Asphalt-based preservative for anti-etching cement concrete and processing method of asphalt-based preservative

Abstract

The invention discloses an asphalt-based preservative for anti-etching cement concrete and a processing method of the asphalt-based preservative, belongs to the technical field, and aims to solve the technical problem that the improvement effect of the asphalt-based preservative on the corrosion resistance and wear resistance of concrete needs to be further improved in the prior art. The asphalt-based preservative specifically comprises the following raw materials in parts by weight: 40-60 parts of matrix asphalt, 8-10 parts of a composite binder and 15-21 parts of an auxiliary material, the composite binder is obtained by mixing the prepared phosphate-based binder and epoxy-based binder, and the asphalt-based preservative is obtained by mixing the asphalt, the composite binder and the auxiliary material. And the additive is used as an additive component of concrete, so that the erosion resistance and the mechanical property of the concrete are improved.

Description

Technical Field

[0001] The present invention relates to the technical field of preservative preparation, and in particular to an asphalt-based preservative for anti-corrosion cement concrete and a processing method thereof. Background Art

[0002] The development of asphalt-based preservatives for anti-corrosion cement concrete has evolved from traditional materials to high-performance composite systems. In the early days, they were mainly based on coal tar and natural asphalt, relying on their good hydrophobicity and adhesion to resist the penetration of corrosive media, but their durability and environmental performance were poor.

[0003] With the increase in engineering demand, modified asphalt technology was introduced in the late 20th century. By adding polymer materials such as SBS, epoxy resin, and polyurethane, the flexibility, chemical corrosion resistance and bonding strength were greatly improved. In the 21st century, environmental protection regulations promoted the trend of water-based asphalt, and emulsion-type asphalt-based preservatives gradually developed, taking into account both construction convenience and environmental friendliness. Current research focuses on composite modification, microstructure control, and service behavior simulation, striving to meet the long-term protection needs of concrete structures in complex environments.

[0004] For example, the prior art CN108249799B provides a concrete corrosion-resistant preservative, the raw materials of which are selected from colored tailings extracts. The colored tailings extracts contain amorphous silica, calcium oxide, aluminum oxide and rare metal oxides. The proportions of various substances in the colored tailings extracts are: 70-80% amorphous silica, 5-10% calcium oxide, 5-10% aluminum oxide, 5-8% rare metal oxides, and the rest are the remainder. The colored tailings extracts are ultrafine nano-scale particles with a particle size of 1 to 100 nm. The corrosion-resistant preservative is added to the concrete material at 5-20% of the weight of 1 part of cement, so that the corrosion-resistant preservative is evenly dispersed in the concrete, and after stirring and hydration reaction with cement, after solidification, a concrete structure with good corrosion resistance and durability is formed.

[0005] However, the above invention only mixes colored tailings slag extract into the concrete structure to improve the corrosion resistance of the concrete. However, the ultrafine nanoparticles are added to the concrete mainly to enhance the corrosion resistance through hydration reaction. Therefore, there is a lack of a chemical-physical composite protection system, resulting in weak hydrophobic mutual solubility and sulfate corrosion resistance, and a lack of toughness and efficient stress dispersion mechanism, resulting in the wear resistance and flexural resistance of the material need to be further improved. Summary of the Invention

[0006] The purpose of the present invention is to provide an asphalt-based preservative for anti-corrosion cement concrete and a processing method thereof, so as to solve the technical problem in the prior art that the effect of asphalt-based preservatives on the corrosion resistance and wear resistance of concrete needs to be further improved.

[0007] The object of the present invention can be achieved by the following technical solution: an asphalt-based preservative for anti-erosion cement concrete, comprising the following raw materials in parts by weight: 40-45 parts of base asphalt, 8-10 parts of composite binder and 15-21 parts of auxiliary materials;

[0008] The auxiliary materials include the following raw materials in parts by weight: 1-2 parts of anti-settling agent, 1-2 parts of leveling agent, 1-2 parts of toughening agent and 12-15 parts of solvent;

[0009] The composite adhesive is obtained by mixing a phosphate-based adhesive and an epoxy-based adhesive in a dosage ratio of 2-3 g:1 g.

[0010] Furthermore, the anti-settling agent is one or both of white carbon black and organic bentonite; the leveling agent is one or more of polyether modified silicone oil and dimethyl silicone oil; the toughening agent is styrene-butadiene rubber; and the solvent is one or both of terpineol, eucalyptus oil and xylene.

[0011] Furthermore, the preparation method of the phosphoric acid-based binder comprises the following steps:

[0012] A1. Add propyl orthosilicate and deionized water to a reactor, stir at room temperature for 10-12 minutes, add 30-40 wt% phosphoric acid solution to the reactor, adjust the pH of the system to 3-4, let it stand for 1-2 hours, and then post-treat to obtain oligomeric silicon phosphate;

[0013] A2. Aluminum dihydrogen phosphate, ferric phosphate and deionized water are added to a reactor, and the pH of the reaction system is adjusted to 8-9 using a saturated sodium hydroxide aqueous solution. The temperature of the reactor is raised to 60-80° C., and the reaction mixture is stirred at this temperature for 30-40 minutes. Then, oligomeric silicon phosphate and the modifying liquid are slowly added to the reactor, and the mixture is stirred at this temperature for 60-80 minutes. The reaction mixture is naturally cooled to room temperature, aged naturally for 24-28 hours, and then post-treated to obtain a phosphate-based binder.

[0014] The reaction principle for preparing the phosphate-based binder is as follows: propyl orthosilicate hydrolyzes under acidic conditions to form silanols, which react with phosphoric acid to form oligomeric silicon phosphate, building a siloxane-phosphate network structure to produce oligomeric silicon phosphate. Aluminum dihydrogen phosphate and ferric phosphate hydrolyze under alkaline conditions to form a phosphate matrix containing aluminum and iron. After the addition of the modifying liquid, the oligomeric silicon phosphate forms a stable composite network with the phosphate matrix through chemical bonding and cross-linking reactions. High-temperature stirring promotes cross-linking of the molecular chains, and the aging process stabilizes the structure, ultimately forming the phosphate-based binder.

[0015] Furthermore, in step A1, the ratio of propyl orthosilicate to deionized water is 10-12 g:30-36 mL, and the post-treatment includes: after the reactor is cooled to room temperature, the reaction solution is added to a rotary evaporator with a salt bath temperature of 80-100° C., and distilled under reduced pressure until no liquid is extracted to obtain oligomeric silicon phosphate;

[0016] Furthermore, in step A2, the amount ratio of aluminum dihydrogen phosphate, iron phosphate, deionized water, oligomeric silicon phosphate and modifying liquid is 6-8g:4-6g:50-60mL:8-10g:10-12mL, wherein the modifying liquid is obtained by mixing 3-aminopropyltrimethoxysilane and anhydrous ethanol in an amount ratio of 1-2g:10-12mL, and the post-treatment includes: after the reactor is cooled to room temperature, the reaction liquid is added to a rotary evaporator with a salt bath temperature of 80-100°C, and after reduced pressure distillation until no liquid is extracted, it is passed through a 200-300 mesh sieve to obtain a phosphate-based binder.

