Preparation Method and Application of a Solvent-Free Special Heavy-Duty Anti-Corrosion Material

Abstract

The invention discloses a preparation method and application of a solvent-free special heavy-duty anti-corrosion material, belonging to the technical field of anti-corrosion coatings. The raw materials include the following parts by weight: 80-100 parts of bisphenol A epoxy resin, 10-20 parts of diluent, 1-2 parts of leveling agent, 5-15 parts of organic modifier, 1-2 parts of defoaming agent, 24-36 parts of inorganic filler, and 15-25 parts of curing agent. Using bisphenol epoxy resin as the matrix endows the material with excellent corrosion resistance; among them, the inorganic filler can greatly enhance the heat resistance, wear resistance and anti-corrosion performance of the material; among them, the organic modifier molecules can enhance the heat resistance, flame retardancy and a certain degree of corrosion resistance of the material, and the performance is long-term stable and not easy to fall off; therefore, the heavy-duty anti-corrosion material prepared by the invention has excellent wear resistance, and also has stable and efficient heat resistance, anti-corrosion property and flame retardancy, and is environmentally friendly, and has important application value in harsh corrosion environments such as desulfurization towers, gas pipelines and gas holders.

Description

Technical Field

[0001] The present invention belongs to the technical field of anticorrosive coatings, and specifically relates to a preparation method and application of a solvent-free special heavy-duty anticorrosive material. Background Art

[0002] With the increasingly prominent global environmental problems, the concept of "environmental protection, energy conservation, and health" has become more and more deeply rooted in people's hearts. As an important industry in the chemical industry, coatings are facing a severe test of environmental protection. Therefore, the development of environmentally friendly coatings has broad market prospects.

[0003] Environmentally friendly coatings include waterborne coatings, high-solids coatings, powder coatings, solvent-free coatings, radiation-cured coatings, etc. Among them, solvent-free coatings do not add organic solvents during both the coating preparation process and the coating use process. Therefore, they can effectively control the emission of volatile organic compounds (VOCs) and are environmentally friendly. Solvent-free epoxy coatings are the most widely used and most used in solvent-free coatings. Epoxy resins have excellent anti-corrosion performance, good adhesion to metal and non-metal composite materials, excellent anti-chemical safety performance, high hardness, good flexibility, etc., and have a wide range of applications in the field of anticorrosive coatings.

[0004] Anticorrosive coatings are generally divided into conventional anticorrosive coatings and heavy-duty anticorrosive coatings. Conventional anticorrosive coatings play an anti-corrosion role for metals, etc. under general conditions and protect the service life of non-ferrous metals; while heavy-duty anticorrosive coatings refer to anticorrosive coatings that can be applied in harsh corrosion environments such as desulfurization towers, gas pipelines, and gas holders relative to conventional anticorrosive coatings, and are a type of anticorrosive coating that can achieve a longer protection period than conventional anticorrosive coatings. However, general solvent-free epoxy coatings are still difficult to meet the use requirements in harsh environments and do not meet the standards of heavy-duty anticorrosive coatings; in addition, the oxygen index of epoxy resins is relatively low and the flame retardancy is poor. To sum up, there is an urgent need to invent a solvent-free special heavy-duty anticorrosive material that can solve the above problems to meet the application of solvent-free epoxy coatings in harsh corrosion environments such as desulfurization towers, gas pipelines, and gas holders. Summary of the Invention

[0005] The purpose of the present invention is to overcome the defects of the prior art and provide a preparation method and application of a solvent-free special heavy-duty anticorrosive material.

[0006] The purpose of the present invention can be achieved by the following technical solutions:

[0007] A preparation method of a solvent-free special heavy-duty anticorrosive material includes the following steps:

[0008] Add bisphenol A epoxy resin and diluent to a blender and stir for 15 - 30 min. Then, add a leveling agent, an organic modifier, and an antifoaming agent in sequence and stir for 15 - 30 min. Next, add inorganic filler and stir for 15 - 30 min. Finally, mix with a curing agent and stir evenly to obtain a solvent-free special heavy-duty anticorrosive material.

