Preparation method of smoke-suppression type emulsion explosive composite wax resin

Abstract

The present application relates to a kind of preparation methods of smoke-suppression type emulsion explosive composite wax resin, including using the C5 olefin rich component of 50~75 ℃ of cracking C5 rectification interception as raw material, first by the cationic polymerization of anhydrous aluminium chloride catalysis to obtain refined resin liquid D, then copolymerization with p-divinylbenzene and allyl phosphoric acid diester.The emulsion explosive composite wax prepared by the present application has good environmental protection and comprehensive physicochemical properties, and has important significance for the preparation and application of environmental protection type emulsion explosive.

Description

Technical Field

[0001] This invention belongs to the field of synthetic resins, and specifically relates to a method for preparing a resin for smoke-suppressing emulsion explosive composite wax. Background Technology

[0002] C5 petroleum resin is a medium-to-low molecular weight polymer in solid or viscous liquid form, obtained primarily from C5 cracking, a byproduct of ethylene plants, via catalytic polymerization or free radical polymerization. Based on the monomers and molecular structure, it can be broadly classified into aliphatic and alicyclic petroleum resins. Aliphatic and alicyclic petroleum resins are obtained from different C5 raw materials and polymerization processes. The former is predominantly composed of branched straight-chain alkanes and is mostly obtained through direct Friedel-Crafts alkylation catalytic polymerization; the latter is predominantly composed of polycyclic rings and typically requires free radical polymerization to obtain C5. 10 C 15 C 20 Prepolymers are obtained by catalytic polymerization to yield alicyclic petroleum resins. Due to the differences in molecular structure between the two types of resins, they each have wide applications in hot melt adhesives, coatings, medical supplies, sanitary materials, and other specialty fields.

[0003] Emulsion explosives typically use an aqueous solution of an oxidizing agent as the dispersed phase and oily or waxy substances as the continuous phase. They are water-in-oil emulsion industrial explosives prepared using emulsifiers and emulsification technology. They have advantages such as high density, high detonation velocity, high saturation, good water resistance, and good stability, and have been widely used in various civil blasting operations.

[0004] Emulsion explosives require a high-performance continuous phase, and its main oil phase material, namely composite wax, plays a key role in emulsification, controlling the initiation speed, and improving the stability of the explosive. In addition to the main raw material petroleum-based wax, adding an appropriate amount of petroleum resin can play a good role in the uniform dispersion of the oil phase of the emulsion explosive, controlling the crystal form, and improving storage stability.

[0005] Finished emulsion explosives possess strong detonation and sympathetic detonation characteristics, easily generating massive amounts of explosive dust during operation. Therefore, in the civil blasting industry, in addition to improving the design and control of blasting operations, controlling and enhancing the smoke suppression performance of explosives from the source is also an important research direction. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to provide a method for preparing a resin for smoke-suppressing emulsion explosive composite wax. While ensuring the excellent physicochemical properties of the emulsion explosive composite wax, it also enables it to have a certain smoke-suppressing ability, improves environmental protection and stability, and is of great significance to the preparation and application of environmentally friendly emulsion explosives.

[0007] This invention provides a method for preparing a resin for smoke-suppressing emulsion explosive composite wax, comprising the following steps:

[0008] (1) The cracked C5 fraction was extracted by distillation to obtain the C5 olefin enrichment fraction A with a boiling point of 50-75℃, and dehydrated to below 150 ppm;

[0009] (2) In a high-pressure reactor under nitrogen protection and with stirring, 40-60% of the total material mass of saturated cycloalkane solvent and 0.5-1.5% of anhydrous aluminum trichloride catalyst are pre-placed and stirred thoroughly. At a temperature of 0-75℃, 38.5-59.5% of the total material mass of C5 olefin enrichment fraction A is added dropwise. After the dropwise addition is completed, the reaction continues for 0.25-5.0h to obtain polymer solution B.