[0017] Furthermore, the preparation method of the epoxy adhesive comprises the following steps:

[0018] B1. Add 4,4'-(hexafluoroisopropylene) diphthalic anhydride, 4,6-triamino-1,3,5-triazine, triethylamine and N,N-dimethylformamide to a reactor, raise the temperature of the reactor to 40-60°C, keep the temperature for reaction for 1-2 hours, add hydrophobic particles to the reactor, keep the temperature for reaction for 20-40 minutes, and post-treat to obtain a binder precursor;

[0019] B2. Add the binder precursor and N,N-dimethylformamide into a low-temperature reactor. After the temperature of the low-temperature reactor is reduced to 20-25°C, add m-chloroperbenzoic acid into the reactor, keep the temperature for 8-10 hours, and then post-treat to obtain the epoxy binder.

[0020] The reaction equation for preparing epoxy adhesive is:

[0021]

[0022] Where: Indicates hydrophobic particles.

[0023] The reaction principle for preparing the epoxy adhesive is as follows: 4,4'-(hexafluoroisopropylene) diphthalic anhydride and 4,6-triamino-1,3,5-triazine undergo an amidation reaction at 40-60°C under the catalysis of N,N-dimethylformamide and triethylamine to generate a fluorine-containing aromatic amide structure. After the hydrophobic particles are added, the amino groups react with the blocked anhydride groups to act as chain extenders and dispersing carriers, forming a stable polymer precursor network to obtain an adhesive precursor. The adhesive precursor reacts with meta-chloroperbenzoic acid under low temperature conditions, and the peracid oxidizes the double bonds to generate epoxy groups, thereby finally preparing the epoxy adhesive.

[0024] Furthermore, in step B1, the amount ratio of 4,4'-(hexafluoroisopropylene) diphthalic anhydride, 4,6-triamino-1,3,5-triazine, triethylamine, N,N-dimethylformamide and hydrophobic particles is 4.0-4.4g:1.0g:0.1g:30mL:0.3-0.5g, and the post-treatment includes: after the reactor is cooled to room temperature, the reaction solution is added to a rotary evaporator with a salt bath temperature of 80-100°C, and distilled under reduced pressure until no liquid is extracted to obtain a binder precursor;

[0025] Furthermore, in step B2, the amount ratio of the binder precursor, N,N-dimethylformamide and m-chloroperbenzoic acid is 4-5g:20-25mL:0.5-0.7g, and the post-treatment includes: after the reactor is cooled to room temperature, the reaction liquid is added to a rotary evaporator with a salt bath temperature of 80-100°C, and distilled under reduced pressure until no liquid is extracted to obtain an epoxy binder.

[0026] Furthermore, the preparation method of the hydrophobic particles comprises the following steps:

[0027] C1. Add styrene, tetraethyl orthosilicate, sorbitan oleate, and potassium persulfate to a reactor, stir at 500-540 rpm for 8-10 minutes at room temperature, then add 0.5-0.8 wt% polyvinyl alcohol aqueous solution to the reactor while stirring, and continue stirring for 10-15 minutes to obtain a mixed solution;

[0028] C2. Add 1.0-1.2 wt% sodium lauryl sulfate aqueous solution to the reactor, stir at 500-540 rpm for 2-3 min at room temperature, add the mixed solution to the reactor under stirring, continue stirring for 10-15 min, stop stirring, adjust the pH of the reaction system to 8-10 with 25 wt% ammonia aqueous solution, raise the temperature of the reactor to 70-80° C., keep the reaction temperature for 2-3 h, and perform post-treatment to obtain hollow microparticles;

[0029] C3. Add the hollow microparticles, tridecafluorooctyltrimethoxysilane, 3-aminopropyltrimethoxysilane, anhydrous ethanol and deionized water into the reactor. After the temperature of the reactor is raised to 40-60°C, use a protective sodium hydroxide aqueous solution to adjust the pH of the reaction system to 8-10, continue to keep the reaction warm for 1-2 hours, and post-treat to obtain hydrophobic particles.

[0030] The reaction principle for preparing hydrophobic particles is as follows: styrene, tetraethyl orthosilicate and sorbitan oleate are initiated by potassium persulfate, and polyvinyl alcohol aqueous solution is used as a stabilizer to promote the formation of microemulsion to generate a uniformly dispersed mixed liquid, which provides a template basis for the subsequent formation of hollow microparticles. Sodium dodecyl sulfate is used as a surfactant to enhance the emulsification stability. The mixed liquid is polymerized under alkaline conditions, and styrene and tetraethyl orthosilicate are cross-linked and cured through free radical polymerization at high temperature. The polystyrene template structure is removed by dissolution to obtain hollow microparticles; further, the surface of the hollow microparticles is hydrolyzed and condensed by tridecafluorooctyltrimethoxysilane and 3-aminopropyltrimethoxysilane under alkaline conditions, and perfluoro groups and amino groups are grafted to obtain hydrophobic particles.

[0031] Furthermore, in step C1, the ratio of styrene, tetraethyl orthosilicate, sorbitan oleate, potassium persulfate and 0.5-0.8 wt % polyvinyl alcohol aqueous solution is 3-4 g: 3-4 g: 0.01 g: 0.02-0.03 g: 3-4 g;

[0032] Furthermore, in step C2, the ratio of the 1.0-1.2 wt% sodium lauryl sulfate aqueous solution to the mixed solution is 10 g:3-4 g, and the post-treatment includes: after the reaction is completed, after the temperature of the reactor is lowered to room temperature, the reaction liquid is filtered to collect the filter cake, the filter cake is transferred to an ultrasonic instrument with a dispersion medium of polytetrahydrofuran, ultrasonicated for 2-3 hours, the filter cake is filtered to collect, and washed with anhydrous ethanol and deionized water 3-5 times to obtain hollow microparticles;

[0033] Furthermore, in step C3, the amount ratio of the hollow particles, tridecafluorooctyltrimethoxysilane, 3-aminopropyltrimethoxysilane, anhydrous ethanol and deionized water is 2-3g:0.2-0.3g:0.1-0.2g:10-12mL:6-8mL, and the post-treatment includes: after the reaction is completed, after the temperature of the reactor is lowered to room temperature, the reaction liquid is filtered to collect the filter cake, the filter cake is washed 3-5 times with anhydrous ethanol and deionized water, and the filter cake is transferred to a drying oven at a temperature of 60-80°C and vacuum dried until the filter cake has a constant weight to obtain hydrophobic particles.

