Emulsion explosive compound emulsifier and preparation method thereof

Abstract

The invention relates to the technical field of emulsion explosive additives, in particular to an emulsion explosive compound emulsifier and a preparation method thereof. The composite emulsifier for the emulsion explosive comprises the following raw materials in parts by weight: 50-70 parts of a modified oleic acid emulsifier and 10-30 parts of a modified polyisobutylene succinic anhydride derivative, the modified oleic acid emulsifier is prepared from Span-80 and modified maleated rosin through a reaction. The composite emulsifier for the emulsion explosive has excellent emulsion forming ability, and the explosive prepared from the composite emulsifier has excellent storage stability.

Description

Technical Field

[0001] This application relates to the technical field of additives for emulsion explosives. More specifically, it relates to a composite emulsifier for emulsion explosives and a preparation method thereof. Background Art

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

[0003] Currently, the commonly used emulsifiers for emulsion explosives are Span-80 and polyisobutylene succinic anhydride derivatives. Among them, Span-80 has strong emulsifying ability but a small molecular weight, and the prepared emulsion explosives have poor storage stability. The polyisobutylene succinic anhydride derivative has a high molecular weight and can form a three-dimensional network system in the emulsion explosive, thereby improving the storage stability of the emulsion explosive. However, the emulsifying ability of the polyisobutylene succinic anhydride derivative is poor, and the emulsion-forming ability is weak.

[0004] In order to improve the emulsifying ability of the emulsifier and the stability of the prepared emulsion explosive at the same time, scientific research personnel compound Span-80 and polyisobutylene succinic anhydride derivatives to combine the advantages of the two emulsifiers. However, although the emulsion-forming ability of this composite emulsifier and the storage stability of the prepared explosive have been improved to a certain extent, the effect is still insufficient. Summary of the Invention

[0005] In order to further improve the emulsion-forming ability of the emulsifier for emulsion explosives and the storage stability of the prepared explosive, this application provides a composite emulsifier for emulsion explosives and a preparation method thereof.

[0006] In the first aspect, this application provides a composite emulsifier for emulsion explosives, adopting the following technical solution:

[0007] A composite emulsifier for emulsion explosives, comprising the following raw materials in parts by weight: 50 - 70 parts of modified oleic acid emulsifier and 10 - 30 parts of modified polyisobutylene succinic anhydride derivative; the modified oleic acid emulsifier is prepared by reacting SPan-80 with modified maleic rosin.

[0008] Span-80 contains multiple hydroxyl groups, and maleic rosin contains a large number of carboxyl groups. Therefore, when Span-80 is mixed with maleic rosin, the rosin group can be loaded on Span-80. The rosin group has the advantages of being resistant to hard water, high temperature, and non-toxic. Thus, without affecting the emulsifying ability of Span-80, the stability of Span-80 can be effectively improved, and then the prepared emulsion explosive has relatively excellent storage stability.

[0009] In addition, the maleic rosin segment can also serve as a hydrophobic segment, which can promote intramolecular association between macromolecular chains to form a spatial network structure, thereby improving the temperature resistance of Span-80 and further improving the storage stability of the prepared emulsion explosive.

[0010] Preferably, the mass ratio of Span-80 to modified maleic rosin is (2 - 4):1.

[0011] When Span-80 adopts the above mass ratio, due to the large content of Span-80, the addition of modified maleic rosin has little effect on the emulsifying ability of Span-80. And when the modified maleic acid rosin is at the above mass ratio, the modified maleic rosin can be effectively loaded on Span-80, thereby improving the temperature resistance and stability of Span-80, and further improving the storage stability of the prepared emulsion explosive.

[0012] Preferably, the preparation method of the modified oleic acid emulsifier is as follows: Add hydroquinone as an inhibitor to Span-80, then add concentrated sulfuric acid as a catalyst and zeolite, then raise the temperature to 100 - 120 °C and add silica gel as a water absorbent, and then slowly add modified maleic rosin until the reaction is completed, and finally filter to obtain the modified oleic acid emulsifier.

