A composite emulsifier suitable for emulsion explosive and preparation method thereof

Abstract

The present invention relates to a composite emulsifier suitable for emulsion explosives and a preparation method thereof, belonging to the technical field of emulsifiers, wherein the composite emulsifier mainly comprises the following raw materials: acrylic acid, triethylenetetramine, poly(isobutylene-alt-maleic anhydride), sorbitol, N-hydroxyethyl-ethylenediamine, hydrogen peroxide, vitamin C, nonylphenol polyoxyethylene ether (10), urea and sodium lauryl sulfonate. The present invention selects sorbitol, poly(isobutylene-alt-maleic anhydride) and N-hydroxyethyl-ethylenediamine as main raw materials, increases the hydrophilicity of the system, and the intermediate material A synthesized from triethylenetetramine and acrylic acid reduces the surface tension of the system, so that the finished emulsifier has excellent emulsification effect. Nonylphenol polyoxyethylene ether (10), urea and sodium lauryl sulfonate are also used to reduce the crystallization point and inhibit the generation of crystal nuclei, so that the emulsion explosive prepared by the composite emulsifier of the present invention has excellent storage stability, is not easy to crystallize and harden.

Description

Technical Field

[0001] The invention belongs to the technical field of emulsifiers, and in particular relates to a composite emulsifier suitable for emulsion explosives and a preparation method thereof. Background Art

[0002] In the explosives industry, emulsion explosives, as an important type of industrial explosives, are widely used due to their good explosive performance, low cost and low impact on the environment. The core of emulsion explosives lies in their stable emulsification system, and the emulsifier is indispensable in the emulsification system. However, traditional emulsifiers often have large particle size, uneven distribution, and low emulsification efficiency during the preparation process, which leads to insufficient storage stability, easy crystallization and hardening of the emulsion explosives prepared using the emulsifier. These problems seriously affect the storage stability and explosive performance of the emulsion explosives. Therefore, the development of a composite emulsifier with high emulsification ability that can significantly improve the storage stability of emulsion explosives and make them less prone to crystallization and hardening has become an urgent problem to be solved in the field of emulsion explosives. Summary of the invention

[0003] The object of the present invention is to provide a composite emulsifier suitable for emulsion explosives and a preparation method thereof, so as to solve the problems that the emulsifiers in the prior art have poor emulsification effect and the emulsion explosives obtained by using the emulsifiers to prepare emulsion explosives have poor storage stability and are easy to crystallize and harden.

[0004] The purpose of the present invention can be achieved through the following technical solutions:

[0005] A composite emulsifier suitable for emulsion explosives, the composite emulsifier comprising the following raw materials:

[0006] Acrylic acid, triethylenetetramine, poly(isobutylene-al t-maleic anhydride), sorbitol, N-hydroxyethyl-ethylenediamine, hydrogen peroxide, vitamin C, nonylphenol polyoxyethylene ether (10), urea, sodium lauryl sulfate and deionized water.

[0007] Furthermore, the mass concentration of the hydrogen peroxide is 50%.

[0008] Furthermore, the acrylic acid is 15-16.5 parts by weight, triethylenetetramine is 30-33 parts by weight, poly(isobutylene-al t-maleic anhydride) is 50-55 parts by weight, sorbitol is 8.5-10 parts by weight, N-hydroxyethyl-ethylenediamine is 3-3.5 parts by weight, hydrogen peroxide is 2-2.2 parts by weight, vitamin C is 0.6-0.7 parts by weight, nonylphenol polyoxyethylene ether (10) is 0.1-0.2 parts by weight, urea is 2-2.5 parts by weight, sodium lauryl sulfate is 0.4-0.5 parts by weight, and deionized water is 100-105 parts by weight.