[0009] Further, the raw materials are as follows by weight parts: 80 - 100 parts of bisphenol A epoxy resin, 10 - 20 parts of diluent, 1 - 2 parts of leveling agent, 5 - 15 parts of organic modifier, 1 - 2 parts of antifoaming agent, 24 - 36 parts of inorganic filler, and 15 - 25 parts of curing agent.

[0010] Further, the diluent is one of n-butyl glycidyl ether, allyl glycidyl ether, and phenyl glycidyl ether.

[0011] Further, the curing agent is one of triethylamine, triethanolamine, and o-hydroxybenzyl dimethylamine.

[0012] Using bisphenol epoxy resin as the matrix endows the material with excellent corrosion resistance; the curing agent is a tertiary amine curing agent, which can effectively promote the curing of epoxy resin.

[0013] Further, the inorganic filler is prepared through the following steps:

[0014] Add nano titanium powder, graphene oxide, and ethanol aqueous solution to a flask, mix them, place the flask in a magnetic stirrer and stir magnetically for 30 - 60 min, then perform ultrasonic treatment for 30 - 60 min to disperse the nano titanium powder and graphene oxide evenly. Add silane coupling agent KH-550, control the reaction temperature at 60 °C, react for 6 h, keep stirring during the reaction. After the reaction is completed, perform reduced pressure distillation, washing, and freeze drying to obtain the inorganic filler.

[0015] Further, the dosage ratio of nano titanium powder, graphene oxide, ethanol aqueous solution, and silane coupling agent KH-550 is 1 g:1 g:100 mL:4.3 g.

[0016] The prepared inorganic filler is a composite filler of nano titanium powder and graphene oxide, and the filler is modified by silane coupling agent KH-550, that is, an organic layer is formed on its surface, which can improve the surface hydrophobicity of the filler, improve the compatibility between the inorganic filler and the epoxy resin matrix, promote the dispersion of the inorganic filler, give full play to the performance of the inorganic filler, and greatly enhance the heat resistance, wear resistance, and corrosion resistance of the material.

[0017] Further, the organic modifier is prepared through the following steps:

[0018] S1. In a three-necked flask equipped with a stirring device at room temperature, mix tris(hydroxymethyl)aminomethane hydrochloride, triethylamine, and N,N-dimethylformamide (DMF), place it in an ice-water bath at 5 °C, stir well for 35 min, then slowly add phosphorus oxychloride dropwise while controlling the temperature during the dropping process not to exceed 20 °C. After the dropping is completed, raise the temperature to 80 °C and keep the reaction for 8 h. After the reaction is completed, remove the solvent by vacuum filtration, wash the filter cake with absolute ethanol 3 - 4 times, dry it in vacuum, and grind it to obtain Intermediate 1; the dosage ratio of tris(hydroxymethyl)aminomethane hydrochloride, triethylamine, N,N-dimethylformamide, and phosphorus oxychloride is 16.3 g:15 mL:100 mL:15.3 g;

[0019] Tris(hydroxymethyl)aminomethane hydrochloride reacts with phosphorus oxychloride to obtain Intermediate 1; the specific reaction process is as follows:

[0020]

[0021] S2. In a three-necked flask equipped with a stirring device, mix Intermediate 1, hexafluoroglutaroyl chloride, and N,N-dimethylformamide and stir continuously for 5 min, then add dicyclohexylcarbodiimide (DCC), keep the reaction in a water bath at 55 °C for 4 h. After the reaction is completed, filter, rotary evaporate, and remove the solvent by vacuum distillation to obtain Intermediate 2; the dosage ratio of Intermediate 1, hexafluoroglutaroyl chloride, N,N-dimethylformamide, and dicyclohexylcarbodiimide is 16.5 g:28.4 g:150 mL:20.6 g;