[0013] When preparing the modified oleic acid emulsifier, the above reaction temperature and reaction time can significantly improve the yield and preparation rate of the modified oleic acid emulsifier.

[0014] Preferably, the modified maleic rosin is sulfonated maleic rosin.

[0015] Since there is a benzene ring on maleic rosin, the sulfonic acid group can be loaded on maleic rosin under the action of concentrated sulfuric acid, and then the sulfonic acid group can be connected to Span-80 driven by maleic rosin. The introduction of the sulfonic acid group can increase the rigidity of the polymer molecular chain and enhance the anti-shear performance of the polymer. When the temperature rises, the sulfonic acid group can enhance the intermolecular association of Span-80, increase the system viscosity, thereby further improving the stability of the emulsifier and further improving the storage stability of the prepared emulsion explosive.

[0016] Preferably, the preparation method of the sulfonated maleic rosin is as follows: Heat rosin to 150 - 180 °C, then add maleic anhydride, raise the temperature to 190 - 220 °C and react for 4 - 5 h, then lower the temperature to 150 - 160 °C, and finally add concentrated sulfuric acid and react for 1 - 2 h to finally obtain sulfonated maleic rosin; wherein, the mass ratio of maleic anhydride to rosin is 1:5.

[0017] When preparing sulfonated maleic rosin, the above reaction temperature, reaction time, and mass ratio of maleic anhydride to rosin can all contribute to obtaining a purer sulfonated maleic rosin, and both the preparation yield and speed of sulfonated maleic rosin are significantly improved.

[0018] The addition of the modified maleic rosin is carried out through a quantitative discharging device;

[0019] The quantitative discharging device includes a storage barrel, a sealing cover, and a telescopic assembly. An inlet hole is opened at the top of the storage barrel, and a cover door is arranged on the inlet hole; an outlet hole is opened at the bottom of the storage barrel, the sealing cover is arranged at the bottom of the storage barrel, the sealing cover seals the outlet hole, and an inclined surface is arranged on the upper end surface of the sealing cover;

[0020] The telescopic assembly includes a driving member and a reset member. The driving member is used to control the sealing cover to open the outlet hole, and the reset member is used to control the sealing cover to close the outlet hole;

[0021] The driving member includes a driving motor, a driving gear, a driving rack, and a connecting rod. The driving motor is arranged on the storage barrel, the driving gear is arranged at the output end of the driving motor, and the driving gear includes a tooth part and a void part that are connected to each other;

[0022] The connecting rod is slidably connected to the storage barrel, the sliding direction of the connecting rod is parallel to the axis of the storage barrel, one end of the connecting rod is fixedly connected to the sealing cover, the other end of the connecting rod is fixedly connected to the driving rack, and the driving rack meshes with the tooth part;

[0023] The reset member includes a limiting cylinder, a compression spring, and a limiting plate. The limiting cylinder is sleeved on the connecting rod, the compression spring is arranged in the limiting cylinder, the limiting plate is slidably connected in the limiting cylinder, the limiting plate is fixedly connected to the connecting rod, one end of the compression spring abuts against the limiting plate, and the other end of the compression spring abuts against the upper end surface of the storage barrel.

[0024] When it is necessary to add the modified maleic rosin, the staff can first add the modified maleic rosin into the storage barrel through the inlet hole, and then turn on the driving motor. At this time, the driving motor drives the driving gear to rotate, the tooth part drives the driving rack to move downward, the driving rack drives the sealing cover to move downward through the connecting rod, thereby releasing the sealing of the outlet hole by the sealing cover, and the modified maleic rosin in the discharging barrel is transferred to the flask under the action of gravity and the guiding effect of the inclined surface. At the same time, the compression spring remains compressed under the action of the limiting plate.

[0025] When the tooth part is disengaged from the driving rack, that is, when the empty part is located at the driving rack, the compression spring rebounds, so as to prompt the connecting rod to drive the sealing cover and the driving rack to reset, and then complete the sealing of the discharge hole, realize the quantitative addition of modified maleic rosin, and at the same time realize the reciprocating movement of the driving rack.

