Highly alkali-resistant modified sulfur-based adhesive and preparation method thereof

Abstract

The application relates to the technical field of adhesives, in particular to a high-alkali-resistance modified sulfur-based adhesive and a preparation method thereof, which comprises the following steps: S1. uniformly mixing aggregates, mineral fillers and Portland cement, and preheating in an oil bath pot to obtain primary mixture; S2. stirring modified sulfur and modified fibers into the primary mixture to obtain secondary mixture; and S3. pouring the secondary mixture into a preheated mold, keeping at 130-140 DEG C for 10-15 min, and obtaining the high-alkali-resistance modified sulfur-based adhesive after cooling and demolding. The interface bonding strength of fibers and the sulfur matrix is remarkably improved by the modified fibers, and the folding resistance and impact resistance of the material are improved. The synergistic effect of the modified fibers, the copolymerization accelerator and the modified sulfur creates multi-component and multi-level synergistic modification, a high-alkali-resistance, high-toughness, high-interface and environment-friendly sulfur-based adhesive is successfully prepared, and a reliable material basis is provided for the application of the adhesive in the fields of building engineering, corrosion prevention engineering and rapid repair.

Description

Technical Field

[0001] This invention relates to the field of adhesive technology, specifically to a highly alkali-resistant modified sulfur-based adhesive and its preparation method. Background Technology

[0002] The increasing availability of sulfur resources has prompted many researchers to explore new uses for sulfur, and using sulfur as a building material offers many advantages that cement lacks. Sulfur-based materials possess excellent mechanical properties, corrosion resistance, rapid hardening, extremely low permeability, year-round production and installation capabilities, and the ability to be melted and recycled. In contrast, cement, as the most widely used traditional building material, consumes a large amount of electricity and materials such as limestone during its production. Furthermore, the large amounts of carbon dioxide, sulfur dioxide, and nitrogen dioxide emitted during production have a significant impact on and damage the environment. Statistics show that nearly a quarter of global carbon dioxide emissions are generated by the construction industry. However, my country is still in a period of rapid construction and development, and the demand for cement continues to increase, exacerbating resource consumption and environmental pollution problems. Existing technology involves adding coarse aggregate, fine aggregate, and filler to molten sulfur, followed by cooling to produce sulfur-based composite materials. Experiments show that this material has superior physical and mechanical properties compared to traditional cement concrete. Therefore, the use of sulfur as a rapid-hardening, high-strength binder in construction projects is worth considering. Sulfur, as an environmentally friendly material, has significant potential to replace cement as a building material binder.

[0003] However, pure sulfur undergoes a phase transformation from monoclinic to orthorhombic crystals during cooling, accompanied by volume shrinkage. This can easily lead to stress concentration and microcrack propagation within the material, severely impacting its durability, especially in humid, alkaline, or freeze-thaw cycles. To suppress the crystal transformation of sulfur, existing technologies typically employ organic modifiers for copolymerization modification or physical composites using inorganic fillers. Nevertheless, existing sulfur-based binders are susceptible to chemical corrosion of sulfur and its modified systems in alkaline environments (such as concrete pore fluid), resulting in strength degradation. Furthermore, the poor interfacial compatibility between sulfur and aggregates / fibers affects overall mechanical properties and durability. Most studies focus solely on sulfur modification without systematically coordinating fiber reinforcement and interfacial control, making it difficult to achieve comprehensive performance improvements.

[0004] Therefore, developing a modified sulfur-based adhesive with excellent alkali resistance, strong interfacial bonding, simple preparation process, and controllable cost has become the key to promoting the practical application of sulfur-based building materials. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the purpose of this invention is to provide a highly alkali-resistant modified sulfur-based adhesive and its preparation method.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] A method for preparing a highly alkali-resistant modified sulfur-based adhesive includes the following preparation steps:

[0008] S1. By weight, mix 60-65 parts of aggregate, 5-10 parts of mineral filler and 3-5 parts of silicate cement evenly, and preheat in an oil bath to 130-140℃ to obtain a preliminary mixture;

[0009] S2. Add 30-35 parts of modified sulfur and 3-6 parts of modified fiber to the preliminary mixture obtained in step S1, maintain the temperature at 130-140℃, and stir at a speed of 200-300r / min for 10-15min to obtain the secondary mixture.

