Solubility-resistant fluoride-free aqueous film-forming foam extinguishing agent and preparation method thereof

Abstract

The invention discloses a solubility-resistant fluoride-free aqueous film-forming foam extinguishing agent and a preparation method thereof, and relates to the technical field of extinguishing agents. The invention discloses a soluble-resistant fluoride-free aqueous film-forming foam extinguishing agent. The cleaning agent is prepared from the following raw materials in parts by weight: 8 to 12 parts of a compound surfactant, 15 to 20 parts of modified polyvinyl acetate, 3 to 5 parts of modified xanthan gum, 5 to 8 parts of ethylene glycol butyl ether, 4 to 6 parts of propylene glycol, 0.5 to 1 part of benzotriazole, 0.3 to 0.6 part of triethanolamine, 0.2 to 0.4 part of disodium ethylene diamine tetraacetate, 0.8 to 1.2 parts of hydroxyethyl cellulose, 0.1 to 0.3 part of polyether modified silicone oil and 0.05 to 0.1 part of isothiazolinone. 6-9 parts of ammonium dihydrogen phosphate and the balance of deionized water. According to the anti-dissolution fluoride-free aqueous film-forming foam extinguishing agent, fluoride-free components are more environmentally friendly, and the requirement for green development is met; the compound surfactant has a synergistic effect with the modified polyvinyl acetate and the modified xanthan gum, so that the fire extinguishing efficiency and the solubility resistance are improved; the process is clear, parameters are clear, the product stability is good through ultrasonic dispersion and high-pressure homogenization treatment, the performance is optimized through multiple additives, and the application scene is wide.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of fire extinguishing agents, in particular to an anti-solubility fluorine-free water film forming foam fire extinguishing agent and a preparation method thereof. BACKGROUND

[0002] In the field of fire safety, water film forming foam fire extinguishing agents are widely used in oil and various flammable liquid fire extinguishing due to their ability to quickly form a closed water film on the surface of burning liquids, which has both foam covering and oxygen exclusion asphyxiation dual fire extinguishing effects. However, traditional water film forming foam fire extinguishing agents rely on fluorine-containing surfactants, which are difficult to degrade naturally after use and can accumulate in water and soil, causing long-term pollution to the ecological environment and damaging the ozone layer, which does not meet the current global green environmental protection and sustainable development policy requirements and industry trends. Fluorine-free has become an important direction for the development of fire extinguishing agents.

[0003] At the same time, the application of polar flammable liquids such as alcohols and esters in industrial production is increasingly widespread. Such substances are prone to dissolution and corrosion with ordinary foam fire extinguishing agents, resulting in foam rupture and fire extinguishing failure. Therefore, there is a higher requirement for the anti-solubility of fire extinguishing agents. However, existing fluorine-free water film forming foam fire extinguishing agents often face problems such as insufficient anti-solubility, poor foam stability, and low fire extinguishing efficiency. Some products have achieved fluorine-free, but when extinguishing polar flammable liquid fires, they are difficult to form stable foam layers and water films and are easily penetrated and damaged by flammable liquids. Other products excessively increase the amount of high molecular additives to improve anti-solubility, resulting in abnormal viscosity and poor flowability of the fire extinguishing agent, affecting the spraying performance and fire extinguishing timeliness, and causing stability problems such as layering and precipitation during storage, which cannot meet the actual fire fighting scene usage requirements.

[0004] In addition, the preparation process of existing fluorine-free water film forming foam fire extinguishing agents also has room for optimization. Some process parameters are ambiguous and the modification effect of key components is not good, resulting in poor product performance consistency and unstable batch production. In summary, the development of a fluorine-free water film forming foam fire extinguishing agent with excellent anti-solubility, high fire extinguishing efficiency, good stability, and environmental friendliness is the key to solving the current industry pain points and meeting the dual requirements of fire safety and environmental protection. SUMMARY

[0005] In view of the deficiencies of the prior art, the present application provides an anti-solubility fluorine-free water film forming foam fire extinguishing agent and a preparation method thereof, which solves the problems of fluorine pollution, insufficient anti-solubility, and poor stability of traditional fire extinguishing agents.

[0006] To achieve the above purpose, the present application is realized by the following technical scheme:

[0007] The application discloses a kind of anti-soluble fluorine-free water film forming foam extinguishing agent, comprising the following raw materials by weight: 8-12 parts of compound surfactant, 15-20 parts of modified polyvinyl acetate, 3-5 parts of modified xanthan gum, 5-8 parts of ethylene glycol butyl ether, 4-6 parts of propylene glycol, 0.5-1 part of benzotriazole, 0.3-0.6 part of triethanolamine, 0.2-0.4 part of disodium ethylenediaminetetraacetate, 0.8-1.2 part of hydroxyethyl cellulose, 0.1-0.3 part of polyether modified silicone oil, 0.05-0.1 part of isothiazolinone, 6-9 parts of ammonium dihydrogen phosphate, and the balance is deionized water.

[0008] Further, the compound surfactant is compounded by cocamidopropyl betaine and lauryl polyoxyethylene ether-7 at a mass ratio of 3:2. This ratio of compounding takes into account the hard water resistance of cocamidopropyl betaine and the emulsification and foaming property of lauryl polyoxyethylene ether-7, can quickly spread on the surface of polar and non-polar flammable liquids to form a continuous water film to block oxygen, and can also cooperatively build a dense foam layer, so as to avoid the deficiency of a single surfactant in terms of anti-solubility or film forming speed, and improve the fire extinguishing efficiency and applicability.

[0009] Further, the modified polyvinyl acetate has the following preparation steps:

[0010] A1, polyvinyl acetate and N,N-dimethylformamide are added to a four-necked flask, stirred at 250-300 r / min, and heated to 65-70 DEG C to form a transparent solution; ethanolamine is slowly added dropwise, heated to 80-85 DEG C after dropping, and kept for 4-5 h to realize amine modification and introduce hydrophilic groups; then, the temperature is reduced to 55-60 DEG C, silane coupling agent KH-560 and dibutyltin dilaurate are added, uniformly stirred at 350-400 r / min, heated to 70-75 DEG C, and kept for 3-4 h to promote grafting reaction; the product is poured into deionized water, stirred and dispersed, and then left to separate into two layers; the lower water phase is discarded, the upper product is washed with deionized water for 3-4 times, and then dried at 60-65 DEG C for 8-10 h to obtain the first modified polyvinyl acetate; the balance between hydrophilicity and hydrophobicity of polyvinyl acetate is preliminarily optimized, which lays a foundation for subsequent modification;

