar ratio of 1:2 - 1:5.

[0023] In any embodiment, in step A, the dispersion is carried out under ultrasonic dispersion.

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

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

[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 dispersion promoter, and the dispersion promoter is selected from at least one of C1-4 alcohols, DMF, and DMSO.

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

[0029] Another aspect of the present application provides a method for preparing an emulsion explosive with an integrated oil phase, including the following steps:

[0030] Provide an aqueous phase component, the aqueous phase component containing a modified oxidant formed by loading a nitrate oxidant component on p-aminophenyl POSS; the preparation process of the modified oxidant includes: A. Sufficiently disperse the nitrate oxidant component and p-aminophenyl POSS in an aqueous solution so that the nitrate oxidant component is fully attached to p-aminophenyl POSS; B. Separate the solid phase component from the solution system obtained in step B, which is the modified oxidant;

[0031] Provide an oil phase component;

[0032] Continuously add the oil phase component to the aqueous phase component and disperse it sufficiently until a homogeneous emulsion is formed.

[0033]

Invention Effect

[0034] The emulsion explosive with an integrated oil phase and its preparation method provided by the present application can better balance sensitivity and power. Specific Embodiments

[0035] Hereinafter, the embodiments of the present application will be specifically described in detail. However, there may be cases where unnecessary details are omitted. For example, there may be cases where the detailed description of well-known matters and the repeated description of actually identical structures are omitted. This is to prevent the following description from becoming unnecessarily lengthy and to facilitate the understanding of those skilled in the art. In addition, the following description is provided for those skilled in the art to fully understand the present application and is not intended to limit the subject matter recited in the claims.

[0055] The "ranges" disclosed in this application are defined in the form of a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundaries of a particular range. The ranges defined in this way can include or exclude the end values, and can be combined arbitrarily, that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a specific parameter, ranges of 60-110 and 80-120 are also contemplated. In addition, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this application, unless otherwise specified, the numerical range "a-b" represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" are fully listed herein, and "0-5" is only an abbreviated representation of these numerical combinations. Additionally, when stating that a certain parameter is an integer ≥2, it is equivalent to disclosing that the parameter is, for example, the integers 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0036] If there is no special instruction, all embodiments and optional embodiments of this application can be combined with each other to form a new technical solution.

[0037] If there is no special instruction, all technical features and optional technical features of this application can be combined with each other to form a new technical solution.

[0038] If there is no special instruction, all steps of this application can be carried out in sequence or randomly, and preferably in sequence. For example, the method includes steps (a) and (b), which means that the method can include steps (a) and (b) carried out in sequence, or can also include steps (b) and (a) carried out in sequence. For example, it is mentioned that the method may further include step (c), which means that step (c) can be added to the method in any order. For example, the method can include steps (a), (b), and (c), or can also include steps (a), (c), and (b), or can also include steps (c), (a), and (b), etc.

[0039] If there is no special instruction, the "including" and "comprising" mentioned in this application mean open-ended, and can also be closed-ended. For example, the "including" and "comprising" can mean that other components not listed can also be included or comprised, or can only include or comprise the listed components.

[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, any of the following conditions satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist); A is false (or does not exist) while B is true (or exists); or both A and B are true (or exist).

[0041]

Emulsion Explosive

[0042] The raw materials of the emulsion explosive include an aqueous phase component, an oil phase component, and an emulsifier for emulsifying the aqueous phase component and the oil phase component; wherein, the aqueous phase component contains a modified oxidizer formed by loading a nitrate oxidizer component on amine phenyl POSS.

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

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

[0045] Here, the term "nitrate oxidizer component" means that the main component is a nitrate oxidizer. Suitable but non-limiting specific examples are that the nitrate oxidizer component includes:

[0046] Nitrate oxidizers selected from at least one of sodium nitrate and ammonium nitrate;

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

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

[0049] The function of the oil phase component is, on the one hand, to provide the fuel required for the explosion of the explosive, and on the other hand, to disperse the lipophilic components. The form of the oil phase component can be the form conventionally used in emulsion explosives. As 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, the base oil covers vegetable oil, mineral oil, synthetic oil, etc.