[0010] S3. Pour the mixture obtained in step S2 into a preheated mold, keep it at 130-140℃ for 10-15 minutes, and after cooling and demolding, obtain a highly alkali-resistant modified sulfur-based adhesive.

[0011] The preparation of modified sulfur includes the following steps:

[0012] S11. By weight, heat 70-80 parts of sulfur to melt in an oil bath, add 5-10 parts of copolymerization accelerator and maintain the temperature, stir at 200-250 r / min for 15-20 min to obtain a preliminary modifier;

[0013] S12. Add 8-10 parts of waste ceramic powder and 4-6 parts of rubber granules to the preliminary modifier obtained in step S11, and stir at a speed of 250-300 r / min for 25-30 min to obtain the secondary modifier.

[0014] S13. Reduce the temperature to 125-130℃, add 0.2-0.3 parts of antioxidant 1010 and 0.5-1 parts of dimethyl silicone oil, stir at 250-300 r / min for 8-10 min, cool to room temperature and crush to finally obtain modified sulfur.

[0015] Preferably, the preparation of modified fibers includes the following steps:

[0016] S21. By mass, mix 4-5 parts of silane coupling agent with 36-45 parts of deionized water, adjust the pH to 4-5, and hydrolyze for 25-30 minutes to obtain the coupling agent treatment solution.

[0017] S22. Add 80-90 parts of basalt fiber and 5-10 parts of polypropylene fiber to the coupling agent treatment solution obtained in step S21, disperse ultrasonically for 15-20 minutes, take it out, and dry it at 80℃ for 40-50 minutes to obtain the preliminary modified fiber.

[0018] S23. Mix 4-5 parts of epoxy resin emulsion with 0.5-1 parts of sodium dodecylbenzenesulfonate, stir evenly, add the preliminary modified fiber obtained in step S22, stir at 150-200 r / min for 25-30 min, take it out and dry at 100℃ for 1-2 h to obtain modified fiber.

[0019] Preferably, the preparation of the copolymerization accelerator includes the following steps:

[0020] S111. By mass, mix 2-3 parts of dicyclopentadiene, 1-3 parts of styrene and 5-8 parts of anhydrous ethanol, and stir at 150-200 r / min for 5-10 min to obtain a preliminary mixture;

[0021] S112. Add 0.5-1 parts of tetramethylthiuram disulfide and 0.3-0.5 parts of benzoyl peroxide to the preliminary mixture obtained in step S111, and stir the mixture at 150-200 r / min for 1-2 h at 83-85℃ to obtain the secondary mixture.

[0022] S113. When the temperature drops to 55-60℃, add 0.2-0.3 parts of antioxidant 1010, continue stirring for 10-15 minutes, and cool to room temperature to obtain the copolymerization accelerator.

[0023] Preferably, the oil bath temperature in step S11 is 135-145℃.

[0024] Preferably, the mineral filler is selected from one or more of fly ash, silica fume, coal gangue powder, waste glass powder, sludge ash, metallurgical dust, slag powder, rice husk ash, and straw ash.

[0025] Preferably, the particle size is controlled to be 2 mm during crushing in step S13.

[0026] Preferably, the aggregate is selected from one or more of the following: river sand, quartz sand, manufactured sand, lake sand, tailings sand, recycled fine aggregate, and aeolian sand.

[0027] Preferably, the frequency of ultrasonic dispersion in step S22 is 40 kHz.

[0028] Preferably, the epoxy resin emulsion is selected from a bisphenol A type waterborne epoxy resin emulsion with a solid content of 50%.