[0011] A2, add the first modified polyvinyl acetate, ethyl acetate and azobisisobutyronitrile into a four-necked flask, stir at 250-300 r / min, and heat to 75-80℃ for 15-20 min to initiate free radical polymerization; slowly drop the mixed monomers composed of butyl acrylate, hydroxyethyl methacrylate and acrylamide into the flask, control the dropping time at 2-2.5 h, keep the temperature at 78-82℃ during the dropping process, and keep stirring at 350-400 r / min to ensure sufficient copolymerization reaction; after the dropping is completed, heat to 85-90℃, continue to react for 2-3 h, then cool to room temperature, pour the product into petroleum ether, precipitate and filter, wash the precipitate with petroleum ether for 2-3 times, then dry at 55-60℃ for 6-8 h to obtain the second modified polyvinyl acetate; by introducing different functional monomers, the foam stability and the anti-solubility of polyvinyl acetate are enhanced;

[0012] A3, add the second modified polyvinyl acetate and tetrahydrofuran into a four-necked flask, stir at 250-300 r / min, and heat to 65-70℃ to completely dissolve the polymer, then add the modified nano-silica, ultrasonic at 250-300 W and stir at 200-250 r / min, react at 70-75℃ for 3-4 h; after the reaction is completed, concentrate the composite system to a solid content of 60%-70% at a temperature of 60-65℃ and a vacuum degree of -0.08 to -0.09 MPa by rotary evaporation to obtain the modified polyvinyl acetate. The mechanical properties and film-forming compactness of polyvinyl acetate are improved by the nano-enhancing effect, and the anti-solubility is further strengthened.

[0013] Further, the modified nano-silica in A3 is modified as follows: take 10 g of nano-silica, add 60 mL of anhydrous ethanol, ultrasonic disperse for 30 min at 350 W, then add 5 g of silane coupling agent KH-550, and react at 65℃ with stirring at 300 r / min for 2 h, then centrifugalize and dry at 60℃ under vacuum for 5 h. The combination of the modified nano-silica and the second modified polyvinyl acetate is mainly non-covalent interaction: on the one hand, the amino and silicon hydroxyl groups on the surface of the nano-silica form strong hydrogen bonds with the hydroxyl and amide groups on the polymer molecular chain, realizing stable anchoring of the particles and the polymer; on the other hand, the hydrophobic carbon chains on the surface of the nano-silica and the hydrophobic segments of the polymer are combined through van der Waals force, further improving the dispersion uniformity. The complex effect can enhance the mechanical properties and film-forming compactness of polyvinyl acetate, and provide support for the anti-solubility of the fire extinguishing agent.

[0014] Further, the amount ratio of polyvinyl acetate, N,N-dimethylformamide, ethanolamine, silane coupling agent KH-560 and dibutyltin dilaurate in A1 is 80-100 g: 150-180 mL: 25-30 g: 12-15 g: 0.8-1.0 g.

[0015] Further, the use amount ratio of the first modified polyvinyl acetate, ethyl acetate, azobisisobutyronitrile, butyl acrylate, hydroxyethyl methacrylate, and acrylamide in A2 is 60-70 g: 80-100 mL: 1.2-1.5 g: 20-25 g: 10-12 g: 5-8 g.

[0016] Further, the use amount ratio of the second modified polyvinyl acetate, tetrahydrofuran, and modified nano-silicon dioxide in A3 is 50-60 g: 120-150 mL: 10 g.

[0017] Further, the modified xanthan gum has the following specific preparation steps:

[0018] B1, xanthan gum and isopropyl alcohol are added to a three-necked flask, stirred at 200-250 r / min until uniformly dispersed, a 30% by mass sodium hydroxide solution is slowly added dropwise, stirred at 30-35°C for 1.5-2 h to activate the active groups of the xanthan gum; after activation is completed, chloroacetic acid is added, the temperature is raised to 50-55°C, and the reaction is maintained for 3-4 h to achieve carboxymethylation modification; after the reaction is completed, the product is precipitated by adding anhydrous ethanol, the precipitate is washed with anhydrous ethanol for 2-3 times after filtration, and the precipitate is dried at 55-60°C for 6-8 h to obtain the first modified xanthan gum; the introduction of carboxyl groups improves the water solubility and hydrophilicity of the xanthan gum and prepares for subsequent modification;

[0019] B2, the first modified xanthan gum and deionized water are added to a three-necked flask, stirred at 250-300 r / min, and the temperature is raised to 45-50°C to completely dissolve the xanthan gum; 2,3-epoxypropyltrimethylammonium chloride is slowly added dropwise, the temperature is raised to 60-65°C after the dropwise addition is completed, and the reaction is maintained for 2.5-3 h at 300-350 r / min to achieve quaternary ammonium modification; after the reaction is completed, the product solution is placed in a dialysis bag with a molecular weight cutoff of 10,000, and deionized water is used for dialysis for 24-36 h, with the deionized water being changed every 8 h; after dialysis is completed, anhydrous ethanol is added to the product solution to precipitate the product, the product is filtered after standing for 30-40 min, the precipitate is washed with a 70% by mass ethanol aqueous solution for 2 times and then with anhydrous ethanol for 1 time, and finally the precipitate is dried at 55-60°C for 6-8 h to obtain the second modified xanthan gum; the introduction of cationic groups enhances the compatibility of the xanthan gum with other components and improves the foam stability;

[0020] B3, the second modified xanthan gum and MES buffer solution with pH=5.5 are added into a four-mouth flask to maintain pH stability, and the temperature is raised to 40-45℃ under stirring at 300-350 r / min, and the xanthan gum is completely dissolved after 40-50 min; EDC hydrochloride is added, stirred at 250-300 r / min for 10 min, and then N-hydroxysuccinimide is added, and stirred for 30-40 min; then polyethylene glycol is added dropwise within 30-40 min, the temperature is raised to 50-55℃, and the reaction is carried out under stirring at 250-300 r / min for 5-6 h to realize graft modification; after the reaction is completed, anhydrous sodium sulfate is added into the system, stirred at 200-250 r / min for 20-30 min, and filtered with a 0.45 μm filter membrane; anhydrous ethanol is added into the filtrate to precipitate, and after 30-40 min, the precipitate is extracted by suction filtration, the filter cake is washed with 70% ethanol water for 2-3 times, and then washed with anhydrous ethanol once, and dried at 50-55℃ for 8-10 h; after drying, the product is crushed to 100-200 meshes to obtain the modified xanthan gum. EDC hydrochloride and N-hydroxysuccinimide activate the carboxyl groups on the second modified xanthan gum; the rheological properties and foam toughness of the xanthan gum are optimized by grafting polyethylene glycol, and the anti-solubility and stability effects are enhanced. Anhydrous sodium sulfate is used as a salting-out agent, the solubility of the modified xanthan gum in the MES buffer solution is reduced by increasing the ionic strength of the system, and the conditions for precipitating the product by anhydrous ethanol are provided, so that the product can be fully recovered.

