Polyurethane-polyacrylate hybrid emulsion and preparation method thereof

Abstract

The invention discloses a polyurethane-polyacrylate hybrid emulsion and a preparation method thereof, and belongs to the technical field of polymer functional materials. The preparation method of the polyurethane-polyacrylate hybrid emulsion comprises the following steps: taking diisocyanate and oligomer polyol as raw materials, taking organic tin as a catalyst, reacting, adding a hydrophilic chain extender and a fluorescent chain extender containing naphthalene rings and fluoroalkyl, and reacting to obtain a-NCO-terminated fluorescent polyurethane prepolymer; the preparation method comprises the following steps: by taking hydroxyethyl acrylate as a modifier, carrying out modification treatment on the-NCO-terminated fluorescent polyurethane prepolymer, so as to obtain a polyurethane prepolymer of which the two sides are terminated; the preparation method comprises the following steps: reacting polyurethane acrylate with a neutralizing agent, adding water for dispersion and emulsification, adding acrylate and a fluorine-containing acrylate monomer, uniformly dispersing, adding an initiator solution, and reacting to obtain the polyurethane-polyacrylate hybrid emulsion. The polyurethane-polyacrylate hybrid emulsion has excellent quality in three aspects of fluorescence property, hydrophobic property and mechanical property.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer functional materials, and more particularly to a polyurethane-polyacrylate hybrid emulsion and a preparation method thereof. Background Art

[0002] Waterborne polyurethane is a new type of polymer material, which is an aqueous dispersion prepared by reacting polyurethane resin with an aqueous solvent or an aqueous emulsifier. Compared with traditional organic solvent-based polyurethanes, waterborne polyurethanes have the advantages of environmental protection, non-toxicity, odorlessness, easy processing, convenient use, and low cost, and thus have been widely used in recent years.

[0003] With the improvement of living standards, people's requirements for materials are no longer limited to single performance indicators, but they more need materials to have multiple functions. Therefore, materials with multifunctionality have become a hot research topic. Fluorescent waterborne polyurethane has good water resistance, weather resistance, chemical corrosion resistance and good flexibility. At the same time, it also has a fluorescent effect, which can improve the visibility of the material, making it easier to be discovered in a dim environment. It is of great significance to be applied in night construction or occasions where high visibility is required. Therefore, it is widely used in fields such as anti-counterfeiting materials, architectural coatings, fluorescent coatings, waterproof coatings, sealing materials, and ship coatings.

[0004] Currently, there are various ways to endow waterborne polyurethane with fluorescent properties and other properties, such as doping fluorescent substances in polyurethane emulsion by physical blending method or binding fluorescent substances to the polyurethane molecular chain by chemical bonding. For example, in Chinese Patent CN 115991854 A, product 1 and product 2 were prepared, and then the two products were introduced into the reaction of polyurethane to play a modification role, so that the polyurethane material has fluorescent and antibacterial properties. In Chinese Patent CN 116478366 A, a borate compound M was prepared to modify polyurethane, so that polyurethane has fluorescent and repairable functions. In Chinese Patent CN117586471 A, an aminophenylboronic acid was used to react to obtain a polyurethane emulsion, and then it was blended with modified nano-silica, so as to have fluorescent properties and hydrophobic properties. In Chinese Patent CN 116622045 A, curcumin was dissolved in a liquid containing a chain extender, and then reacted with a polyurethane prepolymer to obtain a polyurethane emulsion with fluorescent properties. Through the research of the above documents, it can be found that the preparation of functional polyurethane is often obtained by modifying polyurethane with a functional chain extender. Then, multiple chain extenders may need to be added in the preparation process of multifunctional polyurethane, and the preparation process is complex and cumbersome, wasting manpower and material resources. In addition, polyurethane as a film-forming material has a relatively high cost.

[0005] Polyacrylate, as a film-forming material, has low cost, good gloss, strong adhesion, flexibility and elasticity, and good weather resistance, but its tensile strength is not high. Summary of the Invention

[0006] In view of the above problems, the present invention provides a polyurethane-polyacrylate hybrid emulsion and a preparation method thereof. The preparation of the polyurethane-polyacrylate hybrid emulsion is mainly obtained by modifying polyurethane with a fluorescent chain extender containing a rigid central naphthalene ring and a fluoroalkyl group. The preparation process is simple, and it has excellent qualities in three aspects: fluorescence performance, hydrophobic performance, and mechanical performance. It can be applied to fields such as anti-counterfeiting coatings or films, anti-corrosion coatings, photosensitive materials, anti-counterfeiting labels, traffic signs, elastic materials, chemical detection, fluorescent inks, and fluorescent coatings.

[0007] The first object of the present invention is to provide a preparation method of a polyurethane-polyacrylate hybrid emulsion, comprising the following steps: Using diisocyanate and oligomeric polyol as raw materials, and organotin as a catalyst, a prepolymerization reaction occurs, and then a hydrophilic chain extender and a fluorescent chain extender containing a naphthalene ring and a fluoroalkyl group are added to carry out a modification reaction to obtain an -NCO-terminated fluorescent polyurethane prepolymer.