[0029] A highly alkali-resistant modified sulfur-based adhesive is prepared by the above-described preparation method.

[0030] Compared with the prior art, the beneficial effects of the present invention are:

[0031] 1. This invention forms a cross-linked network through the synergistic effect of copolymerization accelerator and modified sulfur, which effectively inhibits sulfur crystal transformation and volume shrinkage, further buffers internal stress, reduces the generation of microcracks, and can also enhance the hydrophobicity of the system and reduce the erosion rate of alkaline media.

[0032] 2. This invention significantly enhances the interfacial bonding strength between the modified fiber and the sulfur matrix, thereby improving the material's flexural and impact resistance. The synergistic effect of the modified fiber, copolymerization accelerator, and modified sulfur creates a multi-component, multi-level synergistic modification, successfully preparing a highly alkali-resistant, high-strength, high-toughness, excellent interfacial properties, and environmentally friendly sulfur-based adhesive, providing a reliable material basis for its application in construction engineering, corrosion protection engineering, and rapid repair. Attached Figure Description

[0033] Figure 1 This is a process flow diagram for preparing the highly alkali-resistant modified sulfur-based adhesive of the present invention;

[0034] Figure 2 This is a flow chart of the preparation process of the modified sulfur of this invention;

[0035] Figure 3 This is a flow chart of the preparation process of the modified fiber of the present invention;

[0036] Figure 4 This is a process flow diagram for preparing the copolymerization accelerator of the present invention. Detailed Implementation

[0037] The present invention will now be clearly and completely described in conjunction with embodiments thereof. Obviously, the described embodiments are merely some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0038] Please see Figure 1-4 The present invention provides a technical solution:

[0039] Example 1

[0040] A method for preparing a highly alkali-resistant modified sulfur-based adhesive:

[0041] Before preparing the highly alkali-resistant modified sulfur-based adhesive, the copolymerization accelerator, modified sulfur, and modified fibers are prepared first:

[0042] The preparation of copolymerization accelerators includes the following steps:

[0043] S111. Mix 2g of dicyclopentadiene, 1g of styrene and 5g of anhydrous ethanol, and stir at 150r / min for 5min to obtain a preliminary mixture;

[0044] S112. Add 0.5g tetramethylthiuram disulfide and 0.3g benzoyl peroxide to the preliminary mixture obtained in step S111, and stir the mixture at 150r / min for 1h at 83℃ to obtain the secondary mixture.

[0045] S113. When the temperature drops to 55℃, add 0.2g of antioxidant 1010, continue stirring for 10min, and cool to room temperature to obtain the copolymerization accelerator.

[0046] The preparation of modified sulfur includes the following steps:

[0047] S11. Heat 70g of sulfur in an oil bath at 135℃ until it melts, add 5g of copolymerization accelerator and maintain the temperature, then stir at 200r / min for 15min to obtain a preliminary modifier;

[0048] S12. Add 8g of waste ceramic powder and 4g of rubber particles to the preliminary modifier obtained in step S11, and stir at 250r / min for 25min to obtain the secondary modifier;

[0049] S13. Reduce the temperature to 125℃, add 0.2g antioxidant 1010 and 0.5g dimethyl silicone oil, stir at 250r / min for 8min, cool to room temperature and crush, control the particle size to 2mm, and finally obtain modified sulfur.

[0050] The preparation of modified fibers includes the following steps:

[0051] S21. Mix 4g of silane coupling agent (KH-550) with 36g of deionized water, adjust the pH to 4, and hydrolyze for 25min to obtain the coupling agent treatment solution;

[0052] S22. Add 80g of basalt fiber and 5g of polypropylene fiber to the coupling agent treatment solution obtained in step S21, ultrasonically disperse at a frequency of 40kHz for 15min, take it out, and dry it at 80℃ for 40min to obtain the preliminary modified fiber.

