A composite emulsifier for emulsion explosives

Abstract

The present invention belongs to the technical field of emulsifying explosive additives, and discloses a composite emulsifier for emulsifying explosives. By mass, it includes component A and component B. Component A is 70-80 parts of a modified oleic acid emulsifier, which is prepared by reacting Span-80 with hydroxypropionic acid. Component B is 20-30 parts of a modified nano-metal powder stabilizer. The beneficial effects of the present invention are as follows: After emulsifying the aqueous phase in the explosive with the modified oleic acid emulsifier, a W / O structure is formed, with the hydrophilic group facing inwards and the lipophilic group facing outwards. The modified oleic acid emulsifier forms an interfacial film outside the aqueous phase droplets. The modified oleic acid emulsifier is prepared by reacting Span-80 with hydroxypropionic acid. Hydroxypropionic acid has a hydroxyl group and a carboxyl group. After the carboxyl group is acyl chlorinated, it undergoes an esterification reaction with the hydroxyl group of Span-80, causing a hydroxypropionate group to be connected to Span-80, increasing the molecular weight of Span-80, increasing the spatial volume of the lipophilic group, and making the interfacial film more dense, thereby improving the storage stability of the emulsifying explosive.

Description

Technical Field

[0001] The present invention belongs to the technical field of emulsifying explosive additives, and particularly relates to a composite emulsifier for emulsifying explosives. Background Art

[0002] An emulsifier is a key component in emulsifying explosives. The emulsifier has extremely important effects on the explosion performance and storage performance of emulsifying explosives. Therefore, the performance of emulsifiers has attracted more and more attention in the emulsifying explosive industry.

[0003] Currently, the emulsifiers for emulsifying explosives are commonly Span-80 and polyisobutylene succinic anhydride derivatives. Among them, Span-80 has strong emulsifying ability but a small molecular weight, and the emulsifying explosives prepared have poor storage stability. When Span-80 and a high-molecular emulsifier are configured into a composite emulsifier in a certain proportion, the stability of the emulsifying explosives can be improved. However, the emulsifying ability of the high-molecular emulsifier is weak, and an excessive addition amount will affect the detonation ability of the emulsifying explosives. Summary of the Invention

[0004] The purpose of the present invention is to provide a composite emulsifier for emulsifying explosives, which has good emulsifying effect, and the emulsifying explosives prepared have the effects of high storage stability and good explosion performance.

[0005] The above technical purpose of the present invention is achieved through the following technical solutions: by mass, it includes component A and component B. Component A is 70-80 parts of a modified oleic acid emulsifier, and the modified oleic acid emulsifier is prepared by reacting Span-80 with hydroxypropionic acid. Component B is 20-30 parts of a modified nano metal powder stabilizer.

[0006] The further setting of the present invention is: the preparation method of the modified oleic acid emulsifier includes the following steps:

[0007] S1. Drop hydroxypropionic acid into thionyl chloride. After the reaction is completed, remove the hydrogen chloride and sulfur dioxide gases generated by the reaction by vacuum distillation to obtain hydroxypropionyl chloride;

[0008] S2. After dissolving Span-80 in ethanol, add sodium carbonate to form a mixed solution, and drop the mixed solution into hydroxypropionyl chloride and stir for 2-3 h;

[0009] S3. Add an ethanol solution of sodium hydroxide to the mixed solution that has reacted completely in step S2, adjust the pH to 7, add anhydrous magnesium sulfate for drying, and then filter and distill to remove the solvent to obtain the modified oleic acid emulsifier.

[0010] The further setting of the present invention is: TiCl is added to the mixed solution in step S2 4 .

[0011] Through this setting: TiCl 4 can be used as a catalyst to cause an esterification reaction between hydroxypropionyl chloride and multiple hydroxyl groups in Span-80, so that multiple hydroxypropionate groups are connected to Span-80.

[0012] A further setting of the present invention is that the modified nano metal powder stabilizer is prepared by mixing nano metal powder and oleic acid.

[0013] A further setting of the present invention is that the preparation method of the modified nano metal powder stabilizer includes, by mass, mixing 50 parts of ethanol, 10-20 parts of nano metal powder, and 2-4 parts of oleic acid, and ultrasonicating for 20-30 min to obtain the modified nano metal powder stabilizer.

[0014] A further setting of the present invention is that the modified nano metal powder includes one or more of nano aluminum powder, nano zinc powder, and nano titanium powder.