[0022] Under the catalysis of DCC, Intermediate 1 and hexafluoroglutaroyl chloride undergo an amidation reaction. By controlling the molar ratio of the two to be close to 1:1 and hexafluoroglutaroyl chloride being slightly in excess, Intermediate 2 is obtained; the specific reaction process is as follows:

[0023]

[0024] S3. In a three-necked flask equipped with a stirring device, mix Intermediate 2, 4,4'-diaminodiphenyl sulfone, and N,N-dimethylformamide and stir evenly, then add dicyclohexylcarbodiimide, keep the reaction in a water bath at 55 °C for 8 h. After the reaction is completed, filter, rotary evaporate to remove part of the solvent, and then purify by column chromatography (the eluent uses a mixed solvent of benzene / ethyl acetate, and the volume ratio of the two is 2:1), rotary evaporate to remove the eluent to obtain Intermediate 3; the dosage ratio of Intermediate 2, 4,4'-diaminodiphenyl sulfone, N,N-dimethylformamide, and dicyclohexylcarbodiimide is 40.4 g:25.6 g:200 mL:20.6 g;

[0025] In the presence of dicyclohexylcarbodiimide as a catalyst, intermediate 2 and 4,4'-diaminodiphenyl sulfone undergo an amidation reaction. By controlling the molar ratio of the two to be close to 1:1 and having 4,4'-diaminodiphenyl sulfone slightly in excess, intermediate 3 is obtained. The specific reaction process is as follows:

[0026]

[0027] S4. In a three-necked flask equipped with a stirring device, p-phenylene diisocyanate, intermediate 3, and N,N-dimethylformamide are mixed, and tributyltin (catalyst) is added and stirred evenly. The temperature is gradually raised to 70 °C and kept warm for 6 h. Stirring is continuous during the reaction. After the reaction is completed, the solvent is removed by vacuum distillation, washed 2 - 3 times with toluene, and dried in vacuo to obtain the organic modifier. The dosage ratio of p-phenylene diisocyanate, intermediate 3, N,N-dimethylformamide, and tributyltin is 18.3 g:61.7 g:200 mL:0.2 g;

[0028] The isocyanate group in p-phenylene diisocyanate reacts with the amino group on intermediate 3 to form a ureido group. By controlling the molar ratio of the two to be close to 1:1 and having p-phenylene diisocyanate slightly in excess, only one isocyanate group on p-phenylene diisocyanate participates in the reaction to obtain the organic modifier. The specific reaction process is as follows:

[0029]

[0030] The prepared organic modifier molecule contains C-F bonds, diphenyl sulfone, cage-like phosphonate, and isocyanate group structures. Among them, the C-F bond has a small polarity, and at the same time, the C-F bond has a very strong bond energy. The higher the chemical bond energy, the better the stability. It not only improves the heat resistance of the epoxy resin matrix, but also the C-F bond can well coat the C-C main chain, improving the corrosion resistance of the matrix; the introduced diphenyl sulfone can not only enhance the heat resistance of the matrix, but also generate SO2, sulfurous acid, and water by thermal desulfurization, which can promote the Fries rearrangement reaction of the matrix and accelerate the carbonization of the matrix, effectively enhancing the flame retardancy of the matrix; in addition, the introduced cage-like phosphonate structure is a green and environmentally friendly flame retardant with strong stability. During combustion, it will promote the formation of a carbon layer and inhibit the release of smoke, and can play a synergistic role with the diphenyl sulfone in the organic modifier molecule, greatly improving the flame retardancy of the matrix; finally, the isocyanate group in the organic modifier molecule can react with the epoxy group in the epoxy resin matrix to form a five-membered ring oxazolidinone structure, which can further improve the heat resistance and mechanical properties of the epoxy resin matrix to a certain extent; moreover, the organic modifier and the epoxy resin matrix are connected by chemical bonds, improving the migration resistance and exudation resistance of the small organic modifier molecules and enhancing the stability of the organic modifier.