[0010] (3) The polymer solution B is sent to the water washing device. The polymer solution B and water are fully mixed at a mass ratio of 1:(3~10). The catalyst is removed by washing with water at 20~90℃ for 0.5~5.0h. The oil-water mixture is sent to the electro-desalting device to remove free inorganic salts and other impurities in the polymer solution B. The mixture is allowed to stand and separate to obtain the upper layer to obtain the polymer solution C.

[0011] (4) The polymer solution C is fed into a distillation column and distilled under a vacuum of -0.080 to -0.095 MPa and a temperature of 200 to 260°C. The recovered solvent and unreacted components are obtained at the top of the column, and the resin solution D is obtained at the bottom of the column.

[0012] (5) After removing the water from the resin liquid D through a molecular sieve packed tower, it is sent to a melting tank. Then, 0.01-2.0% of divinylbenzene and 0.01-3.0% of allyl phosphate diester are added simultaneously. The mixture is heated to 150-250°C and reacted for 5-30 minutes. After granulation, the resin for smoke-suppressing emulsion explosive composite wax is obtained.

[0013] The composition of C5 olefin enrichment fraction A in step (1) is as follows: 1-pentene 0.1-8.0 wt%, isopentene 0.1-15.0 wt%, isoprene 0.1-20.0 wt%, 1,3-pentadiene 0.1-50.0 wt%, cyclopentadiene 0.1-20.0 wt%, cyclopentene 0.1-15.0 wt%, 1-hexene 0.1-3.0 wt%, and the remainder being C5-C6 saturated alkanes.

[0014] The dehydration in step (1) is performed using low-nitrogen calcium hydride or molecular sieve dehydration; wherein the low-nitrogen calcium hydride has a purity ≥98.0% and a total nitrogen content ≤200ppm; the molecular sieve dehydration is performed using... or

[0015] The saturated cycloalkane solvent in step (2) is one or more of cyclohexane, methylcyclohexane, and dimethylcyclohexane.

[0016] The time for adding fraction A in step (2) is 0.5-3 hours.

[0017] The operating conditions of the electro-desalination device in step (3) are as follows: polyvinyl alcohol demulsifier is added in advance at a dosage of 20-220 μg / g, the operating temperature is 60-150℃, the electric field strength is 400-2000 V / cm, and the residence time is 20-120 min.

[0018] The solid content of the polymerization liquid C in step (3) is 5-50%, and the total chlorine content is ≤300ppm.

[0019] The softening point of the resin liquid D in step (4) is in the range of 80 to 130°C.

[0020] In step (5), the resin solution D is dehydrated to ≤150ppm.

[0021] The allyl phosphate diester in step (5) is one or more of allyl dimethyl phosphate, allyl diethyl phosphate, allyl dipropyl phosphate, allyl dibutyl phosphate, allyl dipentyl phosphate, allyl dihexyl phosphate, allyl diheptyl phosphate, and allyl dioctyl phosphate.

[0022] The resin for smoke-suppressing emulsion explosive composite wax obtained in step (5) has a softening point of 80-160℃, a Gardner color number ≤6#, and a hydroxyl value of 0.1-10.0 mgKOH / g.

[0023] The resin for smoke-suppressing emulsion explosives composite wax obtained in step (5) is applied to smoke-suppressing emulsion explosives, and the formula is as follows:

[0024] Fischer-Tropsch wax 5-50 wt%, microcrystalline wax 5-50 wt%, refined hydrogenated white oil 5-40 wt%, and resin for composite waxes 1-10 wt%.

[0025] The Fischer-Tropsch wax is preferably one of 45#, 50#, 60#, 70#, 80#, 90#, or 105#.

[0026] The microcrystalline wax is preferably one of 60#, 70#, or 80#.

[0027] The refined hydrogenated white oil is required to have a distillation range of 160–260°C, a Hazen color of ≤30, and a kinematic viscosity (40°C) of 55–110 mm. 2 / s, flash point ≥200℃, aromatic content ( 1 H-NMR) ≤5%.

[0028] The properties of the smoke-suppressing emulsion explosive composite wax are as follows: dropping point 55–75℃, kinematic viscosity (100℃) 7–10 mm. 2 / s, flash point ≥180℃, oxygen index OI ≥35%, maximum smoke density ≤100mg / L.