[0015] A further setting of the present invention is that the particle size of the nano metal powder is 5-50 nm.

[0016] Through this setting: when the particle size of the powder is 5-50 nm, it can affect the stability of the emulsification interface layer. If the powder is well treated with lipophilicity, it is very helpful for stabilizing the water-in-oil system. Generally, the particles of a relatively stable emulsification system are 500-5000 nm, and the thickness of the emulsification interface is 5-25 nm. Therefore, only when the size of the solid particles is close to or a multiple of the thickness of the interface layer, it is more conducive to the interface stability of the emulsification system.

[0017] The beneficial effects of the present invention are:

[0018] 1. After emulsifying the water phase in the explosive with the modified oleic acid emulsifier, a W / O structure is formed, with the hydrophilic group facing inwards and the lipophilic group facing outwards. The modified oleic acid emulsifier forms an interfacial film outside the water phase droplets. The modified oleic acid emulsifier is obtained by the reaction of Span-80 and hydroxypropionic acid. Hydroxypropionic acid has a hydroxyl group and a carboxyl group. After the carboxyl group is acyl chlorinated, it undergoes an esterification reaction with the hydroxyl group of Span-80, so that multiple hydroxypropionate groups are connected to Span-80, increasing the molecular weight of Span-80, increasing the spatial volume of the lipophilic group, making the interfacial film more dense, and thus improving the storage stability of the emulsion explosive. 4 Under the action of, it can cause an esterification reaction between hydroxypropionyl chloride and multiple hydroxyl groups in Span-80, so that multiple hydroxypropionate groups are connected to Span-80, increasing the molecular weight of Span-80, increasing the spatial volume of the lipophilic group, making the interfacial film more dense, and thus improving the storage stability of the emulsion explosive.

[0019] 2. Due to the relatively small particle size and high surface activity of the nano metal powder, it can have a coordination effect with the hydroxypropionate groups in the modified oleic acid emulsifier, so that the nano metal particles are adsorbed on the interfacial film, enhancing the rigidity of the interfacial film.

[0020] 3. Oleic acid carries a negative charge in an ethanol solvent, which causes oleic acid to be attracted to the surface of the nano metal powder, forming a film on the surface of the nano metal powder particles. Using the electrostatic steric effect, the particles are repelled from each other, thereby making the dispersion of the nano metal powder good, which is conducive to the embedding of nano metal particles into the interfacial film and plays a good stabilizing role in the interfacial layer of the emulsifier.

[0021] 4. Incorporating nano metal powder into emulsion explosives can improve the stability and persistence of the combustion of pyrotechnics; adding metal powder to explosives can increase the heat of detonation and greatly improve the work capacity; increasing the combustion rate in propellants. Therefore, the nano metal powder stabilizer can, on the one hand, play a role in improving the storage stability of emulsion explosives, and on the other hand, can improve the detonation performance of explosives after detonation. Specific embodiments

[0022] The technical solutions in the embodiments will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.

[0023] Example 1

[0024] A composite emulsifier for emulsion explosives, by mass, includes component A and component B. Component A is 80 parts of a modified oleic acid emulsifier, and the modified oleic acid emulsifier is prepared by reacting Span-80 with hydroxypropionic acid. Component B is 20 parts of a modified nano metal powder stabilizer.

[0025] The preparation method of the modified oleic acid emulsifier includes the following steps:

[0026] S1. Drop 100 parts of hydroxypropionic acid into 120 parts of thionyl chloride. After the reaction is completed, remove the hydrogen chloride and sulfur dioxide gases generated by the reaction by vacuum distillation to obtain hydroxypropionyl chloride;

[0027] S2. Dissolve 500 parts of Span-80 in ethanol, add 200 parts of sodium carbonate to form a mixed solution, drop the mixed solution into 250 parts of hydroxypropionyl chloride, add TiCl 4 as a catalyst, and stir for 3 h;

[0028] S3. Add an ethanol solution of sodium hydroxide to the mixed solution that has reacted completely in step S2, adjust the pH to 7, add anhydrous magnesium sulfate for drying, and then filter and distill to remove the solvent to obtain the modified oleic acid emulsifier.

[0029] The preparation method of the modified nano metal powder stabilizer includes, by mass, mixing 50 parts of ethanol, 10 parts of nano aluminum powder with a particle size of 5 - 50 nm, and 4 parts of oleic acid, and ultrasonicating for 20 min to obtain the modified nano metal powder stabilizer.