[0021] Further, the number average molecular weight of the polyethylene glycol in B3 is 1000-1500, which can balance the hydrophilicity and grafting effect, avoid poor compatibility caused by too large molecular weight, or insufficient modification caused by too small molecular weight; and the pH is adjusted to 7.5 by 0.1 mol / L NaOH in advance, which can eliminate the interference of the acidity of the polyethylene glycol on the reaction system, ensure the smooth progress of the grafting reaction, and ensure the stable performance of the modified xanthan gum.

[0022] Further, the amount ratio of the xanthan gum, isopropyl alcohol, sodium hydroxide solution, and chloroacetic acid in B1 is 20-25 g:80-100 mL:15-18 g:20-25 g.

[0023] Further, the amount ratio of the first modified xanthan gum, deionized water, and 2,3-epoxypropyltrimethylammonium chloride in B2 is 15-20 g:60-70 mL:12-15 g.

[0024] Further, the amount ratio of the second modified xanthan gum, MES buffer solution, EDC hydrochloride, N-hydroxysuccinimide, polyethylene glycol, and anhydrous sodium sulfate in B3 is 12-15 g:80-100 mL:0.8-1.0 g:0.5-0.6 g:18-22 g:3-5 g.

[0025] A preparation method of an anti-solubility fluorine-free water film-forming foam extinguishing agent, specifically comprising the following steps:

[0026] S1, add ethylene glycol butyl ether and propylene glycol in a reaction kettle, stir at room temperature at 200-250 r / min for 15-20 min to form a uniform transparent mixed solvent system, slowly add modified polyvinyl acetate, control the stirring speed at 500-600 r / min, and heat to 65-75 DEG C at the same time, heat and stir for 2-3 h, take samples every 30 min during the period to observe, until a particle-free, uniform viscous solution system is formed, which lays a foundation for subsequent component mixing and avoids the influence of uneven dispersion of modified polyvinyl acetate on film formation and anti-solubility;

[0027] S2, when the solution temperature drops to 40-45 DEG C, first add the compound surfactant system to avoid damage to the activity at high temperature, stir at 250-300 r / min for 30-40 min, then add modified xanthan gum, heat and stir at 400-450 r / min at 40-45 DEG C for 90-120 min to promote the dissolution of modified xanthan gum and form a colloid, keep the solution temperature at 40-45 DEG C, reduce the speed to 300-350 r / min, slowly add ammonium dihydrogen phosphate, and stir for 40-60 min until completely dissolved, then add hydroxyethyl cellulose in 3-4 times, stir for 15-20 min after each addition until completely dispersed, adjust the system viscosity to 200-300 mPa·s at 25 DEG C, ensure the stability of the system, and consider the flowability and foam forming property;

[0028] S3, sequentially add benzotriazole, disodium ethylenediaminetetraacetate, polyether modified silicone oil and isothiazolinone to the reaction kettle, stir at 250-300 r / min for 20-25 min after adding each additive, and after all are dispersed, filter at 0.1-0.2 MPa with a polypropylene filter bag with a pore size of 5-25 mu to remove impurities, return the filtered solution to the reaction kettle, slowly add triethanolamine, adjust the pH to 7.0-7.5 to avoid the influence of acid and alkali on the stability of the system, add deionized water to make up to 100 parts, and stir at 200-250 r / min for 30-40 min until uniform, ensure that the proportion of the fire extinguishing agent components is accurate, the performance is stable, and there is no impurity to interfere with the fire extinguishing effect;

[0029] S4, the material is first dispersed by ultrasonic at 400-450 W and 30-35 DEG C for 30-40 min, then treated by high pressure homogenization at 20-25 MPa for 2-3 times, loaded into a special sealed container, stored in the dark and cool place, prevented from stratification and deterioration, and ensured that the fire extinguishing agent still maintains excellent fire extinguishing and anti-solubility performance after long-term storage.

[0030] The application provides an anti-solubility fluorine-free water film forming foam extinguishing agent and a preparation method thereof, and has the following beneficial effects:

[0031] 1、The fire extinguishing agent takes "fluorine-free" as the core design concept, discards the fluorine-containing components in the traditional water film-forming foam fire extinguishing agent which can cause ecological pollution, avoids the risk of fluorine-containing substances remaining in water and soil after extinguishing fire and damaging the ozone layer from the source, and meets the policy guidance and industry development trend of environmentally friendly fire-fighting products worldwide. At the same time, the raw materials used, such as modified polyvinyl acetate and modified xanthan gum, have good biocompatibility and can be gradually degraded in the natural environment without long-term environmental burden, meeting the fire safety needs and protecting the ecological environment, and are suitable for scenes with strict environmental protection requirements such as chemical industry parks, food processing enterprises and water source protection areas, widening the application range of fluorine-free fire extinguishing agents.

[0032] 2、Through the synergistic effect of the complex surfactant and the modified polymer material, the fire extinguishing agent can effectively resist the erosion of polar liquid to the foam when extinguishing polar flammable liquid fire. Among them, the modified polyvinyl acetate is modified by ethanolamine, silane coupling agent and modified nano silicon dioxide in multiple steps, and the hydrophilic and oleophobic balanced groups are introduced into the molecular structure, which can quickly form a dense and stable water film on the surface of polar flammable liquid to block the contact between flammable liquid and air; the modified xanthan gum is modified by carboxymethylation, quaternization and polyethylene glycol grafting, which improves the viscosity adjustment ability and foam stability, and can form a durable and not easy to break foam layer with the complex surfactant, avoiding the problem of easy breakage of ordinary fluorine-free fire extinguishing agent in polar liquid fire, greatly shortening the extinguishing time and improving the success rate of fire fighting, especially suitable for high-risk scenes of polar flammable liquid storage and production.