[0053] S23. Mix 4g of epoxy resin emulsion (50% solid content bisphenol A type waterborne epoxy resin emulsion) with 0.5g of sodium dodecylbenzenesulfonate, stir evenly, add the preliminary modified fiber obtained in step S22, stir at 150r / min for 25min, take it out and dry at 100℃ for 1h to obtain modified fiber.

[0054] The preparation of highly alkali-resistant modified sulfur-based adhesives includes the following steps:

[0055] S1. Mix 60g river sand, 5g fly ash and 3g silicate cement evenly, and preheat in an oil bath to 130℃ to obtain a preliminary mixture;

[0056] S2. Add 30g of modified sulfur and 3g of modified fiber to the preliminary mixture obtained in step S1, maintain the temperature at 130℃, and stir at a speed of 200r / min for 10min to obtain the secondary mixture.

[0057] S3. Pour the mixture obtained in step S2 into a preheated mold, keep it at 130°C for 10 minutes, and after cooling and demolding, obtain a highly alkali-resistant modified sulfur-based adhesive.

[0058] Example 2

[0059] A method for preparing a highly alkali-resistant modified sulfur-based adhesive:

[0060] Before preparing the highly alkali-resistant modified sulfur-based adhesive, the copolymerization accelerator, modified sulfur, and modified fibers are prepared first:

[0061] The preparation of copolymerization accelerators includes the following steps:

[0062] S111. Mix 3g of dicyclopentadiene, 3g of styrene and 8g of anhydrous ethanol, and stir at 200r / min for 10min to obtain a preliminary mixture;

[0063] S112. Add 1g of tetramethylthiuram disulfide and 0.5g of benzoyl peroxide to the preliminary mixture obtained in step S111, and stir the mixture at 200r / min for 2h at 85℃ to obtain the secondary mixture.

[0064] S113. When the temperature drops to 60℃, add 0.3g of antioxidant 1010, continue stirring for 15min, and cool to room temperature to obtain the copolymerization accelerator.

[0065] The preparation of modified sulfur includes the following steps:

[0066] S11. Heat 80g of sulfur in an oil bath at 145℃ until it melts, add 10g of copolymerization accelerator and maintain the temperature, then stir at 250r / min for 20min to obtain a preliminary modifier;

[0067] S12. Add 10g of waste ceramic powder and 6g of rubber particles to the preliminary modifier obtained in step S11, and stir at 300r / min for 30min to obtain the secondary modifier;

[0068] S13. Reduce the temperature to 130℃, add 0.3g antioxidant 1010 and 1g dimethyl silicone oil, stir at 300r / min for 10min, cool to room temperature and crush, control the particle size to 2mm, and finally obtain modified sulfur.

[0069] The preparation of modified fibers includes the following steps:

[0070] S21. Mix 5g of silane coupling agent (KH-550) with 45g of deionized water, adjust the pH to 5, and hydrolyze for 30min to obtain the coupling agent treatment solution;

[0071] S22. Add 90g of basalt fiber and 10g of polypropylene fiber to the coupling agent treatment solution obtained in step S21, ultrasonically disperse at a frequency of 40kHz for 20min, take it out, and dry it at 80℃ for 50min to obtain the preliminary modified fiber.

[0072] S23. Mix 5g of epoxy resin emulsion (50% solid content bisphenol A type waterborne epoxy resin emulsion) with 1g of sodium dodecylbenzenesulfonate, stir evenly, add the preliminary modified fiber obtained in step S22, stir at 200r / min for 30min, take it out and dry at 100℃ for 2h to obtain modified fiber.

[0073] The preparation of highly alkali-resistant modified sulfur-based adhesives includes the following steps:

[0074] S1. Mix 65g of quartz sand, 10g of silica fume and 5g of silicate cement evenly, and preheat in an oil bath to 140℃ to obtain a preliminary mixture;

[0075] S2. Add 35g of modified sulfur and 6g of modified fiber to the preliminary mixture obtained in step S1, maintain the temperature at 140℃, and stir at 300r / min for 15min to obtain the secondary mixture.