[0031] Advantages of the present invention:

[0032] 1. The heavy-duty anti-corrosion material prepared by the present invention uses bisphenol epoxy resin as a matrix to give the material excellent corrosion resistance;

[0033] 2. By modifying the composite filler of nano titanium powder and graphene oxide, the compatibility with the epoxy resin matrix is ​​improved, and the heat resistance, wear resistance and corrosion resistance of the material are greatly enhanced;

[0034] 3. The various groups in the prepared organic modifier molecules work synergistically, significantly enhancing the heat resistance, flame retardancy and corrosion resistance of the material to a certain extent, and the performance is long-lasting and stable and not easy to fall off;

[0035] Therefore, the heavy-duty anti-corrosion material prepared by the present invention has excellent wear resistance, stable and efficient heat resistance, corrosion resistance and flame retardancy, is solvent-free, has low VOC volatility, is environmentally friendly, and has important application value in harsh corrosive environments such as desulfurization towers, gas pipelines and gas tanks. DETAILED DESCRIPTION

[0036] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0037] Embodiment 1

[0038] Preparation of organic modifiers:

[0039] S1. In a three-necked flask equipped with a stirring device, 16.3 g of tris(hydroxymethyl)aminomethane hydrochloride, 15 mL of triethylamine and 100 mL of N,N-dimethylformamide were mixed at room temperature, placed in an ice-water bath at 5°C, and stirred for 35 min. Then, 15.3 g of phosphorus oxychloride was slowly added dropwise, and the temperature was controlled not to exceed 20°C during the addition. After the addition was completed, the temperature was raised to 80°C and kept for reaction for 8 h. After the reaction was completed, the solvent was removed by filtration under reduced pressure, and the filter cake was washed 3 times with anhydrous ethanol, vacuum dried, and ground to obtain intermediate 1.

[0040] S2. In a three-necked flask equipped with a stirring device, 16.5 g of intermediate 1, 28.4 g of hexafluoroglutaryl chloride and 150 mL of N,N-dimethylformamide were mixed and stirred continuously for 5 min, and then 20.6 g of dicyclohexylcarbodiimide was added. The mixture was kept in a water bath at 55°C for 4 h. After the reaction was completed, the mixture was filtered, rotary evaporated, and the solvent was removed by reduced pressure distillation to obtain intermediate 2.

[0041] S3. In a three-necked flask equipped with a stirring device, 40.4 g of Intermediate 2, 25.6 g of 4,4'-diaminodiphenyl sulfone, and 200 mL of N,N-dimethylformamide were mixed and stirred evenly. Then, 20.6 g of dicyclohexylcarbodiimide was added, and the mixture was kept at 55 °C in a water bath for 8 h for reaction. After the reaction was completed, filtration was carried out, and part of the solvent was removed by rotary evaporation. Then, purification was carried out by column chromatography (the eluent was a mixed solvent of benzene / ethyl acetate, and the volume ratio of the two was 2:1). The eluent was removed by rotary evaporation to obtain Intermediate 3;

[0042] S4. In a three-necked flask equipped with a stirring device, 18.3 g of p-phenylene diisocyanate, 61.7 g of Intermediate 3, and 200 mL of N,N-dimethylformamide were mixed, 0.2 g of tributyltin was added, and the mixture was stirred evenly. The temperature was gradually raised to 70 °C, and the mixture was kept at this temperature for 6 h for reaction. Stirring was carried out continuously during the reaction. After the reaction was completed, the solvent was removed by vacuum distillation, washed twice with toluene, and dried under vacuum to obtain the organic modifier.