[0033] 3、From the preparation process to the ingredient collocation, the fire extinguishing agent guarantees the long-term stability of the product in all aspects. In the preparation process, by strictly controlling the stirring speed and temperature of the mixed solvent system, adding hydroxyethyl cellulose in stages and adjusting the viscosity to 200-300 mPa・s, and subsequent ultrasonic dispersion and high-pressure homogenization treatment, it is ensured that the components are fully integrated to form a uniform and stable colloidal solution, effectively avoiding problems such as separation, precipitation and caking during storage. At the same time, the addition of benzotriazole, ethylenediaminetetraacetic acid disodium and other additives in the formula can inhibit the oxidative degradation of raw materials and metal ion catalytic deterioration, further extending the shelf life of the product; the pH of the product is adjusted to the neutral range by triethanolamine, which also reduces the corrosiveness of the fire extinguishing agent to the storage container. In addition, the product does not require special storage conditions and only needs to be stored in a dark and cool place in a sealed manner, and has good flowability when used, which can be adapted to conventional fire-fighting spraying equipment without the need for additional pretreatment, greatly improving the convenience and reliability in actual fire-fighting operations.

[0034] 4、The fire extinguishing agent breaks through the technical bottleneck that the traditional fluorine-free water film-forming foam extinguishing agent is difficult to balance the anti-solubility and extinguishing efficiency, and the stability and fluidity are mutually restricted, and realizes the balanced optimization of multiple performance dimensions. On the one hand, through the cooperation of modified polymer materials and compounded surfactants, the anti-solubility effect on polar flammable liquid is ensured, and the ability of rapid film formation and high efficiency extinguishing is maintained, which can play an excellent role in non-polar oil fire and polar flammable liquid fire. On the other hand, reasonable additive ratio and precise preparation process control make the product have higher viscosity to ensure the stability of the foam, while still maintaining good fluidity, which can be sprayed by various equipment such as fire pipe network, hand-held fire extinguisher, etc. for long-distance or close-range spraying, and is suitable for different scales and types of fire fighting scenes such as industrial plant, warehouse, ship engine room, large oil tank area, etc. In addition, the dosage of each raw material is clear and the process parameters are controllable during the preparation of the product. For example, the preparation steps of modified polyvinyl acetate and modified xanthan gum have strict temperature, time and speed control, which can ensure the consistency of product performance in batch production, meet the demand of large-scale fire fighting product procurement and storage, and provide stable and reliable product support for fire safety in different scenes. DETAILED DESCRIPTION

[0035] The technical solutions in the embodiments of the present application will be described below. Obviously, the described embodiments are only part of the embodiments of the present application, not all. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0036] Embodiment 1, preparation of anti-solubility fluorine-free water film-forming foam extinguishing agent, the specific preparation steps are as follows:

[0037] S1, add 5 parts of ethylene glycol butyl ether and 4 parts of propylene glycol in a reaction kettle, stir at 200 r / min at room temperature for 15 min to form a uniform transparent mixed solvent system; slowly add 15 parts of polyvinyl acetate, control the stirring speed to 500 r / min, and heat to 65℃ at the same time, and keep stirring for 2 h, during which the sample is taken every 30 min for observation until a particle-free, uniform viscous solution system is formed;

[0038] S2, when the solution temperature drops to 40℃, first add 8 parts of compounded surfactant system, stir at 250 r / min for 30 min; then add 3 parts of xanthan gum, stir at 400 r / min for 90 min at 40℃ to form a uniform colloidal solution; keep the solution temperature at 40℃, reduce the speed to 300 r / min, slowly add 6 parts of ammonium dihydrogen phosphate, and stir for 40 min until completely dissolved; then add 0.8 parts of hydroxyethyl cellulose, add it in three times, and stir for 15 min after each addition until completely dispersed, adjust the system viscosity to 200 mPa·s at 25℃;

[0039] S3, 0.5 parts of benzotriazole, 0.2 parts of disodium ethylenediaminetetraacetate, 0.1 parts of polyether modified silicone oil and 0.05 parts of isothiazolinone were sequentially added to the reaction kettle, after adding each additive, stirring at 250 r / min for 20 min, after all dispersion, 0.1 MPa pressure filtration was carried out with a polypropylene filter bag with a pore size of 5 μm to remove impurities; the filtered solution was returned to the reaction kettle, 0.3 parts of triethanolamine was slowly added, the pH was adjusted to 7.0, deionized water was added to make up to 100 parts, and stirring was carried out at 200 r / min for 30 min until uniform;

[0040] S4, the material was first dispersed by ultrasonic at 400 W and 30℃ for 30 min, then treated by high pressure homogenization at 20 MPa twice, loaded into a special sealed container, and stored in the dark and cool place.

[0041] Example 2, preparation of anti-soluble fluorine-free water film forming foam extinguishing agent, the specific preparation steps are as follows:

[0042] S1, 8 parts of ethylene glycol butyl ether and 6 parts of propylene glycol were added to the reaction kettle, stirred at 250 r / min at room temperature for 20 min to form a uniform transparent mixed solvent system; 20 parts of polyvinyl acetate were slowly added, the stirring speed was controlled at 600 r / min, and the temperature was increased to 75℃, and the solution was stirred for 3 h, during which the sample was taken every 30 min to observe until a particle-free, uniform viscous solution system was formed;

[0043] S2, when the solution temperature dropped to 45℃, 12 parts of the compounded surfactant system was first added, and stirred at 300 r / min for 40 min; then 5 parts of xanthan gum was added, and stirred at 450 r / min at 45℃ for 120 min to form a uniform colloidal solution; the solution temperature was kept at 45℃, the speed was reduced to 350 r / min, 9 parts of ammonium dihydrogen phosphate was slowly added, and stirred for 60 min until completely dissolved; then 1.2 parts of hydroxyethyl cellulose was added in 4 times, and stirred for 20 min after each addition until completely dispersed, and the system viscosity was adjusted to 300 mPa·s at 25℃;

[0044] S3, 1 part of benzotriazole, 0.4 parts of disodium ethylenediaminetetraacetate, 0.3 parts of polyether modified silicone oil and 0.1 parts of isothiazolinone were sequentially added to the reaction kettle, after adding each additive, stirring at 300 r / min for 25 min, after all dispersion, 0.2 MPa pressure filtration was carried out with a polypropylene filter bag with a pore size of 25 μm to remove impurities; the filtered solution was returned to the reaction kettle, 0.6 parts of triethanolamine was slowly added, the pH was adjusted to 7.5, deionized water was added to make up to 100 parts, and stirring was carried out at 250 r / min for 40 min until uniform;

[0045] S4, the material is first treated by 420W, 32℃ ultrasonic dispersion for 35min, and then by 22MPa high pressure homogenization for 3 times, and then is loaded into a special sealed container for storage in dark and cool place.