[0008] Using hydroxyethyl acrylate as a modifier, the -NCO-terminated fluorescent polyurethane prepolymer is modified to obtain a double-terminated polyurethane prepolymer; after the double-terminated polyurethane prepolymer and a neutralizing agent undergo a neutralization reaction at 40°C to 50°C, water is added for dispersion and emulsification to obtain a mixture.

[0009] After adding acrylate and fluoroacrylate monomers to the mixture and dispersing them evenly, an initiator solution is added at 80°C to 90°C to carry out a free radical polymerization reaction to obtain a polyurethane-polyacrylate hybrid emulsion.

[0010] In a preferred embodiment of the present invention, the preparation of the fluorescent chain extender containing a naphthalene ring and a fluoroalkyl group comprises the following steps: Under ice bath conditions, using ethylenediamine and perfluorobutanesulfonyl fluoride as raw materials, a first acylation reaction occurs to obtain N-aminoethyl-perfluorobutanesulfonamide.

[0011] In an alcoholic organic solution, 4-bromo-1,8-naphthalic anhydride and 2-amino-1,3-propanediol undergo a second acylation reaction to obtain 4-bromo-N-(2-hydroxy-1-hydroxymethylethyl)-1,8-naphthalenedicarboxamide.

[0012] In a sulfur-containing organic solvent, N-aminoethyl-perfluorobutanesulfonamide and 4-bromo-N-(2-hydroxy-1-hydroxymethylethyl)-1,8-naphthalenedicarboxamide undergo an alkylation reaction to obtain a fluorescent chain extender containing a naphthalene ring and a fluoroalkyl group.

[0013] In a preferred embodiment of the present invention, the molar ratio of ethylenediamine to perfluorobutanesulfonyl fluoride is 3 - 7:1; more preferably, the molar ratio of ethylenediamine to perfluorobutanesulfonyl fluoride is 5:1.

[0014] The reaction temperature of the first acylation reaction is 0°C - 5°C, and the reaction time is 5 h - 6 h.

[0015] In a preferred embodiment of the present invention, the molar ratio of 4-bromo-1,8-naphthalic anhydride to 2-amino-1,3-propanediol is 1:2 - 5; more preferably, the molar ratio of 4-bromo-1,8-naphthalic anhydride to 2-amino-1,3-propanediol is 1:3.

[0016] The reaction temperature of the second acylation reaction is 80°C - 90°C, and the reaction time is 8 h - 9 h.

[0017] In a preferred embodiment of the present invention, the addition amount of the alcoholic organic solution is 20 - 22 times the total mass of 4-bromo-1,8-naphthalic anhydride and 2-amino-1,3-propanediol.

[0018] In a preferred embodiment of the present invention, the molar ratio of 4-bromo-N-(2-hydroxy-1-hydroxymethylethyl)-1,8-naphthalenedicarboxamide to N-aminoethyl-perfluorobutanesulfonamide is 1:2 - 5; more preferably, the molar ratio of 4-bromo-N-(2-hydroxy-1-hydroxymethylethyl)-1,8-naphthalenedicarboxamide to N-aminoethyl-perfluorobutanesulfonamide is 1:3.

[0019] The reaction temperature of the alkylation reaction is 100°C - 110°C, and the reaction time is 7 h - 8 h.

[0020] In a preferred embodiment of the present invention, the addition amount of the sulfur-containing organic solvent is 15 - 17 times the total mass of 4-bromo-N-(2-hydroxy-1-hydroxymethylethyl)-1,8-naphthalenedicarboxamide and N-aminoethyl-perfluorobutanesulfonamide.

[0021] In a preferred embodiment of the present invention, the molar ratio of diisocyanate to oligomeric polyol is 1:0.2 - 0.4; further, the diisocyanate is one of isophorone diisocyanate or 2,4-toluene diisocyanate. The oligomeric polyol is one of polyethylene glycol, polytetrahydrofuran diol, polybutylene adipate, or polycarbonate diol. The molecular weight of the oligomeric polyol is 1000; the organotin is dibutyltin dilaurate (DBTDL).

[0022] The molar ratio of diisocyanate to hydrophilic chain extender is 1:0.4 - 0.6; further, the hydrophilic chain extender is dimethylolpropionic acid (DMPA) or dimethylolbutanoic acid.

[0023] The molar ratio of the diisocyanate to the fluorescent chain extender containing naphthalene ring and fluoroalkyl group is 1:0.04 - 0.05.

[0024] The molar ratio of the diisocyanate to hydroxyethyl acrylate is 1:0.2 - 0.3.

[0025] The molar ratio of the diisocyanate to the neutralizing agent is 1:0.4 - 0.6; further, the neutralizing agent is triethylamine (Et3N).

[0026] The reaction time of the neutralization reaction is 30 min to 40 min.

[0027] In a preferred embodiment of the present invention, the ratio of the total mass of acrylate and fluoroacrylate to the total mass of diisocyanate, oligomeric polyol, hydrophilic chain extender, fluorescent chain extender containing naphthalene ring and fluoroalkyl group, hydroxyethyl acrylate and neutralizing agent is 1 / 4 - 2 / 3.