[0026] Preferably, the modified polyisobutylene succinic anhydride derivative comprises the following raw materials in parts by weight: 50-70 parts of polyisobutylene succinic anhydride, 10-30 parts of soybean phospholipid and 5-15 parts of diethanolamine.

[0027] Due to the amino groups contained in phosphatidylethanolamine in soybean phospholipid, the amino groups can undergo acylation reaction with polyisobutylene succinic anhydride, and then graft with diethanolamine, so as to promote the stable connection of phospholipid groups on the modified polyisobutylene succinic anhydride derivative, thereby obtaining more functional groups, and then improving the emulsifying performance and stability of the modified polyisobutylene succinic anhydride derivative, and further improving the storage stability of the prepared emulsion explosive. <s

[0028] Preferably, the preparation method of the modified polyisobutylene succinic anhydride derivative is as follows: mix soybean phospholipid with polyisobutylene succinic anhydride, then carry out vacuum reaction at a temperature of 60-80 °C for 5-6 h, then add diethanolamine, and finally react at a temperature of 100-130 °C for 5-7 h to obtain the modified polyisobutylene succinic anhydride derivative.

[0029] When preparing the modified polyisobutylene succinic anhydride derivative, the above reaction temperature and reaction time can promote the more stable and rapid connection of phospholipid groups to the polyisobutylene succinic anhydride derivative, thereby improving the yield and output of the modified polyisobutylene succinic anhydride derivative.

[0030] In the second aspect, the present application provides a preparation method of an emulsion explosive composite emulsifier, adopting the following technical scheme:

[0031] A preparation method of an emulsion explosive composite emulsifier includes the following steps:

[0032] S1. Preparation of modified oleic acid emulsifier: Add hydroquinone as a polymerization inhibitor to Span-80, then add concentrated sulfuric acid as a catalyst and zeolite, then raise the temperature to 100-120 °C and add silica gel as a water absorbent, and then slowly add modified maleic rosin until the reaction is completed, and finally filter to obtain the modified oleic acid emulsifier;

[0033] S2. Preparation of modified polyisobutylene succinic anhydride derivative: Mix soybean phospholipid with polyisobutylene succinic anhydride, then carry out vacuum reaction at a temperature of 60-80 °C for 5-6 h, then add diethanolamine, and finally react at a temperature of 100-130 °C for 5-7 h to obtain the modified polyisobutylene succinic anhydride derivative;

[0034] S3. Preparation of composite emulsifier for emulsion explosive: Add the modified polyisobutylene succinic anhydride derivative to the modified oleic acid emulsifier, and then mix at a temperature of 100 - 120 °C for 4 - 5 h to obtain the composite emulsifier for emulsion explosive.

[0035] When preparing the composite emulsifier for emulsion explosive, the above reaction temperature and reaction time can significantly improve both the yield and preparation rate of the composite emulsifier for emulsion explosive.

[0036] In summary, the present application has the following beneficial effects:

[0037] 1. The rosin group has the advantages of being resistant to hard water, high temperature, and non-toxic. Therefore, when the rosin group is loaded on Span - 80, it can effectively improve the stability of Span - 80 without affecting its emulsifying ability, thereby promoting the prepared emulsion explosive to have relatively excellent storage stability.

[0038] 2. The maleic rosin segment can serve as a hydrophobic segment, thereby promoting intramolecular association between macromolecular chains to form a spatial network structure, further improving the temperature resistance of Span - 80, and further improving the storage stability of the prepared emulsion explosive.

[0039] 3. The introduction of sulfonic acid groups can increase the rigidity of the polymer molecular chain and enhance the shear resistance of the polymer. Furthermore, when the temperature rises, the sulfonic acid groups can enhance the intermolecular association of Span - 80 and increase the system viscosity, thereby further improving the stability of the emulsifier and further improving the storage stability of the prepared emulsion explosive.