[0009] A method for preparing a composite emulsifier suitable for emulsion explosives specifically comprises the following steps:

[0010] S1. Heat acrylic acid, introduce nitrogen, and dropwise add triethylenetetramine while stirring and controlling the temperature to obtain intermediate material A;

[0011] S2, heating poly(isobutylene-al t-maleic anhydride), introducing nitrogen, adding sorbitol while stirring, controlling the temperature and stirring, and after the stirring is completed, adding N-hydroxyethyl-ethylenediamine while controlling the temperature and stirring to obtain intermediate material B;

[0012] S3, after mixing the intermediate material A and deionized water evenly, add the intermediate material B and control the temperature and stir once, after the stirring is completed, add hydrogen peroxide and vitamin C and mix evenly and control the temperature and stir again to obtain the intermediate material C;

[0013] S4, the intermediate material C, nonylphenol polyoxyethylene ether (10), urea and sodium lauryl sulfonate are mixed uniformly under temperature control to obtain a finished composite emulsifier.

[0014] As a preferred technical solution of the present invention, the heating in step S1 is heating to 125-130° C.; the temperature of the temperature-controlled stirring is 130-135° C., and the time is 3-4 hours.

[0015] As a preferred technical solution of the present invention, the heating in step S2 is heating to 115-120°C; the temperature of the temperature-controlled stirring is 135-140°C, and the time is 3-4h; the stirring temperature of the temperature-controlled addition of N-hydroxyethyl-ethylenediamine is 95-100°C, and the stirring time is 2-2.5h.

[0016] As a preferred technical solution of the present invention, the temperature of the first temperature-controlled stirring in step S3 is 90-95°C, and the time is 1-1.5h; the temperature of the second temperature-controlled stirring is 60-65°C, and the time is 1-2h.

[0017] As a preferred technical solution of the present invention, the temperature of the temperature control in step S4 is 85-90°C.

[0018] Beneficial effects of the present invention:

[0019] (1) The present invention uses sorbitol, poly(isobutylene-al t-maleic anhydride) and N-hydroxyethyl-ethylenediamine as main raw materials to synthesize an emulsifier with a small particle diameter and a hydrophilic structure, thereby increasing the hydrophilicity of the system, making the emulsifier exhibit excellent emulsification ability, reducing the interfacial tension of the system, and making the latex matrix particles prepared using the emulsifier smaller and more uniform and stable; on this basis, an intermediate material A synthesized from triethylenetetramine and acrylic acid is added to the system to introduce amide groups and amine groups, thereby further increasing the hydrophilicity of the system, and making the finished emulsifier produce intermolecular hydrogen bonds, thereby reducing the surface tension of the system, and making the finished emulsifier have excellent emulsification effect.

[0020] (2) The present invention uses nonylphenol polyoxyethylene ether (10) to attract ammonium ions in the essential components of emulsion explosives, so that the ammonium ions combined with nitrate ions are reduced, thereby reducing the water phase crystallization point; urea and the components in the emulsion explosive form a low eutectic mixture, which further reduces the water phase crystallization point; on this basis, sodium lauryl sulfonate is used to affect the growth and aggregation of crystals to inhibit the formation of crystal nuclei; that is, nonylphenol polyoxyethylene ether (10), urea and sodium lauryl sulfonate respectively start from reducing the crystallization point and inhibiting the formation of crystal nuclei, and synergistically make the emulsion explosive prepared by the composite emulsifier prepared by the present invention have excellent storage stability and are not easy to crystallize and harden. DETAILED DESCRIPTION

[0021] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0022] The poly(isobutylene-al t-maleic anhydride) used in the examples of the present invention was purchased from Merck; no further details will be given below.

[0023] Example 1

[0024] A composite emulsifier suitable for emulsion explosives, the composite emulsifier comprising the following raw materials in parts by weight:

[0025]

[0026]

[0027] A method for preparing a composite emulsifier suitable for emulsion explosives specifically comprises the following steps:

[0028] S1. Heat acrylic acid to 125°C, introduce nitrogen, and dropwise add triethylenetetramine while stirring, controlling the temperature at 135°C and stirring for 3 hours to obtain intermediate material A;

[0029] S2, heat poly(isobutylene-al t-maleic anhydride) to 118° C., introduce nitrogen, add sorbitol while stirring, control the temperature at 135° C. and stir for 3 h, then control the temperature at 100° C. and add N-hydroxyethyl-ethylenediamine and stir for 2 h to obtain intermediate material B;

[0030] S3, after mixing the intermediate material A and deionized water evenly, add the intermediate material B, control the temperature at 93°C and stir for 1 hour, after the stirring is completed, add hydrogen peroxide and vitamin C, mix evenly, control the temperature at 65°C and stir for 1 hour, to obtain the intermediate material C;

[0031] S4, the intermediate material C, nonylphenol polyoxyethylene ether (10), urea and sodium lauryl sulfonate are mixed uniformly at a temperature of 87° C. to obtain a finished composite emulsifier.