[0028] The mass ratio of acrylate to fluoroacrylate is 1 - 2.4:1. Further, the acrylate is butyl acrylate (BA), and the fluoroacrylate is one of dodecafluoroheptylmethacrylate (DFMA), trifluoroethyl methacrylate and hexafluorobutylmethacrylate (HFBA).

[0029] The reaction time of the free radical polymerization reaction is 6 h to 8 h.

[0030] Further, the initiator is one of ammonium persulfate and potassium persulfate.

[0031] The second object of the present invention is to provide a polyurethane - polyacrylate hybrid emulsion prepared by the above - mentioned preparation method.

[0032] Compared with the prior art, the present invention has the following beneficial effects: 1. The present invention uses a fluorescent chain extender with a rigid naphthalene ring and a low - surface - energy fluoroalkyl structure to modify polyurethane, and then conducts free radical polymerization with polyacrylate to prepare a polyurethane - polyacrylate hybrid material, which can increase the hydrogen - bond interaction, mechanical hinge effect of the rigid naphthalene ring, fluorescence performance and hydrophobic performance in the molecular chain of the hybrid material, thereby endowing the hybrid material with properties in terms of fluorescence, antifouling, high mechanical strength and self - repair.

[0033] 2. The multifunctional polyurethane - polyacrylate hybrid material designed and synthesized in the present invention combines the advantages of polyurethane and polyacrylate materials, which not only reduces the cost but also improves the comprehensive performance of the materials.

[0034] 3. The multifunctional polyurethane-polyacrylate hybrid material prepared by the present invention has strong fluorescence effect, hydrophobic property, mechanical and self-healing properties. Therefore, the application fields of the present invention are extensive, such as anti-counterfeiting labels, fluorescent inks and fluorescent coatings, anti-fouling, waterproof and anti-corrosion coatings or films, building materials, elastic materials and other fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 It is the reaction equation of the fluorescent chain extender containing naphthalene ring and fluoroalkyl group.

[0036] Figure 2 It is the reaction equation of the polyurethane-polyacrylate hybrid emulsion.

[0037] Figure 3 It is the infrared spectra of the reactant BA and the intermediate products BAA, PFSF-E and the fluorescent chain extender BA-F.

[0038] Figure 4 It is the optical photos of the fluorescent multifunctional polyurethane-polyacrylate hybrid emulsion in Example 1 at different concentrations: (A) visible light, (B) ultraviolet light.

[0039] Figure 5 It is the photo of the surface water contact angle of the fluorescent multifunctional polyurethane-polyacrylate hybrid latex film in Example 1.

[0040] Figure 6 It is the self-healing diagram of the fluorescent multifunctional polyurethane-polyacrylate hybrid latex film in Example 1, where (a) is 0 h, (b) is 3 h, (c) is 6 h, and (d) is 9 h.

[0041] Figure 7 It is the stress-strain curve of the fluorescent multifunctional polyurethane-polyacrylate hybrid latex film DETAILED DESCRIPTION OF THE INVENTION

[0042] 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 creative efforts shall fall within the protection scope of the present invention.

[0043] The present invention first provides a preparation method of a fluorescent chain extender containing naphthalene ring and fluoroalkyl group, as Figure 1 shown, which includes the following steps: Under ice bath conditions, using ethylenediamine and perfluorobutanesulfonyl fluoride as raw materials, a first acylation reaction occurs to obtain N-aminoethyl-perfluorobutanesulfonamide.

[0044] In an alcoholic organic solution, 4-bromo-1,8-naphthalic anhydride and 2-amino-1,3-propanediol undergo a second acylation reaction to obtain 4-bromo-N-(2-hydroxy-1-hydroxymethylethyl)-1,8-naphthalenedicarboxamide; further, the alcoholic organic solution is ethanol.

[0045] In a sulfur-containing organic solvent, N-aminoethyl-perfluorobutanesulfonamide and 4-bromo-N-(2-hydroxy-1-hydroxymethylethyl)-1,8-naphthalenedicarboxamide undergo an alkylation reaction to obtain a fluorescent chain extender; further, the sulfur-containing organic solvent is dimethyl sulfoxide (DMSO).

[0046] The fluorescent chain extender prepared by the present invention is a fluorescent chain extender containing a rigid naphthalene ring and a low surface energy fluoroalkyl group in the molecule. It is used to prepare a polyurethane-polyacrylate hybrid emulsion, as Figure 2 shown, and the specific preparation method is as follows:

[0047] Using diisocyanate and oligomeric polyol as raw materials and organotin as a catalyst, a prepolymerization reaction occurs, and then a hydrophilic chain extender and a fluorescent chain extender containing a naphthalene ring and a fluoroalkyl group are added to carry out a polyaddition reaction to obtain an -NCO-terminated fluorescent polyurethane prepolymer.