[0040] 4. The introduction of phospholipid groups can improve the emulsifying performance and stability of the modified polyisobutylene succinic anhydride derivative, and further improve the storage stability of the prepared emulsion explosive. Brief Description of the Drawings

[0041] Figure 1 is a schematic structural diagram of the quantitative discharging device.

[0042] Figure 2 is along Figure 1 the sectional view taken along line A - A in

[0043] Figure 3 is a partial explosion schematic diagram of the telescopic component.

[0044] Description of the reference numerals: 1, storage cylinder; 2, sealing cover; 3, telescopic assembly; 11, feed hole; 12, cover door; 13, discharge hole; 21, inclined surface; 31, driving member; 32, reset member; 311, driving motor; 312, driving gear; 313, driving rack; 314, connecting rod; 321, limiting cylinder; 322, compression spring; 323, limiting plate; 3121, tooth portion; 3122, empty portion. Detailed implementation manners

[0045] The present application will be further described in detail below in conjunction with Examples 1-10 and Comparative Example 1.

[0046] Raw materials

[0047] Hydroquinone CAS: 629-94-7; concentrated sulfuric acid 98 wt%; rosin CAS: 8050-09-7; maleic anhydride CAS: 108-31-6; polyisobutylene succinic anhydride CAS: 67762-77-0; soybean phospholipid CAS: 8002-43-5; diethanolamine CAS: 111-42-2.

[0048] Examples

[0049] Example 1

[0050] An emulsifying explosive composite emulsifier is obtained by mixing 60 g of modified oleic acid emulsifier and 20 g of modified polyisobutylene succinic anhydride derivative.

[0051] A preparation method of an emulsifying explosive composite emulsifier comprises the following steps:

[0052] S1. Preparation of the modified oleic acid emulsifier: Add 60 g of Span-80 and 0.13 g of the polymerization inhibitor hydroquinone to a 100 ml dry four-necked flask. Slowly add 4 g of the catalyst concentrated sulfuric acid while shaking. After mixing evenly, add 3 zeolites. Install a thermometer and a reflux condenser. Then raise the temperature to 110 °C (100-120 °C is appropriate), add 11 g of the water absorbent silica gel, and finally slowly add 20 g of modified maleic rosin to Span-80. Take samples every 5 min to detect the reaction esterification rate until the esterification rate hardly changes, and then stop the reaction;

[0053] Among them, the modified maleic rosin is sulfonated maleic rosin, and its preparation method is: Heat 10 g of rosin to 165 °C (150-180 °C is appropriate), then add 50 g of maleic anhydride, raise the temperature to 210 °C (190-220 °C is appropriate) and react for 4.5 h (4-5 h is appropriate). Then lower the temperature to 155 °C (150-160 °C is appropriate), and finally add 20 ml of concentrated sulfuric acid and react for 1.5 h. Finally, filter, dry and grind to obtain sulfonated maleic rosin.

[0054] In addition, in this embodiment, the addition of the modified maleic rosin is carried out by a metering and discharging device;

[0055] Referring to Figure 1 and Figure 2 , the metering and discharging device includes a storage cylinder 1, a sealing cover 2 and a telescopic assembly 3. Among them, a feed hole 11 is opened at the top of the storage cylinder 1, a cover door 12 is embedded in the feed hole 11, a discharge hole 13 is opened at the bottom of the storage cylinder 1, and the sealing cover 2 is arranged at the discharge hole 13. The sealing cover 2 seals the discharge hole 13, so as to promote the storage cylinder 1 to store the modified maleic rosin, and the telescopic assembly 3 is used to control the sealing cover 2 to seal or open the discharge hole 13.

[0056] In addition, an inclined surface 21 is arranged on the upper end surface of the sealing cover 2, so as to promote the modified maleic rosin to be more simply and quickly transferred into the four-necked flask under the action of gravity and the guiding effect of the inclined surface 21, and at the same time, the addition of the modified maleic rosin is more evenly dispersed.