[0029] This invention prepares C5 petroleum resin liquid through cationic catalytic polymerization, and then, at a certain temperature, adds divinylbenzene (DVB) and allyl phosphate diester for free radical copolymerization to obtain an end-group modified functionalized resin with certain comprehensive smoke suppression properties. Allyl phosphate diester monomers are one of the key raw materials commonly used to improve the flame retardant properties of different polymers and composite materials; common modification methods include physical blending and chemical modification. This invention, by controlling the directional grafting of a certain amount of allyl phosphate diester into C5 resin using DVB, can significantly improve the oxygen index of the composite wax and reduce the maximum smoke density without affecting the application performance of the emulsion explosive composite wax, thus achieving better smoke suppression performance.

[0030] Beneficial effects

[0031] (1) This invention modifies the end groups of C5 petroleum resin molecules with phosphate ester groups, thereby improving its smoke suppression performance and environmental protection performance without affecting the overall performance of the emulsion explosive composite wax.

[0032] (2) The present invention uses divinylbenzene (DVB), allyl phosphate diester and C5 petroleum resin to perform free radical copolymerization, thereby improving the grafting efficiency of allyl phosphate diester groups and controlling the softening point and molecular sequence structure within a certain range to obtain an ideal modified resin.

[0033] (3) The resin for smoke-suppressing emulsion explosive composite wax prepared by the present invention has excellent compatibility with other oil phase components in the composite wax formulation, and has good dispersion effect in the system, which is conducive to exerting its thickening, plasticizing and smoke-suppressing effects in the composite wax. Attached Figure Description

[0034] Figure 1 This is a schematic diagram of the process flow of the present invention. Detailed Implementation

[0035] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0036] The oxygen index and maximum smoke density testing methods for the emulsion explosive composite wax in this invention are as follows:

[0037] NB / SH / T 0815-2010 "Determination of Asphalt Combustion Performance by Oxygen Index Method";

[0038] GB / T 8323.2-2008 Plastic smoke generation - Part 2: Determination of optical density by single-chamber method.

[0039] The typical composition of the cracked C5 fraction involved in this invention is shown in Table 1 below. Its specific components and contents may vary depending on the origin of the raw materials and the ethylene cracking process.

[0040] Table 1 Typical composition of cracked C5 fraction

[0041]

[0042]

[0043] The C5 olefin enrichment fraction A involved in this invention is derived from the components with boiling points of 55-75°C extracted by distillation of cracked C5. Its typical composition is shown in Table 2 below. Its specific components and contents may vary due to changes in the composition of cracked C5.

[0044] Table 2 Typical composition of C5 olefin-enriched fraction A

[0045]

[0046]

[0047] The emulsion explosive composite wax formulations used in the following embodiments and comparative examples of the present invention are shown in Table 3 below. The formulations and raw materials should not be limited to the following three types.

[0048] Table 3 Typical Formulation of Emulsion Explosive Composite Wax

[0049]

[0050] *Selection criteria for refined hydrogenated white oil: distillation range 180–230°C, Hazen color 15, kinematic viscosity (40°C) 60 mmHg. 2 / s, flash point 215℃, aromatic content ( 1 H-NMR) 1.55%.

[0051] Example 1

[0052] In a nitrogen-protected, stirred high-pressure reactor, 50% methylcyclohexane and 1.0% anhydrous aluminum trichloride (catalyst) were pre-added and thoroughly stirred. At 40°C, 49.0% C5 olefin enrichment fraction A (trace water content 85 ppm) was slowly added dropwise over 1.5 hours. After the addition was complete, the reaction was continued at 70°C for 2.0 hours to obtain polymerization solution B, which was then sent to a water washing device. Polymerization solution B was thoroughly mixed with water at a mass ratio of 1:7 and washed at 85°C for 1.0 hour to remove the catalyst. An oil-water mixture was obtained by adding an agent and then feeding it into an electrostatic desalting unit. 160 μg / g polyvinyl alcohol (PVA) was pre-added to the electrostatic desalting unit. The unit was operated at 120°C, with an electric field strength of 1500 V / cm and a residence time of 40 min to remove impurities. After standing and separation, the upper layer was collected to obtain polymer solution C. This polymer solution C was then fed into a distillation column and distilled under a vacuum of -0.090 MPa and a temperature of 240°C. The recovered solvent and unreacted components were obtained at the top of the column. The resulting resin solution D was dehydrated to 105 ppm using a molecular sieve packed column and then fed into a high-temperature melting tank.