[0048] Using hydroxyethyl acrylate as a modifier, the -NCO-terminated fluorescent polyurethane prepolymer is modified by an addition reaction, so that the hydroxy acrylate caps both sides of the polyurethane macromolecular chain to obtain a bilaterally capped polyurethane prepolymer; the temperature of the system is lowered to 40°C - 50°C, and after adding a neutralizing agent for neutralization reaction, water is added for dispersion and emulsification to obtain a mixed solution.

[0049] After adding acrylate and fluoroacrylate monomers to the mixed solution and dispersing them evenly, an initiator solution is added at 80°C - 90°C to carry out a radical polymerization reaction to obtain a polyurethane-polyacrylate hybrid emulsion.

[0050] The polyurethane-polyacrylate hybrid emulsion prepared by this method can synergistically exert the "hinging" effect of the rigid naphthalene ring center in the molecular chain in the fluorescent multifunctional chain extender, the hydrophobic effect of the fluorescence and low surface energy perfluoroalkyl group, the hydrogen bond effect between the hard and soft segments of the polyurethane, and combine the advantages of polyurethane and polyacrylate materials, thereby endowing the hybrid material with multifunctions such as fluorescence performance, hydrophobic performance, self-healing, and high mechanical properties.

[0051] In order to make the objectives, technical solutions, and advantages of the present invention clearer and more understandable, the present invention will be further described in detail below in conjunction with embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention. In the following embodiments, the oligomeric polyol used is polybutylene adipate with a molecular weight of 1000.

[0052] Example 1: A preparation method of a fluorescent antifouling self-healing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion, comprising the following steps: 1) Synthesis of the fluorescent multifunctional chain extender BA-F: Under ice bath conditions (0 °C), first add 3.00 g (50 mmol) of ethylenediamine to a three-necked flask equipped with a stirring device, and then weigh 3.02 g (10 mmol) of perfluorobutanesulfonyl fluoride in a constant pressure funnel and slowly add it dropwise to the above three-necked flask. After the addition is completed, react for another 5 h. After the reaction is completed, use a rotary evaporator to remove the excess ethylenediamine to obtain a small amount of yellow viscous liquid. Add a large amount of deionized water for washing, filter, and finally obtain a white solid product N-aminoethyl-perfluorobutanesulfonamide, denoted as PFSF-E.

[0053] In a new three-necked flask equipped with a stir bar and a condenser, successively add 2.77 g (10 mmol) of 4-bromo-1,8-naphthalic anhydride and 2.73 g (30 mmol) of 2-amino-1,3-propanediol, then add 110 ml of ethanol and stir to dissolve. Stir and react at 80 °C for 9 h. After the reaction is completed, use a rotary evaporator to remove the excess ethanol, wash the sample with deionized water repeatedly 3 times, and vacuum dry at 50 °C for 12 h to obtain a light gray powder, denoted as intermediate product BAA.

[0054] In a new three-necked flask equipped with a stir bar and a condenser, successively add 1.75 g (5 mmol) of BAA and 5.13 g (15 mmol) of PFSF-E, then add 100 ml of DMSO and stir to dissolve. Place the three-necked flask in a heating reflux reaction at 100 °C for 8 h. After the reaction is completed, pour the solution into 150 mL of deionized water and filter, then wash with deionized water repeatedly 3 times, and vacuum dry at 50 °C for 12 h to obtain a yellow powder. Finally, purify the dried yellow powder by silica gel chromatography to obtain a brown solid product, which is the fluorescent chain extender BA-F.

[0055] 2) Synthesis of the fluorescent antifouling self-healing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion: In a three-necked flask equipped with a stirring device, 11.11 g of isophorone diisocyanate and 16.67 g of polybutylene adipate were added. Dibutyltin dilaurate was used as a catalyst, and the addition amount of dibutyltin dilaurate was 0.01% of the total mass of isophorone diisocyanate and polybutylene adipate. The reaction was carried out at 90 °C for 1 h. Subsequently, 3.35 g of dimethylolpropionic acid and 1.28 g of the fluorescent multifunctional chain extender BA-F obtained in step 1) were added to the system, and the reaction was carried out for 2 h to obtain an -NCO-terminated fluorescent polyurethane prepolymer; at a temperature of 90 °C, 1.45 g of hydroxyethyl acrylate was added to the above reaction system, and the mixture was heated and stirred for 3 h to carry out double-sided capping of the polyurethane prepolymer; the temperature of the system was lowered to 40 °C, 2.53 g of triethylamine was added to neutralize the reaction for 0.5 h, and then under the condition of high-speed stirring, 132 g of deionized water was slowly added, and after dispersion and emulsification for 1 h. Subsequently, 16.98 g of butyl acrylate and 7.28 g of dodecafluorooctyl methacrylate were added to the reaction system and stirred and dispersed for half an hour; the temperature was raised to 80 °C, and then 0.51 g of ammonium persulfate dissolved in 10 g of deionized water was slowly dropped into the reaction system, and then the mixture was kept warm and polymerized for 6 h to obtain a fluorescent antifouling self-healing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion.