[0057] Referring to Figure 2 and Figure 3 , the telescopic assembly 3 includes a driving member 31 and a reset member 32. Among them, the driving member 31 is used to control the sealing cover 2 to release the sealing of the discharge hole 13, and the reset member 32 is used to control the sealing cover 2 to close the discharge hole 13 again.

[0058] The driving member 31 includes a driving motor 311, a driving gear 312, a driving rack 313 and a connecting rod 314. The driving motor 311 is fixedly connected to the upper end surface of the storage cylinder 1, the driving gear 312 is fixedly connected to the output end of the driving motor 311, and the driving gear 312 includes a tooth portion 3121 and a void portion 3122 connected to each other.

[0059] The connecting rod 314 is slidably connected to the storage cylinder 1, and the sliding direction of the connecting rod 314 is parallel to the axial direction of the storage cylinder 1. One end of the connecting rod 314 is fixedly connected to the center of the upper end surface of the sealing cover 2, the other end of the connecting rod 314 is fixedly connected to the lower end of the driving rack 313, and the driving rack 313 meshes with the tooth portion 3121.

[0060] The reset member 32 includes a limiting cylinder 321, a compression spring 322 and a limiting plate 323. Among them, the limiting sleeve is sleeved on the outer peripheral surface of the connecting rod 314, and the lower end of the limiting sleeve is fixedly connected to the upper end of the storage cylinder 1. The limiting plate 323 is slidably connected in the limiting cylinder 321, the limiting plate 323 is fixedly connected to the connecting rod 314, one end of the compression spring 322 abuts against the limiting plate 323, and the other end of the compression spring 322 abuts against the upper end surface of the storage cylinder 1.

[0061] When it is necessary to add sulfonated maleic rosin, the staff can first add the sulfonated maleic rosin into the storage cylinder 1 through the feed hole 11, and then embed the cover door 12 on the feed hole 11. Then, turn on the drive motor 311. The drive motor 311 drives the drive gear 312 to rotate, and the tooth part 3121 drives the drive rack 313 to move downward. The drive rack 313 drives the connecting rod 314 to move downward, and the connecting rod 314 drives the plugging cover 2 to release its plugging of the discharge hole 13. Then, the sulfonated maleic rosin in the discharge cylinder is transferred to the four-necked flask under the action of gravity and the guiding of the inclined surface 21. At the same time, the compression spring 322 remains compressed under the action of the limit plate 323.

[0062] When the tooth part 3121 is disengaged from the drive rack 313, that is, when the empty part 3122 is located at the drive rack 313, the compression spring 322 rebounds, so as to promote the connecting rod 314 to drive the plugging cover 2 and the drive rack 313 to reset, and then complete the plugging of the discharge hole 13, realize the quantitative addition of sulfonated maleic rosin, and at the same time realize the reciprocating movement of the drive rack 313.

[0063] It should be noted that in this embodiment, the above fixed connection can be selected according to the actual situation by conventional fixed connection methods such as welding fixation, integral molding, and threaded connection.

[0064] S2. Preparation of modified polyisobutylene succinic anhydride derivative:

[0065] Put 20 g of soybean phospholipid and 60 g of polyisobutylene succinic anhydride into the reactor for mixing. Then, under the conditions of a temperature of 70 °C (60 - 80 °C is appropriate) and a vacuum degree of 0.05 - 0.1 Mpa, react for 5.5 h (5 - 6 h is appropriate). Stop when the acylation rate ≥ 85%. Then add 10 g of diethanolamine. Finally, under the conditions of a temperature of 120 °C (100 - 130 °C is appropriate) and a vacuum degree of 0.05 - 0.1 Mpa, react for 6 h (5 - 7 h is appropriate) to finally obtain the modified polyisobutylene succinic anhydride derivative;

[0066] S3. Preparation of composite emulsifier for emulsion explosive: Add 20 g of the modified polyisobutylene succinic anhydride derivative to 60 g of the modified oleic acid emulsifier, and then mix at a temperature of 110 °C (100 - 120 °C is appropriate) for 4.5 h (4 - 5 h is appropriate) to obtain the composite emulsifier for emulsion explosive.

