Fluorescent monomer, fluorinated polyacrylate soap-free emulsion and preparation method of fluorinated polyacrylate soap-free emulsion

Abstract

The invention belongs to the technical field of fluorescent polymers, and particularly relates to a fluorescent monomer, a fluorinated polyacrylate soap-free emulsion and a preparation method of the fluorinated polyacrylate soap-free emulsion. The fluorescent monomer is 4-O-octafluoropentyl-N-ethyl acrylate group-1, 8-naphthalimide, and the structural formula of the fluorescent monomer is as shown in the formula (1); wherein Rf is CF2CF2CF2CF2H, and Rf is CF2CF2CF2H. The molecular structure of the fluorescent monomer provided by the invention contains a fluorescent rigid group, and the fluorescent monomer is connected with a fluorine-containing group, so that the structural stability of a fluorine-containing chain segment on a two-phase interface is facilitated, a structural rearrangement phenomenon is not easy to occur, and the fluorescent monomer has excellent hydrophobic stability and fluorescent property; the stable antifouling property and the high mechanical property of the fluorinated polyacrylate soap-free emulsion are improved. And by utilizing a'hinging 'effect of a rigid center of a side chain in a molecular chain and a chemical bond crosslinking effect between self-crosslinking groups, the fluorinated polyacrylate film has relatively high mechanical properties. And # imgabs0 #.

Description

Technical Field

[0001] The present invention belongs to the technical field of fluorescent polymers, and particularly relates to fluorescent monomers, fluorinated polyacrylate soap-free emulsions and preparation methods thereof. Background Art

[0002] Traditional waterborne polyacrylates have good film-forming properties, adhesion and mechanical properties, which have attracted people's attention, but they have the disadvantages of poor weather resistance, chemical resistance and water resistance. The introduction of fluorine-containing groups can endow them with excellent chemical stability, heat resistance, low surface energy and excellent weather resistance, making them better applied in pressure-sensitive adhesives, anticorrosive coatings, waterborne coatings, waterborne inks, fireproof materials, fabric finishing, aerospace and other fields. With the development of technology, in order to better meet the application requirements, polyacrylates with antibacterial, ultraviolet absorption, self-healing and fluorescence multifunctions have emerged one after another. Among them, polyacrylates with fluorescence function have great application prospects in anti-counterfeiting, biological imaging, chemical sensing and other aspects.

[0003] When a fluoropolymer coating comes into contact with a polar medium, the groups on the coating surface will rearrange, the hydrophilic groups migrate to the surface, and the hydrophobic fluorine-containing groups flip to the inside of the matrix, resulting in poor water resistance of the coating. By introducing rigid units into fluorinated polyacrylates, the fluorinated polyacrylates have stable antifouling properties. Integrating multiple functions into a polymer system can greatly broaden the application range of materials. Combining monomers containing fluorescence functions with acrylates can endow acrylates with fluorescence properties. Wang [Korean Journal of Chemical Engineering, 2013, 30, 1609-1613] et al. synthesized a blue-fluorescent polyacrylate anti-counterfeiting pressure-sensitive adhesive with coumarin as the main chain. The introduction of the blue-fluorescent monomer makes the anti-counterfeiting performance better. The structure of the fluorescent monomer is as follows:

[0004] 。

[0005] Hui et al. [The Journal of Adhesion, 2022, 98, 1151-1167] used N, N-dicyclohexylcarbodiimide (DCC) / 4-dimethylaminopyridine (DMAP) as catalysts to successfully synthesize a novel fluorescent polymer (FCPA) through the esterification reaction between acrylate copolymer (CPA) and fluorescein. The polymer has excellent photoluminescence properties, solubility and film-forming ability. Its structure is as follows: 。

[0006] However, none of the above products have anti-fouling ability and are prone to pollution. The market demand for fluorescent-based multifunctional fluorinated polyacrylate aqueous products has shown explosive growth. Abrakhi et al. [Langmuir, 2013, 29, 30, 9499–9509] prepared fluorinated acrylate and fluorescent monomers by reacting acryloyl chloride with perfluorohexyl ethanol and 4-phenylazophenol respectively, and then carried out free radical polymerization reaction to prepare a series of fluorinated polyacrylate spin coatings with photo-controllable wettability. Zhou et al. [Journal of Applied Polymer Science, 2023, 140(16), 10.1002 / app.53757.] prepared cellulose nanocrystal and coumarin-modified fluorinated polyacrylate emulsion by RAFT-assisted Pickering emulsion polymerization method. The latex film has self-healing performance, and the treated fabric has waterproof and oil-proof performance. Introducing fluorescent monomers into the above fluorinated polyacrylate emulsion can endow the acrylate with fluorescent properties, but the waterproof and oil-proof stability is not ideal. Summary of the Invention

[0007] In order to solve the above problems, the present invention provides a fluorescent monomer, a soap-free emulsion of fluorinated polyacrylate and its preparation method. The fluorescent monomer provided by the present invention contains a fluorescent rigid group in its molecular structure. By connecting a fluorine-containing group through it, it is beneficial to the structural stability of the fluorine-containing chain segment at the two-phase interface, is not prone to structural rearrangement, has excellent hydrophobic stability and fluorescent properties, and improves the stable anti-fouling and high mechanical properties of the soap-free emulsion of fluorinated polyacrylate.

[0008] The present invention solves the above technical problems through the following technical solutions.

[0009] The first object of the present invention is to provide a fluorescent monomer, which is 4-O-octafluoropentyl-N-ethyl acryloyl-1,8-naphthalimide, and its structure is shown in formula (1): .

[0010] Among them, R f is -CF2CF2CF2CF2H.

[0011] The second object of the present invention is to provide a preparation method of the above fluorescent monomer, including the following steps: S1. Using 4-bromo-1,8-naphthalic anhydride and monoethanolamine as raw materials, dissolving them in the first solvent, and carrying out an amidation reaction at 70 °C to 90 °C to obtain 4-bromo-N-hydroxyethyl-1,8-naphthalimide.

[0012] S2. Mix 4-bromo-N-hydroxyethyl-1,8-naphthalimide and triethylamine solution to form a mixed solution, then add acryloyl chloride solution, and carry out an esterification reaction at 0°C to 5°C to obtain 4-bromo-N-ethyl acrylate-1,8-naphthalimide.

[0013] S3. Using 4-bromo-N-ethyl acrylate-1,8-naphthalimide and octafluoropentanol as raw materials, carry out a substitution reaction at 110°C to 130°C in a reaction system of a catalyst and a second solvent to obtain 4-O-octafluoropentyl-N-ethyl acrylate-1,8-naphthalimide.