[0056] Example 2 A preparation method of a fluorescent antifouling self-healing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion, comprising the following steps: 1) Synthesis of the fluorescent multifunctional chain extender BA-F: Under ice bath conditions (0 °C), 3.00 g (50 mmol) of ethylenediamine was first added to a three-necked flask equipped with a stirring device, and 3.02 g (10 mmol) of perfluorobutanesulfonyl fluoride was weighed in a constant pressure funnel and slowly added dropwise to the above three-necked flask. After the addition was completed, the reaction was carried out for another 5 h. After the reaction was completed, the excess ethylenediamine was removed using a rotary evaporator to obtain a small amount of yellow viscous liquid, which was washed with a large amount of deionized water, filtered, and finally a white solid product N-aminoethyl-perfluorobutanesulfonamide, denoted as PFSF-E, was obtained.

[0057] In a new three-necked flask equipped with a stirring rod and a condenser, 2.77 g (10 mmol) of 4-bromo-1,8-naphthalic anhydride and 2.73 g (30 mmol) of 2-amino-1,3-propanediol were successively added, and then 110 ml of ethanol was added and stirred to dissolve. The reaction was continuously stirred at 80 °C for 9 h. After the reaction was completed, the excess ethanol was removed using a rotary evaporator, the sample was washed with deionized water repeatedly 3 times, and vacuum dried at 50 °C for 12 h to obtain a light gray powder, denoted as the intermediate product BAA.

[0058] In a new three-necked flask equipped with a stir bar and a condenser, 1.75 g (5 mmol) of BAA and 5.13 g (15 mmol) of PFSF-E were successively added, and then 100 ml of DMSO was added and stirred until dissolved. The three-necked flask was placed in a heating reflux at 100 °C for 8 h. After the reaction was completed, the solution was poured into 150 mL of deionized water and filtered, then washed repeatedly with deionized water 3 times, and dried in vacuo at 50 °C for 12 h to obtain a yellow powder. Finally, the dried yellow powder was purified by silica gel chromatography to obtain a brown solid product, which was the fluorescent chain extender BA-F.

[0059] 2) Synthesis of a fluorescent anti-fouling self-healing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion: In a three-necked flask equipped with a stirring device, 8.71 g of toluene diisocyanate and 16.6 g of polyethylene glycol were added, and dibutyltin dilaurate was used as a catalyst. The addition amount of dibutyltin dilaurate was 0.01% of the total mass of isophorone diisocyanate and polybutylene adipate. The reaction was carried out at 90 °C for 1 h. Subsequently, 3.7 g of dimethylolbutyric acid and 1.28 g of the fluorescent multifunctional chain extender BA-F obtained in step 1) were added to the system and reacted for 2 h to prepare an -NCO-terminated fluorescent polyurethane prepolymer; at a temperature of 90 °C, 1.45 g of hydroxyethyl acrylate was added to the above reaction system, and heated and stirred for 3 h to perform double-sided capping on the polyurethane prepolymer; the system temperature was lowered to 40 °C, 2.53 g of triethylamine was added to neutralize the reaction for 0.5 h, and then under the condition of high-speed stirring, 105 g of deionized water was slowly added and dispersed and emulsified for 1 h. Subsequently, 7.35 g of butyl acrylate and 7.35 g of hexafluorobutyl methacrylate (HFBA) were added to the reaction system and stirred and dispersed for half an hour; the temperature was raised to 80 °C, and then 0.32 g of ammonium persulfate dissolved in 10 g of deionized water was slowly dropped into the reaction system, and then polymerized at a constant temperature for 6 h to prepare a fluorescent anti-fouling self-healing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion.

[0060] Example 3 A preparation method of a fluorescent anti-fouling self-healing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion, comprising the following steps: 1) Synthesis of the fluorescent multifunctional chain extender BA-F: Under ice bath conditions (0 °C), 3.00 g (50 mmol) of ethylenediamine was first added to a three-necked flask equipped with a stirring device. Then, 3.02 g (10 mmol) of perfluorobutanesulfonyl fluoride was weighed into a constant pressure funnel and slowly added dropwise to the above three-necked flask. After the addition was completed, the reaction was continued for 5 h. After the reaction was completed, the excess ethylenediamine was removed using a rotary evaporator to obtain a small amount of yellow viscous liquid. A large amount of deionized water was added for washing, and then filtration was carried out. Finally, the white solid product N-aminoethyl-perfluorobutanesulfonamide, denoted as PFSF-E, was obtained.

[0061] In a new three-necked flask equipped with a stir bar and a condenser, 2.77 g (10 mmol) of 4-bromo-1,8-naphthalic anhydride and 2.73 g (30 mmol) of 2-amino-1,3-propanediol were added successively. Then, 110 ml of ethanol was added and stirred until dissolved. The mixture was continuously stirred and reacted at 80 °C for 9 h. After the reaction was completed, the excess ethanol was removed using a rotary evaporator. The sample was washed repeatedly with deionized water 3 times and vacuum dried at 50 °C for 12 h to obtain a light gray powder, denoted as intermediate product BAA.