[0034] The present invention also proposes a processing method for an asphalt-based preservative for anti-corrosion cement concrete, comprising the steps of adding matrix asphalt to a vacuum stirring kettle, raising the temperature of the vacuum stirring kettle to 160-180°C, adding a composite binder to the vacuum stirring kettle, and maintaining the temperature and stirring for 20-30 minutes. Then, an anti-settling agent, a leveling agent, and a toughening agent are added. After maintaining the temperature and stirring for 10-15 minutes, the temperature of the vacuum stirring kettle is lowered to 60-80°C, and a solvent is added. After stopping heating and allowing the vacuum stirring kettle to cool naturally to room temperature, vacuum degassing is performed for 5-8 minutes to obtain the asphalt-based preservative.

[0035] The present invention has the following beneficial effects:

[0036] 1. The low surface energy of the perfluorinated groups on the surface of the hydrophobic particles prepared by the present invention effectively repels water molecules and blocks water penetration. The amino groups strengthen the bond between the particles and the epoxy binder through chemical bonding, forming a uniform and stable hydrophobic network. The mixing of the phosphate binder and the epoxy binder optimizes interfacial compatibility and ensures uniform distribution of the hydrophobic particles in the concrete matrix. The hydrophobic particles in the process act as chain extenders to further enhance the durability of the hydrophobic function, thereby significantly reducing the wettability of the concrete. The high chemical stability of the oligosilicon phosphate and phosphate in the phosphate binder is utilized to effectively resist corrosion and slow down the chemical reaction with calcium. The epoxy binder forms a dense cross-linked network through an oxidation process, which, in conjunction with the pore-filling effect of the hydrophobic particles, significantly reduces sulfate ion permeability. Ultimately, the phosphate group provides chemical protection, the epoxy group strengthens the physical barrier, and the hydrolysis template method and polymerization process ensure uniform distribution and structural stability of each component, thereby constructing an efficient protection system and comprehensively improving the hydrophobicity and erosion resistance of the concrete.

[0037] 2. The oligomeric silicon phosphate and phosphate in the phosphate-based binder prepared by the present invention have high hardness and chemical stability, forming a tough matrix that can effectively resist mechanical wear. The epoxy-based binder generates a dense cross-linked network through an oxidation process, which enhances the impact resistance and toughness of the concrete surface and reduces wear. The perfluoro groups and amino groups modified on the surface of the hydrophobic particles are tightly combined with the epoxy groups through chemical bonding, which improves the uniform dispersion and interfacial bonding strength of the particles in the matrix, forms a high-strength composite structure, and reduces surface wear. The hollow porous structure of the particles can absorb and disperse stress when subjected to force, reduce crack propagation, and further improve wear resistance. Finally, the complementary effect of the phosphate group and the epoxy group is utilized to enhance the overall mechanical properties. The phosphate group provides hardness support, and the epoxy group contributes to the toughness barrier. Through the combination of high-hardness matrix, tough network and stress dispersion mechanism, a wear-resistant composite system is constructed, which effectively improves the durability of concrete under friction and impact.

[0038] 3. The oligomeric silicon phosphate and phosphate in the phosphate-based binder prepared by the present invention have high hardness and chemical stability, forming a tough matrix that can effectively resist bending stress and inhibit crack initiation. The epoxy-based binder generates a dense cross-linked network through an oxidation process, which significantly enhances the toughness and tensile properties of the matrix, absorbs energy during bending, and delays crack propagation. The hydrophobic particles, the surface-modified perfluoro groups and amino groups are tightly combined with the epoxy groups through chemical bonding, which improves the uniform dispersion and interfacial bonding of the particles in the matrix, enhances the overall mechanical properties, and the hollow porous structure disperses stress when subjected to stress, reduces local stress concentration, and effectively improves the bending resistance. The phosphate group provides rigid support, the epoxy group enhances toughness, and the hydrophobic particles optimize stress distribution. The three work together to form a high-strength and tough composite system, enhance the integrity of the matrix, and ultimately significantly improve the bearing capacity and durability of concrete under bending loads through the combination of a rigid matrix, a tough network, and a stress dispersion mechanism. DETAILED DESCRIPTION

[0039] The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0040] The polyether-modified silicone oil used in the present invention was purchased from Yisheng Mall, product number 41008ES10;

[0041] The fly ash used in the present invention was purchased from Wuhan Jiyesheng Chemical Co., Ltd. with the item number A01085;

[0042] The matrix asphalt used in the present invention was purchased from Guangdong Wengjiang Chemical Reagent Co., Ltd. with the product number WB93918;

[0043] The fine aggregate used in the present invention is obtained by passing natural river sand through a 40-60 mesh sieve, and the coarse aggregate used in the present invention is building crushed stone with a particle size of 4.0-5.0 mm;

[0044] The cement used in the present invention was purchased from Jiaozuo Qianye Cement Co., Ltd., and the model is P.O42.5 Portland cement;

[0045] The polycarboxylate water-reducing agent used in the present invention was purchased from Guangdong Wengjiang Chemical Reagent Co., Ltd. with the product number PA96208.

[0046] The organobentonite used in the present invention was purchased from Guangdong Wengjiang Chemical Reagent Co., Ltd., with the product number PA88764-500g;

[0047] The hydroxypropyl methylcellulose ether used in the present invention was purchased from Shanghai Yuanye Biotechnology Co., Ltd., with the product number S25213-250g;

[0048] The styrene-butadiene rubber used in the present invention was purchased from Shanghai Jiadeer Chemical Technology Co., Ltd. with the product number JD191122165504.

[0049] The sorbitan oleate used in the present invention was purchased from Tianjin Xiens Biochemical Technology Co., Ltd. with the product number S-0449256+100ml.

[0050] Example 1

[0051] This embodiment provides a method for preparing a phosphate-based binder for use in processing an asphalt-based preservative for anti-corrosion cement concrete, comprising the following steps:

[0052] Step ①: Preparation of oligomeric silicon phosphate

[0053] 100.0 g of propyl orthosilicate and 300.0 mL of deionized water were weighed and added to a reactor. After stirring at room temperature for 10 min, 30 wt % phosphoric acid solution was added to the reactor. After adjusting the pH of the system to 3, the reactor was allowed to stand for 1 h. After the reactor was cooled to room temperature, the reaction solution was added to a rotary evaporator with a salt bath temperature of 80° C. and distilled under reduced pressure until no liquid was recovered to obtain oligomeric silicon phosphate.