[0043] Example 2

[0044] Preparation of organic modifier:

[0045] S1. At room temperature, in a three-necked flask equipped with a stirring device, 32.6 g of tris(hydroxymethyl)aminomethane hydrochloride, 30 mL of triethylamine, and 200 mL of N,N-dimethylformamide were mixed, placed in an ice-water bath at 5 °C, and stirred thoroughly for 35 min. Then, 30.6 g of phosphorus oxychloride was slowly added dropwise, and the temperature during the dropwise addition was controlled not to exceed 20 °C. After the dropwise addition was completed, the temperature was raised to 80 °C and kept for 8 h for reaction. After the reaction was completed, the solvent was removed by vacuum filtration, and the filter cake was washed three times with absolute ethanol and dried under vacuum and ground to obtain Intermediate 1;

[0046] S2. In a three-necked flask equipped with a stirring device, 33 g of Intermediate 1, 56.8 g of hexafluoroglutaroyl chloride, and 300 mL of N,N-dimethylformamide were mixed and stirred continuously for 5 min. Then, 41.2 g of dicyclohexylcarbodiimide was added, and the mixture was kept at 55 °C in a water bath for 4 h for reaction. After the reaction was completed, filtration was carried out, and rotary evaporation and vacuum distillation were carried out to remove the solvent to obtain Intermediate 2;

[0047] S3. In a three-necked flask equipped with a stirring device, 80.8 g of Intermediate 2, 51.2 g of 4,4'-diaminodiphenyl sulfone, and 400 mL of N,N-dimethylformamide were mixed and stirred evenly. Then, 41.2 g of dicyclohexylcarbodiimide was added, and the mixture was kept at 55 °C in a water bath for 8 h for reaction. After the reaction was completed, filtration was carried out, and part of the solvent was removed by rotary evaporation. Then, purification was carried out by column chromatography (the eluent was a mixed solvent of benzene / ethyl acetate, and the volume ratio of the two was 2:1). The eluent was removed by rotary evaporation to obtain Intermediate 3;

[0048] S4. In a three-necked flask equipped with a stirring device, 36.6 g of p-phenylene diisocyanate, 123.4 g of intermediate 3, and 400 mL of N,N-dimethylformamide were mixed. 0.4 g of tributyltin was added and the mixture was stirred evenly. The temperature was gradually raised to 70 °C and the reaction was carried out for 6 h while stirring continuously during the reaction. After the reaction was completed, the solvent was removed by distillation under reduced pressure, washed twice with toluene, and dried in vacuo to obtain an organic modifier.

[0049] Example 3

[0050] Preparation of inorganic filler:

[0051] In a flask, 1 g of nano titanium powder, 1 g of graphene oxide, and 100 mL of ethanol aqueous solution were mixed, then placed in a magnetic stirrer and stirred magnetically for 30 min, and then ultrasonicated for 30 min to disperse the nano titanium powder and graphene oxide evenly. 4.3 g of silane coupling agent KH-550 was added, the reaction temperature was controlled at 60 °C, and the reaction was carried out for 6 h while stirring continuously during the reaction. After the reaction was completed, it was distilled under reduced pressure, washed, and freeze-dried to obtain an inorganic filler.

[0052] Example 4

[0053] Preparation of inorganic filler:

[0054] In a flask, 2 g of nano titanium powder, 2 g of graphene oxide, and 200 mL of ethanol aqueous solution were mixed, then placed in a magnetic stirrer and stirred magnetically for 60 min, and then ultrasonicated for 60 min to disperse the nano titanium powder and graphene oxide evenly. 8.6 g of silane coupling agent KH-550 was added, the reaction temperature was controlled at 60 °C, and the reaction was carried out for 6 h while stirring continuously during the reaction. After the reaction was completed, it was distilled under reduced pressure, washed, and freeze-dried to obtain an inorganic filler.

