Preparation method of high-fluorescence-intensity water-soluble penetrant

Abstract

The invention relates to the technical field of chemical materials, in particular to a preparation method of a high-fluorescence-intensity water-soluble penetrant, which comprises the following steps: S1, synthesizing a fluorescent dye monomer and hydroxyethyl acrylate into a modified fluorescent dye; s2, dissolving methyl phenyl silicone resin in ethyl acetate to generate a carboxyl-containing carrier solution; s3, adding the modified fluorescent dye into the carboxyl-containing carrier solution to generate a fluorescent grafted carrier; s4, adding a permeation activating agent into the fluorescent grafting carrier; s5, adding a fluorine-containing surfactant and a light stabilizer into the pre-polymerized permeation phase, and carrying out high-speed micro-emulsification treatment; s6, adjusting the pH value of the emulsion to 8.0 to 8.5; and S7, filtering the stabilized penetrant crude product. According to the preparation method disclosed by the invention, a preparation scheme of the penetrating agent with high fluorescence intensity, good water solubility and structural stability is realized by constructing a grafting system of the modified fluorescent dye and the carboxylated silicon carrier and combining a multi-component synergistic emulsification and pH regulation process.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of chemical materials, and particularly relates to a preparation method of a high-fluorescence-intensity water-soluble penetrant. BACKGROUND

[0002] With the wide application of high-performance dyes in the fields of biological imaging, trace detection, optical probes and the like, higher requirements are put forward for the performance of fluorescent materials, especially in the aqueous environment, the functional molecules need to have high fluorescence intensity, good stability and high permeability; in order to meet this demand, researchers gradually combine fluorescent dyes with polymer carriers or surfactant systems to prepare water-soluble fluorescent penetrants.

[0003] However, the current technology generally has two bottleneck problems: on the one hand, the fluorescent dye molecules often have strong hydrophobicity and are prone to aggregation and quenching, which leads to a significant decrease in the light-emitting efficiency of the fluorescent dye molecules in the aqueous solution; on the other hand, the system coordination of the dye stability, the surfactant selection and the emulsification uniformity in the structure design of the penetrant is insufficient, which leads to the difficulty in balancing the dispersibility and the fluorescence intensity of the final product. Therefore, there is an urgent need for a preparation method of a high-fluorescence-intensity water-soluble penetrant to solve the above problems. SUMMARY

[0004] Based on the above purpose, the present application provides a preparation method of a high-fluorescence-intensity water-soluble penetrant.

[0005] The preparation method of the high-fluorescence-intensity water-soluble penetrant comprises the following steps:

[0006] S1: reacting a fluorescent dye monomer with hydroxyethyl acrylate under nitrogen protection to synthesize a modified fluorescent dye with an olefin group;

[0007] S2: dissolving methylphenyl silicone resin in ethyl acetate, adding a carboxylation reagent to react to generate a carboxyl-containing carrier solution;

[0008] S3: adding the modified fluorescent dye of S1 to the carboxyl-containing carrier solution of S2 to generate a fluorescent grafted carrier through esterification;

[0009] S4: adding a penetration activator to the fluorescent grafted carrier of S3, and stirring at a preset temperature to form a prepolymerized penetration phase;

[0010] S5: adding a fluorine-containing surfactant and a light stabilizer to the prepolymerized penetration phase of S4 to perform high-speed microemulsion treatment to form an emulsion;

[0011] S6: adjusting the pH of the emulsion obtained in S5 to 8.0-8.5 with ammonia water to obtain a stabilized penetrant crude product;

[0012] S7: Filter the stabilized crude penetrant obtained in S6 to obtain a high-fluorescence-intensity water-soluble penetrant product.

[0013] Optionally, the fluorescent dye monomer is a sulfonated pyranonium salt or a benzoxazole derivative.