[0014] Furthermore, the molar ratio of 4-bromo-1,8-naphthalic anhydride to monoethanolamine is 1:1 to 5, the dosage of the first solvent is 15 to 25 times the mass of 4-bromo-1,8-naphthalic anhydride, and the amideification reaction time is 4h to 8h.

[0015] Furthermore, the molar ratio of 4-bromo-N-hydroxyethyl-1,8-naphthalimide, triethylamine and acryloyl chloride is 1:1 to 2:1 to 2.

[0016] Furthermore, the triethylamine solution is a dichloromethane solution of triethylamine, the acryloyl chloride solution is a dichloromethane solution of acryloyl chloride. In the esterification reaction system, the total dosage of dichloromethane is 5 to 15 times the mass of 4-bromo-N-hydroxyethyl-1,8-naphthalimide, the esterification reaction time is 4h to 6h, and the dichloromethane solution of acryloyl chloride is added dropwise to the mixed solution, and the dropping time is 20min to 40min.

[0017] Furthermore, the molar ratio of 4-bromo-N-ethyl acrylate-1,8-naphthalimide to octafluoropentanol is 1:2 to 4, the catalyst is potassium carbonate and zinc powder, the molar ratio of 4-bromo-N-ethyl acrylate-1,8-naphthalimide, potassium carbonate and zinc powder is 1:1 to 2:1 to 2, the dosage of the second solvent is 5 to 15 times the mass of 4-bromo-N-ethyl acrylate-1,8-naphthalimide, and the substitution reaction time is 8h to 12h.

[0018] The third object of the present invention is to provide a fluorinated polyacrylate soap-free emulsion, and the polyacrylate emulsion is prepared by polymerizing component A and component B in a volume ratio of 1:1, wherein, Component A is a prepolymer prepared from reactive monomer A, the first emulsifier, the first chain transfer agent, and the first initiator. Among them, reactive monomer A is a mixture of the above-mentioned fluorescent monomer and the first polymerizable non-fluorinated monomer in a mass ratio of 0.5-5:90-95. The dosage of the first emulsifier is 0.5wt%-5wt% of the mass of reactive monomer A, the dosage of the first chain transfer agent is 0.5wt%-2wt% of the mass of reactive monomer A, and the dosage of the first initiator is 0.5wt%-3wt% of the mass of reactive monomer A.

[0019] Component B is prepared by mixing reactive monomer B, the second emulsifier, and the second chain transfer agent. Reactive monomer B is a mixture of a polymerizable fluorinated monomer, a second polymerizable non-fluorinated monomer, and a self-crosslinking monomer in a mass ratio of 40-70:10-30:5-15. The dosage of the second emulsifier is 0.5wt%-5wt% of the mass of reactive monomer B, and the second chain transfer agent is 0.5wt%-2wt% of the mass of reactive monomer B. [[ID=!5]]

[0020] Furthermore, both the first polymerizable non-fluorinated monomer and the second polymerizable non-fluorinated monomer are one of n-butyl acrylate, isooctyl acrylate, and lauryl methacrylate.

[0021] Furthermore, the polymerizable fluorinated monomer is one of trifluoroethyl methacrylate, hexafluorobutyl methacrylate, and dodecafluoroheptyl methacrylate.

[0022] Furthermore, the crosslinking monomer is one of N-hydroxymethyl acrylamide and γ-(methacryloyloxy)propyltrimethoxysilane.

[0023] Furthermore, both the first emulsifier and the second emulsifier are ammonium 1-allyloxy-3-(4-nonylphenol)-2-propanol polyoxyethylene (10) ether sulfate.

[0024] Furthermore, both the first chain transfer agent and the second chain transfer agent are dodecyl mercaptan.

[0025] Furthermore, the first initiator is ammonium persulfate or potassium persulfate.

[0026] The fourth object of the present invention is to provide a method for preparing the above-mentioned fluorinated polyacrylate soap-free emulsion, including the following steps: Step 1, weigh Component A and Component B respectively according to the component ratio.

[0027] Step 2, mix reactive monomer A, the first emulsifier, and the first chain transfer agent, and under the atmosphere of a protective gas, heat up to 75°C-80°C, and add the first initiator for polymerization reaction to obtain a polymerization reaction system.

[0028] Step 3, mix reactive monomer B, the second emulsifier, and the second chain transfer agent to obtain Component B.

[0029] Step 4: Add Component B and the second initiator into the polymerization reaction system respectively, and then carry out the secondary polymerization reaction at 75°C to 80°C to obtain the fluorinated polyacrylate soap-free emulsion.

[0030] Furthermore, the polymerization reaction time is 0.5 h to 1 h, the secondary polymerization reaction time is 2 h to 6 h. Component B and the second initiator solution are respectively added to the mixed solution in a dropping manner, the dropping time is 1 h to 2 h, the dosage of the second initiator solution is 0.5 wt% to 3 wt% of the mass of monomer B, and the second initiator is ammonium persulfate or potassium persulfate.

[0031] The present invention has the following beneficial effects compared with the prior art: The fluorescent monomer provided by the present invention contains a fluorescent rigid group in its molecular structure. By connecting the fluorine-containing group through it, it is beneficial to the structural stability of the fluorine-containing chain segment at the two-phase interface, and it is not easy to have a structural rearrangement phenomenon. It has excellent hydrophobic stability and fluorescent properties, and improves the stable anti-fouling and high mechanical properties of the fluorinated polyacrylate soap-free emulsion.

[0032] The present invention prepares a fluorescent monomer containing a rigid naphthalene ring connecting a fluorine-containing group through acylation reaction, esterification reaction and alkylation reaction between 4-bromo-1,8-naphthalic anhydride and monoethanolamine, acryloyl chloride and octafluoropentanol in sequence. By copolymerizing it with other monomers, on the one hand, the fluorine-containing chain segment is not easy to have a rearrangement phenomenon at the two-phase interface and has structural stability; on the other hand, the riveting or physical cross-linking effect of this fluorescent rigid center between the polymer molecular chains can endow the fluorinated polyacrylate soap-free emulsion with stable anti-fouling, high mechanical properties and fluorescent functions.