[0030] Example 2

[0031] A composite emulsifier for emulsion explosives includes component A and component B by mass. Component A is 70 parts of modified oleic acid emulsifier, which is prepared by reacting Span - 80 with hydroxypropionic acid, and component B is 30 parts of modified nano metal powder stabilizer.

[0032] The preparation method of the modified oleic acid emulsifier includes the following steps:

[0033] S1. Add 100 parts of hydroxypropionic acid dropwise to 120 parts of thionyl chloride. After the reaction is completed, remove the hydrogen chloride and sulfur dioxide gases generated by the reaction by vacuum distillation to obtain hydroxypropionyl chloride.

[0034] S2. Dissolve 500 parts of Span - 80 in ethanol, add 200 parts of sodium carbonate to form a mixed solution, drop the mixed solution into 250 parts of hydroxypropionyl chloride, add TiCl 4 as a catalyst, and stir for 2 h.

[0035] S3. Add an ethanol solution of sodium hydroxide to the completely reacted mixed solution in step S2, adjust the pH to 7, add anhydrous magnesium sulfate for drying, filter, and distill to remove the solvent to obtain the modified oleic acid emulsifier.

[0036] The preparation method of the modified nano metal powder stabilizer includes, by mass, mixing 50 parts of ethanol, 20 parts of nano titanium powder with a particle size of 5 - 50 nm, and 2 parts of oleic acid, and ultrasonicating for 30 min to obtain the modified nano metal powder stabilizer.

[0037] Example 3

[0038] A composite emulsifier for emulsion explosives includes component A and component B by mass. Component A is 70 parts of modified oleic acid emulsifier, which is prepared by reacting Span - 80 with hydroxypropionic acid, and component B is 30 parts of nano metal powder.

[0039] The preparation method of the modified oleic acid emulsifier includes the following steps:

[0040] S1. Add 100 parts of hydroxypropionic acid dropwise to 120 parts of thionyl chloride. After the reaction is completed, remove the hydrogen chloride and sulfur dioxide gases generated by the reaction by vacuum distillation to obtain hydroxypropionyl chloride.

[0041] S2. Dissolve 500 parts of Span-80 in ethanol, add 200 parts of sodium carbonate to form a mixed solution, drop the mixed solution into 250 parts of hydroxypropionyl chloride, and add TiCl 4 as a catalyst, and stir for 2 h;

[0042] S3. Add an ethanol solution of sodium hydroxide to the mixed solution that has completely reacted in step S2, adjust the pH to 7, add anhydrous magnesium sulfate for drying, filter and distill to remove the solvent, and then a modified oleic acid emulsifier can be obtained.

[0043] Example 4

[0044] A composite emulsifier for emulsion explosives, by mass, includes component A and component B. Component A is 70 parts of a modified oleic acid emulsifier, and the modified oleic acid emulsifier is prepared by reacting Span-80 with hydroxypropionic acid.

[0045] The preparation method of the modified oleic acid emulsifier includes the following steps:

[0046] S1. Drop 100 parts of hydroxypropionic acid into 120 parts of thionyl chloride. After the reaction is completed, distill under reduced pressure to remove the hydrogen chloride and sulfur dioxide gases generated by the reaction to obtain hydroxypropionyl chloride;

[0047] S2. Dissolve 500 parts of Span-80 in ethanol, add 200 parts of sodium carbonate to form a mixed solution, drop the mixed solution into 250 parts of hydroxypropionyl chloride, and add TiCl 4 as a catalyst, and stir for 2 h;

[0048] S3. Add an ethanol solution of sodium hydroxide to the mixed solution that has completely reacted in step S2, adjust the pH to 7, add anhydrous magnesium sulfate for drying, filter and distill to remove the solvent, and then a modified oleic acid emulsifier can be obtained.

[0049] Example 5

[0050] A composite emulsifier for emulsion explosives, by mass, includes component A and component B. Component A is 70 parts of Span-80, and component B is 30 parts of a modified nano-metal powder stabilizer.

[0051] The preparation method of the modified nano-metal powder stabilizer includes, by mass, mixing 50 parts of ethanol, 20 parts of nano-titanium powder with a particle size of 5 - 50 nm, and 2 parts of oleic acid, and ultrasonicating for 30 min to obtain the modified nano-metal powder stabilizer.

[0052] Comparative Example 1

[0053] A composite emulsifier for emulsion explosives, by mass, includes 100 parts of Span-80.