[0067] Example 2 - 3

[0068] The difference from Example 1 is that the addition amounts of the modified polyisobutylene succinic anhydride derivative and the modified oleic acid emulsifier are different, as shown in Table 1 specifically.

[0069] Table 1 Addition amounts of each component of the composite emulsifier for emulsion explosive in Examples 1 - 3 (g)

[0070]

[0071] Examples 4 - 5

[0072] It is different from Example 1 in that in the preparation of the modified oleic acid emulsifier, the addition amounts of Span - 80 and the modified maleic rosin are different, as specifically shown in Table 2.

[0073] Table 2 Addition amounts of each component of the modified oleic acid emulsifier in Example 1 and Examples 4 - 5 (g)

[0074] Span-80 Modified maleic rosin Example 1 60 20 Example 4 64 16 Example 5 54 27

[0075] Example 6

[0076] It is different from Example 1 in that in the preparation of the modified oleic acid emulsifier, the sulfonated maleic rosin is replaced with maleic rosin having the same addition amount.

[0077] Example 7

[0078] It is different from Example 1 in that in the preparation of the modified oleic acid emulsifier, maleic rosin is not added.

[0079] Examples 8 - 9

[0080] It is different from Example 1 in that in the preparation of the modified polyisobutylene succinic anhydride derivative, the addition amounts of polyisobutylene succinic anhydride, soybean phospholipid and diethanolamine are different, as specifically shown in Table 3.

[0081] Table 3 Addition amounts of each component of the modified polyisobutylene succinic anhydride derivative in Example 1 and Examples 8 - 9 (g)

[0082] Polyisobutylene succinic anhydride Soybean phospholipid Diethanolamine Example 1 60 20 10 Example 8 70 10 5 Example 9 50 30 15

[0083] Example 10

[0084] It is different from Example 1 in that the modified polyisobutylene succinic anhydride derivative is replaced with polyisobutylene succinic acid alkanolamine having the same addition amount.

[0085] Comparative example

[0086] Comparative example 1

[0087] A composite emulsifier for emulsion explosive is obtained by mixing 60 g of Span - 80 and 20 g of polyisobutylene succinic acid alkanolamine at a temperature of 110 °C for 4.5 h.

[0088] Performance detection test

[0089] Test method

[0090] I. Emulsification Performance Test

[0091] Take out 3 samples of 1.2 g each from Examples 1 - 10 and Comparative Example 1 respectively, then add them to emulsion explosives respectively and carry out emulsification at an emulsification speed of 800 r / min for 1 min. Then, refer to GB / T 13228 - 1991 "Determination Method for Detonation Velocity of Industrial Bombs" to test the detonation velocity of the samples and take the average value.

[0092] Among them, the emulsion explosive consists of 70 g of ammonium nitrate, 9 g of sodium nitrate, 15 g of water, 6 g of diesel, 1.2 g of emulsifier and 2 g of glass microspheres.

[0093] II. Storage Stability Test

[0094] Take out 3 samples of 1.2 g each from Examples 1 - 10 and Comparative Example 1 respectively, then add them to emulsion explosives respectively and carry out emulsification at an emulsification speed of 800 r / min for 1 min. Then, refer to GB / T 13228 - 1991 "Determination Method for Detonation Velocity of Industrial Bombs" 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.

[0095] The test data are shown in Table 4:

[0096] Table 4 Detection Data Table of Examples 1 - 10 and Comparative Example 1

[0097]

[0098] Referring to Examples 1 - 3, Comparative Example 1 and combining with Table 4, it can be seen that compared with Comparative Example 1, the original detonation velocities of Examples 1 - 3 basically have no change. Among them, the original detonation velocity of Example 2 is relatively low, and the original detonation velocity of Example 3 is relatively high. The reason is the change in the proportion of the modified oleic acid emulsifier.