[0033] The semi-continuous seeded emulsion polymerization technology with the fluorescent monomer and the soft monomer as the core phase and the polymerizable fluorine-containing monomer, non-fluorine monomer and self-crosslinking monomer as the shell phase aims to prepare a fluorinated polyacrylate emulsion with a core-shell structure with the fluorescent component inside and the fluorine chain segment outside. By using the "hinging" effect of the side-chain rigid center in the molecular chain and the chemical bond cross-linking effect between the self-crosslinking groups, the fluorinated polyacrylate film has high mechanical properties. A fluorinated polyacrylate soap-free emulsion with fluorescence, anti-fouling and high mechanical properties is prepared by using a polymerizable emulsifier. The emulsifier molecules are copolymerized in the polymer molecular chain, and there are no free emulsifier molecules in the emulsion, so it is beneficial to environmental protection and the hydrophobicity of the product. This emulsion has excellent fluorescence, anti-fouling and mechanical properties and can be used in the fields of anti-counterfeiting coatings or films, anti-corrosion coatings, photosensitive materials, anti-counterfeiting marks, traffic signs, elastic materials, building materials, fluorescent inks, fluorescent coatings, etc., and has a wide range of applications. Description of the Drawings

[0034] Figure 1The infrared spectra of the fluorescent monomer and the fluorescent multifunctional fluorinated polyacrylate prepared in Example 1 of the present invention.

[0035] Figure 2 The ultraviolet absorption spectrum of the fluorescent monomer prepared in Example 1 of the present invention.

[0036] Figure 3 The fluorescence emission spectra of the soap-free emulsions of the fluorescent multifunctional fluorinated polyacrylate prepared in Examples 1 to 3 of the present invention.

[0037] Figure 4 The graph showing the change of the contact angle of the fabric surface treated with the soap-free emulsion of the fluorescent multifunctional fluorinated polyacrylate prepared in Examples 1 to 3 of the present invention over time. Detailed implementation manners

[0038] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.

[0039] It should be noted that the professional terms used in the present invention are only for the purpose of describing specific embodiments and are not intended to limit the protection scope of the present invention. In the present invention, certain terms are used to refer to specific components. Those skilled in the art should understand that technicians may use different nouns to refer to the same component. The present invention does not distinguish components by the difference in nouns, but by the difference in the functions of the components. As mentioned throughout the specification and claims, "including" is an open term and should be understood as "including but not limited to".

[0040] In the existing fluorinated polyacrylate emulsion, introducing a fluorescent monomer into the fluorinated polyacrylate can endow the acrylate with fluorescent properties, but the water and oil repellent stability is not ideal.

[0041] Based on the above problems, the present invention provides a fluorescent monomer, and the fluorescent monomer is 4-O-octafluoropentyl-N-ethyl acrylate-1,8-naphthalimide, and its structure is shown in formula (1): .

[0042] Among them, R f is -CF2CF2CF2CF2H.

[0043] It should be noted that the fluorescent monomer provided by the present invention contains a fluorescent rigid group in its molecular structure. By connecting a fluorine-containing group through it, it is beneficial to the structural stability of the fluorine-containing chain segment at the two-phase interface, is not prone to structural rearrangement, has excellent hydrophobic stability and fluorescent properties, and improves the stable anti-fouling and high mechanical properties of the fluorinated polyacrylate soap-free emulsion.

[0044] The present invention also provides a preparation method of the above fluorescent monomer, which includes the following steps: S1. Using 4-bromo-1,8-naphthalic anhydride and monoethanolamine as raw materials, dissolving them in a first solvent, and carrying out an amidation reaction at 70°C to 90°C to obtain 4-bromo-N-hydroxyethyl-1,8-naphthalimide. The reaction route is as follows:

[0045] 。

[0046] S2. Mix 4-bromo-N-hydroxyethyl-1,8-naphthalimide and triethylamine solution to form a mixed solution, then add acryloyl chloride solution, and carry out an esterification reaction at 0°C to 5°C to obtain 4-bromo-N-ethyl acrylate-1,8-naphthalimide. The reaction route is as follows:

[0047] 。

[0048] S3. Using 4-bromo-N-ethyl acrylate-1,8-naphthalimide and octafluoropentanol as raw materials, in a reaction system of a catalyst and a second solvent, carry out a substitution reaction at 110°C to 130°C to obtain 4-O-octafluoropentyl-N-ethyl acrylate-1,8-naphthalimide. The reaction route is as follows:

[0049] 。

[0050] It should be noted that the present invention prepares a fluorescent monomer containing a rigid naphthalene ring connecting a fluorine-containing group in its molecule through acylation reaction, esterification reaction and alkylation reaction of 4-bromo-1,8-naphthalic anhydride with monoethanolamine, acryloyl chloride and octafluoropentanol in sequence. Using it to copolymerize with other monomers, on the one hand, the fluorine-containing chain segment is not prone to rearrangement at the two-phase interface and has structural stability; on the other hand, the riveting or physical cross-linking effect of this fluorescent rigid center between polymer molecular chains can endow the fluorinated polyacrylate soap-free emulsion with stable anti-fouling, high mechanical properties and fluorescent function.

[0051] In some embodiments, the molar ratio of 4-bromo-1,8-naphthalic anhydride to monoethanolamine is 1:1 to 5, the dosage of the first solvent is 15 times to 25 times the mass of 4-bromo-1,8-naphthalic anhydride, and the reflux reaction time of the first time is 4 to 8 hours.

[0052] In some embodiments, the molar ratio of 4-bromo-N-hydroxyethyl-1,8-naphthalimide, triethylamine and acryloyl chloride is 1:1-2:1-2.

[0053] In some embodiments, the triethylamine solution is a dichloromethane solution of triethylamine, and the acryloyl chloride solution is a dichloromethane solution of acryloyl chloride. In the second reflux reaction system, the total amount of dichloromethane used is 5 to 15 times the mass of 4-bromo-N-hydroxyethyl-1,8-naphthalimide, and the time of the second reflux reaction is 4h to 6h. Among them, the dichloromethane solution of acryloyl chloride is added to the mixed solution dropwise, and the dropping time is 20min to 40min.

[0054] In some embodiments, the molar ratio of 4-bromo-N-ethyl acrylate-1,8-naphthalimide and octafluoropentanol is 1:2-4, the catalyst is potassium carbonate and zinc powder, and the molar ratio of 4-bromo-N-ethyl acrylate-1,8-naphthalimide, potassium carbonate and zinc powder is 1:1-2:1-2. The amount of the second solvent used is 5 to 15 times the mass of 4-bromo-N-ethyl acrylate-1,8-naphthalimide, and the substitution reaction time is 8h to 12h.

[0055] On the other hand, the present invention also provides a soap-free fluorinated polyacrylate emulsion, and the polyacrylate emulsion is prepared by polymerizing component A and component B in a volume ratio of 1:1, wherein, Component A is a prepolymer prepared from a reactive monomer A, a first emulsifier, a first chain transfer agent and a first initiator. Among them, the reactive monomer A is a mixture of the above-mentioned fluorescent monomer and a first polymerizable non-fluorinated monomer in a mass ratio of 0.5-5:90-95. The amount of the first emulsifier used is 0.5wt%-5wt% of the mass of the reactive monomer A, the amount of the first chain transfer agent used is 0.5wt%-2wt% of the mass of the reactive monomer A, and the amount of the first initiator used is 0.5wt%-3wt% of the mass of the reactive monomer A.