[0014] Optionally, S1 specifically includes:

[0015] S11: Add fluorescent dye monomer and hydroxyethyl acrylate to the reactor at a molar ratio of 1:1.2-1.5, followed by adding 15-20% N,N-dimethylformamide solvent by total mass;

[0016] S12: Continuously introduce nitrogen to replace air, and control the nitrogen flow rate at 5 mL / min per gram of raw material;

[0017] S13: Add the catalyst dibutyltin dilaurate, the mass of which is 0.8-1.2% of the mass of the fluorescent dye monomer;

[0018] S14: Heat to 80-85℃ and react for 2.5-3 hours;

[0019] S15: After the reaction is complete, cool the temperature to 25-30℃ and separate the solid product by vacuum filtration to obtain the modified fluorescent dye.

[0020] Optionally, S2 specifically includes:

[0021] S21: Weigh methylphenyl silicone resin and add it to ethyl acetate at a mass concentration of 10-15%. Stir and dissolve the resin at room temperature (20-25℃) for 1-2 hours to obtain a clear and homogeneous organosilicon resin solution.

[0022] S22: Slowly add maleic anhydride or maleic anhydride dropwise to the organosilicon resin solution. The amount added is 5-8% of the mass of methylphenyl silicone resin. Continue stirring and react for 3-4 hours.

[0023] S23: Maintain the temperature at 60-70℃ during the reaction, and allow it to cool naturally to room temperature after the reaction is complete to obtain a carrier solution containing carboxyl groups.

[0024] Optionally, S3 specifically includes:

[0025] S31: Add the modified fluorescent dye obtained in S1 and the carboxyl-containing carrier solution obtained in S2 into the reaction vessel at a mass ratio of 1:4-6, and start stirring;

[0026] S32: Add p-toluenesulfonic acid, an esterification catalyst, to the mixture of S31. The amount added is 1.0-1.5% of the mass of the modified fluorescent dye. At the same time, maintain the reaction temperature at 85-90℃ and the reaction time is 4-5 hours.

[0027] S33: After the reaction is complete, cool to room temperature and remove the solvent by rotary evaporation to obtain the fluorescent grafting support.

[0028] Optionally, S4 specifically includes:

[0029] S41: Add the fluorescent grafting support of S3 and the permeation activator to the reaction vessel at a mass ratio of 10:1-3. The permeation activator is selected from lauramidopropyl betaine or alkyl polysaccharide glycoside.

[0030] S42: Under constant temperature water bath conditions, control the temperature at 50-60℃, start the mechanical stirring device, control the stirring speed at 500-700rpm, and continue stirring for 1.5-2 hours.

[0031] S43: After stirring, a uniformly dispersed prepolymerized permeate phase is obtained.

[0032] Optionally, S5 specifically includes:

[0033] S51: The prepolymerized penetrating phase obtained in S4 is transferred to a high-speed dispersion emulsification device, and a fluorinated surfactant and a light stabilizer are added thereto in sequence, wherein the amount of fluorinated surfactant added is 1.0-1.5% of the mass of the prepolymerized penetrating phase, and the amount of light stabilizer added is 0.3-0.6%; the light stabilizer is selected from 2-benzotriazole;

[0034] S52: Set the speed of the high-speed dispersion device to 8000-10000 rpm, maintain the emulsification temperature at 30-35℃, and continue the treatment for 10-15 minutes until a uniform emulsion is formed.

[0035] Optionally, S6 specifically includes:

[0036] S61: Place the emulsion obtained in S5 into an alkali-resistant reaction vessel, start the stirring device, and control the stirring speed to 300-500 rpm;

[0037] S62: Slowly add an ammonia solution with a concentration of 1.0-2.0 mol / L, controlling the dropping rate to 0.5-1.0 mL / min;

[0038] S63: Monitor the pH value of the reaction system in real time. Stop adding the solution when the pH reaches the target range of 8.0-8.5. Then continue stirring for 10-15 minutes to obtain the crude stabilized penetrant.

[0039] Optionally, S7 specifically includes:

[0040] S71: Place the stabilized crude permeate obtained in S6 into a vacuum filtration device and perform multi-stage filtration using a polytetrafluoroethylene microporous filter membrane.