[0054] Step 2: Preparation of phosphate-based binder

[0055] Weigh: 10.0 g of 3-aminopropyltrimethoxysilane and 100.0 mL of anhydrous ethanol and mix to obtain a modified solution;

[0056] Weigh: 60.0g of aluminum dihydrogen phosphate, 40.0g of ferric phosphate and 500.0mL of deionized water were added to the reactor, and the pH of the reaction system was adjusted to 8 with saturated sodium hydroxide aqueous solution. The temperature of the reactor was raised to 60°C, and after stirring for 30 minutes, 80.0g of oligomeric silicon phosphate and 100.0mL of the modified liquid were slowly added to the reactor, stirred for 60 minutes, naturally cooled to room temperature, and aged naturally for 24 hours. After the reactor was cooled to room temperature, the reaction solution was added to a rotary evaporator with a salt bath temperature of 80°C, and distilled under reduced pressure until no liquid was extracted, and then passed through a 200-mesh sieve to obtain a phosphate-based binder.

[0057] Example 2

[0058] This embodiment provides a method for preparing a phosphate-based binder for use in processing an asphalt-based preservative for anti-corrosion cement concrete, comprising the following steps:

[0059] Step ①: Preparation of oligomeric silicon phosphate

[0060] 120.0 g of propyl orthosilicate and 360.0 mL of deionized water were weighed and added to a reactor. After stirring at room temperature for 12 minutes, 40 wt % phosphoric acid solution was added to the reactor. After adjusting the pH of the system to 4, the reactor was allowed to stand for 2 hours. After the reactor was cooled to room temperature, the reaction solution was added to a rotary evaporator with a salt bath temperature of 100° C. and distilled under reduced pressure until no liquid was recovered to obtain oligomeric silicon phosphate.

[0061] Step 2: Preparation of phosphate-based binder

[0062] Weigh 20.0 g of 3-aminopropyltrimethoxysilane and mix with 120.0 mL of anhydrous ethanol to obtain a modified solution;

[0063] Weigh: 80.0g of aluminum dihydrogen phosphate, 60.0g of ferric phosphate and 600.0mL of deionized water were added to the reactor, and the pH of the reaction system was adjusted to 9 with a saturated sodium hydroxide aqueous solution. The temperature of the reactor was raised to 80°C, and after stirring for 40 minutes, 100.0g of oligomeric silicon phosphate and 120.0mL of the modified liquid were slowly added to the reactor, stirred for 80 minutes, naturally cooled to room temperature, and naturally aged for 28 hours. After the reactor was cooled to room temperature, the reaction solution was added to a rotary evaporator with a salt bath temperature of 100°C, and distilled under reduced pressure until no liquid was extracted, and then passed through a 300-mesh sieve to obtain a phosphate-based binder.

[0064] Example 3

[0065] This embodiment provides a method for preparing a phosphate-based binder for use in processing an asphalt-based preservative for anti-corrosion cement concrete, comprising the following steps:

[0066] Step ①: Preparation of oligomeric silicon phosphate

[0067] 120.0 g of propyl orthosilicate and 320.0 mL of deionized water were weighed and added to a reactor. After stirring at room temperature for 12 minutes, 36 wt % phosphoric acid solution was added to the reactor. After adjusting the pH of the system to 3, the reactor was allowed to stand for 2 hours. After the reactor was cooled to room temperature, the reaction solution was added to a rotary evaporator with a salt bath temperature of 90° C. and distilled under reduced pressure until no liquid was recovered to obtain oligomeric silicon phosphate.

[0068] Step 2: Preparation of phosphate-based binder

[0069] Weigh 16.0 g of 3-aminopropyltrimethoxysilane and 120.0 mL of anhydrous ethanol to obtain a modified solution.

[0070] Weigh: 72.0g of aluminum dihydrogen phosphate, 50.0g of ferric phosphate and 540.0mL of deionized water were added to the reactor, and the pH of the reaction system was adjusted to 9 with a saturated sodium hydroxide aqueous solution. The temperature of the reactor was raised to 70°C, and after stirring for 36 minutes, 90.0g of oligomeric silicon phosphate and 120.0mL of the modified liquid were slowly added to the reactor, stirred for 70 minutes, naturally cooled to room temperature, and naturally aged for 28 hours. After the reactor was cooled to room temperature, the reaction solution was added to a rotary evaporator with a salt bath temperature of 90°C, and distilled under reduced pressure until no liquid was extracted, and then passed through a 250-mesh sieve to obtain a phosphate-based binder.

[0071] Example 4

[0072] This embodiment provides a method for preparing hydrophobic particles for processing asphalt-based preservatives for anti-corrosion cement concrete, comprising the following steps:

[0073] Step I: Preparation of mixed solution

[0074] 30.0 g of styrene, 30.0 g of ethyl orthosilicate, 0.1 g of sorbitan oleate, and 0.2 g of potassium persulfate were weighed and added to a reactor. The mixture was stirred at 500 rpm at room temperature for 8 min. Then, 30.0 g of a 0.5 wt% aqueous solution of polyvinyl alcohol was added to the reactor while stirring. The mixture was further stirred for 10 min to obtain a mixed solution.

[0075] Step II: Preparation of hollow microparticles

[0076] Weigh: 100.0g 1.0wt% sodium lauryl sulfate aqueous solution was added to the reactor, stirred at 500rpm for 2min at room temperature, and then 30.0g of the mixed solution was added to the reactor under stirring. After stirring for 10min, stirring was stopped, and the pH of the reaction system was adjusted to 8 using 25wt% ammonia solution. The reactor temperature was raised to 70°C and kept warm for 2h. After the reaction was completed, the reactor temperature was lowered to room temperature, the reaction liquid was filtered to collect the filter cake, and the filter cake was transferred to an ultrasonic instrument with a dispersion medium of polytetrahydrofuran, ultrasonicated for 2h, and the filter cake was collected by filtration and washed 3 times with anhydrous ethanol and deionized water to obtain hollow microparticles.

[0077] Step III: Preparation of hydrophobic particles

[0078] Weigh: 20.0g hollow microparticles, 2.0g tridecafluorooctyltrimethoxysilane, 1.0g 3-aminopropyltrimethoxysilane, 100.0mL anhydrous ethanol and 60.0mL deionized water and add them to the reactor. After the temperature of the reactor is raised to 40°C, the pH of the reaction system is adjusted to 8 using a protective sodium hydroxide aqueous solution, and the reaction is continued for 1h. After the reaction is completed, the temperature of the reactor is lowered to room temperature, the reaction liquid is filtered to collect the filter cake, and the filter cake is washed 3 times with anhydrous ethanol and deionized water. The filter cake is transferred to a drying oven at a temperature of 60°C and vacuum dried until the filter cake has a constant weight to obtain hydrophobic particles.

[0079] Example 5

[0080] This embodiment provides a method for preparing hydrophobic particles for processing asphalt-based preservatives for anti-corrosion cement concrete, comprising the following steps:

[0081] Step I: Preparation of mixed solution

[0082] 40.0 g of styrene, 40.0 g of ethyl orthosilicate, 0.1 g of sorbitan oleate, and 0.3 g of potassium persulfate were weighed and added to a reactor. The mixture was stirred at 540 rpm at room temperature for 10 min. Then, 40.0 g of a 0.8 wt% aqueous solution of polyvinyl alcohol was added to the reactor while stirring. The mixture was further stirred for 15 min to obtain a mixed solution.