[0055] Example 5

[0056] In a blender, 80 g of bisphenol A epoxy resin and 10 g of n-butyl glycidyl ether were stirred for 15 min, then 1 g of leveling agent (BYK-358N), 5 g of the organic modifier prepared in Example 1, and 1 g of defoaming agent (BYK-024) were added in sequence and stirred for 15 min. Then 24 g of the inorganic filler prepared in Example 3 was added and stirred for 15 min. Finally, it was mixed and stirred evenly with 15 g of triethylamine to obtain a solvent-free special heavy-duty anti-corrosion material.

[0057] Example 6

[0058] After adding 90 g of bisphenol A epoxy resin and 15 g of allyl glycidyl ether into a blender and stirring for 30 min, 1.5 g of a leveling agent (BYK-358N), 10 g of the organic modifier prepared in Example 2, and 1.5 g of an antifoaming agent (BYK-024) were added in sequence and stirred for 30 min. Then, 30 g of the inorganic filler prepared in Example 4 was added and stirred for 30 min. Finally, it was mixed and stirred evenly with 20 g of triethanolamine to obtain a solvent-free special heavy-duty anti-corrosion material.

[0059] Example 7

[0060] After adding 100 g of bisphenol A epoxy resin and 20 g of phenyl glycidyl ether into a blender and stirring for 30 min, 2 g of a leveling agent (BYK-358N), 15 g of the organic modifier prepared in Example 2, and 2 g of an antifoaming agent (BYK-024) were added in sequence and stirred for 30 min. Then, 36 g of the inorganic filler prepared in Example 4 was added and stirred for 30 min. Finally, it was mixed and stirred evenly with 25 g of o-hydroxybenzyl dimethylamine to obtain a solvent-free special heavy-duty anti-corrosion material.

[0061] Comparative Example 1

[0062] The organic modifier in Example 7 was replaced with a commercially available phosphorus-based flame retardant of the same quality, and the remaining steps were the same as those in Example 7 to prepare the material.

[0063] Comparative Example 2

[0064] A commercially available heavy-duty anti-corrosion epoxy resin coating was used.

[0065] Examples 5, 6, and 7, and Comparative Examples 1 and 2 were subjected to the following performance tests according to different test standards:

[0066] The adhesion was measured according to the national standard GB / T 9286-2021 "Cross-Cut Test Method for Paints and Varnishes";

[0067] The non-volatile content was measured according to the national standard GB / T 1725-2007 "Determination of Non-Volatile Content of Paints, Varnishes and Plastics";

[0068] The water resistance was measured according to the national standard GB / T 1733-1993 "Method for Determining Water Resistance of Paint Films";

[0069] The acid and alkali resistance was measured according to the national standard GB / T 1763 "Method for Determining Resistance of Paint Films to Chemical Reagents";

[0070] The abrasion resistance was measured according to the national standard GB / T 1768-2006 "Determination of Abrasion Resistance of Paints and Varnishes - Rotating Rubber Wheel Method";

[0071] The mass loss of the specimen before and after 180 days was measured in accordance with the national standard GB 12441-2005 "Fire-retardant coating for finishing".

[0072] The specimen was sprayed on a square steel plate with a side length of 10 cm, placed in an oven at 300 °C, taken out after 7 days, and the surface condition of the specimen was observed.

[0073] The measured results are shown in the following table:

[0074]

[0075]

[0076] As can be seen from the above table, the heavy-duty anti-corrosion material prepared in the embodiment of the present invention has better heat resistance and flame retardancy than the comparative example, and excellent wear resistance and anti-corrosion performance, less VOC volatilization, is environmentally friendly, has long-term stable performance, and has important application value in harsh corrosion environments such as desulfurization towers, gas pipelines and gas holders.

[0077] In the description of the specification, the description with reference to terms such as "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0078] The above content is only an example and illustration of the present invention. Those skilled in the art of the present technology can make various modifications or supplements to the described specific embodiments or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined by the claims of the present invention, they should all belong to the protection scope of the present invention.