[0041] S72: The primary filtration uses a filter membrane with a pore size of 5.0-10.0μm to remove large particles and unreacted residues;

[0042] S73: Fine filtration uses a filter membrane with a pore size of 0.22-0.45μm and performs impurity removal operation under a pressure of 0.08-0.1MPa to obtain the penetrant filtrate, which is the finished product of high fluorescence intensity water-soluble penetrant.

[0043] The beneficial effects of this invention are:

[0044] This invention effectively improves the dispersion stability and structural binding force of fluorescent dyes in aqueous phase by introducing modified fluorescent dyes with olefin groups and esterifying them with carboxylated organosilicon resin carriers, thus avoiding the aggregation and quenching of fluorophores during use. Furthermore, by introducing penetrant activators, fluorinated surfactants, and light stabilizers, and combining them with high-speed microemulsification and precise pH adjustment, the emulsion system achieves uniform particle size and stable fluorescence signal during formation, significantly improving the structural uniformity and optical performance of the penetrant in the aqueous system. Attached Figure Description

[0045] To more clearly illustrate the technical solutions in this invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only for this invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0046] Figure 1 This is a schematic diagram of the penetrant preparation method according to an embodiment of the present invention. Detailed Implementation

[0047] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. It should also be noted that, to make the embodiments more comprehensive, the following embodiments are the best and preferred embodiments, and those skilled in the art can use other alternative methods to implement some well-known technologies; moreover, the accompanying drawings are only for more specific description of the embodiments and are not intended to specifically limit the present invention.

[0048] It should be noted that the use of terms such as "an embodiment," "an embodiment," "an exemplary embodiment," and "some embodiments" in the specification indicates that the described embodiment may include a specific feature, structure, or characteristic, but not every embodiment necessarily includes that specific feature, structure, or characteristic. Furthermore, when a specific feature, structure, or characteristic is described in connection with an embodiment, implementing such a feature, structure, or characteristic in conjunction with other embodiments (whether explicitly described or not) should be within the knowledge of those skilled in the art.

[0049] Generally, terms can be understood at least partly from their use in context. For example, depending at least partly on the context, the term "one or more" as used herein can be used to describe any feature, structure, or characteristic in a singular sense, or a combination of features, structures, or characteristics in a plural sense. Additionally, the term "based on" can be understood not necessarily to convey an exclusive set of factors, but rather, alternatively, depending at least partly on the context, to allow for the presence of other factors that are not necessarily explicitly described.

[0050] Example 1

[0051] like Figure 1 As shown, a method for preparing a high-fluorescence-intensity water-soluble penetrant includes the following steps:

[0052] S1: A modified fluorescent dye with olefin groups is synthesized by reacting fluorescent dye monomers with hydroxyethyl acrylate under nitrogen protection.

[0053] S2: Dissolve methylphenyl silicone resin in ethyl acetate, add carboxylating reagent and react to generate a carboxyl-containing carrier solution;

[0054] S3: The modified fluorescent dye of S1 is added to the carboxyl-containing support solution of S2, and a fluorescent grafted support is generated through esterification reaction.

[0055] S4: Add a permeation activator to the fluorescent grafting support of S3 and stir at a preset temperature to form a prepolymerized permeation phase;

[0056] S5: Add fluorinated surfactant and light stabilizer to the prepolymerized penetrating phase of S4, and perform high-speed microemulsification treatment to form an emulsion;

[0057] S6: Adjust the pH value of the emulsion obtained in S5 with ammonia water to obtain the crude stabilized penetrant;

[0058] S7: Filter the stabilized crude penetrant obtained in S6 to obtain a high-fluorescence-intensity water-soluble penetrant product.

[0059] The fluorescent dye monomer is a sulfonated pyranium salt.