[0054] Test data

[0055] I. Emulsification Performance Test

[0056] Take 3 portions of the composite emulsifier from Examples 1 - 5 and Comparative Example 1, with a total of 1.2 g of Component A and Component B. First, add Component A to the emulsion explosive and emulsify it at an emulsification speed of 800 r / min for 1 min, then add Component B and emulsify it at an emulsification speed of 800 r / min for 1 min. Subsequently, refer to GB / T13228 - 1991 "Industrial Bomb Detonation Velocity Measurement Method" to test the detonation velocity of the sample and take the average value.

[0057] Among them, the emulsion explosive consists of 70 g of ammonium nitrate, 9 g of sodium nitrate, 15 g of water, 6 g of base oil, 1.2 g of emulsifier, and 2 g of glass microspheres.

[0058] II. Storage Stability Test

[0059] Take 3 portions of 1.2 g of samples from Examples 1 - 5 and Comparative Example 1, then add them to the emulsion explosive respectively and emulsify them at an emulsification speed of 800 r / min for 1 min. Subsequently, refer to GB / T13228 - 1991 "Industrial Bomb Detonation Velocity Measurement Method" to test the detonation velocity of the samples stored for 0 days, 7 days, 15 days, 1 month, and 2 months, and take the average value.

[0060] The test data are shown in Table 1:

[0061] Table 1 Test Data Table of Examples 1 - 5 and Comparative Example 1

[0062]

[0063] As can be seen from Table 1, in Examples 1 and 2, after storage for 2 months, the decrease in the detonation velocity of the emulsion explosive is relatively small, and it still has good explosion performance. Combining with the data of the traditional Span - 80 emulsifier in Comparative Example 1, it can be seen that the composite emulsifier in this application can greatly improve the storage stability of the emulsion explosive. In Example 3, the nano - metal powder added was not improved with a dispersant. Compared with Example 2, the initial detonation velocities in Example 3 are not much different, but as the storage days increase, the difference in the detonation velocities of the emulsion explosives in Example 2 and Example 3 gradually increases, indicating that the nano - metal powder treated with a dispersant can improve the stability of the emulsion explosive. In Example 4, no nano - metal powder was added, and compared with Example 2, the initial detonation velocity in Example 4 is smaller, indicating that adding nano - metal powder can improve the explosion effect of the emulsion explosive. In Example 5, Component A uses the unmodified emulsifier Span - 80, and the detonation velocity after storage for 2 months in Example 5 is less than that in Example 2, indicating that the modified Span - 80 emulsifier has a better binding force with the nano - metal powder.

Claims

1. A composite emulsifier for emulsion explosives, characterized in that: by mass, it includes component A and component B. Component A is 70-80 parts of modified oleic acid emulsifier, and the modified oleic acid emulsifier is prepared by reacting Span-80 with hydroxypropionic acid. Component B is 20-30 parts of modified nano metal powder stabilizer, and the modified nano metal powder stabilizer is prepared by mixing nano metal powder with oleic acid; The preparation method of the modified oleic acid emulsifier includes the following steps: S1. Drop hydroxypropionic acid into thionyl chloride. After the reaction is completed, distill under reduced pressure to remove the hydrogen chloride and sulfur dioxide gases generated by the reaction to obtain hydroxypropionyl chloride; S2. Dissolve Span-80 in ethanol, add sodium carbonate to form a mixed solution, and drop the mixed solution into hydroxypropionyl chloride and stir for 2-3 h; S3. Add an ethanol solution of sodium hydroxide to the mixed solution that has reacted completely in step S2, adjust the pH to 7, add anhydrous magnesium sulfate for drying, filter and distill to remove the solvent to obtain the modified oleic acid emulsifier.

2. The composite emulsifier for emulsion explosives according to claim 1, characterized in that: TiCl is added to the mixture in step S2 4 .

3. The composite emulsifier for emulsion explosives according to claim 1, characterized in that: The preparation method of the modified nano metal powder stabilizer includes, by mass, mixing 50 parts of ethanol, 10-20 parts of nano metal powder, and 2-4 parts of oleic acid, and ultrasonicating for 20-30 min to obtain the modified nano metal powder stabilizer.

4. The composite emulsifier for emulsion explosives according to claim 1, characterized in that: The modified nano metal powder includes one or more of nano aluminum powder, nano zinc powder, and nano titanium powder.

5. The composite emulsifier for emulsion explosives according to claim 1, characterized in that: The particle size of the nano metal powder is 5-50 nm.

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