Claims

1. A method for preparing a solvent-free special heavy-duty anti-corrosion material, characterized in that: The following steps are involved: Add bisphenol A epoxy resin and diluent into a mixer and stir, then add leveling agent, organic modifier and defoamer in sequence and stir, then add inorganic filler and stir, finally mix with curing agent and stir evenly to obtain solvent-free special heavy anti-corrosion material; Wherein, the organic modifier is prepared by the following steps: S1. Tris(hydroxymethyl)aminomethane hydrochloride, triethylamine and N,N-dimethylformamide were mixed at room temperature, placed in an ice-water bath at 5°C, and stirred for 35 minutes. Phosphorus oxychloride was added dropwise, and the temperature was controlled not to exceed 20°C during the addition. After the addition was completed, the mixture was reacted at 80°C for 8 hours. After the reaction was completed, the mixture was filtered under reduced pressure, washed, dried in vacuo, and ground to obtain intermediate 1. S2, the intermediate 1, hexafluoroglutaryl chloride and N,N-dimethylformamide were mixed and stirred continuously for 5 minutes, and then dicyclohexylcarbodiimide was added, and the mixture was kept in a water bath at 55°C for 4 hours. After the reaction was completed, the mixture was filtered, rotary evaporated, and distilled under reduced pressure to obtain the intermediate 2; S3, after mixing and stirring the intermediate 2, 4,4'-diaminodiphenyl sulfone and N,N-dimethylformamide, dicyclohexylcarbodiimide was added, and the mixture was reacted at 55°C for 8 hours. After the reaction was completed, the mixture was filtered, rotary evaporated, purified by column chromatography, and rotary evaporated to obtain the intermediate 3; S4, mixing p-phenylene diisocyanate, intermediate 3 and N,N-dimethylformamide, adding tributyltin and stirring evenly, gradually raising the temperature to 70°C, keeping the temperature for 6 hours, stirring continuously during the reaction, and after the reaction is completed, performing reduced pressure distillation, washing, and vacuum drying to obtain an organic modifier; Among them, the ratio of tris(hydroxymethyl)aminomethane hydrochloride, triethylamine, N,N-dimethylformamide, and phosphorus oxychloride in step S1 is 16.3g:15mL:100mL:15.3g; the ratio of intermediate 1, hexafluoroglutaryl chloride, N,N-dimethylformamide, and dicyclohexylcarbodiimide in step S2 is 16.5g:28.4g:150mL:20.6g; the ratio of intermediate 2, 4,4'-diaminodiphenyl sulfone, N,N-dimethylformamide, and dicyclohexylcarbodiimide in step S3 is 40.4g:25.6g:200mL:20.6g; the ratio of p-phenylene diisocyanate, intermediate 3, N,N-dimethylformamide, and tributyltin in step S4 is 18.3g:61.7g:200mL:0.2g.

2. The method for preparing a solvent-free special heavy-duty anticorrosive material according to claim 1, characterized in that: The raw materials are calculated in parts by weight as follows: 80-100 parts of bisphenol A epoxy resin, 10-20 parts of diluent, 1-2 parts of leveling agent, 5-15 parts of organic modifier, 1-2 parts of defoamer, 24-36 parts of inorganic filler, and 15-25 parts of curing agent.

3. The method for preparing a solvent-free special heavy-duty anticorrosive material according to claim 1, characterized in that: The inorganic filler is prepared by the following steps: Nano-titanium powder, graphene oxide and ethanol aqueous solution were added to a flask and mixed, and then placed in a magnetic stirrer for magnetic stirring and ultrasonic treatment to evenly disperse the nano-titanium powder and graphene oxide. Silane coupling agent KH-550 was added, and the reaction temperature was controlled at 60°C. The reaction was carried out for 6 hours with continuous stirring during the reaction. After the reaction was completed, the inorganic filler was obtained by vacuum distillation, washing and freeze-drying.

4. Application of the heavy-duty anti-corrosion material obtained by the preparation method according to claim 1 in the fields of desulfurization towers, gas pipelines, and gas tanks.

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