[0060] S1 specifically includes:

[0061] S11: Add fluorescent dye monomer and hydroxyethyl acrylate to the reactor at a molar ratio of 1:1.3, followed by adding 18% N,N-dimethylformamide solvent by total mass;

[0062] S12: Continuously introduce nitrogen to replace air, and control the nitrogen flow rate at 5 mL / min per gram of raw material;

[0063] S13: Add catalyst dibutyltin dilaurate, the mass of which is 1% of the mass of the fluorescent dye monomer;

[0064] S14: Heat to 83℃ and react for 2.8 hours;

[0065] S15: After the reaction is complete, the temperature is lowered to 28°C, and the solid product is separated by vacuum filtration to obtain the modified fluorescent dye.

[0066] S2 specifically includes:

[0067] S21: Weigh out methylphenyl silicone resin and add it to ethyl acetate at a mass concentration of 12%. Stir and dissolve at room temperature (22°C) for 1.5 hours to obtain a clear and homogeneous organosilicon resin solution.

[0068] S22: Slowly add maleic anhydride dropwise to the organosilicon resin solution, the amount added being 6% of the mass of methylphenyl silicone resin, and continue stirring for 3.5 hours;

[0069] S23: Maintain the temperature at 65℃ during the reaction, and allow it to cool naturally to room temperature after the reaction is complete to obtain a carrier solution containing carboxyl groups. The above steps, by controlling the dissolution ratio of silicone resin and the amount of carboxylating reagent added, ensure that carboxyl groups can be uniformly introduced into the organosilicon backbone, providing reaction sites for the subsequent esterification grafting of fluorescent dyes, and improving the stability and consistency of the subsequent grafting reaction.

[0070] S3 specifically includes:

[0071] S31: Add the modified fluorescent dye obtained in S1 and the carboxyl-containing carrier solution obtained in S2 into the reaction vessel at a mass ratio of 1:5, and start stirring;

[0072] S32: Add p-toluenesulfonic acid, an esterification catalyst, to the mixture of S31. The amount added is 1.3% of the mass of the modified fluorescent dye. At the same time, maintain the reaction temperature at 88℃ and continue the reaction for 4-5 hours.

[0073] S33: After the reaction is completed, the temperature is lowered to room temperature, and the solvent is removed by rotary evaporation to obtain the fluorescent grafted support. The above steps, by controlling the mass ratio of the modified fluorescent dye to the carboxyl-containing support solution and the esterification conditions, achieve covalent grafting of fluorescent molecules to the support, ensuring the stable distribution of fluorophores in the subsequent permeation phase, and providing a reaction basis for subsequent emulsification and functional addition.

[0074] S4 specifically includes:

[0075] S41: Add the fluorescent grafting support of S3 and the permeation activator to the reaction vessel at a mass ratio of 10:2. The permeation activator is selected from lauramidopropyl betaine.

[0076] S42: Under constant temperature water bath conditions, control the temperature at 55℃, start the mechanical stirring device, control the stirring speed at 600 rpm, and continue stirring for 1.8 hours.

[0077] S43: After stirring, a uniformly dispersed prepolymerized permeation phase is obtained; the above steps ensure that the fluorescent grafted carrier is fully dispersed in the permeation system, providing a uniform precursor system basis for subsequent microemulsification, which is beneficial to emulsification stability and consistency of subsequent reactions.

[0078] S5 specifically includes:

[0079] S51: The prepolymerized penetrating phase obtained in S4 is transferred to a high-speed dispersion emulsification device, and a fluorinated surfactant and a light stabilizer are added thereto in sequence, wherein the amount of fluorinated surfactant added is 1.3% of the mass of the prepolymerized penetrating phase, and the amount of light stabilizer added is 0.5%; the light stabilizer is selected from 2-benzotriazole;

[0080] S52: Set the speed of the high-speed dispersion device to 9000 rpm, maintain the emulsification temperature at 32°C, and continue processing for 12 minutes until a uniform emulsion is formed.