[0099] However, compared with Comparative Example 1, the decrease in detonation velocity of Examples 1 - 3 after storage for a period of time is significantly slowed down, that is, compared with Comparative Example 1, the storage stability of Examples 1 - 3 is relatively better. Among them, the decrease amplitude of Example 2 is lower, and the decrease amplitude of Example 3 is higher. Considering the original detonation velocity comprehensively, the original detonation velocity and storage stability of Example 1 are more balanced, that is, the addition amounts of the components of the composite emulsifier in the emulsion explosive in Example 1 are more suitable.

[0100] Referring to Example 1, Examples 4-5 and in combination with Table 4, it can be seen that compared with Example 1, the initial detonation velocity of Example 4 has slightly increased, but the reduction rate of Example 4 has also significantly increased. The initial detonation velocity of Example 5 has slightly decreased, but the reduction rate of Example 5 has also slightly slowed down. Considering the initial detonation velocity and storage stability comprehensively, the ratio of Span-80 to modified maleic rosin in Example 1 is relatively optimal.

[0101] Referring to Example 1, Examples 6-7 and in combination with Table 4, it can be seen that compared with Example 1, the initial detonation velocity of Example 6 has basically remained unchanged, but the reduction rate has significantly increased. This shows that the presence of sulfonic acid groups can effectively improve the storage stability of the prepared emulsion explosive. The reason lies in that the intermolecular association of Span-80 is enhanced by sulfonic acid groups, and the viscosity of the system increases, thereby further improving the stability of the emulsifier.

[0102] Compared with Example 6, the initial detonation velocity of Example 7 still has not changed much, but the reduction rate of Example 7 has further increased. This shows that rosin-based groups also have the effect of improving the storage stability of the prepared emulsion explosive. The reason lies in that rosin-based groups have the advantages of being resistant to hard water, high temperature resistance, non-toxic, etc., so that without affecting the emulsifying ability of Span-80, the stability of Span-80 can be effectively improved, and then the prepared emulsion explosive has relatively excellent storage stability.

[0103] Referring to Example 1, Examples 8-10 and in combination with Table 4, it can be seen that compared with Example 10, the initial detonation velocities of Example 1, Examples 8-9 have basically remained unchanged, but the reduction rates of Example 1, Examples 8-9 have significantly increased. This shows that the addition of soybean phospholipids can effectively improve the storage stability of the composite emulsifier of emulsion explosives.

[0104] This specific embodiment is only an interpretation of the present application, and it is not a limitation of the present application. Those skilled in the art can make modifications without creative contributions to this embodiment after reading this specification, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. An emulsifying explosive composite emulsifier, characterized in that, It comprises the following raw materials in parts by weight: 50 - 70 parts of modified oleic acid emulsifier and 10 - 30 parts of modified polyisobutylene succinic anhydride derivative; the modified oleic acid emulsifier is prepared by reacting Span - 80 with modified maleic rosin.

2. The composite emulsifier for emulsion explosive according to claim 1, characterized in that: The mass ratio of Span - 80 to modified maleic rosin is (2 - 4):

1.

3. The composite emulsifier for emulsion explosive according to claim 1, wherein, The preparation method of the modified oleic acid emulsifier is as follows: Add hydroquinone as an inhibitor to Span - 80, then add concentrated sulfuric acid as a catalyst and zeolite, then raise the temperature to 100 - 120 °C and add silica gel as a water absorbent, and then slowly add modified maleic rosin until the reaction is complete, and finally filter to obtain the modified oleic acid emulsifier.

4. The composite emulsifier for emulsion explosive according to claim 3, wherein: The modified maleic rosin is sulfonated maleic rosin.

5. The composite emulsifier for emulsion explosive according to claim 4, characterized in that, The preparation method of the sulfonated maleic rosin is as follows: Heat rosin to 150 - 180 °C, then add maleic anhydride, raise the temperature to 190 - 220 °C and react for 4 - 5 h, then lower the temperature to 150 - 160 °C, and finally add concentrated sulfuric acid and react for 1 - 2 h to finally obtain sulfonated maleic rosin; wherein, the mass ratio of maleic anhydride to rosin is 1:

5.