[0032] Example 2

[0033] A composite emulsifier suitable for emulsion explosives, the composite emulsifier comprising the following raw materials in parts by weight:

[0034]

[0035]

[0036] A method for preparing a composite emulsifier suitable for emulsion explosives specifically comprises the following steps:

[0037] S1. Heat acrylic acid to 128°C, introduce nitrogen, and dropwise add triethylenetetramine while stirring, controlling the temperature at 130°C and stirring for 3 hours to obtain intermediate material A;

[0038] S2, heat poly(isobutylene-al t-maleic anhydride) to 185° C., introduce nitrogen, add sorbitol while stirring, control the temperature at 140° C. and stir for 3.5 hours, then control the temperature at 95° C. and add N-hydroxyethyl-ethylenediamine and stir for 2 hours to obtain intermediate material B;

[0039] S3, after mixing the intermediate material A and deionized water evenly, add the intermediate material B, control the temperature at 90°C and stir for 1 hour, after the stirring is completed, add hydrogen peroxide and vitamin C, mix evenly, control the temperature at 60°C and stir for 2 hours, to obtain the intermediate material C;

[0040] S4, the intermediate material C, nonylphenol polyoxyethylene ether (10), urea and sodium lauryl sulfonate are mixed uniformly at a temperature of 85° C. to obtain a finished composite emulsifier.

[0041] Example 3

[0042] A composite emulsifier suitable for emulsion explosives, the composite emulsifier comprising the following raw materials in parts by weight:

[0043]

[0044]

[0045] A method for preparing a composite emulsifier suitable for emulsion explosives specifically comprises the following steps:

[0046] S1. Heat acrylic acid to 130°C, introduce nitrogen, and dropwise add triethylenetetramine while stirring, controlling the temperature at 132°C and stirring for 4 hours to obtain intermediate material A;

[0047] S2, heat poly(isobutylene-al t-maleic anhydride) to 120°C, introduce nitrogen, add sorbitol while stirring, control the temperature at 138°C and stir for 4 hours, then control the temperature at 98°C and add N-hydroxyethyl-ethylenediamine and stir for 2.5 hours to obtain intermediate material B;

[0048] S3, after mixing the intermediate material A and deionized water evenly, add the intermediate material B, control the temperature at 95°C and stir for 1.5 hours, after the stirring is completed, add hydrogen peroxide and vitamin C, mix evenly, control the temperature at 63°C and stir for 1 hour, to obtain the intermediate material C;

[0049] S4, the intermediate material C, nonylphenol polyoxyethylene ether (10), urea and sodium lauryl sulfonate are mixed uniformly at a temperature of 90° C. to obtain a finished composite emulsifier.

[0050] Comparative Example 1

[0051] Compared with Example 1, the difference is that the poly(isobutylene-al t-maleic anhydride) in Comparative Example 1 is replaced by polyisobutylene succinic anhydride, and the other operating steps and parameters remain unchanged.

[0052] Comparative Example 2

[0053] Compared with Example 1, the difference is that the N-hydroxyethyl-ethylenediamine in Comparative Example 2 is replaced by ethylenediamine, and the other operating steps and parameters remain unchanged.

[0054] Comparative Example 3

[0055] Compared with Example 1, the difference is that in Comparative Example 3, intermediate material A is not added, and the other operating steps and parameters remain unchanged.

[0056] Comparative Example 4

[0057] Compared with Example 1, the difference is that in Comparative Example 4, no nonylphenol polyoxyethylene ether (10) is added, but urea is 2.07 parts by weight, sodium lauryl sulfate is 0.53 parts by weight, and the other operating steps and parameters remain unchanged.

[0058] Comparative Example 5

[0059] Compared with Example 1, the difference is that in Comparative Example 5, no urea is added, but the amount of nonylphenol polyoxyethylene ether (10) is 1.15 parts by weight, and the amount of sodium lauryl sulfonate is 1.45 parts by weight, and the other operating steps and parameters remain unchanged.