[0081] S6 specifically includes:

[0082] S61: Place the emulsion obtained in S5 into an alkali-resistant reaction vessel, start the stirring device, and control the stirring speed to 400 rpm;

[0083] S62: Slowly add ammonia solution with a concentration of 1.5 mol / L, controlling the dropping rate to 0.8 mL / min;

[0084] S63: Monitor the pH value of the reaction system in real time. Stop adding the solution when the pH reaches the target range of 8.2. Then continue stirring for 13 minutes to obtain the crude stabilized penetrant.

[0085] S7 specifically includes:

[0086] S71: Place the stabilized crude permeate obtained in S6 into a vacuum filtration device and perform multi-stage filtration using a polytetrafluoroethylene microporous filter membrane.

[0087] S72: The primary filtration uses a filter membrane with a pore size of 8μm to remove large particles and unreacted residues;

[0088] S73: Fine filtration uses a filter membrane with a pore size of 0.35μm and performs impurity removal operation under a pressure of 0.09MPa to obtain a clear and transparent permeate filtrate, which is the high-fluorescence-intensity water-soluble permeate product. The above filtration steps, by setting graded pore sizes and controlling filtration pressure, ensure the removal of coarse particles and micelle aggregates remaining during the emulsification process, and obtain a permeate product with uniform particle size distribution and high optical purity, providing purity assurance for its subsequent application in water systems.

[0089] Example 2

[0090] S1: Fluorescent dye monomer (benzoxazole derivative) and hydroxyethyl acrylate were added to a reaction vessel at a molar ratio of 1:1.2. N,N-dimethylformamide was added as a solvent, accounting for 15% of the total mass. Nitrogen gas was continuously introduced to replace the air. Dibutyltin dilaurate catalyst was added, accounting for 0.8% of the mass of the fluorescent dye monomer. The mixture was heated to 80°C and reacted for 2.5 hours. After the reaction, the temperature was lowered to 25°C, and the modified fluorescent dye was obtained by vacuum filtration.

[0091] S2: Add methylphenyl silicone resin to ethyl acetate at a concentration of 10% and stir to dissolve for 1 hour at room temperature (20°C); then add maleic anhydride, accounting for 5% of the mass of methylphenyl silicone resin, and control the reaction temperature at 60°C. React for 3 hours and then cool to room temperature to obtain a carboxyl-containing carrier solution.

[0092] S3: The modified fluorescent dye obtained in S1 and the carrier solution obtained in S2 are mixed at a mass ratio of 1:4. P-Toluenesulfonic acid is added as an esterification catalyst, accounting for 1.0% of the mass of the modified fluorescent dye. The reaction temperature is controlled at 85℃ and the reaction is carried out for 4 hours. After cooling, the solvent is removed by rotary evaporation to obtain the fluorescent grafted carrier.

[0093] S4: The fluorescent grafting support and alkyl polysaccharide were mixed at a mass ratio of 10:1, placed in a reactor, and stirred at a constant temperature of 50°C and a stirring speed of 500 rpm for 1.5 hours to form a uniform prepolymerized permeation phase.

[0094] S5: Transfer the permeated phase obtained in S4 into an emulsification device, add a fluorinated surfactant (1.0% by mass) and a light stabilizer 2-benzotriazole (0.3% by mass), set the rotation speed to 8000 rpm, maintain the emulsification temperature at 30℃, and process for 10 minutes to obtain an emulsion.

[0095] S6: Place the emulsion into an alkali-resistant container, set the stirring speed to 300 rpm, add 1.0 mol / L ammonia water at a dropping rate of 0.5 mL / min, and stop adding when the pH reaches 8.0. Continue stirring for 10 minutes to obtain the crude stabilized penetrant.

[0096] S7: Two-stage filtration is performed using polytetrafluoroethylene (PTFE) membranes. The primary filtration membrane has a pore size of 5 μm, and the fine filtration membrane has a pore size of 0.22 μm. Filtration is carried out at 0.08 MPa to obtain a high-fluorescence-intensity water-soluble penetrant product.