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

[0052] The emulsifier can be in a conventional form, such as S-80 emulsifier, succinimide emulsifier, sodium dodecyl sulfonate, and alkynediol, etc., which is not limited to this. The emulsifier can be added to the oil phase components, or added to the water phase components, or partially added to the oil phase components and partially added to the water phase components.

[0053]

Modified Oxidant

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

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

[0056] B. Separate the solid phase component from the solution system obtained in step B, which is the modified oxidant.

[0057] The above p-aminophenyl POSS, also known as octa(aminophenyltrioxysilane), octa(aminophenyltrioxysilane) polyhedral oligomeric silsesquioxane, and its CAS number is 518359-82-5. In view of its physical and chemical properties being well-known in the art, it will not be elaborated here. Here, p-aminophenyl POSS can be prepared by the methods mastered by those skilled in the art, and of course, it can also be obtained through established commercial channels, and the commercial channel method has been clearly stated in the following examples.

[0058] It can be understood that in step A, the nitrate oxidant component is fully attached to the p-aminophenyl POSS. On the one hand, it depends on the physical adsorption force generated by the micropores of the silicon-oxygen skeleton of the p-aminophenyl POSS, and on the other hand, it mainly depends on the molecular hydrogen bond formed between the phenylamino group on the p-aminophenyl POSS and the nitrate radical. The reason for the formation of the molecular hydrogen bond between the phenylamino group and the nitrate radical is that the oxygen atom on the nitrate radical has a strong electronegativity; for the phenylamino group, after the N atom attracts the electron of the H, its electron movement orbit can be better dispersed through the delocalized space provided by the benzene ring, thus promoting the formation of a more stable phenylamine anion by the phenylamino group, which is more conducive to the formation of a molecular hydrogen bond with the nitrate radical. That is to say, the benzene ring on the phenylamino group promotes the possibility of forming a molecular hydrogen bond with the nitrate radical compared with molecules without a similar benzene ring structure.

[0059] For suitable but non-limiting specific examples, the feeding amount of the nitrate oxidant component is such that the concentration of the nitrate oxidant in the aqueous solution is 1-5 mol / L.

[0060] In a suitable but non-limiting specific example, in step A, the dispersion is performed under ultrasonic dispersion.

[0061] In a suitable but non-limiting specific example, in step A, the dispersion temperature is 50-70°C.

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

[0063] In a suitable but non-limiting specific example, the pH of the dispersion is 5-7, and particularly preferably 6. Thus, a slightly acidic environment is conducive to a small amount of protonation of aniline to improve its dispersibility. If the acidity is too high, an oxidation reaction may occur between the amino group of aniline and the nitrate.

[0064] In a suitable but non-limiting specific example, in step A, the aqueous solution further comprises a dispersant, and the dispersant is selected from at least one of C1-4 alcohol, DMF, and DMSO. In this way, the dispersant is used to improve the dispersibility of the p-aminophenyl POSS in the aqueous solution.

[0065] [Preparation method of emulsion explosive]

[0066] The preparation method of emulsion explosive can be combined with conventional feeding methods, oil phase raw materials,

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

[0068] Hereinafter, the embodiments of the present application will be described. The embodiments described below are exemplary and are only used to explain the present application, and should not be construed as limiting the present application. If no specific techniques or conditions are indicated in the embodiments, the techniques or conditions described in the literature in this area or the product specifications are used. If the manufacturer is not indicated in the reagents or instruments used, they are all conventional products that can be obtained commercially.