[0053] In a melting tank, 0.5% DVB and 1.0% diethyl allyl phosphate (DEAP) by mass of the total material are added simultaneously. The mixture is heated to 175°C and reacted for 15 minutes. After granulation, a smoke-suppressing emulsion explosive composite wax resin with a softening point of 105°C, Gardner color number 4.0#, and hydroxyl value of 1.15 mgKOH / g is obtained.

[0054] The composition of the C5 fraction A is as follows: 1.5 wt% 1-pentene, 12.5 wt% isopentene, 6.0 wt% isoprene, 30.0 wt% 1,3-pentadiene, 1.5 wt% cyclopentadiene, 13.0 wt% cyclopentene, 1.0 wt% 1-hexene, and the remainder are C5-C6 saturated alkanes.

[0055] According to Formula 2 in Table 3 above, the emulsion explosive composite wax prepared has the following properties: dropping point 58.5℃, kinematic viscosity (100℃) 8.2mm. 2 / s, flash point 217℃, oxygen index OI 40.0%, maximum smoke density 84mg / L.

[0056] Examples 2-4

[0057] Examples 2-4 used C5 olefin enriched fraction A with different components as raw materials (see Table 4), and the remaining process conditions were the same as in Example 1. The properties of the resin for smoke-suppressing emulsion explosive composite wax and the properties of the composite wax are shown in Table 5.

[0058] Table 4. Main composition and content of C5 olefin enriched fraction A from Examples 2-4

[0059]

[0060] Table 5. Comparison of properties of resins and composite waxes for smoke-suppressing emulsion explosives prepared from different raw materials.

[0061]

[0062]

[0063] Comparative data from Tables 4 and 5 show that as the content of C5 olefin-enriched fraction A, such as 1-pentene, isopentene, and cyclopentene, increases, the softening point of the resin used in smoke-suppressing emulsion explosive composite wax decreases significantly. The dropping point, kinematic viscosity, and flash point of the emulsion explosive composite wax prepared using this resin as a raw material all show a decreasing trend. However, the use of different raw materials for the resin used in smoke-suppressing emulsion explosive composite wax does not significantly affect the oxygen index and maximum smoke density of the composite wax, indicating that the content of end-grafted allyl phosphate groups (corresponding to hydroxyl values) plays a key role in the above two indicators.

[0064] Examples 5-8, Comparative Example 1

[0065] In Examples 5-8, the composition and reaction conditions of the raw material C5 olefin enrichment fraction A were the same as in Example 3. The emulsion explosive composite wax was formulated as Formula 1. By adjusting the content of divinylbenzene (DVB) and diethyl allyl phosphate (DEAP), the properties of the modified C5 petroleum resin and composite wax are shown in Table 6 below.

[0066] Comparative Example 1: Resin liquid D was used without the addition of DVB during the grafting modification reaction, and the composite wax was also selected from Formulation 1.

[0067]

[0068]

[0069] As shown in the table above, increasing the DVB content during the copolymerization reaction of C5 resin with DVB and DEAP helps to increase the end-group grafting rate of allyl phosphate diester groups such as DEAP, thus improving the softening point, color number, and hydroxyl value of the modified resin. When no DVB is involved in the reaction (such as in Comparative Example 1), the hydroxyl value of the resin used for smoke-suppressing emulsion explosive composite wax decreases significantly, and the softening point does not improve significantly. Instead, the color number of the product is significantly improved because the ester groups are not fully reacted.