[0097] Example 3

[0098] S1: Fluorescent dye monomer (sulfonated pyranium salt) and hydroxyethyl acrylate were added to a reaction vessel at a molar ratio of 1:1.5. N,N-dimethylformamide was added as a solvent, accounting for 20% of the total mass. Nitrogen gas was continuously introduced to replace the air. Dibutyltin dilaurate catalyst was added, accounting for 1.2% of the mass of the fluorescent dye monomer. The mixture was heated to 85°C and reacted for 3 hours. After the reaction, the temperature was lowered to 30°C, and the modified fluorescent dye was obtained by vacuum filtration.

[0099] S2: Add methylphenyl silicone resin to ethyl acetate at a concentration of 15% and stir to dissolve for 2 hours at room temperature (25°C); then add maleic anhydride, accounting for 8% of the mass of methylphenyl silicone resin, and control the reaction temperature at 70°C. React for 4 hours and then cool to room temperature to obtain a carboxyl-containing carrier solution.

[0100] S3: The modified fluorescent dye obtained in S1 and the carrier solution obtained in S2 are mixed at a mass ratio of 1:6. P-Toluenesulfonic acid is added as an esterification catalyst, accounting for 1.5% of the mass of the modified fluorescent dye. The reaction temperature is controlled at 90℃ and the reaction is carried out for 5 hours. After cooling, the solvent is removed by rotary evaporation to obtain the fluorescent grafted carrier.

[0101] S4: The fluorescent grafting carrier and lauramidopropyl betaine were mixed at a mass ratio of 10:3, placed in a reactor, and stirred at a constant temperature of 60°C and a stirring speed of 700 rpm for 2 hours to form a uniform prepolymerized permeation phase.

[0102] S5: Transfer the permeated phase obtained in S4 into an emulsification device, add a fluorinated surfactant (1.5% by mass) and a light stabilizer 2-benzotriazole (0.6% by mass), set the rotation speed to 10000 rpm, maintain the emulsification temperature at 35℃, and process for 15 minutes to obtain an emulsion.

[0103] S6: Place the emulsion into an alkali-resistant container, set the stirring speed to 500 rpm, add 2.0 mol / L ammonia water at a dropping rate of 1.0 mL / min, and stop the dropping when the pH reaches 8.5. Continue stirring for 15 minutes to obtain the crude stabilized penetrant.

[0104] S7: Two-stage filtration is performed using a polytetrafluoroethylene (PTFE) filter membrane. The primary filter membrane has a pore size of 10 μm, and the fine filter membrane has a pore size of 0.45 μm. Filtration is carried out at 0.1 MPa to obtain a high-fluorescence-intensity water-soluble penetrant product.

[0105] Comparative Example 1

[0106] Step 1: Weigh 100g of polymethylsiloxane, 10g of alkylphenol polyoxyethylene ether, and 30g of ethanol, add them to a three-necked flask, start the stirring device, and stir at room temperature for 30 minutes to form a homogeneous mixture.

[0107] Step 2: Heat the mixture to 70°C and react at a constant temperature for 1 hour to promote enhanced intermolecular compatibility. After the reaction is complete, allow it to cool naturally to room temperature.

[0108] Step 3: After cooling, filter the crude penetrant to remove impurities and bottle it to obtain the conventional non-water-soluble penetrant product.

[0109] Table 1 Comparison of performance parameters of finished penetrant products

[0110]

[0111] As shown in Table 1, Example 1 exhibits the best performance across multiple key performance indicators. Its fluorescence intensity reaches 980, significantly superior to Examples 2 and 3, and far exceeding Comparative Example 1. It demonstrates excellent water solubility, with a maximum solubility of 120 mg / mL, while Comparative Example 1 is water-insoluble and cannot be dispersed in the aqueous phase at all. Regarding particle size control and stability, Example 1 exhibits the smallest particle size (58.6 nm) and the lowest PDI (0.162), along with a more negative Zeta potential, indicating the most stable emulsion dispersion system. In terms of storage resistance and UV stability, Example 1 maintains stability for over 90 days, with an anti-attenuation rate of 87.3%, significantly better than other examples and the comparative example. Regarding penetration performance, the leather penetration test shows that Example 1 achieves a penetration depth of 2.6 mm, demonstrating higher effective diffusion capacity. Therefore, Example 1 surpasses Examples 2 and 3 and Comparative Example 1 in terms of fluorescence performance, dispersibility, stability, and applicability, and can be considered the optimal implementation method of this invention.