[0046] Example 3, preparation of anti-soluble fluorine-free water film forming foam extinguishing agent, the specific preparation steps are as follows:

[0047] S1, in the reaction kettle, 6 parts of ethylene glycol butyl ether and 5 parts of propylene glycol are added, and stirred at 220r / min at room temperature for 17min to form a uniform transparent mixed solvent system; 17 parts of polyvinyl acetate are slowly added, the stirring speed is controlled at 550r / min, and the temperature is increased to 70℃, and the stirring is kept for 2.5h, during which the sample is taken every 30min for observation, until a uniform viscous solution system without particles is formed;

[0048] S2, when the solution temperature drops to 42℃, first add 10 parts of compound surfactant system, stir at 270r / min for 35min; then add 4 parts of xanthan gum, stir at 425r / min for 110min at 42℃ to form a uniform colloidal solution; keep the solution temperature at 42℃, reduce the speed to 330r / min, slowly add 7 parts of ammonium dihydrogen phosphate, stir for 50min until completely dissolved; then add 1 part of hydroxyethyl cellulose, add in 3 times, stir for 17min after each addition until completely dispersed, adjust the system viscosity to 250mPa·s at 25℃;

[0049] S3, 0.7 parts of benzotriazole, 0.3 parts of disodium ethylenediaminetetraacetate, 0.2 parts of polyether modified silicone oil and 0.08 parts of isothiazolinone are added to the reaction kettle in turn, and after adding each additive, the stirring speed is 270r / min and the stirring time is 22min, and after all the additives are dispersed, the impurities are removed by 0.1MPa pressure filtration with a polypropylene filter bag with a pore size of 15μm; the filtered solution is returned to the reaction kettle, 0.4 parts of triethanolamine is slowly added dropwise, the pH is adjusted to 7.2, deionized water is added to make up to 100 parts, and the stirring speed is 220r / min and the stirring time is 35min until uniform;

[0050] S4, the material is first treated by 420W, 32℃ ultrasonic dispersion for 35min, and then by 22MPa high pressure homogenization for 3 times, and then is loaded into a special sealed container for storage in dark and cool place.

[0051] Example 4, preparation of modified polyvinyl acetate, the specific preparation steps are as follows:

[0052] A1, into a four-necked flask were added 80 g of polyvinyl acetate and 150 mL of N,N-dimethylformamide, and stirred at 250 r / min to be heated to 65°C to form a transparent solution; 25 g of ethanolamine was slowly added dropwise, and after the dropwise addition was completed, the temperature was increased to 80°C and kept for 4 h; then the temperature was decreased to 55°C, 12 g of silane coupling agent KH-560 and 0.8 g of dibutyltin dilaurate were added, and after being uniformly stirred at 350 r / min, the temperature was increased to 70°C and kept for 3 h; the product was poured into deionized water, stirred and dispersed, and then allowed to stand to separate into layers, the lower aqueous phase was discarded, the upper product was washed with deionized water for 3 times, and then dried at 60°C for 8 h to obtain the first modified polyvinyl acetate;

[0053] A2, into a four-necked flask were added 60 g of the first modified polyvinyl acetate, 80 mL of ethyl acetate and 1.2 g of azobisisobutyronitrile, and stirred at 250 r / min to be heated to 75°C and kept for 15 min; a mixture of monomers composed of 20 g of butyl acrylate, 10 g of hydroxyethyl methacrylate and 5 g of acrylamide was slowly added dropwise into the flask, the dropwise addition time was controlled to be 2 h, and the temperature was kept at 78°C during the dropwise addition process, and the stirring was kept at 350 r / min; after the dropwise addition was completed, the temperature was increased to 85°C, and the reaction was continued for 2 h, then the temperature was decreased to room temperature, the product was poured into petroleum ether, the precipitate was filtered after being precipitated, the precipitate was washed with petroleum ether for 2 times, and then dried at 55°C for 6 h to obtain the second modified polyvinyl acetate;

[0054] A3, into a four-necked flask were added 50 g of the second modified polyvinyl acetate and 120 mL of tetrahydrofuran, and stirred at 250 r / min to be heated to 65°C, so that the polymer was completely dissolved, then 10 g of modified nano-silica was added, and ultrasonic treatment was performed at 250 W and stirring was performed at 200 r / min, and the reaction was performed at 70°C for 3 h; after the reaction was completed, the composite system was concentrated to a solid content of 60% under the conditions of a temperature of 60°C and a vacuum degree of -0.08 MPa by rotary evaporation to obtain the modified polyvinyl acetate.

[0055] Example 5, the modified polyvinyl acetate was prepared, and the specific preparation steps were as follows:

[0056] A1, into a four-necked flask were added 80 g of polyvinyl acetate and 150 mL of N,N-dimethylformamide, and stirred at 250 r / min to be heated to 65°C to form a transparent solution; 25 g of ethanolamine was slowly added dropwise, and after the dropwise addition was completed, the temperature was increased to 80°C and kept for 4 h; then the temperature was decreased to 55°C, 12 g of silane coupling agent KH-560 and 0.8 g of dibutyltin dilaurate were added, and after being uniformly stirred at 350 r / min, the temperature was increased to 70°C and kept for 3 h; the product was poured into deionized water, stirred and dispersed, and then allowed to stand to separate into layers, the lower aqueous phase was discarded, the upper product was washed with deionized water for 3 times, and then dried at 60°C for 8 h to obtain the first modified polyvinyl acetate;

[0057] A2, 70 g of the first modified polyvinyl acetate, 100 mL of ethyl acetate and 1.5 g of azobisisobutyronitrile were added to a four-necked flask, and stirred at 300 r / min and heated to 80℃ for 20 min; a mixture of 25 g of butyl acrylate, 12 g of hydroxyethyl methacrylate and 8 g of acrylamide was slowly added dropwise into the flask, the dropwise time was controlled at 2.5 h, and the temperature was kept at 82℃ during the dropwise process, and the stirring speed was kept at 400 r / min; after the dropwise addition was completed, the temperature was increased to 90℃, and the reaction was continued for 3 h, then the temperature was decreased to room temperature, the product was poured into petroleum ether, and the precipitate was filtered after being precipitated, the precipitate was washed with petroleum ether for 3 times, then dried at 60℃ for 8 h, and the second modified polyvinyl acetate was obtained;

[0058] A3, 60 g of the second modified polyvinyl acetate and 150 mL of tetrahydrofuran were added to a four-necked flask, and stirred at 300 r / min and heated to 70℃, so that the polymer was completely dissolved, then 10 g of modified nano-silicon dioxide was added, and ultrasonic was performed at 300 W and stirring was performed at 250 r / min, and the reaction was performed at 75℃ for 4 h; after the reaction was completed, the composite system was concentrated to a solid content of 60%-70% under the conditions of a temperature of 65℃ and a vacuum degree of-0.09 MPa by rotary evaporation, and the modified polyvinyl acetate was obtained.