[0070] Comparing the properties of composite waxes prepared by resin compounding of different smoke-suppressing emulsion explosive composite waxes, the high hydroxyl value modified resin can obtain a higher oxygen index and its maximum smoke density index is also significantly reduced, indicating that the grafting of allyl phosphate diester groups helps to improve the overall smoke suppression performance of composite waxes.

[0071] The DEAP-grafted modified resin for smoke-suppressing emulsion explosive composite wax without DVB participation in the reaction (Comparative Example 1) is presumably due to its relatively large steric hindrance and more compact structure. At similar softening points, it has greater cohesive strength, which further affects its compatibility with emulsion explosive composite wax substrates such as microcrystalline wax and Fischer-Tropsch wax. For example, the dropping point and kinematic viscosity of composite waxes prepared with it as raw material are significantly increased, while the test data of oxygen index and maximum smoke density show that its overall smoke suppression ability is relatively weak.

[0072] Example 9

[0073] Example 9 uses the same raw material as Example 4, C5 olefin enrichment fraction A.

[0074] In a nitrogen-protected, stirred high-pressure reactor, 50% methylcyclohexane and 0.75% anhydrous aluminum trichloride were pre-added and thoroughly stirred. At 40°C, 49.0% C5 fraction A (with a trace water content of 50 ppm) was slowly added dropwise over 1.5 hours. After the addition was complete, the reaction continued at 70°C for 2.0 hours to obtain polymerization solution B, which was then sent to a water washing device. Polymerization solution B was thoroughly mixed with water at a mass ratio of 1:10 and washed at 85°C for 2.0 hours to remove the catalyst, yielding an oil-water mixture which was then sent to an electrostatic desalting device. 160 μg / g polyvinyl alcohol (PVA) was pre-added to the electrostatic desalting device. At an operating temperature of 120°C, an electric field strength of 2000 V / cm, and a residence time of 120 minutes, impurities were removed. The mixture was then allowed to stand and separate to obtain the upper polymerization solution C. Polymerization solution C had a solid content of 28.8% and a total chlorine content of 70 ppm.

[0075] The above polymer solution C is fed into a distillation column and distilled under a vacuum of -0.090 MPa and a temperature of 260°C. The recovered solvent and unreacted components are obtained at the top of the column. The resin solution D obtained from the bottom of the column is dehydrated to 100 ppm and then sent to a high-temperature melting tank.

[0076] In a melting tank, 0.5% DVB and 1.0% dimethyl allyl phosphate (DIAP) by mass of the total material are added simultaneously. The mixture is heated to 175°C and reacted for 15 minutes. After granulation, a smoke-suppressing emulsion explosive composite wax resin with a softening point of 92.0°C, Gardner color number 3.0#, and hydroxyl value of 1.14 mgKOH / g is obtained.

[0077] The properties of the emulsion explosive composite wax prepared according to Formula 3 are as follows: dropping point 58.6℃, kinematic viscosity (100℃) 7.3mm. 2 / s, flash point 208℃, oxygen index OI 39.5%, maximum smoke density 55mg / L.

[0078] Comparative Example 2

[0079] Comparative Example 2 used the same raw material as Example 4, C5 olefin enrichment fraction A.

[0080] In a nitrogen-protected, stirred high-pressure reactor, 50% methylcyclohexane and 2.0% anhydrous aluminum trichloride were pre-added and thoroughly stirred. At 40°C, 49.0% C5 fraction A (with a trace water content of 50 ppm) was slowly added dropwise over 1.5 hours. After the addition was complete, the reaction continued at 70°C for 2.0 hours to obtain polymerization solution B, which was then sent to a water washing device. Polymerization solution B was thoroughly mixed with water at a mass ratio of 1:3 and washed at 85°C for 0.5 hours to remove the catalyst, yielding an oil-water mixture which was then sent to an electrostatic desalting device. 160 μg / g polyvinyl alcohol (PVA) was pre-added to the electrostatic desalting device. At an operating temperature of 120°C, an electric field strength of 600 V / cm, and a residence time of 20 minutes, impurities were removed. The mixture was then allowed to stand and separate to obtain the upper polymerization solution C. Polymerization solution C had a solid content of 29.1% and a total chlorine content of 480 ppm.