[0112] Table 2 Comparison of other performance parameters

[0113]

[0114] As shown in Table 2 above, Example 1 still exhibits the best overall performance. Specifically, in terms of permeation efficiency, Example 1 can complete permeation within 48 seconds, which is far superior to the 196 seconds of Comparative Example 1, thus improving the permeation response speed. The film formation is more uniform, with a thickness deviation of only ±0.8μm, which helps to achieve homogeneity in the dyeing or coating process. It has a wider range of applicability and can be used in a wider pH range (5.0–9.5), adapting to more application environments. It has strong solvent resistance, with no obvious stratification within 72 hours after dilution with organic solvents, which is far superior to Comparative Example 1. It has low VOC emissions and meets green environmental protection requirements, while Comparative Example 1 has as high as 180mg / L, further confirming that Example 1 is the optimal implementation scheme.

[0115] This invention encompasses any substitutions, modifications, equivalent methods, and solutions made within the spirit and scope of this invention. To provide the public with a thorough understanding of this invention, specific details are described in detail in the following preferred embodiments; however, those skilled in the art will fully understand the invention even without these details. Furthermore, to avoid unnecessary misunderstanding of the essence of this invention, well-known methods, processes, procedures, components, and circuits are not described in detail.

[0116] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a high-fluorescence-intensity water-soluble penetrant, characterized in that, Includes the following steps: S1: A modified fluorescent dye with olefin groups is synthesized by reacting fluorescent dye monomers with hydroxyethyl acrylate under nitrogen protection. S2: Dissolve methylphenyl silicone resin in ethyl acetate, add carboxylating reagent and react to generate a carboxyl-containing carrier solution; S3: The modified fluorescent dye of S1 is added to the carboxyl-containing support solution of S2, and a fluorescent grafted support is generated through esterification reaction. S4: Add a permeation activator to the fluorescent grafting support of S3 and stir at a preset temperature to form a prepolymerized permeation phase; S5: Add fluorinated surfactant and light stabilizer to the prepolymerized penetrating phase of S4, and perform high-speed microemulsification treatment to form an emulsion; S6: Adjust the pH of the emulsion obtained in S5 to 8.0-8.5 with ammonia water to obtain the crude stabilized penetrant; S7: Filter the stabilized crude penetrant obtained in S6 to obtain a high-fluorescence-intensity water-soluble penetrant product.

2. The method for preparing a high-fluorescence-intensity water-soluble penetrant according to claim 1, characterized in that, The fluorescent dye monomer is a sulfonated pyranonium salt or a benzoxazole derivative.

3. The method for preparing a high-fluorescence-intensity water-soluble penetrant according to claim 1, characterized in that, S1 specifically includes: S11: Add fluorescent dye monomer and hydroxyethyl acrylate to the reactor at a molar ratio of 1:1.2-1.5, followed by adding 15-20% N,N-dimethylformamide solvent by total mass; S12: Continuously introduce nitrogen to replace air, and control the nitrogen flow rate at 5 mL / min per gram of raw material; S13: Add the catalyst dibutyltin dilaurate, the mass of which is 0.8-1.2% of the mass of the fluorescent dye monomer; S14: Heat to 80-85℃ and react for 2.5-3 hours; S15: After the reaction is complete, cool the temperature to 25-30℃ and separate the solid product by vacuum filtration to obtain the modified fluorescent dye.