[0059] Example 6, the modified xanthan gum was prepared, and the specific preparation steps were as follows:

[0060] B1, 20 g of xanthan gum and 80 mL of isopropyl alcohol were added to a three-necked flask, and stirred at 200 r / min until uniformly dispersed, 15 g of a 30% sodium hydroxide solution was slowly added dropwise, and stirred at 30℃ for 1.5 h for activation, after the activation was completed, 20 g of chloroacetic acid was added, heated to 50℃, and reacted for 3 h; after the reaction was completed, neutralized to pH=6.5 with a 10% hydrochloric acid, then added anhydrous ethanol to precipitate the product, filtered, the precipitate was washed with anhydrous ethanol for 2 times, and dried at 55℃ for 6 h, and the first modified xanthan gum was obtained;

[0061] B2, 15 g of the first modified xanthan gum and 60 mL of deionized water were added to a three-necked flask, and stirred at 250 r / min and heated to 45℃ until the xanthan gum was completely dissolved; 12 g of 2,3-epoxypropyltrimethylammonium chloride was slowly added dropwise, after the dropwise addition was completed, the temperature was increased to 60℃, and stirred at 300 r / min for 2.5 h for reaction; after the reaction was completed, the product solution was placed in a dialysis bag with a molecular weight cut-off of 10000, and dialyzed with deionized water for 24 h, and the deionized water was changed every 8 h; after the dialysis was completed, anhydrous ethanol was added to the product solution to precipitate the precipitate, and after standing for 30 min, the precipitate was filtered, washed with a 70% ethanol aqueous solution for 2 times, then washed with anhydrous ethanol for 1 time, and finally dried at 55℃ for 6 h, and the second modified xanthan gum was obtained;

[0062] B3, 12 g of the second modified xanthan gum and 80 mL of MES buffer solution with pH = 5.5 were added into a four-mouth flask, and the xanthan gum was completely dissolved by heating to 40℃ with stirring at 300 r / min for 40 min; 0.8 g of EDC hydrochloride was added, and stirred at 250 r / min for 10 min, and then 0.5 g of N-hydroxysuccinimide was added, and stirred for 30 min; then 18 g of polyethylene glycol was added dropwise within 30 min, and the reaction was carried out by heating to 50℃ with stirring at 250 r / min for 5 h; after the reaction was completed, 3 g of anhydrous sodium sulfate was added into the system, and stirred at 200 r / min for 20 min, and then filtered with a 0.45 μm filter membrane; anhydrous ethanol was added into the filtrate to precipitate the product, and then the product was extracted by suction filtration after standing for 30 min, and the filter cake was washed twice with 70% ethanol water and once with anhydrous ethanol, and then dried at 50℃ for 8 h, and then ground to 100 mesh to obtain the modified xanthan gum.

[0063] Example 7, preparation of modified xanthan gum, and the specific preparation steps are as follows:

[0064] B1, 25 g of xanthan gum and 100 mL of isopropyl alcohol were added into a three-mouth flask, and stirred at 250 r / min until uniformly dispersed, and then 18 g of 30% sodium hydroxide solution by mass fraction was slowly added dropwise, and the xanthan gum was activated by stirring at 35℃ for 2 h; after the activation was completed, 25 g of chloroacetic acid was added, and the reaction was carried out by heating to 55℃ for 4 h; after the reaction was completed, the product was precipitated by adding anhydrous ethanol, and then the precipitate was washed three times with anhydrous ethanol after filtration, and then dried at 60℃ for 8 h to obtain the first modified xanthan gum;

[0065] B2, 20 g of the first modified xanthan gum and 70 mL of deionized water were added into a three-mouth flask, and the xanthan gum was completely dissolved by heating to 50℃ with stirring at 300 r / min; 15 g of 2,3-epoxypropyltrimethylammonium chloride was slowly added dropwise, and then the reaction was carried out by heating to 65℃ with stirring at 350 r / min for 3 h after the dropwise addition was completed; after the reaction was completed, the product solution was placed in a dialysis bag with a molecular weight cut-off of 10000, and then dialyzed with deionized water for 36 h, and the deionized water was changed every 8 h; after the dialysis was completed, the product solution was precipitated by adding anhydrous ethanol, and then the precipitate was extracted by suction filtration after standing for 40 min, and then the precipitate was washed twice with 70% ethanol water by mass fraction and once with anhydrous ethanol, and finally dried at 60℃ for 8 h to obtain the second modified xanthan gum;

[0066] B3, 15 g of the second modified xanthan gum and 100 mL of MES buffer solution with pH = 5.5 were added into a four-mouth flask, and the temperature was increased to 45°C under stirring at 350 r / min, and the xanthan gum was completely dissolved after 50 min; 1.0 g of EDC hydrochloride was added, and stirred at 300 r / min for 10 min, and then 0.6 g of N-hydroxysuccinimide was added, and stirred for 40 min; then 22 g of polyethylene glycol was added dropwise within 40 min, and the temperature was increased to 55°C, and stirred at 300 r / min for 6 h; after the reaction was completed, 5 g of anhydrous sodium sulfate was added into the system, and stirred at 250 r / min for 30 min, and filtered with a 0.45 μm filter membrane; anhydrous ethanol was added into the filtrate to precipitate, and after 40 min, the precipitate was extracted by suction filtration, and the filter cake was washed with 70% ethanol water for 3 times, and washed with anhydrous ethanol for 1 time, and dried at 55°C for 10 h, and then ground to 200 mesh to obtain the modified xanthan gum.

[0067] Comparative Example 1, preparation of a fluorine-free water film-forming foam extinguishing agent resistant to dissolution, the specific preparation steps are as follows:

[0068] The remaining steps are unchanged, only the polyvinyl acetate of Example 3 is replaced with the modified polyvinyl acetate prepared in Example 4, and a fluorine-free water film-forming foam extinguishing agent resistant to dissolution is prepared.

[0069] Comparative Example 2, preparation of a fluorine-free water film-forming foam extinguishing agent resistant to dissolution, the specific preparation steps are as follows:

[0070] The remaining steps are unchanged, only the xanthan gum of Example 3 is replaced with the modified xanthan gum prepared in Example 7, and a fluorine-free water film-forming foam extinguishing agent resistant to dissolution is prepared.