[0056] Component B is made by mixing a reactive monomer B, a second emulsifier and a second chain transfer agent. The reactive monomer B is a mixture of a polymerizable fluorinated monomer, a second polymerizable non-fluorinated monomer and a self-crosslinking monomer in a mass ratio of 40-70:10-30:5-15. The amount of the second emulsifier used is 0.5wt%-5wt% of the mass of the reactive monomer B, and the second chain transfer agent is 0.5wt%-2wt% of the mass of the reactive monomer B.

[0057] It should be noted that the present invention uses a fluorescent monomer and a soft monomer as the core phase, and a semi - continuous seeded emulsion polymerization technology with a polymerizable fluorinated monomer, a non - fluorinated monomer, and a self - crosslinking monomer as the shell phase aims to prepare a core - shell structure with the fluorescent component in the inner layer and the fluorine chain segment in the outer layer. This is beneficial for shortening the migration path of the fluorine - containing chain segment to the two - phase interface after the fluorinated polyacrylate emulsion is applied to the substrate, thereby efficiently exerting the antifouling performance.

[0058] In some embodiments, the first polymerizable non - fluorinated monomer and the second polymerizable non - fluorinated monomer are both one of n - butyl acrylate, isooctyl acrylate, and lauryl methacrylate. The polymerizable fluorinated monomer is one of trifluoroethyl methacrylate, hexafluorobutyl methacrylate, and dodecafluoroheptyl methacrylate. The cross - linking monomer is one of N - hydroxymethyl acrylamide and γ - (methacryloyloxy) propyltrimethoxysilane. The first emulsifier and the second emulsifier are both ammonium 1 - allyloxy - 3 - (4 - nonylphenol) - 2 - propanol polyoxyethylene (10) ether sulfate. The first chain transfer agent and the second chain transfer agent are both dodecyl mercaptan. The first initiator is ammonium persulfate or potassium persulfate.

[0059] The present invention also provides a method for preparing the above - mentioned soap - free fluorinated polyacrylate emulsion, which includes the following steps: Step 1, weigh component A and component B respectively according to the component ratio.

[0060] Step 2, mix the reaction monomer A, the first emulsifier, and the first chain transfer agent, and under the atmosphere of a protective gas, heat up to 75 °C - 80 °C, and add the first initiator to carry out a polymerization reaction to obtain a polymerization reaction system.

[0061] Step 3, mix the reaction monomer B, the second emulsifier, and the second chain transfer agent to obtain component B.

[0062] Step 4, add component B and the second initiator into the polymerization reaction system respectively, and then carry out a secondary polymerization reaction at 75 °C - 80 °C to obtain a soap - free fluorinated polyacrylate emulsion. The reaction route is as follows:

[0063] 。

[0064] It should be noted that the soap-free fluorinated polyacrylate emulsion prepared by the present invention is an aqueous solution, and the solid content of the soap-free fluorinated polyacrylate emulsion can be selected according to actual conditions. Preferably, the solid content of the soap-free fluorinated polyacrylate emulsion is 30% - 60%. During the preparation of component A, deionized water is added to component A for polymerization to form a prepolymer, and the solid content of component A is also 30% - 60%. The first initiator is dissolved in deionized water and then added dropwise to the reaction system, but the concentration of the first initiator solution does not need to be limited. It only needs to be dissolved in deionized water to form a solution and added dropwise within a controllable time range. After the prepolymer formed by component A is mixed with component B, water also needs to be added for polymerization to form the soap-free fluorinated polyacrylate emulsion. Under the condition of determining the solid content selected according to actual conditions, the amount of deionized water is selected, and the second initiator is also dissolved in deionized water and then added dropwise to the reaction system, but the concentration of the second initiator solution does not need to be limited. It only needs to be dissolved in deionized water to form a solution and added dropwise within a controllable time range.

[0065] In the present invention, 1-allyloxy-3-(4-nonylphenol)-2-propanol polyoxyethylene (10) ether ammonium sulfate (DNS-86) is used as a polymerizable emulsifier. A semi-continuous seeded emulsion polymerization is carried out under the conditions that the fluorescent monomer and part of the non-fluorinated monomers are the core phase, the fluorinated monomers, non-fluorinated monomers and self-crosslinking monomers are the shell phase, and the aqueous persulfate is the initiator, aiming to prepare a fluorescent multifunctional soap-free fluorinated polyacrylate emulsion. Since the emulsifier molecule contains an unsaturated double bond, it can participate in the polymerization reaction during the reaction process and finally bond into the polymer molecular chain instead of being free in the emulsion. In this way, when the emulsion is applied to the substrate and forms a film, it can greatly reduce the adverse effects of free emulsifier on the film adhesion performance and hydrophobic performance.

[0066] Furthermore, the polymerization reaction time is 0.5 h - 1 h, the secondary polymerization reaction time is 2 h - 6 h. Component B and the second initiator solution are respectively added to the mixed solution in a dropwise manner, the dropping time is 1 h - 2 h, the dosage of the second initiator is 0.5 wt% - 3 wt% of the mass of monomer B, and the second initiator is ammonium persulfate or potassium persulfate.

[0067] The following is further illustrated by specific examples.

[0068] Example 1 A preparation method of a soap-free fluorinated polyacrylate emulsion, comprising the following steps: S1. Preparation of the fluorescent monomer: Weigh 13.85 g (50 mmol) of 4-bromo-1,8-naphthalic anhydride and 14.03 g (150 mmol) of monoethanolamine and add them to a three-necked flask equipped with a stirring device. Add 300 mL of absolute ethanol and stir to completely dissolve the reactants. Then reflux the reaction mixture at 80 °C for 6 h, carry out suction filtration under reduced pressure, and wash the filter cake with deionized water three times. Then dry it in vacuo at 80 °C for 12 h to obtain a light yellow product, 4-bromo-N-hydroxyethyl-1,8-naphthalimide, denoted as BHNA.

[0069] Under ice bath conditions, slowly add a dichloromethane solution containing 2.2 g (30 mmol) of acryloyl chloride dropwise to a dichloromethane solution containing 9.6 g (30 mmol) of BHNA and 3.04 g (30 mmol) of triethylamine. Finish the dropping within 30 min, react for 5 h, carry out suction filtration to obtain the filtrate, then distill off the dichloromethane solvent under reduced pressure, and wash it with deionized water three times. Dry it in vacuo at 80 °C to obtain a light yellow solid product, 4-bromo-N-ethyl acrylate-1,8-naphthalimide, denoted as BENA.