[0069] 1. [Manufacturing Example of Modified Oxidant]

[0070] A mixture of water and ethanol (ethanol accounts for 9 vol% of the volume of water) was placed in a round-bottom flask, and p-aminophenyl POSS (produced by Xi'an Qiyue Biotechnology Co., Ltd., with a molecular weight of 1153.63 and a molecular formula of C) was added to the flask. 48 H 48 N8O 128) 23 to 40 parts by weight of Si, 76 to 85 parts by weight of ammonium nitrate, 2 to 5 parts by weight of sodium nitrate, 0 to 4 parts by weight of sodium perchlorate, 0 to 4 parts by weight of ammonium chloride, 0 to 0.3 parts by weight of sodium nitrite, 0 to 0.08 parts by weight of zinc nitrate, in the water bath of an ultrasonic oscillation water bath (produced by Bandelin SONOSHAKE, Germany). Then, control the temperature of the reaction system in the water bath to 60 °C and control the pH of the reaction system in the water bath to a predetermined value by a pH meter assembled on the water bath. Then, turn on the ultrasonic dispersion and control the ultrasonic power to 1000 W. After reacting for 3 h, transfer the liquid in the water bath to a conical flask for suction filtration, wash the filter residue with deionized water, and dry it under vacuum to obtain a modified oxidant.

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

[0072] 2. [Examples]

[0073] S1. Prepare the aqueous phase component. Put a series of the above - mentioned modified oxidants A1 - A10 and sodium dodecyl sulfate into a flask (equipped with a mechanical stirrer) containing a mixture of water and ethanol (ethanol accounts for 9 vol% of the volume of water), and the feeding amount of the modified oxidant accounts for 56 - 74 wt% of the weight of the water - ethanol mixture, and the feeding amount of sodium dodecyl sulfate accounts for 10 wt% of the weight of the water - ethanol mixture. Place the flask in a water bath and adjust the heating temperature to 50 °C, and turn on the mechanical stirrer to fully disperse the modified oxidant in the water - ethanol mixture, thus obtaining the aqueous phase component.

[0074] S2. Prepare the oil phase component. According to the weight - part ratio of the raw materials of the oil phase component: 10 parts of composite wax, 9 parts of fully - refined paraffin wax, 18 parts of microcrystalline wax, 22 parts of vegetable oil, 15 parts of S - 80 emulsifier, 4 parts of succinimide emulsifier. Put the above - mentioned raw materials of the oil phase component into a flask equipped with a mechanical stirrer, place the flask in a water bath and adjust the temperature to 50 °C, turn on the mechanical stirrer to fully disperse, thus obtaining the oil phase component.

[0075] S3. Load the oil phase component into a dropping funnel, install the dropping funnel on the flask for preparing the aqueous phase component, place the flask in a water bath and adjust the temperature to 50 °C. Turn on the mechanical stirring device in the flask, open the valve of the dropping funnel and keep the dropping speed into the aqueous phase component basically constant, and control the mechanical stirring and dispersion time to 40 min.

[0076] Using the above operations in this part "[Manufacturing Example of Emulsion Explosive]" and combining with the process conditions in Table 2, a series of examples were prepared.

[0077] 3. [Comparative Examples]

[0078] Comparative Example 1

[0079] Based on the previous "Example", the modified oxidant is 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 component and p-aminophenyl POSS is controlled to be the same as the amount of nitrate oxidant component and p-aminophenyl POSS used to manufacture modified oxidant A1.

[0080] Comparative Example 2

[0081] Based on the above “[Example]”, the p-aminophenyl POSS used in the manufacturing process of the 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 mixed solution in the manufacturing process of the modified oxidant A1 was replaced with an ethanol-tetrahydrofuran mixed solution (the volume ratio of tetrahydrofuran: ethanol was 1:5). The prepared modified oxidant was named B1, and other conditions remained unchanged.