6. The composite emulsifier for emulsion explosive according to claim 3, wherein: The addition of the modified maleic rosin is carried out through a metering discharging device; The metering discharging device includes a storage barrel (1), a sealing cover (2) and a telescopic assembly (3). The top of the storage barrel (1) is provided with a feeding hole (11), and a cover door (12) is arranged on the feeding hole (11); the bottom of the storage barrel (1) is provided with a discharging hole (13), the sealing cover (2) is arranged at the bottom of the storage barrel (1), the sealing cover (2) seals the discharging hole (13), and an inclined surface (21) is arranged on the upper end surface of the sealing cover (2); The telescopic assembly (3) includes a driving member (31) and a resetting member (32). The driving member (31) is used to control the sealing cover (2) to open the discharging hole (13), and the resetting member (32) is used to control the sealing cover (2) to close the discharging hole (13); The driving member (31) includes a driving motor (311), a driving gear (312), a driving rack (313) and a connecting rod (314). The driving motor (311) is arranged on the storage barrel (1), the driving gear (312) is arranged at the output end of the driving motor (311), and the driving gear (312) includes a tooth part (3121) and a hollow part (3122) which are connected to each other; The connecting rod (314) is slidably connected to the storage barrel (1), the sliding direction of the connecting rod (314) is parallel to the axis of the storage barrel (1), one end of the connecting rod (314) is fixedly connected to the sealing cover (2), the other end of the connecting rod (314) is fixedly connected to the driving rack (313), and the driving rack (313) meshes with the tooth part (3121); The reset member (32) includes a limit cylinder (321), a compression spring (322) and a limit plate (323). The limit cylinder (321) is sleeved on the connecting rod (314). The compression spring (322) is arranged in the limit cylinder (321). The limit plate (323) is slidably connected in the limit cylinder (321). The limit plate (323) is fixedly connected to the connecting rod (314). One end of the compression spring (322) abuts against the limit plate (323), and the other end of the compression spring (322) abuts against the upper end face of the storage cylinder (1).

7. The composite emulsifier for emulsion explosive according to claim 1, wherein The modified polyisobutylene succinic anhydride derivative comprises the following raw materials in parts by weight: 50-70 parts of polyisobutylene succinic anhydride, 10-30 parts of soybean phospholipid and 5-15 parts of diethanolamine.

8. The composite emulsifier for emulsion explosive according to claim 7, wherein The preparation method of the modified polyisobutylene succinic anhydride derivative is as follows: Mix soybean phospholipid and polyisobutylene succinic anhydride, then carry out a vacuum reaction at a temperature of 60-80 °C for 5-6 h, then add diethanolamine, and finally carry out a reaction at 100-130 °C for 5-7 h to obtain the modified polyisobutylene succinic anhydride derivative.

9. A preparation method of the composite emulsifier for emulsion explosive according to any one of claims 1-8, characterized in that, It includes the following steps: S1. Preparation of modified oleic acid emulsifier: The preparation method of the modified oleic acid emulsifier is as follows: Add hydroquinone as a polymerization inhibitor to Span-80, then add concentrated sulfuric acid as a catalyst and zeolite, then raise the temperature to 100-120 °C and add silica gel as a water absorbent, and then slowly add modified maleic rosin until the reaction is completed, and finally filter to obtain the modified oleic acid emulsifier; S2. Preparation of modified polyisobutylene succinic anhydride derivative: Mix soybean phospholipid and polyisobutylene succinic anhydride, then carry out a vacuum reaction at a temperature of 60-80 °C for 5-6 h, then add diethanolamine, and finally carry out a reaction at 100-130 °C for 5-7 h to obtain the modified polyisobutylene succinic anhydride derivative; S3. Preparation of composite emulsifier for emulsion explosive: Add the modified polyisobutylene succinic anhydride derivative to the modified oleic acid emulsifier, and then mix at a temperature of 100-120 °C for 4-5 h to obtain the composite emulsifier for emulsion explosive.

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