[0062] In a new three-necked flask equipped with a stir bar and a condenser, 1.75 g (5 mmol) of BAA and 5.13 g (15 mmol) of PFSF-E were added successively. Then, 100 ml of DMSO was added and stirred until dissolved. The three-necked flask was placed in a heating reflux at 100 °C for 8 h. After the reaction was completed, the solution was poured into 150 mL of deionized water and filtered. Then, it was washed repeatedly with deionized water 3 times and vacuum dried at 50 °C for 12 h to obtain a yellow powder. Finally, the dried yellow powder was purified by silica gel chromatography to obtain a brown solid product, which is the fluorescent chain extender BA-F.

[0063] 2) Synthesis of fluorescent anti-fouling self-healing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion: In a three-necked flask equipped with a stirring device, 11.11 g of isophorone diisocyanate and 16.67 g of polytetrahydrofuran diol were added. Dibutyltin dilaurate was used as a catalyst, and the addition amount of dibutyltin dilaurate was 0.01% of the total mass of isophorone diisocyanate and polybutylene adipate. The reaction was carried out at 90 °C for 1 h. Subsequently, 3.35 g of dimethylolpropionic acid and 1.28 g of the fluorescent multifunctional chain extender BA-F obtained in step 1) were added to the system, and the reaction was carried out for 2 h to obtain an -NCO-terminated fluorescent polyurethane prepolymer; at a temperature of 90 °C, 0.7 g of hydroxyethyl acrylate was added to the above reaction system, and the mixture was heated and stirred for 3 h to perform double-sided capping on the polyurethane prepolymer; the temperature of the system was lowered to 40 °C, 2.53 g of triethylamine was added to neutralize the reaction for 0.5 h, and then under the condition of high-speed stirring, 109 g of deionized water was slowly added, and after dispersion and emulsification for 1 h. Subsequently, 10.8 g of butyl acrylate and 4.59 g of dodecafluoroheptyl methacrylate were added to the reaction system and stirred and dispersed for half an hour; the temperature was raised to 80 °C, and then 0.32 g of ammonium persulfate dissolved in 10 g of deionized water was slowly dropped into the reaction system, and then the mixture was kept warm and polymerized for 6 h to obtain a fluorescent antifouling self-healing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion.

[0064] Example 4 A preparation method of a fluorescent antifouling self-healing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion, comprising the following steps: 1) Synthesis of the fluorescent multifunctional chain extender BA-F: Under ice bath conditions (0 °C), 3.00 g (50 mmol) of ethylenediamine was first added to a three-necked flask equipped with a stirring device, and then 3.02 g (10 mmol) of perfluorobutanesulfonyl fluoride was weighed in a constant pressure funnel and slowly added dropwise to the above three-necked flask. After the addition was completed, the reaction was carried out for another 5 h. After the reaction was completed, an excess of ethylenediamine was removed using a rotary evaporator to obtain a small amount of yellow viscous liquid, which was washed with a large amount of deionized water, filtered, and finally a white solid product N-aminoethyl-perfluorobutanesulfonamide, denoted as PFSF-E, was obtained.

[0065] In a new three-necked flask equipped with a stirring rod and a condenser, 2.77 g (10 mmol) of 4-bromo-1,8-naphthalic anhydride and 2.73 g (30 mmol) of 2-amino-1,3-propanediol were successively added, and then 110 ml of ethanol was added and stirred to dissolve. The reaction was continuously stirred at 80 °C for 9 h. After the reaction was completed, an excess of ethanol was removed using a rotary evaporator, the sample was washed with deionized water repeatedly 3 times, and vacuum dried at 50 °C for 12 h to obtain a light gray powder, denoted as intermediate product BAA.

[0066] In a new three-necked flask equipped with a stir bar and a condenser, 1.75 g (5 mmol) of BAA and 5.13 g (15 mmol) of PFSF-E were successively added, and then 100 ml of DMSO was added and stirred until dissolved. The three-necked flask was placed in a heating reflux at 100 °C for 8 h. After the reaction was completed, the solution was poured into 150 mL of deionized water and filtered, then washed repeatedly with deionized water 3 times, and dried in vacuo at 50 °C for 12 h to obtain a yellow powder. Finally, the dried yellow powder was purified by silica gel chromatography to obtain a brown solid product, which is the fluorescent chain extender BA-F.