[0071] Comparative Example 3, preparation of a fluorine-free water film-forming foam extinguishing agent resistant to dissolution, the specific preparation steps are as follows:

[0072] The remaining steps are unchanged, only the polyvinyl acetate of Example 3 is replaced with the modified polyvinyl acetate prepared in Example 4, and the xanthan gum is replaced with the modified xanthan gum prepared in Example 7, and a fluorine-free water film-forming foam extinguishing agent resistant to dissolution is prepared.

[0073] Performance test

[0074] Test item Test standard Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Extinguishing time (s) - 95% ethanol fire GB 15308-2006 130 115 100 80 75 60 Extinguishing time (s) - 0# diesel oil fire GB 15308-2006 90 82 75 60 55 48 Burn resistance time (min) - 95% ethanol fire GB 15308-2006 5 6 7 10 11 13 Burn resistance time (min) - 0# diesel oil fire GB 15308-2006 11 13 15 20 22 24 Foam stability (25% drainage time, min) GB 15308-2006 5 6 7 9 10 12 Storage stability (30℃ / 90d) GB 15308-2006 Layering obvious Slight layering Substantially stable Stable Stable No change Spreading / film formation time (s) ISO 7203 25 22 20 15 13 10

[0075] According to the performance test results, in terms of fire extinguishing efficiency, the polyvinyl acetate of Comparative Example 3 and the xanthan gum are both modified, and the 95% ethanol fire extinguishing time is only 60s, and the 0# diesel oil fire extinguishing time is 48s, which is greatly shortened compared with 100s and 75s of Example 3 respectively; in terms of burn resistance, Comparative Example 3 also leads, and the 95% ethanol fire and 0# diesel oil fire resistance times are 13min and 24min respectively, which are significantly higher than 7min and 15min of Example 3, and the single modification groups of Comparative Examples 1 and 2 are also stronger than the unmodified Example; in terms of foam stability, the 25% liquid separation time of Comparative Example 3 is 12min, and the 25% liquid separation time of Example 3 is 7min, and the modified group is better as a whole; in terms of storage stability, Example 1 is obviously stratified, and Example 2 is slightly stratified, while Comparative Examples 1-3 are stable, and Comparative Example 3 has no change; in terms of spreading and film forming, the film forming time of Comparative Example 3 is 10s, which is much faster than 20s of Example 3, and the modified group has higher film forming efficiency. In summary, the fire extinguishing agent with the synergistic effect of modified polyvinyl acetate and modified xanthan gum has optimal improvement in fire extinguishing, burn resistance, foam stability, storage stability and spreading and film forming performance.

[0076] The above is only an example and description of the present application, and those skilled in the art can make various modifications or supplements or use similar ways to replace the described specific examples, as long as they do not deviate from the invention or exceed the scope defined by the present claims, which shall belong to the protection scope of the present application.

Claims

1. An alcohol-resistant, fluorine-free aqueous film-forming foam extinguishing agent, characterized in that: It contains the following raw materials by weight: 8-12 parts compound surfactant, 15-20 parts modified polyvinyl acetate, 3-5 parts modified xanthan gum, 5-8 parts ethylene glycol butyl ether, 4-6 parts propylene glycol, 0.5-1 part benzotriazole, 0.3-0.6 parts triethanolamine, 0.2-0.4 parts disodium ethylenediaminetetraacetate, 0.8-1.2 parts hydroxyethyl cellulose, 0.1-0.3 parts polyether modified silicone oil, 0.05-0.1 parts isothiazolinone, 6-9 parts ammonium dihydrogen phosphate, and the balance deionized water.

2. The alcohol-resistant, fluorine-free aqueous film-forming foam fire extinguishing agent according to claim 1, characterized in that: The compound surfactant is composed of cocamidopropyl betaine and lauryl alcohol polyoxyethylene ether-7 in a mass ratio of 3:

2.

3. The alcohol-resistant, fluorine-free aqueous film-forming foam extinguishing agent according to claim 1, characterized in that: The modified polyvinyl acetate is prepared using the following specific steps: A1. Add polyvinyl acetate and N,N-dimethylformamide to a four-necked flask, stir at 250-300 rpm and heat to 65-70°C to form a transparent solution; slowly add ethanolamine dropwise, and after the addition is complete, heat to 80-85°C and keep the temperature for 4-5 hours; then cool to 55-60°C, add silane coupling agent KH-560 and dibutyltin dilaurate, stir at 350-400 rpm until homogeneous, and heat to 70-75°C and keep the temperature for 3-4 hours; pour the product into deionized water, stir to disperse, and let it stand to separate into layers. Discard the lower aqueous phase, wash the upper product with deionized water 3-4 times, and then dry at 60-65°C for 8-10 hours to obtain the first modified polyvinyl acetate; A2. Add the first-modified polyvinyl acetate, ethyl acetate, and azobisisobutyronitrile to a four-necked flask, stir at 250-300 rpm, and heat to 75-80℃ for 15-20 min. Slowly add the mixed monomers composed of butyl acrylate, hydroxyethyl methacrylate, and acrylamide dropwise to the flask over a period of 2-2.5 h, maintaining a stable temperature of 78-82℃ and stirring at 350-400 rpm. After the addition is complete, heat to 85-90℃ and continue the reaction for 2-3 h, then cool to room temperature. Pour the product into petroleum ether, filter after precipitation, wash the precipitate 2-3 times with petroleum ether, and then dry at 55-60℃ for 6-8 h to obtain the second-modified polyvinyl acetate. A3. Add the second modified polyvinyl acetate and tetrahydrofuran to a four-necked flask, stir at 250-300 r / min and heat to 65-70℃ to completely dissolve the polymer. Then add the modified nano-silica, sonicate at 250-300W and stir at 200-250 r / min, and react at 70-75℃ for 3-4 hours. After the reaction is completed, concentrate the composite system by rotary evaporation at 60-65℃ and a vacuum of -0.08 to -0.09 MPa to a solid content of 60%-70% to obtain the modified polyvinyl acetate.

4. The alcohol-resistant, fluorine-free aqueous film-forming foam extinguishing agent according to claim 3, characterized in that: The modified nano-silica in A3 is modified as follows: 10g of nano-silica is added to 60mL of anhydrous ethanol and ultrasonically dispersed at 350W for 30min. Then, 5g of silane coupling agent KH-550 is added and stirred at 300r / min at 65℃ for 2h. After the reaction is completed, the mixture is centrifuged and dried under vacuum at 60℃ for 5h.