[0081] The above-mentioned polymer solution C was fed into a distillation column and distilled under a vacuum of -0.090 MPa and a temperature of 260°C. The recovered solvent and unreacted components were obtained at the top of the column. The resin solution D obtained from the top of the column was dehydrated to 102 ppm and then sent to a high-temperature melting tank.

[0082] In a melting vessel, 0.5% DVB and 1.0% dimethyl allyl phosphate (DIAP) by mass of the total material are added simultaneously. The mixture is heated to 175°C and reacted for 15 minutes. After granulation, a smoke-suppressing emulsion explosive composite wax resin with a softening point of 91.5°C, Gardner color number 6.1#, and hydroxyl value of 1.08 mgKOH / g is obtained.

[0083] The properties of the emulsion explosive composite wax prepared according to Formula 3 are as follows: dropping point 59.0℃, kinematic viscosity (100℃) 7.2mm. 2 / s, flash point 207℃, oxygen index OI 41.5%, maximum smoke density 150mg / L.

[0084] Comparing Example 9 and Comparative Example 2, in the synthesis of resin for smoke-suppressing emulsion explosive composite wax, when the total chlorine content exceeds the standard due to differences in catalyst dosage and post-treatment process, the maximum smoke density index of the composite wax increases significantly. It is speculated that this is due to the combustion of excessive organic chlorine in the formulation. The oxygen index also increases slightly, which should be due to the increase of chlorine-containing groups, which partially improves the flame retardant properties of the composite wax.

[0085] Comparative Example 3

[0086] Comparative Example 3 used the same raw material as Example 4, C5 olefin enrichment fraction A.

[0087] In a nitrogen-protected, stirred high-pressure reactor, 50% methylcyclohexane and 0.75% anhydrous aluminum trichloride were pre-added and thoroughly stirred. At 40°C, 49.0% C5 fraction A (with a trace water content of 50 ppm) was slowly added dropwise over 1.5 hours. After the addition was complete, the reaction continued at 70°C for 2.0 hours to obtain polymerization solution B, which was then sent to a water washing device. Polymerization solution B was thoroughly mixed with water at a mass ratio of 1:10 and washed at 85°C for 2.0 hours to remove the catalyst, yielding an oil-water mixture which was then sent to an electrostatic desalting device. 160 μg / g polyvinyl alcohol (PVA) was pre-added to the electrostatic desalting device. At an operating temperature of 120°C, an electric field strength of 2000 V / cm, and a residence time of 120 minutes, impurities were removed. The mixture was then allowed to stand and separate to obtain the upper polymerization solution C. Polymerization solution C had a solid content of 30.1% and a total chlorine content of 76 ppm.

[0088] The above-mentioned polymer solution C was fed into a distillation column and distilled under a vacuum of -0.090 MPa and a temperature of 260°C. The recovered solvent and unreacted components were obtained at the top of the column. The resin solution D obtained from the bottom of the column was directly granulated to obtain unmodified C5 petroleum resin with a softening point of 88.0°C, Gardner color number 2.8#, and hydroxyl value of 0 mgKOH / g.

[0089] The properties of the emulsion explosive composite wax prepared according to Formula 3 are as follows: dropping point 57.5℃, kinematic viscosity (100℃) 7.0 mm. 2 / s, flash point 202℃, oxygen index OI 1.4%, maximum smoke density 270mg / L.

[0090] Compared with Example 9 and Comparative Example 3, the emulsion explosive composite wax prepared without DIAP and DVB graft modification of C5 petroleum resin has a high maximum smoke density and a low oxygen index, meaning its smoke suppression performance is significantly weakened. Conversely, the novel composite wax prepared by modifying the end groups of C5 petroleum resin with allyl phosphate groups has an oxygen index (OI) ≥ 35% and a maximum smoke density ≤ 100 mg / L, achieving a smoke suppression effect and improving the product's environmental friendliness and stability.