[0070] Weigh 11.23 g (30 mmol) of BENA, 20.89 g (30 mmol) of octafluoropentanol, 4.15 g (30 mmol) of potassium carbonate, and 0.49 g (30 mmol) of zinc powder. Dissolve them in 120 mL of dimethyl sulfoxide and heat up to 120 °C for heat preservation reaction for 10 h. Carry out suction filtration to obtain the filtrate. Add 100 mL of deionized water to the filtrate, collect the lower layer of oily substance, and dry it in vacuo at 80 °C for 6 h to obtain a brown solid product, 4-O-octafluoropentyl-N-ethyl acrylate-1,8-naphthalimide, which is the fluorescent monomer, denoted as OENA.

[0071] S2. Preparation of fluorinated polyacrylate soap-free emulsion: Weigh 0.4 g of the fluorescent monomer, 10 g of butyl acrylate, 0.3 g of DNS-86, and 1.03 g of dodecyl mercaptan. After mixing, add 18 g of deionized water and stir at high speed for 20 min to obtain a mixture. Under the protection of nitrogen, heat the mixture to 78 °C. Dissolve 0.0363 g of ammonium persulfate in 10 g of deionized water to form an ammonium persulfate aqueous solution. Add the ammonium persulfate aqueous solution to the above reaction solution and start the polymerization reaction for 0.5 - 1 h to obtain a polymerization reaction system.

[0072] Weigh 6 g of dodecafluoroheptyl methacrylate, 2 g of butyl acrylate, 1 g of N-methylolacrylamide, 0.28 g of DNS-86, and 0.97 g of dodecyl mercaptan. After mixing, add 13 g of deionized water and stir at high speed for 10 - 30 min to obtain Component B.

[0073] Dissolve 0.0363 g of ammonium persulfate in 10 g of deionized water to form an ammonium persulfate aqueous solution. Slowly add component B and the ammonium persulfate aqueous solution to the above polymerization reaction system respectively, and control the dropping to be completed in about 1.5 h. Then keep the reaction at a constant temperature for 4 h to obtain the fluorescent multifunctional fluorinated polyacrylate soap-free emulsion.

[0074] Example 2 A method for preparing a fluorinated polyacrylate soap-free emulsion, comprising the following steps: S1. Preparation of fluorescent monomer: Weigh 13.85 g (50 mmol) of 4-bromo-1,8-naphthalic anhydride and 14.03 g (150 mmol) of monoethanolamine and add them to a three-necked flask equipped with a stirring device. Add 300 mL of absolute ethanol and stir to completely dissolve the reactants. Then reflux and react at 80 °C for 6 h, carry out vacuum filtration under reduced pressure and wash the filter cake with deionized water 3 times. Then dry it in vacuo at 80 °C for 12 h to obtain a light yellow product 4-bromo-N-hydroxyethyl-1,8-naphthalimide, denoted as BHNA.

[0075] Under ice bath conditions, slowly add a dichloromethane solution containing 2.2 g (30 mmol) of acryloyl chloride to a dichloromethane solution containing 9.6 g (30 mmol) of BHNA and 3.04 g (30 mmol) of triethylamine, and complete the dropping within 30 min. React for 5 h, carry out suction filtration to obtain a filtrate, then remove the dichloromethane solvent by distillation under reduced pressure, and wash it with deionized water 3 times. Dry it in vacuo at 80 °C to obtain a light yellow solid product 4-bromo-N-ethyl acrylate-1,8-naphthalimide, denoted as BENA.

[0076] Weigh 11.23 g (30 mmol) of BENA, 20.89 g (30 mmol) of octafluoropentanol, 4.15 g (30 mmol) of potassium carbonate, and 0.49 g (30 mmol) of zinc powder. Dissolve them in 120 mL of dimethyl sulfoxide and heat to 120 °C and keep the reaction at a constant temperature for 10 h. Carry out suction filtration to obtain a filtrate. Add 100 mL of deionized water to the filtrate, collect the lower layer of oily substance, and dry it in vacuo at 80 °C for 6 h to obtain a brown solid product 4-O-octafluoropentyl-N-ethyl acrylate-1,8-naphthalimide, which is the fluorescent monomer.

[0077] S2. Preparation of fluorinated polyacrylate soap-free emulsion: Weigh 0.4 g of fluorescent monomer, 10 g of isooctyl acrylate, 0.3 g of DNS-86 and 1.03 g of dodecyl mercaptan. After mixing, add 18 g of deionized water and stir at high speed for 20 min to obtain a mixture. Under the protection of nitrogen, heat the mixture to 78 °C. Dissolve 0.1236 g of ammonium persulfate in 10 g of deionized water to form an ammonium persulfate aqueous solution. Add the ammonium persulfate aqueous solution to the above reaction solution and start the polymerization reaction for 1 h to obtain a polymerization reaction system, denoted as OENA.

[0078] Weigh 6 g of dodecafluoroheptyl methacrylate, 2 g of isooctyl acrylate, 1 g of N-methylolacrylamide, 0.28 g of DNS-86 and 0.97 g of dodecyl mercaptan. After mixing, add 13 g of deionized water and stir at high speed for 20 min to obtain Component B.

[0079] Dissolve 0.0363 g of ammonium persulfate in 10 g of deionized water to form an ammonium persulfate aqueous solution. Slowly add Component B and the ammonium persulfate aqueous solution to the above polymerization reaction system respectively, and control the dropping to be completed in about 1.5 h. Then keep the temperature for reaction for 4 h to obtain the soap-free emulsion of fluorescent multifunctional fluorinated polyacrylate.

[0080] Example 3 A preparation method of a fluorinated polyacrylate soap-free emulsion, comprising the following steps: S1. Preparation of fluorescent monomer: Weigh 13.85 g (50 mmol) of 4-bromo-1,8-naphthalic anhydride and 14.03 g (150 mmol) of monoethanolamine and add them to a three-necked flask equipped with a stirring device. Add 300 mL of absolute ethanol and stir to completely dissolve the reactants. Then reflux and react at 80 °C for 6 h. Filter under reduced pressure and wash the filter cake with deionized water 3 times. Then dry in vacuo at 80 °C for 12 h to obtain a light yellow product 4-bromo-N-hydroxyethyl-1,8-naphthalimide, denoted as BHNA.