[0083] Step II: Preparation of hollow microparticles

[0084] Weigh: 100.0g 1.2wt% sodium lauryl sulfate aqueous solution was added to the reactor, stirred at 540rpm for 3min at room temperature, and then 40.0g of the mixed solution was added to the reactor under stirring. After stirring for 15min, stirring was stopped, and the pH of the reaction system was adjusted to 10 with 25wt% ammonia solution. The reactor temperature was raised to 80°C and kept warm for 3h. After the reaction was completed, the reactor temperature was lowered to room temperature, the reaction liquid was filtered to collect the filter cake, and the filter cake was transferred to an ultrasonic instrument with a dispersion medium of polytetrahydrofuran, ultrasonicated for 3h, and the filter cake was collected by filtration and washed 5 times with anhydrous ethanol and deionized water to obtain hollow microparticles.

[0085] Step III: Preparation of hydrophobic particles

[0086] Weigh: 30.0 g hollow microparticles, 3.0 g tridecafluorooctyltrimethoxysilane, 2.0 g 3-aminopropyltrimethoxysilane, 120.0 mL anhydrous ethanol and 80.0 mL deionized water and add them to the reactor. After the temperature of the reactor is raised to 60 ° C, the pH of the reaction system is adjusted to 10 using a protective sodium hydroxide aqueous solution, and the reaction is continued for 2 hours. After the reaction is completed, the temperature of the reactor is lowered to room temperature, the reaction liquid is filtered to collect the filter cake, and the filter cake is washed 5 times with anhydrous ethanol and deionized water. The filter cake is transferred to a drying oven at a temperature of 70 ° C and vacuum dried until the filter cake has a constant weight to obtain hydrophobic particles.

[0087] Example 6

[0088] This embodiment provides a method for preparing hydrophobic particles for processing asphalt-based preservatives for anti-corrosion cement concrete, comprising the following steps:

[0089] Step I: Preparation of mixed solution

[0090] 36.0 g of styrene, 36.0 g of ethyl orthosilicate, 0.1 g of sorbitan oleate, and 0.3 g of potassium persulfate were weighed and added to a reactor. The mixture was stirred at 520 rpm at room temperature for 9 minutes. Then, 40.0 g of a 0.6 wt% aqueous solution of polyvinyl alcohol was added to the reactor while stirring. The mixture was stirred for 12 minutes to obtain a mixed solution.

[0091] Step II: Preparation of hollow microparticles

[0092] Weigh: 100.0g 1.2wt% sodium lauryl sulfate aqueous solution was added to the reactor, stirred at 520rpm for 3min at room temperature, and then 36.0g of the mixed solution was added to the reactor under stirring. After stirring for 12min, stirring was stopped, and the pH of the reaction system was adjusted to 9 with 25wt% ammonia solution. The reactor temperature was raised to 75°C and kept warm for 3h. After the reaction was completed, the reactor temperature was lowered to room temperature, the reaction liquid was filtered to collect the filter cake, and the filter cake was transferred to an ultrasonic instrument with a dispersion medium of polytetrahydrofuran, ultrasonicated for 3h, and the filter cake was collected by filtration and washed 4 times with anhydrous ethanol and deionized water to obtain hollow microparticles.

[0093] Step III: Preparation of hydrophobic particles

[0094] Weigh: 25.0g hollow microparticles, 3.0g tridecafluorooctyltrimethoxysilane, 2.0g 3-aminopropyltrimethoxysilane, 120.0mL anhydrous ethanol and 60.0mL deionized water and add them to the reactor. After the temperature of the reactor is raised to 50°C, the pH of the reaction system is adjusted to 9 using a protective sodium hydroxide aqueous solution, and the reaction is continued for 2h. After the reaction is completed, the temperature of the reactor is lowered to room temperature, the reaction liquid is filtered to collect the filter cake, and the filter cake is washed 4 times with anhydrous ethanol and deionized water. The filter cake is transferred to a drying oven at a temperature of 70°C and vacuum dried until the filter cake has a constant weight to obtain hydrophobic particles.

[0095] Example 7

[0096] This embodiment provides a method for preparing an epoxy-based binder for processing an asphalt-based preservative for anti-corrosion cement concrete, comprising the following steps:

[0097] Step (i) Preparation of binder precursor

[0098] Weigh: 40.0g 4,4'-(hexafluoroisopropylene) diphthalic anhydride, 10.0g 4,6-triamino-1,3,5-triazine, 1.0g triethylamine and 300.0mL N,N-dimethylformamide were added to the reactor, the reactor temperature was raised to 40°C, and the reaction was kept warm for 1 hour. Then, 3.0g of the hydrophobic particles prepared in Example 4 were added to the reactor, and the reaction was kept warm for 20 minutes. After the reactor was cooled to room temperature, the reaction solution was added to a rotary evaporator with a salt bath temperature of 80°C, and distilled under reduced pressure until no liquid was extracted to obtain a binder precursor.

[0099] Step (ii): Preparation of epoxy adhesive

[0100] Weigh: 40.0g of binder precursor and 200.0mL of N,N-dimethylformamide are added to a low-temperature reactor. After the temperature of the low-temperature reactor is reduced to 20°C, 6.0g of m-chloroperbenzoic acid is added to the reactor and the reaction is kept warm for 8 hours. After the reactor is cooled to room temperature, the reaction liquid is added to a rotary evaporator with a salt bath temperature of 80°C, and distilled under reduced pressure until no liquid is extracted to obtain an epoxy binder.

[0101] Example 8

[0102] This embodiment provides a method for preparing an epoxy-based binder for processing an asphalt-based preservative for anti-corrosion cement concrete, comprising the following steps:

[0103] Step (i) Preparation of binder precursor

[0104] Weigh: 44.0g 4,4'-(hexafluoroisopropylene) diphthalic anhydride, 10.0g 4,6-triamino-1,3,5-triazine, 1.0g triethylamine and 300.0mL N,N-dimethylformamide were added to the reactor, the reactor temperature was raised to 60°C, and the reaction was kept warm for 2h. Then, 5.0g of the hydrophobic particles prepared in Example 5 were added to the reactor, and the reaction was kept warm for 40min. After the reactor was cooled to room temperature, the reaction solution was added to a rotary evaporator with a salt bath temperature of 100°C, and distilled under reduced pressure until no liquid was extracted to obtain a binder precursor.

[0105] Step (ii): Preparation of epoxy adhesive

[0106] Weigh: 50.0g of binder precursor and 250.0mL of N,N-dimethylformamide are added to a low-temperature reactor. After the temperature of the low-temperature reactor is reduced to 25°C, 7.0g of m-chloroperbenzoic acid is added to the reactor and the reaction is kept warm for 10 hours. After the reactor is cooled to room temperature, the reaction liquid is added to a rotary evaporator with a salt bath temperature of 100°C, and distilled under reduced pressure until no liquid is extracted to obtain an epoxy binder.