5. The alcohol-resistant, fluorine-free aqueous film-forming foam extinguishing agent according to claim 3, characterized in that: The ratio of polyvinyl acetate, N,N-dimethylformamide, ethanolamine, silane coupling agent KH-560, and dibutyltin dilaurate in A1 is 80-100g: 150-180mL: 25-30g: 12-15g: 0.8-1.0g. The ratio of the first-modified polyvinyl acetate, ethyl acetate, azobisisobutyronitrile, butyl acrylate, hydroxyethyl methacrylate, and acrylamide in A2 is 60-70g: 80-100mL: 1.2-1.5g: 20-25g: 10-12g: 5-8g; The ratio of the second modified polyvinyl acetate, tetrahydrofuran, and modified nano-silica in A3 is 50-60g: 120-150mL: 10g.

6. The alcohol-resistant, fluorine-free aqueous film-forming foam extinguishing agent according to claim 1, characterized in that: The modified xanthan gum is prepared using the following specific steps: B1. Add xanthan gum and isopropanol to a three-necked flask, stir at 200-250 r / min until evenly dispersed, slowly add 30% sodium hydroxide solution, stir and activate at 30-35℃ for 1.5-2 h. After activation, add chloroacetic acid, heat to 50-55℃ and keep the temperature for 3-4 h. After the reaction is complete, neutralize with 10% hydrochloric acid to pH=6.5-7.0, then add anhydrous ethanol to precipitate the product. After filtration, wash the precipitate 2-3 times with anhydrous ethanol and dry at 55-60℃ for 6-8 h to obtain the first modified xanthan gum. B2. Add the first modified xanthan gum and deionized water to a three-necked flask, and heat to 45-50℃ while stirring at 250-300 rpm to completely dissolve the xanthan gum. Slowly add 2,3-epoxypropyltrimethylammonium chloride dropwise. After the addition is complete, heat to 60-65℃ and stir at 300-350 rpm for 2.5-3 hours. After the reaction is complete, dialyze the product solution with deionized water in a dialysis bag with a molecular weight cutoff of 10,000 for 24-36 hours, changing the deionized water every 8 hours. After dialysis, add anhydrous ethanol to the product solution to precipitate the precipitate. After standing for 30-40 minutes, filter the precipitate. Wash the precipitate twice with a 70% ethanol aqueous solution, then wash it once with anhydrous ethanol. Finally, dry it at 55-60℃ for 6-8 hours to obtain the second modified xanthan gum. B3. Add the second modified xanthan gum and MES buffer (pH 5.5) to a four-necked flask. Heat to 40-45°C with stirring at 300-350 rpm and maintain this temperature for 40-50 minutes until the xanthan gum is completely dissolved. Add EDC hydrochloride and stir at 250-300 rpm for 10 minutes. Then add N-hydroxysuccinimide and stir for 30-40 minutes. Next, add polyethylene glycol dropwise over 30-40 minutes, and heat to 50-55°C. Stir and keep warm at 0-300 r / min for 5-6 h; after the reaction is complete, add anhydrous sodium sulfate to the system, stir at 200-250 r / min for 20-30 min, and filter with a 0.45 μm filter membrane; add anhydrous ethanol to the filtrate to precipitate the precipitate, let stand for 30-40 min, and then filter by suction. Wash the filter cake 2-3 times with 70% ethanol and water and once with anhydrous ethanol, and dry at 50-55℃ for 8-10 h. After drying, pulverize to 100-200 mesh to obtain modified xanthan gum.

7. The alcohol-resistant, fluorine-free aqueous film-forming foam extinguishing agent according to claim 6, characterized in that: The polyethylene glycol in B3 has a number-average molecular weight of 1000-1500, and its pH is pre-adjusted to 7.5 with 0.1 mol / L NaOH.

8. The alcohol-resistant, fluorine-free aqueous film-forming foam fire extinguishing agent according to claim 6, characterized in that: The ratio of xanthan gum, isopropanol, sodium hydroxide solution, and chloroacetic acid in B1 is 20-25g: 80-100mL: 15-18g: 20-25g; The ratio of the first modified xanthan gum, deionized water, and 2,3-epoxypropyltrimethylammonium chloride in B2 is 15-20g: 60-70mL: 12-15g. The ratio of the amount of the second modified xanthan gum, MES buffer, EDC hydrochloride, N-hydroxysuccinimide, polyethylene glycol, and anhydrous sodium sulfate in B3 is 12-15g: 80-100mL: 0.8-1.0g: 0.5-0.6g: 18-22g: 3-5g.

9. A method for preparing an alcohol-resistant, fluorine-free aqueous film-forming foam fire extinguishing agent, characterized in that: Specifically, it includes the following steps: S1. Add ethylene glycol butyl ether and propylene glycol to the reactor and stir at room temperature for 15-20 minutes at 200-250 rpm to form a uniform and transparent mixed solvent system. Slowly add modified polyvinyl acetate, control the stirring speed at 500-600 rpm, and simultaneously raise the temperature to 65-75℃. Keep the temperature and stir for 2-3 hours, taking samples every 30 minutes during the process, until a particle-free, uniform, viscous solution system is formed. S2. When the solution temperature drops to 40-45℃, first add the compound surfactant system and stir at 250-300 r / min for 30-40 min; then add the modified xanthan gum and stir at 400-450 r / min at 40-45℃ for 90-120 min to form a homogeneous colloidal solution; keep the solution temperature at 40-45℃, reduce the stirring speed to 300-350 r / min, slowly add ammonium dihydrogen phosphate, and stir for 40-60 min until completely dissolved; then add hydroxyethyl cellulose in 3-4 portions, stirring for 15-20 min after each addition until completely dispersed, and adjust the viscosity of the system at 25℃ to 200-300 mPa·s; S3. Add benzotriazole, disodium ethylenediaminetetraacetate, polyether-modified silicone oil, and isothiazolinone sequentially to the reactor. After each addition, stir at 250-300 rpm for 20-25 min until completely dispersed. Then, filter under 0.1-0.2 MPa pressure using a polypropylene filter bag with a pore size of 5-25 μm to remove impurities. Return the filtered solution to the reactor, slowly add triethanolamine, adjust the pH to 7.0-7.5, add deionized water to make up to 100 parts, and stir at 200-250 rpm for 30-40 min until homogeneous. S4. First, ultrasonically disperse the material at 400-450W and 30-35℃ for 30-40 minutes, then homogenize it under high pressure at 20-25MPa 2-3 times. Then, put it into a special sealed container and store it in a cool, dark place.