[0067] 2) Synthesis of a fluorescent antifouling self-healing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion: In a three-necked flask equipped with a stirring device, 11.11 g of isophorone diisocyanate and 16.67 g of polybutylene adipate were added. Dibutyltin dilaurate was used as a catalyst, and the addition amount of dibutyltin dilaurate was 0.01% of the total mass of isophorone diisocyanate and polybutylene adipate. The reaction was carried out at 90 °C for 1 h. Subsequently, 3.35 g of dimethylolpropionic acid and 1.28 g of the fluorescent multifunctional chain extender BA-F obtained in step 1) were added to the system and reacted for 2 h to prepare an -NCO-terminated fluorescent polyurethane prepolymer; at a temperature of 90 °C, 1.45 g of hydroxyethyl acrylate was added to the above reaction system, and heated and stirred for 3 h to carry out double-sided capping of the polyurethane prepolymer; the temperature of the system was lowered to 40 °C, 2.53 g of triethylamine was added to neutralize the reaction for 0.5 h, and then under the condition of high-speed stirring, 110 g of deionized water was slowly added and dispersed and emulsified for 1 h. Subsequently, 7.64 g of butyl acrylate and 7.64 g of trifluoroethyl methacrylate were added to the reaction system and stirred and dispersed for half an hour; the temperature was raised to 80 °C, and then 0.33 g of ammonium persulfate dissolved in 10 g of deionized water was slowly dropped into the reaction system, and then polymerized at a constant temperature for 6 h to obtain a fluorescent antifouling self-healing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion.

[0068] Example 5: A preparation method of a fluorescent antifouling self-healing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion, comprising the following steps: 1) Synthesis of the fluorescent multifunctional chain extender BA-F: Under ice bath conditions (0 °C), 3.00 g (50 mmol) of ethylenediamine was first added to a three-necked flask equipped with a stirring device. Then, 3.02 g (10 mmol) of perfluorobutanesulfonyl fluoride was weighed into a constant pressure funnel and slowly added dropwise to the above three-necked flask. After the addition, the reaction was continued for 5 h. After the reaction was completed, the excess ethylenediamine was removed using a rotary evaporator to obtain a small amount of yellow viscous liquid. A large amount of deionized water was added for washing, and then filtration was carried out. Finally, a white solid product, N-aminoethyl-perfluorobutanesulfonamide, denoted as PFSF-E, was obtained.

[0069] In a new three-necked flask equipped with a stir bar and a condenser, 2.77 g (10 mmol) of 4-bromo-1,8-naphthalic anhydride and 2.73 g (30 mmol) of 2-amino-1,3-propanediol were added successively. Then, 110 ml of ethanol was added and stirred until dissolved. The mixture was continuously stirred and reacted at 80 °C for 9 h. After the reaction was completed, the excess ethanol was removed using a rotary evaporator. The sample was washed repeatedly with deionized water 3 times and dried in vacuo at 50 °C for 12 h to obtain a light gray powder, denoted as intermediate product BAA.

[0070] In a new three-necked flask equipped with a stir bar and a condenser, 1.75 g (5 mmol) of BAA and 5.13 g (15 mmol) of PFSF-E were added successively. Then, 100 ml of DMSO was added and stirred until dissolved. The three-necked flask was placed in a heating reflux at 100 °C and reacted for 8 h. After the reaction was completed, the solution was poured into 150 mL of deionized water and filtered. Then, it was washed repeatedly with deionized water 3 times and dried in vacuo at 50 °C for 12 h to obtain a yellow powder. Finally, the dried yellow powder was purified by silica gel chromatography to obtain a brown solid product, which is the fluorescent chain extender BA-F.

[0071] 2) Synthesis of fluorescent anti-fouling self-healing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion: In a three-necked flask equipped with a stirring device, 11.11 g of isophorone diisocyanate and 16.67 g of polycarbonate diol were added. Dibutyltin dilaurate was used as a catalyst, and the addition amount of dibutyltin dilaurate was 0.01% of the total mass of isophorone diisocyanate and polybutylene adipate. The reaction was carried out at 90 °C for 1 h. Subsequently, 3.35 g of dimethylolpropionic acid and 1.28 g of the fluorescent multifunctional chain extender BA-F obtained in step 1) were added to the system, and the reaction was carried out for 2 h to obtain an -NCO-terminated fluorescent polyurethane prepolymer; at a temperature of 90 °C, 1.45 g of hydroxyethyl acrylate was added to the above reaction system, and it was heated and stirred for 3 h to carry out double-sided capping on the polyurethane prepolymer; the temperature of the system was lowered to 40 °C, 2.53 g of triethylamine was added to neutralize the reaction for 0.5 h, and then under the condition of high-speed stirring, 109 g of deionized water was slowly added and dispersed and emulsified for 1 h. Subsequently, 10.8 g of butyl acrylate and 4.59 g of dodecafluoroheptyl methacrylate were added to the reaction system and stirred and dispersed for half an hour; the temperature was raised to 80 °C, and then 0.34 g of ammonium persulfate dissolved in 10 g of deionized water was slowly added dropwise to the reaction system, and then it was kept warm and polymerized for 6 h to obtain a fluorescent antifouling self-healing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion.

[0072] Example 6: A preparation method of a fluorescent antifouling self-healing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion, comprising the following steps: 1) Synthesis of the fluorescent multifunctional chain extender BA-F: Under ice bath conditions (5 °C), 1.8 g (30 mmol) of ethylenediamine was first added to a three-necked flask equipped with a stirring device, and then 3.02 g (10 mmol) of perfluorobutanesulfonyl fluoride was weighed in a constant pressure funnel and slowly added dropwise to the above three-necked flask. After the addition was completed, the reaction was carried out for another 5.5 h. After the reaction was completed, an excessive amount of ethylenediamine was removed using a rotary evaporator to obtain a small amount of yellow viscous liquid, which was washed with a large amount of deionized water, filtered, and finally a white solid product N-aminoethyl-perfluorobutanesulfonamide was obtained, denoted as PFSF-E.