[0107] Example 9

[0108] This embodiment provides a method for preparing an epoxy-based binder for processing an asphalt-based preservative for anti-corrosion cement concrete, comprising the following steps:

[0109] Step (i) Preparation of binder precursor

[0110] Weigh: 42.0g 4,4'-(hexafluoroisopropylene) diphthalic anhydride, 10.0g 4,6-triamino-1,3,5-triazine, 1.0g triethylamine and 300.0mL N,N-dimethylformamide were added to the reactor, the reactor temperature was raised to 50°C, and the reaction was kept warm for 2h. Then, 4.0g of the hydrophobic particles prepared in Example 6 were added to the reactor, and the reaction was kept warm for 30min. After the reactor was cooled to room temperature, the reaction solution was added to a rotary evaporator with a salt bath temperature of 90°C, and distilled under reduced pressure until no liquid was extracted to obtain a binder precursor.

[0111] Step (ii): Preparation of epoxy adhesive

[0112] Weigh: 45.0g of binder precursor and 240.0mL of N,N-dimethylformamide are added to a low-temperature reactor. After the temperature of the low-temperature reactor is reduced to 22°C, 6.0g of m-chloroperbenzoic acid is added to the reactor and the reaction is kept warm for 9 hours. After the reactor is cooled to room temperature, the reaction liquid is added to a rotary evaporator with a salt bath temperature of 90°C, and distilled under reduced pressure until no liquid is extracted to obtain an epoxy binder.

[0113] Example 10

[0114] This embodiment provides a method for processing an asphalt-based preservative for anti-corrosion cement concrete, comprising the following steps:

[0115] Step 1: Preparation of composite adhesive

[0116] Weigh 20.0 g of the phosphate-based adhesive prepared in Example 1 and 10.0 g of the epoxy-based adhesive prepared in Example 7 and mix them to obtain a composite adhesive.

[0117] Step 2: Preparation of asphalt-based preservative

[0118] Weigh: 40 parts of matrix asphalt are added to a vacuum stirring kettle. After the temperature of the vacuum stirring kettle is raised to 160°C, 8 parts of composite binder are added to the vacuum stirring kettle. After keeping warm and stirring for 20 minutes, 1 part of organic bentonite, 1 part of polyether modified silicone oil and 1 part of styrene-butadiene rubber are added. After keeping warm and stirring for 10 minutes, the temperature of the vacuum stirring kettle is lowered to 60°C, and 12 parts of xylene are added. Stop heating and wait for the vacuum stirring kettle to cool naturally to room temperature. Vacuum degassing for 5 minutes to obtain an asphalt-based preservative.

[0119] Example 11

[0120] This embodiment provides a method for processing an asphalt-based preservative for anti-corrosion cement concrete, comprising the following steps:

[0121] Step 1: Preparation of composite adhesive

[0122] Weigh 30.0 g of the phosphate-based adhesive prepared in Example 2 and 10.0 g of the epoxy-based adhesive prepared in Example 8 and mix them to obtain a composite adhesive.

[0123] Step 2: Preparation of asphalt-based preservative

[0124] Weigh: 45 parts of matrix asphalt are added to a vacuum stirring kettle. After the temperature of the vacuum stirring kettle is raised to 180°C, 10 parts of composite binder are added to the vacuum stirring kettle. After keeping warm and stirring for 30 minutes, 2 parts of organic bentonite, 2 parts of polyether modified silicone oil and 2 parts of styrene-butadiene rubber are added. After keeping warm and stirring for 15 minutes, the temperature of the vacuum stirring kettle is lowered to 80°C, and 15 parts of xylene are added. Stop heating and wait for the vacuum stirring kettle to cool naturally to room temperature. Vacuum degassing for 8 minutes to obtain an asphalt-based preservative.

[0125] Example 12

[0126] This embodiment provides a method for processing an asphalt-based preservative for anti-corrosion cement concrete, comprising the following steps:

[0127] Step 1: Preparation of composite adhesive

[0128] Weigh 25.0 g of the phosphate-based adhesive prepared in Example 3 and 10.0 g of the epoxy-based adhesive prepared in Example 9 and mix them to obtain a composite adhesive.

[0129] Step 2: Preparation of asphalt-based preservative

[0130] Weigh: 42 parts of matrix asphalt are added to a vacuum stirring kettle. After the temperature of the vacuum stirring kettle is raised to 170°C, 10 parts of composite binder are added to the vacuum stirring kettle. After keeping warm and stirring for 30 minutes, 1 part of organic bentonite, 2 parts of polyether modified silicone oil and 1 part of styrene-butadiene rubber are added. After keeping warm and stirring for 12 minutes, the temperature of the vacuum stirring kettle is lowered to 70°C, and 15 parts of xylene are added. Stop heating and wait for the vacuum stirring kettle to cool naturally to room temperature. Vacuum degassing for 6 minutes to obtain an asphalt-based preservative.

[0131] Comparative Example 1

[0132] The difference between this comparative example and Example 12 is that the use of the phosphate-based binder is omitted in step 1.

[0133] Comparative Example 2

[0134] The difference between this comparative example and Example 12 is that the epoxy adhesive used in step 1 is prepared without using hydrophobic particles.

[0135] Comparative Example 3

[0136] The difference between this comparative example and Example 12 is that the epoxy adhesive is not used in step 1.

[0137] Performance testing:

[0138] Weigh and mix 300.0 g of deionized water, 12.0 g of polycarboxylate water reducer, and 5.0 g of hydroxypropyl methylcellulose ether to obtain an adjuvant;

[0139] Weigh by weight: 60 parts of fine aggregate, 10 parts of fly ash and 30 parts of cement are placed in a stirring tank and mixed evenly. 100 parts of coarse aggregate are added and stirred for 5 minutes. Then, 12 parts of the asphalt-based preservative prepared in Examples 10-12 or Comparative Examples 1-3 and 10 parts of an adjuvant are added and stirred for 8 minutes to obtain a concrete precursor. The concrete precursor is transferred to a mold, and the mold is transferred to a vibration table and vibrated for 2 minutes. The raised parts of the surface are flattened with a scraper and the surface of the material is covered with plastic wrap. The mold is transferred to a standard curing box with a temperature of 25° C. and a humidity of 95%. After constant temperature and humidity curing for 24 hours, the mold is demolded, soaked in room temperature water for 24 hours, and dried to obtain corrosion-resistant concrete.