[0076] S3. Pour the mixture obtained in step S2 into a preheated mold, keep it at 140°C for 15 minutes, and after cooling and demolding, obtain a highly alkali-resistant modified sulfur-based adhesive.

[0077] Example 3

[0078] A method for preparing a highly alkali-resistant modified sulfur-based adhesive:

[0079] Before preparing the highly alkali-resistant modified sulfur-based adhesive, the copolymerization accelerator, modified sulfur, and modified fibers are prepared first:

[0080] The preparation of copolymerization accelerators includes the following steps:

[0081] S111. Mix 2.5g of dicyclopentadiene, 2g of styrene and 6g of anhydrous ethanol, and stir at 180r / min for 8min to obtain a preliminary mixture;

[0082] S112. Add 0.8 g tetramethylthiuram disulfide and 0.4 g benzoyl peroxide to the preliminary mixture obtained in step S111, and stir the mixture at 180 r / min for 1.5 h at 84 °C to obtain the secondary mixture.

[0083] S113. When the temperature drops to 58℃, add 0.25g of antioxidant 1010, continue stirring for 13min, and cool to room temperature to obtain the copolymerization accelerator.

[0084] The preparation of modified sulfur includes the following steps:

[0085] S11. Heat 75g of sulfur in an oil bath at 140℃ until it melts, add 8g of copolymerization accelerator and maintain the temperature, then stir at 240r / min for 18min to obtain a preliminary modifier;

[0086] S12. Add 9g of waste ceramic powder and 5g of rubber particles to the preliminary modifier obtained in step S11, and stir at 280r / min for 28min to obtain the secondary modifier;

[0087] S13. Reduce the temperature to 128℃, add 0.25g antioxidant 1010 and 0.8g dimethyl silicone oil, stir at 280r / min for 9min, cool to room temperature and crush, control the particle size to 2mm, and finally obtain modified sulfur.

[0088] The preparation of modified fibers includes the following steps:

[0089] S21. Mix 4.5g of silane coupling agent (KH-550) with 40g of deionized water, adjust the pH to 4.5, and hydrolyze for 28min to obtain the coupling agent treatment solution;

[0090] S22. Add 85g of basalt fiber and 8g of polypropylene fiber to the coupling agent treatment solution obtained in step S21, ultrasonically disperse at a frequency of 40kHz for 18min, take it out, and dry it at 80℃ for 45min to obtain the preliminary modified fiber.

[0091] S23. Mix 4.5g of epoxy resin emulsion (50% solid content bisphenol A type waterborne epoxy resin emulsion) with 0.8g of sodium dodecylbenzene sulfonate, stir evenly, add the preliminary modified fiber obtained in step S22, stir at 180r / min for 28min, take it out and dry at 100℃ for 1.5h to obtain modified fiber.

[0092] The preparation of highly alkali-resistant modified sulfur-based adhesives includes the following steps:

[0093] S1. Mix 33g of lake sand, 30g of tailings sand, 4g of coal gangue powder, 4g of waste glass powder and 4g of silicate cement evenly, and preheat in an oil bath to 135℃ to obtain a preliminary mixture;

[0094] S2. Add 33g of modified sulfur and 5g of modified fiber to the preliminary mixture obtained in step S1, maintain the temperature at 135℃, and stir at a speed of 240r / min for 13min to obtain the secondary mixture.

[0095] S3. Pour the mixture obtained in step S2 into a preheated mold, keep it at 135°C for 13 minutes, and after cooling and demolding, obtain a highly alkali-resistant modified sulfur-based adhesive.

[0096] Comparative Example 1

[0097] The only difference between Comparative Example 1 and Example 1 is that no copolymerization accelerator was added in this comparative example; the remaining steps are exactly the same in Comparative Example 1 and Example 1.