[0082] Table 1 Process conditions of modified oxidant

[0083]

[0084] Table 2 Processing conditions of emulsion explosives

[0085]

[0086]

[0087]

evaluate

[0088] The following evaluations were performed on the emulsion explosives of each embodiment and comparative example prepared according to Table 1:

[0089] [power]

[0090] The emulsion explosive is made into a 35mm roll, and then the detonation velocity is measured according to the standard "GB / T 13228-2015, "Determination Method for Detonation Velocity of Industrial Explosives", the detonation distance is measured according to the sand method in the standard "WJ / T 9055-2006, "Test Method for Detonation Distance of Industrial Explosives", and the intensity is measured according to the standard "GB / T 12440-1990, "Lead Column Compression Method for Explosive Intensity Test"".

[0091] [Mechanical sensitivity]

[0092] The friction sensitivity is carried out in accordance with the provisions of the reference standard for friction sensitivity "WJ / T 9052.1-2006, Test Methods for Sensitivity of Industrial Explosives, Part 1 Friction Sensitivity", and the impact sensitivity is carried out in accordance with the provisions of the reference standard "WJ / T 9052.2-2006, Test Methods for Sensitivity of Industrial Explosives, Part 2 Impact Sensitivity".

[0093] Table 3 Evaluation Results

[0094]

[0095] It can be seen from Table 3 that the power and mechanical sensitivity of Example 1 are significantly better than those of Comparative Example 1, which shows the technical contribution brought by loading the nitrate oxidant component on p-aminophenyl POSS in this application compared with the simple addition of the nitrate oxidant component and p-aminophenyl POSS.

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

[0097] The power and mechanical sensitivity of Example 1 are significantly better than those of Examples 8, 9, and 10, which shows that a pH value of 5-7 is an optional suitable value during the preparation of 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 shows the technical contribution brought by the addition of the first accelerator and the second accelerator in this application.

[0099] The above embodiments are only used to illustrate the technical solutions of this application, rather than to limit it; although this application has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions 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 the description of this application. In particular, as long as there is no structural conflict, the technical features mentioned in each embodiment can be combined in any way. This application is not limited to the specific embodiments disclosed in the text, but includes all technical solutions that fall within the scope of the claims.

Claims

1. An emulsion explosive with an integrated oil phase, 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: Among them, the aqueous phase component contains a modified oxidant formed by loading a nitrate oxidant component on p-aminophenyl POSS; The preparation process of the modified oxidant includes the following steps: A. Sufficiently disperse the nitrate oxidant component and p-aminophenyl POSS in an aqueous solution so that the nitrate oxidant component is fully attached to p-aminophenyl POSS; B. Separate the solid phase component from the solution system obtained in step B, which is the modified oxidant.

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

3. The emulsion explosive with an integrated oil phase according to claim 1, characterized in that The nitrate oxidant component includes: A nitrate oxidant selected from at least one of sodium nitrate and ammonium nitrate; A first promoter selected from at least one of sodium perchlorate and ammonium chloride; A second promoter selected from at least one of sodium nitrite, calcium nitrate, and zinc nitrate.

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

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

6. The emulsion explosive with an integrated oil phase according to claim 1, wherein In step A, the dispersion time is 2-4 h.

7. The emulsion explosive with an integrated oil phase according to claim 1, wherein, The pH of the dispersion is 5-7.

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

9. The emulsion explosive with an integrated oil phase according to claim 1, wherein The feeding amount of the modified oxidant is 56-74 wt% based on the weight of the solvent of the aqueous phase component.

10. A preparation method of an emulsion explosive with an integrated oil phase, characterized in that, Including the following steps: Provide an aqueous phase component containing a modified oxidant formed by loading a nitrate oxidant component on p-aminophenyl POSS; The preparation process of the modified oxidant includes: A. Sufficiently disperse the nitrate oxidant component and p-aminophenyl POSS in an aqueous solution so that the nitrate oxidant component is fully attached to p-aminophenyl POSS; B. Separate the solid phase component from the solution system obtained in step B, which is the modified oxidant. Provide an oil phase component; Continuously add the oil phase component to the aqueous phase component and disperse it sufficiently until a homogeneous emulsion is formed.

Images