[0140] The flexural strength and abrasion resistance of the erosion-resistant concrete prepared using the asphalt-based preservatives prepared in Examples 10-12 and Comparative Examples 1-3 were tested after 28 days of solidification in accordance with the standard GB / T 50081-2019 "Standard for Test Methods for Physical and Mechanical Properties of Concrete";

[0141] The sulfate erosion resistance of the erosion-resistant concrete prepared using the asphalt-based preservatives prepared in Examples 10-12 and Comparative Examples 1-3 after 28 days of solidification was tested with reference to the standard GB / T 50082-2024 "Standard for Test Methods for Long-term Performance and Durability of Concrete";

[0142] The water absorption rate of the erosion-resistant concrete prepared using the asphalt-based preservatives prepared in Examples 10-12 and Comparative Examples 1-3 was measured with reference to the standard JTG 3432-2024 "Test Procedures for Aggregates in Highway Engineering". Specific data are shown in Table 1.

[0143] Table 1 - Performance test data of each sample

[0144]

[0145] Data Analysis:

[0146] After comparing and analyzing the data in Table 1, it can be found that the flexural strength of the concrete prepared using the asphalt-based preservative prepared by the present invention is 14.58 MPa, and the abrasion loss after 45 cycles is 1.06 kg·m 2 , the sulfate resistance grade is KS150 and the water absorption rate is 3.1%, all the data are better than the comparative example;

[0147] After comparing and analyzing the data in Table 1, it can be found that the concrete prepared using the asphalt-based preservatives prepared in Comparative Examples 1-3 has significantly lower hydrophobic and corrosion resistance than the concrete prepared using the asphalt-based preservative prepared in Example 12, indicating that:

[0148] Comparative Example 1 lacks a phosphate-based binder, and oligomeric silicon phosphate cannot optimize the interfacial compatibility between the epoxy groups and the hydrophobic particles, resulting in uneven particle dispersion, unstable hydrophobic network, weakened hydrophobic effect of perfluoro groups, and increased concrete wettability. Furthermore, the chemical stability of the phosphate is lost, sulfate attack is aggravated, and calcium reactions are accelerated. Although the epoxy groups and hydrophobic particles provide a physical barrier, they lack chemical protection. Ion permeability is high, and the hydrophobicity and sulfate resistance are significantly lower than those of Example 12.

[0149] Comparative Example 2 lacks hydrophobic particles, and the hydrophobic function of perfluoro groups and amino groups is lost, resulting in increased wettability of the concrete surface and failure to form a hydrophobic network. Although the phosphate and epoxy groups provide compatibility, there is no low surface energy layer, resulting in severe water penetration. Furthermore, the hollow porous structure is missing, and the sulfate ion diffusion channel is not restricted, resulting in increased permeability. The chemical stability of the phosphate group cannot be fully exerted, and the sulfate resistance performance is reduced. The overall performance is far lower than that of Example 12.

[0150] Comparative Example 3 lacks epoxy binder and hydrophobic particles, resulting in the loss of hydrophobic functions of perfluoro groups and amino groups, significantly increasing the wettability of the concrete surface. Without a hydrophobic network, the chemical stability of the phosphate group alone cannot form a physical barrier. Sulfate ion permeability is high, diffusion channels are not restricted, and calcium reactions are accelerated. The hydrophobicity and sulfate resistance are the worst, far lower than those of Example 12.

[0151] After comparing and analyzing the data in Table 1, it can be found that the wear resistance of the concrete prepared using the asphalt-based preservatives prepared in Comparative Examples 1-3 is significantly reduced compared to the concrete prepared using the asphalt-based preservative prepared in Example 12, indicating that:

[0152] Comparative Example 1 lacks a phosphate-based binder, and the high-hardness matrix of oligosilicon phosphate is missing, resulting in a decrease in the surface hardness of the concrete and making it susceptible to mechanical wear. The concrete relies solely on the epoxy group to provide toughness, and the hydrophobic particles disperse the stress. However, the rigid support of the phosphate group is lacking, resulting in insufficient interfacial bonding strength. Particle agglomeration leads to stress concentration, accelerated crack propagation, and significantly lower wear resistance than Example 12.

[0153] Comparative Example 2 lacks hydrophobic particles and a hollow porous structure, resulting in a weakened material's ability to disperse stress. Cracks easily form on the concrete surface. Hardness is provided solely by the phosphate groups, while toughness is enhanced by the epoxy groups. However, without the interfacial reinforcement and stress absorption provided by the particles, the matrix bonding strength is insufficient, crack propagation accelerates during wear, and wear resistance is significantly reduced compared to Example 12.

[0154] Comparative Example 3 does not contain epoxy binders and hydrophobic particles, and the toughness network and stress dispersion structure are missing. The concrete surface has poor impact resistance and is susceptible to wear. It relies solely on the phosphate group to provide hardness, lacks toughness and interface strengthening, has insufficient matrix bonding, and cracks propagate rapidly. The wear resistance is much lower than that of Example 12.

[0155] After comparing and analyzing the data in Table 1, it can be found that the concrete prepared using the asphalt-based preservatives prepared in Comparative Examples 1-3 has significantly lower flexural properties than the concrete prepared using the asphalt-based preservative prepared in Example 12, indicating that:

[0156] Comparative Example 1 lacks a phosphate-based binder, resulting in a lack of the rigid matrix of oligomeric silicon phosphate, which reduces the concrete's ability to resist bending stress. Although the epoxy groups provide toughness and the hydrophobic particles disperse stress, the lack of phosphate-based hardness support leads to poor interfacial compatibility, uneven particle dispersion, increased stress concentration, accelerated crack growth, and significantly lower flexural strength than Example 12.

[0157] Comparative Example 2 lacks hydrophobic particles, lacks a hollow porous structure, and has a reduced stress dispersion capability, making the concrete susceptible to stress concentration. Although the phosphate groups provide rigidity and the epoxy groups provide toughness, the lack of particle interface reinforcement weakens the matrix integrity, accelerates crack propagation, and results in a significantly lower flexural strength than Example 12.

[0158] Comparative Example 3 does not contain epoxy binders and hydrophobic particles, and the toughness network and stress dispersion mechanism are missing. The tensile properties of the concrete are reduced and it is easy to break under bending stress. It relies only on the phosphate group to provide rigidity, lacks toughness and interface reinforcement, the matrix integrity is insufficient, stress concentration is serious, crack propagation is accelerated, and the flexural strength is much lower than that of Example 12.

[0159] Finally, it is explained that this solution achieves excellent hydrophobic, sulfate-resistant, wear-resistant and flexural properties of concrete through the synergistic effect of phosphate-based binders, epoxy-based binders and hydrophobic particles, combined with the hydrolysis template method and polymerization process; comparative analysis shows that the lack of any component leads to a significant decline in performance: without phosphate groups, the interface compatibility and hardness are insufficient; without hydrophobic particles, the hydrophobic function and stress dispersion are lost; without epoxy groups and hydrophobic particles, the toughness and physical barrier are lost. Each material and modification step complement each other and are indispensable to jointly construct a composite system of chemical stability and physical protection to ensure comprehensive performance improvement.