[0081] Under ice bath conditions, slowly add a dichloromethane solution containing 2.2 g (30 mmol) of acryloyl chloride to a dichloromethane solution containing 9.6 g (30 mmol) of BHNA and 3.04 g (30 mmol) of triethylamine dropwise within 30 min. React for 5 h, filter to obtain the filtrate, then distill off the dichloromethane solvent under reduced pressure and wash with deionized water 3 times. Dry in vacuo at 80 °C to obtain a light yellow solid product 4-bromo-N-ethyl acrylate-1,8-naphthalimide, denoted as BENA.

[0082] Weigh 11.23 g (30 mmol) of BENA, 20.89 g (30 mmol) of octafluoropentanol, 4.15 g (30 mmol) of potassium carbonate, and 0.49 g (30 mmol) of zinc powder. Dissolve them in 120 mL of dimethyl sulfoxide and heat to 120 °C for a heat-preserving reaction for 10 h. Filter by suction to obtain the filtrate. Add 100 mL of deionized water to the filtrate, collect the lower-layer oily substance, and vacuum-dry it at 80 °C for 6 h to obtain the brown solid product 4-O-octafluoropentyl-N-ethyl acrylate-1,8-naphthalimide, which is the fluorescent monomer, denoted as OENA.

[0083] S2. Preparation of the fluorinated polyacrylate soap-free emulsion: Weigh 0.4 g of the fluorescent monomer, 10 g of lauryl methacrylate, 0.3 g of DNS-86, and 1.03 g of dodecyl mercaptan. After mixing, add 18 g of deionized water and stir at high speed for 20 min to obtain a mixture. Under the protection of nitrogen, heat the mixture to 78 °C. Dissolve 0.1236 g of ammonium persulfate in 10 g of deionized water to form an ammonium persulfate aqueous solution. Add the ammonium persulfate aqueous solution to the above reaction solution and start the polymerization reaction for 1 h to obtain the polymerization reaction system.

[0084] Weigh 6 g of dodecafluoroheptyl methacrylate, 2 g of lauryl methacrylate, 1 g of γ-(methacryloyloxy)propyltrimethoxysilane, 0.28 g of DNS-86, and 0.97 g of dodecyl mercaptan. After mixing, add 13 g of deionized water and stir at high speed for 20 min to obtain Component B.

[0085] Dissolve 0.0363 g of potassium persulfate in 10 g of deionized water to form an ammonium persulfate aqueous solution. Slowly add Component B and the ammonium persulfate aqueous solution to the above polymerization reaction system respectively, and control to finish dropping in about 1.5 h. Then keep the temperature for reaction for 4 h to obtain the fluorescent multifunctional fluorinated polyacrylate soap-free emulsion.

[0086] Example 4 A preparation method of a fluorinated polyacrylate soap-free emulsion, comprising the following steps: S1. Preparation of the fluorescent monomer: Weigh 13.85 g (50 mmol) of 4-bromo-1,8-naphthalic anhydride and 14.03 g (150 mmol) of monoethanolamine and add them to a three-necked flask equipped with a stirring device. Add 3...

[0087] Under ice bath conditions, a dichloromethane solution containing 9.6 g (30 mmol) of BHNA and 3.04 g (30 mmol) of triethylamine was slowly added dropwise to a dichloromethane solution containing 2.2 g (30 mmol) of acryloyl chloride. The addition was completed within 30 min, and the reaction was carried out for 5 h. The mixture was filtered by suction to obtain a filtrate, and then the dichloromethane solvent was removed by distillation under reduced pressure. The residue was washed three times with deionized water and dried in vacuo at 80 °C to obtain a light yellow solid product, 4-bromo-N-ethyl acryloyl-1,8-naphthalimide, denoted as BENA.

[0088] Weigh 11.23 g (30 mmol) of BENA, 20.89 g (30 mmol) of octafluoropentanol, 4.15 g (30 mmol) of potassium carbonate, and 0.49 g (30 mmol) of zinc powder. Dissolve them in 120 mL of dimethyl sulfoxide and heat the solution to 120 °C for a reaction at this temperature for 10 h. The mixture was filtered by suction to obtain a filtrate. 100 mL of deionized water was added to the filtrate, and the lower layer of oily substance was collected and dried in vacuo at 80 °C for 6 h to obtain a brown solid product, 4-O-octafluoropentyl-N-ethyl acryloyl-1,8-naphthalimide, which is the fluorescent monomer, denoted as OENA.

[0089] S2. Preparation of fluorinated polyacrylate soap-free emulsion: Weigh 0.4 g of the fluorescent monomer, 8 g of butyl acrylate, 0.24 g of DNS-86, and 0.82 g of dodecyl mercaptan. After mixing, 18 g of deionized water was added and the mixture was stirred at high speed for 20 min to obtain a mixture. Under the protection of nitrogen, the mixture was heated to 78 °C. 0.0989 g of ammonium persulfate was dissolved in 10 g of deionized water to form an ammonium persulfate aqueous solution. The ammonium persulfate aqueous solution was added to the above reaction solution, and the polymerization reaction was carried out for 1 h to obtain a polymerization reaction system.

[0090] Weigh 8 g of hexafluorobutyl methacrylate, 2 g of butyl acrylate, 1 g of N-methylolacrylamide, 0.34 g of DNS-86, and 1.17 g of dodecyl mercaptan. After mixing, 13 g of deionized water was added and the mixture was stirred at high speed for 20 min to obtain Component B.

[0091] 0.061 g of ammonium persulfate was dissolved in 10 g of deionized water to form an ammonium persulfate aqueous solution. Component B and the ammonium persulfate aqueous solution were slowly added dropwise to the above polymerization reaction system, respectively. The addition was approximately completed within 1.5 h, and then the mixture was kept at a constant temperature for reaction for 4 h to obtain the fluorescent multifunctional fluorinated polyacrylate soap-free emulsion.

[0092] Example 5 A preparation method of a fluorinated polyacrylate soap-free emulsion, comprising the following steps: S1. Preparation of the fluorescent monomer: Weigh 13.85 g (50 mmol) of 4-bromo-1,8-naphthalic anhydride and 14.03 g (150 mmol) of monoethanolamine and add them to a three-necked flask equipped with a stirring device. Add 300 mL of anhydrous ethanol and stir to completely dissolve the reactants. Then reflux the reaction at 80 °C for 6 h, carry out suction filtration under reduced pressure and wash the filter cake with deionized water 3 times. Then dry it in vacuo at 80 °C for 12 h to obtain a light yellow product 4-bromo-N-hydroxyethyl-1,8-naphthalimide, denoted as BHNA.