[0060] Comparative Example 6

[0061] Compared with Example 1, the difference is that in Comparative Example 6, sodium lauryl sulfate is not added, while nonylphenol polyoxyethylene ether (10) is 0.38 parts by weight, urea is 2.22 parts by weight, and the other operating steps and parameters remain unchanged.

[0062] Test Example 1

[0063] Emulsifying power test: The emulsifying power was measured by the measuring cylinder method, and the finished composite emulsifiers obtained in Examples 1-3 and Comparative Examples 1-3 were used as samples. Specifically, turpentine was selected as the oil phase material, 0.1 g of the sample was accurately weighed and dissolved in 50 mL of the oil phase, and then transferred to a 100 mL measuring cylinder with a stopper, and then 50 mL of distilled water was drawn into the same measuring cylinder with a pipette, and the glass stopper was pinched by hand, and after vigorous up and down vibration, the time was immediately recorded with a stopwatch, the water and oil phases gradually separated, and the oil phase slowly appeared, and the time for the oil phase to separate 10 mL was recorded as a relative comparison of the emulsifying power. The stronger the emulsifying power, the longer the time; the results are shown in Table 1.

[0064] Table 1

[0065]

[0066]

[0067] As can be seen from Table 1, the finished emulsifier of the present invention has an excellent emulsifying effect. This is because the present invention uses sorbitol, poly(isobutylene-al t-maleic anhydride) and N-hydroxyethyl-ethylenediamine as main raw materials, and the system has a hydrophilic structure, which increases the hydrophilicity of the system. On this basis, the intermediate material A synthesized from triethylenetetramine and acrylic acid is added to the system to introduce amide groups and amine groups, which further helps to increase the hydrophilicity of the system, and makes the finished emulsifier produce intermolecular hydrogen bonds, thereby reducing the surface tension of the system, so that the finished emulsifier has an excellent emulsifying effect.

[0068] Test Example 2

[0069] The crystallization, hardening and detonation velocity after the high and low temperature cycle test reflect the storage stability of the emulsion explosive made from the composite emulsifier product prepared by the present invention.

[0070] The emulsifying matrix formula is: composite emulsifier, 1.0%; composite wax, 5%; water, 10.0%; sodium nitrate, 10.0%; ammonium nitrate, 74.0%; wherein the composite emulsifier is the finished composite emulsifier obtained in Examples 1-3 and Comparative Examples 4-6, respectively.

[0071] Preparation of emulsified matrix: heat the composite emulsifier and composite wax at 95°C to melt to form an oil phase material, add sodium nitrate and ammonium nitrate into water and dissolve at 95°C to form an aqueous phase material; add the aqueous phase material into the oil phase material, stir evenly at a speed of 550 r / min, and then stir at a speed of 1500 r / min for 60 seconds to obtain an emulsified matrix.

[0072] Preparation of emulsion explosive: adding hollow glass microspheres to the above emulsion matrix and stirring evenly to obtain emulsion explosive;

[0073] The mass ratio of the emulsified matrix to the hollow glass microspheres is 1:0.015.

[0074] (1) Crystallization and hardening: The prepared emulsion explosive was placed in a culture dish, sealed with a lid, and then placed in a refrigerator and an oven for high and low temperature cycle experiments. The experimental conditions were high temperature 50°C constant temperature for 6 hours, and then placed in a low temperature -20°C constant temperature for 6 hours, with each cycle lasting 1 hour. After the high and low temperature cycle, the crystallization and hardening of ammonium nitrate and sodium nitrate were observed; the results are shown in Table 2.

[0075] (2) Detonation velocity test of 20 high and low temperature cycles: The storage stability of emulsion explosives is characterized by the number of high and low temperature cycle experiments. 10 high and low temperature cycles are equivalent to a natural period of 180 days. The high and low temperature cycle test is used to detect the change of emulsion explosives over time and the storage stability of emulsion explosives. The greater the detonation velocity within the same number of cycles, the better the stability. The test method is as follows:

[0076] The emulsion explosive was placed in a constant temperature box at 50°C for 8 hours, and then placed in a -15°C refrigerator for 14 hours. This high and low temperature cycle experiment was repeated 20 times. The results are shown in Table 3.