[0098] Comparative Example 2

[0099] The only difference between Comparative Example 2 and Example 1 is that no modified fiber was added in this comparative example; the other steps are exactly the same in Comparative Example 2 and Example 1.

[0100] Comparative Example 3

[0101] The only difference between Comparative Example 3 and Example 1 is that the modified sulfur is replaced with ordinary sulfur in this comparative example, while the other steps are exactly the same in Comparative Example 3 and Example 1.

[0102] Performance testing:

[0103] According to GB / T 9265-2009 "Determination of Alkali Resistance of Architectural Coatings", GB / T 17671-2021 "Test Method for Strength of Cement Mortar", GB / T 1843-2008 "Determination of Impact Strength of Plastic Cantilever Beams" (adjusted to apply to sulfur-based materials), GB / T 50082-2009 "Standard for Test Methods of Long-Term Performance and Durability of Ordinary Concrete", and GB / T 5486-2008 "Test Methods for Inorganic Rigid Thermal Insulation Products", the alkali resistance, compressive strength, flexural strength, impact strength, drying shrinkage rate and water absorption rate of the high alkali resistance modified sulfur-based adhesives obtained in Examples 1-3 and Comparative Examples 1-3 were tested respectively.

[0104] The adhesives obtained in Examples 1-3 and Comparative Examples 1-3 were poured into standard molds (40mm×40mm×160mm prisms) and cooled and cured at room temperature for 24 hours. For alkali resistance testing, the samples were immersed in a 10% NaOH solution (simulating the alkaline environment of concrete pore fluid) and placed in a 23℃ constant temperature chamber for 28 days to test the compressive strength retention rate. Mechanical property testing was conducted according to GB / T 17671-2021, using a universal testing machine to test compressive and flexural strength; and a cantilever beam impact testing machine with sample dimensions of 55mm×10mm×10mm and a span of 40mm was used to test impact strength. Physical property testing involved determining the drying shrinkage rate by measuring the initial length and the length change over 28 days; and weighing the samples after immersion in water for 24 hours to calculate the water absorption rate. The final data are shown in Table 1 below.

[0105] Table 1

[0106]

[0107] As shown in Table 1, the alkali-resistant modified sulfur-based adhesives obtained in Examples 1-3 exhibit significantly better alkali resistance than the comparative examples. This indicates that the copolymerization accelerator and dimethyl silicone oil synergistically enhance chemical stability under alkaline conditions. Comparative Example 3 (ordinary sulfur) performed the worst, confirming that sulfur crystal transformation leads to microcracks and accelerated alkali corrosion. In terms of mechanical properties, the examples showed stronger performance, demonstrating the synergistic effect of the copolymerization accelerator and modified sulfur in forming a cross-linked network, effectively inhibiting sulfur crystal transformation and volume shrinkage, further buffering internal stress, and reducing microcrack formation. The overall performance of the examples is superior to that of the comparative examples, verifying the effectiveness of the "modified sulfur-modified fiber-copolymerization accelerator" ternary synergistic system. A highly alkali-resistant, high-strength, high-toughness, excellent interface, and environmentally friendly sulfur-based adhesive has been successfully prepared, providing a reliable material basis for its application in construction engineering, corrosion protection engineering, and rapid repair.