[0093] Under ice bath conditions, slowly add dropwise a dichloromethane solution containing 2.2 g (30 mmol) of acryloyl chloride to a dichloromethane solution containing 9.6 g (30 mmol) of BHNA and 3.04 g (30 mmol) of triethylamine within 30 min. React for 5 h, carry out suction filtration to obtain the filtrate, then distill off the dichloromethane solvent under reduced pressure and wash it with deionized water 3 times. Dry it in vacuo at 80 °C to obtain a light yellow solid product 4-bromo-N-ethyl acrylate-1,8-naphthalimide, denoted as BENA.

[0094] Weigh 11.23 g (30 mmol) of BENA, 20.89 g (30 mmol) of octafluoropentanol, 4.15 g (30 mmol) of potassium carbonate, 0.49 g (30 mmol) of zinc powder, dissolve them with 120 mL of dimethyl sulfoxide and heat to 120 °C for heat preservation reaction for 10 h. Carry out suction filtration to obtain the filtrate. Add 100 mL of deionized water to the filtrate, collect the lower layer of oily substance, and dry it in vacuo at 80 °C for 6 h to obtain a brown solid product 4-O-octafluoropentyl-N-ethyl acrylate-1,8-naphthalimide, which is the fluorescent monomer, denoted as OENA.

[0095] S2. Preparation of fluorinated polyacrylate soap-free emulsion: Weigh 0.4 g of the fluorescent monomer, 6 g of butyl acrylate, 0.18 g of DNS-86 and 0.62 g of dodecyl mercaptan, mix them and carry out high-speed stirring for 10 - 30 min to obtain a mixture. Under the protection of nitrogen, start to heat the mixture to 75 - 80 °C. Dissolve 0.0742 g of ammonium persulfate with 10 g of deionized water to form an ammonium persulfate aqueous solution. Add the ammonium persulfate aqueous solution to the above reaction solution and start the polymerization reaction for 1 h to obtain a polymerization reaction system.

[0096] Weigh 10 g of trifluoroethyl methacrylate, 2 g of butyl acrylate, 1 g of N-methylolacrylamide, 0.4 g of DNS-86 and 1.38 g of dodecyl mercaptan, mix them and then add 13 g of deionized water and carry out high-speed stirring for 20 min to obtain component B.

[0097] Dissolve 0.0857 g of ammonium persulfate in 10 g of deionized water to form an ammonium persulfate aqueous solution. Slowly add component B and the ammonium persulfate aqueous solution to the above polymerization reaction system respectively, and control to finish dropping in about 1.5 h, then keep the temperature for reaction for 4 h to obtain the soap-free emulsion of fluorescent multifunctional fluorinated polyacrylate.

[0098] Test the structures and properties of the fluorescent monomers prepared in Examples 1 to 5 and the soap-free emulsion of fluorescent multifunctional fluorinated polyacrylate prepared, and the results are as follows: Figure 1 This is the infrared spectrogram of the fluorescent monomer and the fluorescent multifunctional fluorinated polyacrylate prepared in Example 1 of the present invention. As Figure 1 shown, for the fluorescent monomer, the absorption peaks at 3078 cm -1 and 1660 cm -1 are the stretching vibration absorption peaks of =C-H and C=C in -CH=CH2, the absorption peaks at 2961 cm -1 and 2882 cm -1 are the stretching vibration absorption peaks of -C-H of methylene, the absorption peak at 1580 cm -1 is the aromatic ring skeleton vibration absorption peak, the absorption peaks at 1728 cm -1 and 1706 cm -1 are the stretching vibration absorption peaks of C=O of naphthalenedicarboxamide, the absorption peaks at 1234 cm -1 and 745 cm -1 are the stretching vibration absorption peak and bending vibration absorption peak of -CF2-, and the absorption peak at 1182 cm -1 is the asymmetric stretching vibration absorption peak of C-O-C; in comparison, for the infrared spectrum of the polymer, the absorption peaks at 3078 cm -1 and 1660 cm -1 disappear, indicating that the double bond participates in the polymerization; the absorption peaks at 1300 cm -1 ~1100 cm -1 become stronger and broader because the introduced amount of -C-F increases, and their absorption peaks at this place overlap with the stretching vibration absorption peak of C-O. The absorption peak at 978 cm -1 is the characteristic absorption peak of the butyl acrylate chain segment. The above indicates the successful synthesis of the fluorescent monomer and the polymer.

[0099] Figure 2 This is the ultraviolet absorption spectrogram of the fluorescent monomer prepared in Example 1 of the present invention. As Figure 2 shown, the fluorescent monomer has an ultraviolet absorption peak near 340 nm, confirming the existence of a naphthalene ring conjugate system in its structure.

[0100] Figure 3 This is the fluorescence emission spectrogram of the soap-free emulsion of fluorescent multifunctional fluorinated polyacrylate prepared in Examples 1 to 3 of the present invention. As Figure 3As shown, the soap-free emulsions of fluorescent multifunctional fluorinated polyacrylates prepared in Examples 1 to 3 all exhibit a broad fluorescence emission peak near 420 nm, confirming that the emulsions have good fluorescence function.

[0101] The soap-free emulsion of fluorescent multifunctional fluorinated polyacrylate prepared in Example 1 was used for treating fabrics, which specifically included the following steps: The fabric was cut into specimens with a length × width of 2 cm × 1 cm, and ultrasonically washed with acetone and distilled water for 15 min successively under the temperature condition of 25 ± 2 °C, and then dried at 80 °C. An appropriate amount of the soap-free emulsion of fluorescent multifunctional fluorinated polyacrylate was diluted with 100 parts of water and formulated into a working bath solution at 40 °C. The fabric samples were treated by a small experimental padding mangle in a one-dip-one-roll manner, and the liquor pickup was controlled at 70%. Then the fabric samples were dried at 100 °C for 5 min and then heat-set and baked at 170 °C for 3 min.

[0102] Figure 4 This is a graph showing the change of the contact angle of the fabric surface treated with the soap-free emulsion of fluorescent multifunctional fluorinated polyacrylate prepared in Examples 1 to 3 of the present invention over time. As Figure 4 shown, the initial contact angles of the fabric surfaces treated in Examples 1 to 3 are approximately 130°, about 125° after 30 s, and only drop to about 120° after 120 s, indicating that the fabrics treated with the soap-free emulsion of fluorescent multifunctional fluorinated polyacrylate have good hydrophobic stability.

[0103] It should be noted that when the present invention involves numerical ranges, it should be understood that both endpoints of each numerical range and any value between the two endpoints can be selected. Since the adopted step methods are the same as those in the examples, in order to prevent repetition, the present invention describes the preferred examples. Although the preferred embodiments of the present invention have been described, those skilled in the art can make additional changes and modifications to these embodiments once they know the basic creative concept. Therefore, the appended claims are intended to be construed as including the preferred embodiments and all changes and modifications falling within the scope of the present invention.