4. The method for preparing a high-fluorescence-intensity water-soluble penetrant according to claim 1, characterized in that, S2 specifically includes: S21: Weigh methylphenyl silicone resin and add it to ethyl acetate at a mass concentration of 10-15%. Stir and dissolve the resin at room temperature (20-25℃) for 1-2 hours to obtain a clear and homogeneous organosilicon resin solution. S22: Slowly add maleic anhydride or maleic anhydride dropwise to the organosilicon resin solution. The amount added is 5-8% of the mass of methylphenyl silicone resin. Continue stirring and react for 3-4 hours. S23: Maintain the temperature at 60-70℃ during the reaction, and allow it to cool naturally to room temperature after the reaction is complete to obtain a carrier solution containing carboxyl groups.

5. The method for preparing a high-fluorescence-intensity water-soluble penetrant according to claim 1, characterized in that, S3 specifically includes: S31: Add the modified fluorescent dye obtained in S1 and the carboxyl-containing carrier solution obtained in S2 into the reaction vessel at a mass ratio of 1:4-6, and start stirring; S32: Add p-toluenesulfonic acid, an esterification catalyst, to the mixture of S31. The amount added is 1.0-1.5% of the mass of the modified fluorescent dye. At the same time, maintain the reaction temperature at 85-90℃ and the reaction time is 4-5 hours. S33: After the reaction is complete, cool to room temperature and remove the solvent by rotary evaporation to obtain the fluorescent grafting support.

6. The method for preparing a high-fluorescence-intensity water-soluble penetrant according to claim 1, characterized in that, S4 specifically includes: S41: Add the fluorescent grafting support of S3 and the permeation activator to the reaction vessel at a mass ratio of 10:1-3. The permeation activator is selected from lauramidopropyl betaine or alkyl polysaccharide glycoside. S42: Under constant temperature water bath conditions, control the temperature at 50-60℃, start the mechanical stirring device, control the stirring speed at 500-700rpm, and continue stirring for 1.5-2 hours. S43: After stirring, a uniformly dispersed prepolymerized permeate phase is obtained.

7. The method for preparing a high-fluorescence-intensity water-soluble penetrant according to claim 1, characterized in that, S5 specifically includes: S51: The prepolymerized penetrating phase obtained in S4 is transferred to a high-speed dispersion emulsification device, and a fluorinated surfactant and a light stabilizer are added thereto in sequence, wherein the amount of fluorinated surfactant added is 1.0-1.5% of the mass of the prepolymerized penetrating phase, and the amount of light stabilizer added is 0.3-0.6%; the light stabilizer is selected from 2-benzotriazole; S52: Set the speed of the high-speed dispersion device to 8000-10000 rpm, maintain the emulsification temperature at 30-35℃, and continue the treatment for 10-15 minutes until a uniform emulsion is formed.

8. The method for preparing a high-fluorescence-intensity water-soluble penetrant according to claim 1, characterized in that, S6 specifically includes: S61: Place the emulsion obtained in S5 into an alkali-resistant reaction vessel, start the stirring device, and control the stirring speed to 300-500 rpm; S62: Slowly add an ammonia solution with a concentration of 1.0-2.0 mol / L, controlling the dropping rate to 0.5-1.0 mL / min; S63: Monitor the pH value of the reaction system in real time. Stop adding the solution when the pH reaches the target range of 8.0-8.

5. Then continue stirring for 10-15 minutes to obtain the crude stabilized penetrant.

9. The method for preparing a high-fluorescence-intensity water-soluble penetrant according to claim 1, characterized in that, Specifically, S7 includes: S71: Place the stabilized crude permeate obtained in S6 into a vacuum filtration device and perform multi-stage filtration using a polytetrafluoroethylene microporous filter membrane. S72: The primary filtration uses a filter membrane with a pore size of 5.0-10.0μm to remove large particles and unreacted residues; S73: Fine filtration uses a filter membrane with a pore size of 0.22-0.45μm and performs impurity removal operation under a pressure of 0.08-0.1MPa to obtain the penetrant filtrate, which is the finished product of high fluorescence intensity water-soluble penetrant.

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