[0108] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for producing a high-alkali-resistant modified sulfur-based adhesive, characterized by, The preparation steps include the following: S1. By weight, mix 60-65 parts of aggregate, 5-10 parts of mineral filler and 3-5 parts of silicate cement evenly, and preheat in an oil bath to 130-140℃ to obtain a preliminary mixture; S2. Add 30-35 parts of modified sulfur and 3-6 parts of modified fiber to the preliminary mixture obtained in step S1, maintain the temperature at 130-140℃, and stir at a speed of 200-300r / min for 10-15min to obtain the secondary mixture. S3. Pour the mixture obtained in step S2 into a preheated mold, keep it at 130-140℃ for 10-15 minutes, and after cooling and demolding, obtain a highly alkali-resistant modified sulfur-based adhesive. The preparation of the modified sulfur includes the following steps: S11. By weight, heat 70-80 parts of sulfur to melt in an oil bath, add 5-10 parts of copolymerization accelerator and maintain the temperature, stir at 200-250 r / min for 15-20 min to obtain a preliminary modifier; S12. Add 8-10 parts of waste ceramic powder and 4-6 parts of rubber granules to the preliminary modifier obtained in step S11, and stir at a speed of 250-300 r / min for 25-30 min to obtain the secondary modifier. S13. Lower the temperature to 125-130℃, add 0.2-0.3 parts of antioxidant 1010 and 0.5-1 parts of dimethyl silicone oil, stir at 250-300 r / min for 8-10 min, cool to room temperature and crush to finally obtain modified sulfur; The preparation of the modified fiber includes the following steps: S21. By mass, mix 4-5 parts of silane coupling agent with 36-45 parts of deionized water, adjust the pH to 4-5, and hydrolyze for 25-30 minutes to obtain the coupling agent treatment solution. S22. Add 80-90 parts of basalt fiber and 5-10 parts of polypropylene fiber to the coupling agent treatment solution obtained in step S21, disperse ultrasonically for 15-20 minutes, take it out, and dry it at 80℃ for 40-50 minutes to obtain the preliminary modified fiber. S23. Mix 4-5 parts of epoxy resin emulsion with 0.5-1 parts of sodium dodecylbenzene sulfonate, stir evenly, add the preliminary modified fiber obtained in step S22, stir at 150-200 r / min for 25-30 min, take it out and dry at 100℃ for 1-2 h to obtain modified fiber. The preparation of the copolymerization accelerator includes the following steps: S111. By mass, mix 2-3 parts of dicyclopentadiene, 1-3 parts of styrene and 5-8 parts of anhydrous ethanol, and stir at 150-200 r / min for 5-10 min to obtain a preliminary mixture; S112. Add 0.5-1 parts of tetramethylthiuram disulfide and 0.3-0.5 parts of benzoyl peroxide to the preliminary mixture obtained in step S111, and stir the mixture at 150-200 r / min for 1-2 h at 83-85℃ to obtain the secondary mixture. S113. When the temperature drops to 55-60℃, add 0.2-0.3 parts of antioxidant 1010, continue stirring for 10-15 minutes, and cool to room temperature to obtain the copolymerization accelerator.

2. The method of claim 1, wherein the modified sulfur-based adhesive has high alkali resistance. In step S11, the oil bath temperature is 135-145℃.

3. The method of claim 1, wherein the modified sulfur-based adhesive has high alkali resistance. The mineral filler is selected from one or more of the following: fly ash, silica fume, coal gangue powder, waste glass powder, sludge ash, metallurgical dust, slag powder, rice husk ash, and straw ash.

4. The method of claim 1, wherein the modified sulfur-based adhesive has high alkali resistance. In step S13, the particle size is controlled to be 2 mm during crushing.

5. The method of claim 1, wherein the modified sulfur-based adhesive has high alkali resistance. The aggregate is selected from one or more of the following: river sand, quartz sand, manufactured sand, lake sand, tailings sand, recycled fine aggregate, and aeolian sand.

6. The method of claim 1, wherein the modified sulfur-based adhesive has high alkali resistance. In step S22, the frequency of ultrasonic dispersion is 40 kHz.

7. The method of claim 1, wherein the modified sulfur-based adhesive has high alkali resistance. The epoxy resin emulsion is selected from a bisphenol A type waterborne epoxy resin emulsion with a solid content of 50%.

8. A highly alkali resistant modified sulphur-based adhesive, characterized in that, It is prepared by the preparation method described in any one of claims 1-7.

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