[0104] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalent technologies, the present invention is also intended to include these modifications and variations.

Claims

1. A fluorescent monomer, characterized in that, The fluorescent monomer is 4-O-octafluoropentyl-N-ethyl acrylate-1,8-naphthalimide, and its structure is shown in formula (1): ； Among them, R f is -CF2CF2CF2CF2H.

2. The preparation method of the fluorescent monomer according to claim 1, characterized in that, It includes the following steps: Using 4-bromo-1,8-naphthalic anhydride and monoethanolamine as raw materials, dissolving them in a first solvent, and carrying out an amidation reaction at 70 °C to 90 °C to obtain 4-bromo-N-hydroxyethyl-1,8-naphthalimide; Mixing 4-bromo-N-hydroxyethyl-1,8-naphthalimide and a triethylamine solution to form a mixed solution, then adding an acryloyl chloride solution, and carrying out an esterification reaction at 0 °C to 5 °C to obtain 4-bromo-N-ethyl acrylate-1,8-naphthalimide; Using 4-bromo-N-ethyl acrylate-1,8-naphthalimide and octafluoropentanol as raw materials, carrying out a substitution reaction at 110 °C to 130 °C in a reaction system of a catalyst and a second solvent to obtain 4-O-octafluoropentyl-N-ethyl acrylate-1,8-naphthalimide.

3. The preparation method of the fluorescent monomer according to claim 2, characterized in that, The molar ratio of 4-bromo-1,8-naphthalic anhydride to monoethanolamine is 1:1 to 5, the dosage of the first solvent is 15 to 25 times the mass of 4-bromo-1,8-naphthalic anhydride, and the time of the amidation reaction is 4 h to 8 h.

4. The preparation method of the fluorescent monomer according to claim 2, characterized in that, The molar ratio of 4-bromo-N-hydroxyethyl-1,8-naphthalimide, triethylamine and acryloyl chloride is 1:1 to 2:1 to 2.

5. The preparation method of the fluorescent monomer according to claim 2, characterized in that, The triethylamine solution is a dichloromethane solution of triethylamine, the acryloyl chloride solution is a dichloromethane solution of acryloyl chloride. In the esterification reaction system, the total dosage of dichloromethane is 5 to 15 times the mass of 4-bromo-N-hydroxyethyl-1,8-naphthalimide, the time of the esterification reaction is 4 h to 6 h, and the dichloromethane solution of acryloyl chloride is added dropwise to the mixed solution, and the dropping time is 20 min to 40 min.

6. The preparation method of the fluorescent monomer according to claim 2, characterized in that The molar ratio of 4-bromo-N-ethyl acrylate-1,8-naphthalimide to octafluoropentanol is 1:2 to 4, the catalyst is potassium carbonate and zinc powder, the molar ratio of 4-bromo-N-ethyl acrylate-1,8-naphthalimide, potassium carbonate and zinc powder is 1:1 to 2:1 to 2, the dosage of the second solvent is 5 to 15 times the mass of 4-bromo-N-ethyl acrylate-1,8-naphthalimide, and the time of the substitution reaction is 8 h to 12 h.

7. A soap-free fluorinated polyacrylate emulsion, characterized in that, The polyacrylate emulsion is prepared by polymerizing component A and component B at a volume ratio of 1:1, wherein, Component A is a prepolymer prepared from reaction monomer A, a first emulsifier, a first chain transfer agent and a first initiator. Among them, reaction monomer A is a mixture of the fluorescent monomer described in claim 1 and a first polymerizable non-fluorine monomer at a mass ratio of 0.5 to 5:90 to 95. The dosage of the first emulsifier is 0.5 wt% to 5 wt% of the mass of reaction monomer A, the dosage of the first chain transfer agent is 0.5 wt% to 2 wt% of the mass of reaction monomer A, and the dosage of the first initiator is 0.5 wt% to 3 wt% of the mass of reaction monomer A.

8. Component B is prepared by mixing reactive monomer B, a second emulsifier, and a second chain transfer agent. Reactive monomer B is formed by mixing a polymerizable fluorinated monomer, a second polymerizable non-fluorinated monomer, and a self-crosslinking monomer in a mass ratio of 40 - 70:10 - 30:5 - 15. The dosage of the second emulsifier is 0.5wt% - 5wt% of the mass of reactive monomer B, and the second chain transfer agent is 0.5wt% - 2wt% of the mass of reactive monomer B.

9. The soap-free emulsion of fluorinated polyacrylate according to claim 7, wherein Both the first polymerizable non-fluorinated monomer and the second polymerizable non-fluorinated monomer are one of n-butyl acrylate, isooctyl acrylate, and lauryl methacrylate; The polymerizable fluorinated monomer is one of trifluoroethyl methacrylate, hexafluorobutyl methacrylate, and dodecafluoroheptyl methacrylate; The crosslinking monomer is one of N-methylolacrylamide and γ-(methacryloyloxy)propyltrimethoxysilane; Both the first emulsifier and the second emulsifier are ammonium 1-allyloxy-3-(4-nonylphenol)-2-propanol polyoxyethylene (10) ether sulfate; Both the first chain transfer agent and the second chain transfer agent are dodecyl mercaptan; The first initiator is ammonium persulfate or potassium persulfate.

10. A method for preparing the soap-free fluorinated polyacrylate emulsion according to claim 7 or claim 8, characterized in that, It includes the following steps: Weigh Component A and Component B respectively according to the component ratio; Mix reactive monomer A, the first emulsifier, and the first chain transfer agent, and under the atmosphere of a protective gas, heat up to 75°C - 80°C, then add the first initiator for a polymerization reaction to obtain a polymerization reaction system; Mix reactive monomer B, the second emulsifier, and the second chain transfer agent to obtain Component B; Add Component B and the second initiator into the polymerization reaction system respectively, and then carry out a secondary polymerization reaction at 75°C - 80°C to obtain a soap-free fluorinated polyacrylate emulsion.

11. The preparation method of the soap-free fluorinated polyacrylate emulsion according to claim 9, characterized in that, The time for the polymerization reaction is 0.5h - 1h, and the time for the secondary polymerization reaction is 2h - 6h. Component B and the second initiator solution are respectively added to the mixed solution by dropwise addition, and the dropping time is 1h - 2h. The dosage of the second initiator is 0.5wt% - 3wt% of the mass of reactive monomer B, and the second initiator is ammonium persulfate or potassium persulfate.

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