Claims

1. A method for preparing a resin for a smoke-suppressing emulsion explosive composite wax, comprising the following steps: (1) The cracked C5 fraction was extracted by distillation to obtain C5 olefin enrichment fraction A with a boiling point of 50–75 °C, and then dehydrated to below 150 ppm; among which, The composition of the C5 olefin enriched fraction A is as follows: 1-pentene 0.1–8.0 wt%, isopentene 0.1–15.0 wt%, isoprene 0.1–20.0 wt%, 1,3-pentadiene 0.1–50.0 wt%, cyclopentadiene 0.1–20.0 wt%, cyclopentene 0.1–15.0 wt%, 1-hexene 0.1–3.0 wt%, with the remainder being C5–C6 saturated alkanes; (2) In a high-pressure reactor with nitrogen protection and stirring, 40-60% of the total material mass of saturated cycloalkane solvent and 0.5-1.5% of anhydrous aluminum trichloride catalyst are placed in advance and stirred thoroughly. At a temperature of 0-75℃, 38.5-59.5% of the total material mass of C5 olefin enrichment fraction A is added dropwise. After the dropwise addition is completed, the reaction continues for 0.25-5.0 h to obtain polymer solution B. (3) The polymer solution B is sent to the water washing device. The polymer solution B and water are fully mixed at a mass ratio of 1: (3~10). The catalyst is removed by washing with water at 20~90℃ for 0.5~5.0 h. The oil-water mixture is sent to the electro-desalting device to remove free inorganic salts and other impurities in the polymer solution B. The mixture is allowed to stand and separate to obtain the upper layer to obtain the polymer solution C. (4) The polymer solution C is fed into a distillation column and distilled at a vacuum of -0.080 to -0.095 MPa and a temperature of 200 to 260°C. The recovered solvent and unreacted components are obtained at the top of the column, and the resin solution D is obtained at the bottom of the column. (5) After removing the water from the resin liquid D through a molecular sieve packed tower, it is sent to a melting tank. Then, 0.01-2.0% of divinylbenzene and 0.01-3.0% of allyl phosphate diester are added simultaneously. The mixture is heated to 150-250℃ and reacted for 5-30 minutes. After granulation, the resin for smoke-suppressing emulsion explosive composite wax is obtained.

2. The preparation method according to claim 1, characterized in that: The dehydration in step (1) is performed using low-nitrogen calcium hydride or molecular sieve dehydration; wherein the low-nitrogen calcium hydride has a purity ≥98.0% and a total nitrogen content ≤200 ppm; and the molecular sieve is 4 Å or 5 Å.

3. The preparation method according to claim 1, characterized in that: The saturated cycloalkane solvent in step (2) is one or more of cyclohexane, methylcyclohexane, and dimethylcyclohexane.

4. The preparation method according to claim 1, characterized in that: The operating conditions of the electro-desalting device in step (3) are as follows: polyvinyl alcohol demulsifier is added in advance at a dosage of 20-220 μg / g, the operating temperature is 60-150 ℃, the electric field strength is 400-2000 V / cm, and the residence time is 20-120 min.

5. The preparation method according to claim 1, characterized in that: The solid content of the polymerization liquid C in step (3) is 5-50%, and the total chlorine content is ≤300 ppm.

6. The preparation method according to claim 1, characterized in that: The softening point of the resin liquid D in step (4) is in the range of 80 to 130 °C.

7. The preparation method according to claim 1, characterized in that: In step (5), the resin solution D is dehydrated to ≤150 ppm.

8. The preparation method according to claim 1, characterized in that: The allyl phosphate diester in step (5) is one or more of allyl dimethyl phosphate, allyl diethyl phosphate, allyl dipropyl phosphate, allyl dibutyl phosphate, allyl dipentyl phosphate, allyl dihexyl phosphate, allyl diheptyl phosphate, and allyl dioctyl phosphate.

9. The preparation method according to claim 1, characterized in that: The resin for smoke-suppressing emulsion explosive composite wax obtained in step (5) has a softening point of 80-160 °C, a Gardner color number ≤6#, and a hydroxyl value of 0.1-10.0 mgKOH / g.

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