[0077] Table 2

[0078]

[0079] Table 3

[0080] Explosive speed (m / s) Example 1 4895 Example 2 4627 Example 3 4749 Comparative Example 4 4031 Comparative Example 5 4110 Comparative Example 6 4198

[0081] It can be seen from Table 2 that the emulsion explosive made from the composite emulsifier product prepared by the present invention is not easy to crystallize and harden; it can be seen from Table 3 that the emulsion explosive made from the composite emulsifier product prepared by the present invention still has a high detonation velocity after 20 high and low temperature cycles, indicating that the composite emulsifier product prepared by the present invention has excellent storage stability. This is because the present invention adds nonylphenol polyoxyethylene ether (10), urea and sodium lauryl sulfonate, which respectively start from lowering the crystallization point and inhibiting the formation of crystal nuclei, and synergistically make the emulsion explosive made from the composite emulsifier product prepared by the present invention have excellent storage stability and are not easy to crystallize and harden.

[0082] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0083] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A composite emulsifier suitable for emulsion explosives, characterized in that: The composite emulsifier comprises the following raw materials: 15-16.5 parts by weight of acrylic acid, 30-33 parts by weight of triethylenetetramine, 50-55 parts by weight of poly(isobutylene-alt-maleic anhydride), 8.5-10 parts by weight of sorbitol, 3-3.5 parts by weight of N-hydroxyethyl-ethylenediamine, 2-2.2 parts by weight of hydrogen peroxide, 0.6-0.7 parts by weight of vitamin C, 0.1-0.2 parts by weight of nonylphenol polyoxyethylene ether (10), 2-2.5 parts by weight of urea, 0.4-0.5 parts by weight of sodium lauryl sulfate and 100-105 parts by weight of deionized water; The preparation method of the composite emulsifier comprises the following steps: S1. Heat acrylic acid, introduce nitrogen, and dropwise add triethylenetetramine while stirring and controlling the temperature to obtain intermediate material A; S2, heating poly(isobutylene-alt-maleic anhydride), introducing nitrogen, adding sorbitol while stirring, controlling the temperature and stirring, and after the stirring is completed, adding N-hydroxyethyl-ethylenediamine and stirring at the same time to obtain intermediate material B; S3, after mixing the intermediate material A and deionized water evenly, add the intermediate material B and control the temperature and stir once, after the stirring is completed, add hydrogen peroxide and vitamin C and mix evenly and control the temperature and stir again to obtain the intermediate material C; S4, the intermediate material C, nonylphenol polyoxyethylene ether (10), urea and sodium lauryl sulfonate are mixed uniformly under temperature control to obtain a finished composite emulsifier.

2. The composite emulsifier suitable for emulsion explosive according to claim 1, characterized in that: The mass concentration of the hydrogen peroxide is 50%.

3. The composite emulsifier suitable for emulsion explosive according to claim 1, characterized in that: The heating in step S1 is heating to 125-130° C.; the temperature of the temperature-controlled stirring is 130-135° C., and the time is 3-4 hours.

4. The composite emulsifier suitable for emulsion explosive according to claim 1, characterized in that: The heating in step S2 is heating to 115-120° C.; the temperature of the temperature-controlled stirring is 135-140° C., and the time is 3-4 hours.

5. The composite emulsifier suitable for emulsion explosive according to claim 1, characterized in that: In step S2, the stirring temperature for adding N-hydroxyethyl-ethylenediamine is 95-100° C. and the stirring time is 2-2.5 h.

6. The composite emulsifier suitable for emulsion explosive according to claim 1, characterized in that: The temperature of the first temperature-controlled stirring in step S3 is 90-95° C. and the time is 1-1.5 h.

7. The composite emulsifier suitable for emulsion explosive according to claim 1, characterized in that: The temperature of the secondary temperature-controlled stirring in step S3 is 60-65° C. and the time is 1-2 h.

8. The composite emulsifier suitable for emulsion explosive according to claim 1, characterized in that: The temperature of the temperature control in step S4 is 85-90°C.

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