[0160] The preferred embodiments of the present invention disclosed above are intended only to help illustrate the present invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the present invention to specific embodiments. Obviously, many modifications and variations are possible based on the contents of this specification. These embodiments are selected and described in detail in this specification to better explain the principles and practical applications of the present invention, thereby enabling those skilled in the art to better understand and utilize the present invention. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. An asphalt-based preservative for anti-corrosion cement concrete, characterized in that: The raw material composition includes the following parts by weight: 40-60 parts of base asphalt, 8-10 parts of composite binder and 15-21 parts of auxiliary materials; The auxiliary materials include the following raw materials in parts by weight: 1-2 parts of anti-settling agent, 1-2 parts of leveling agent, 1-2 parts of toughening agent and 12-15 parts of solvent; The composite adhesive is obtained by mixing a phosphate-based adhesive and an epoxy-based adhesive in a dosage ratio of 2-3 g:1 g.

2. The asphalt-based preservative for anti-corrosion cement concrete according to claim 1, characterized in that: The preparation method of the phosphate-based binder comprises the following steps: A1. Add propyl orthosilicate and deionized water to a reactor, stir at room temperature for 10-12 minutes, add 30-40 wt% phosphoric acid solution to the reactor, adjust the pH of the system to 3-4, let it stand for 1-2 hours, and then post-treat to obtain oligomeric silicon phosphate; A2. Aluminum dihydrogen phosphate, ferric phosphate and deionized water are added to a reactor, and the pH of the reaction system is adjusted to 8-9 using a saturated sodium hydroxide aqueous solution. The temperature of the reactor is raised to 60-80° C., and the reaction mixture is stirred at this temperature for 30-40 minutes. Then, oligomeric silicon phosphate and the modifying liquid are slowly added to the reactor, and the mixture is stirred at this temperature for 60-80 minutes. The reaction mixture is naturally cooled to room temperature, aged naturally for 24-28 hours, and then post-treated to obtain a phosphate-based binder.

3. The asphalt-based preservative for anti-corrosion cement concrete according to claim 2, characterized in that: In step A1, the ratio of the amount of the propyl orthosilicate and deionized water is 10-12 g: 30-36 mL; in step A2, the ratio of the amount of the aluminum dihydrogen phosphate, ferric phosphate, deionized water, oligomeric silicon phosphate and modifying liquid is 6-8 g: 4-6 g: 50-60 mL: 8-10 g: 10-12 mL, wherein the modifying liquid is obtained by mixing 3-aminopropyltrimethoxysilane and anhydrous ethanol in a ratio of 1-2 g: 10-12 mL.

4. The asphalt-based preservative for anti-corrosion cement concrete according to claim 1, characterized in that: The preparation method of the epoxy adhesive comprises the following steps: B1. Add 4,4'-(hexafluoroisopropylene) diphthalic anhydride, 4,6-triamino-1,3,5-triazine, triethylamine and N,N-dimethylformamide to a reactor, raise the temperature of the reactor to 40-60°C, keep the temperature for reaction for 1-2 hours, add hydrophobic particles to the reactor, keep the temperature for reaction for 20-40 minutes, and post-treat to obtain a binder precursor; B2. Add the binder precursor and N,N-dimethylformamide into a low-temperature reactor. After the temperature of the low-temperature reactor is reduced to 20-25°C, add m-chloroperbenzoic acid into the reactor, keep the temperature for 8-10 hours, and then post-treat to obtain the epoxy binder.

5. The asphalt-based preservative for anti-corrosion cement concrete according to claim 4, characterized in that: In step B1, the amount ratio of the 4,4'-(hexafluoroisopropylene) diphthalic anhydride, 4,6-triamino-1,3,5-triazine, triethylamine, N,N-dimethylformamide and hydrophobic particles is 4.0-4.4g:1.0g:0.1g:30mL:0.3-0.5g; in step B2, the amount ratio of the binder precursor, N,N-dimethylformamide and m-chloroperbenzoic acid is 4-5g:20-25mL:0.5-0.7g.

6. The asphalt-based preservative for anti-corrosion cement concrete according to claim 4, characterized in that: The preparation method of the hydrophobic particles comprises the following steps: C1. Add styrene, tetraethyl orthosilicate, sorbitan oleate, and potassium persulfate to a reactor, stir at 500-540 rpm for 8-10 minutes at room temperature, then add 0.5-0.8 wt% polyvinyl alcohol aqueous solution to the reactor while stirring, and continue stirring for 10-15 minutes to obtain a mixed solution; C2. Add 1.0-1.2 wt% sodium lauryl sulfate aqueous solution to the reactor, stir at 500-540 rpm for 2-3 min at room temperature, add the mixed solution to the reactor under stirring, continue stirring for 10-15 min, stop stirring, adjust the pH of the reaction system to 8-10 with 25 wt% ammonia aqueous solution, raise the temperature of the reactor to 70-80° C., keep the reaction temperature for 2-3 h, and perform post-treatment to obtain hollow microparticles; C3. Add the hollow microparticles, tridecafluorooctyltrimethoxysilane, 3-aminopropyltrimethoxysilane, anhydrous ethanol and deionized water into the reactor. After the temperature of the reactor is raised to 40-60°C, use a protective sodium hydroxide aqueous solution to adjust the pH of the reaction system to 8-10, continue to keep the reaction warm for 1-2 hours, and post-treat to obtain hydrophobic particles.

7. The asphalt-based preservative for anti-corrosion cement concrete according to claim 6, characterized in that: In step C1, the amount ratio of styrene, tetraethyl orthosilicate, sorbitan oleate, potassium persulfate and 0.5-0.8wt% polyvinyl alcohol aqueous solution is 3-4g:3-4g:0.01g:0.02-0.03g:3-4g; in step C2, the amount ratio of the 1.0-1.2wt% sodium lauryl sulfate aqueous solution and the mixed solution is 10g:3-4g; in step C3, the amount ratio of the hollow particles, tridecafluorooctyltrimethoxysilane, 3-aminopropyltrimethoxysilane, anhydrous ethanol and deionized water is 2-3g:0.2-0.3g:0.1-0.2g:10-12mL:6-8mL.

8. A method for processing the asphalt-based preservative for anti-corrosion cement concrete according to any one of claims 1 to 8, characterized in that: Add the matrix asphalt into the vacuum stirring kettle. After the temperature of the vacuum stirring kettle is increased to 160-180℃, add the composite binder into the vacuum stirring kettle. After keeping warm and stirring for 20-30 minutes, continue to add the anti-settling agent, leveling agent and toughening agent. After keeping warm and stirring for 10-15 minutes, reduce the temperature of the vacuum stirring kettle to 60-80℃, add the solvent, stop heating, wait for the vacuum stirring kettle to cool naturally to room temperature, and then vacuum degas for 5-8 minutes to obtain the asphalt-based preservative.

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