[0073] In a new three-necked flask equipped with a stirring rod and a condenser, 2.77 g (10 mmol) of 4-bromo-1,8-naphthalic anhydride and 1.82 g (20 mmol) of 2-amino-1,3-propanediol were added successively, and then 100 ml of ethanol was added and stirred to dissolve. The reaction was continuously stirred at 85 °C for 8.5 h. After the reaction was completed, an excessive amount of ethanol was removed using a rotary evaporator, the sample was washed with deionized water repeatedly 3 times, and vacuum dried at 50 °C for 12 h to obtain a light gray powder, denoted as intermediate product BAA.

[0074] In a new three-necked flask equipped with a stir bar and a condenser, 1.75 g (5 mmol) of BAA and 3.42 g (10 mmol) of PFSF-E were successively added, and then 90 ml of DMSO was added and stirred to dissolve. The three-necked flask was placed in a heating reflux reaction at 105 °C for 7.5 h. After the reaction was completed, the solution was poured into 150 mL of deionized water and filtered, then washed repeatedly with deionized water 3 times, and dried in vacuo at 50 °C for 12 h to obtain a yellow powder. Finally, the dried yellow powder was purified by silica gel chromatography to obtain a brown solid product, which is the fluorescent chain extender BA-F.

[0075] 2) Synthesis of a fluorescent antifouling self-healing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion: In a three-necked flask equipped with a stirring device, 11.11 g of isophorone diisocyanate and 10 g of polybutylene adipate were added. Dibutyltin dilaurate was used as a catalyst, and the addition amount of dibutyltin dilaurate was 0.02% of the total mass of isophorone diisocyanate and polybutylene adipate. The reaction was carried out at 90 °C for 1 h. Subsequently, 2.68 g of dimethylolpropionic acid and 1.53 g of the fluorescent multifunctional chain extender BA-F obtained in step 1) were added to the system, and the reaction was carried out for 2 h to prepare an -NCO-terminated fluorescent polyurethane prepolymer; at a temperature of 90 °C, 1.16 g of hydroxyethyl acrylate was added to the above reaction system, and the mixture was heated and stirred for 3 h to carry out double-sided capping of the polyurethane prepolymer; the temperature of the system was lowered to 50 °C, 2.02 g of triethylamine was added to neutralize the reaction for 0.5 h, and then under the condition of high-speed stirring, 73 g of deionized water was slowly added and dispersed and emulsified for 1 h. Subsequently, 3.563 g of butyl acrylate and 3.563 g of dodecafluoroheptyl methacrylate were added to the reaction system and stirred and dispersed for half an hour; the temperature was raised to 90 °C, and then 0.51 g of ammonium persulfate dissolved in 10 g of deionized water was slowly dropped into the reaction system, and then the mixture was kept warm and polymerized for 6 h to obtain a fluorescent antifouling self-healing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion.

[0076] Example 7: A preparation method of a fluorescent antifouling self-healing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion, comprising the following steps: 1) Synthesis of the fluorescent multifunctional chain extender BA-F: Under ice bath conditions (3 °C), 4.2 g (70 mmol) of ethylenediamine was first added to a three-necked flask equipped with a stirring device. Then, 3.02 g (10 mmol) of perfluorobutanesulfonyl fluoride was weighed into a constant pressure funnel and slowly added dropwise to the above three-necked flask. After the addition was completed, the reaction was continued for 6 h. After the reaction was completed, the excess ethylenediamine was removed using a rotary evaporator to obtain a small amount of yellow viscous liquid. A large amount of deionized water was added for washing, and then filtration was carried out. Finally, a white solid product, N-aminoethyl-perfluorobutanesulfonamide, denoted as PFSF-E, was obtained.

[0077] In a new three-necked flask equipped with a stir bar and a condenser, 2.77 g (10 mmol) of 4-bromo-1,8-naphthalic anhydride and 4.55 g (50 mmol) of 2-amino-1,3-propanediol were added successively. Then, 160 ml of ethanol was added and stirred until dissolved. The mixture was continuously stirred and reacted at 90 °C for 8 h. After the reaction was completed, the excess ethanol was removed using a rotary evaporator. The sample was washed repeatedly with deionized water 3 times and dried in vacuo at 50 °C for 12 h to obtain a light gray powder, denoted as intermediate product BAA.

[0078] In a new three-necked flask equipped with a stir bar and a condenser, 1.75 g (5 mmol) of BAA and 8.55 g (25 mmol) of PFSF-E were added successively. Then, 175 ml of DMSO was added and stirred until dissolved. The three-necked flask was placed in an oil bath at 110 °C and heated under reflux for 7 h. After the reaction was completed, the solution was poured into 150 mL of deionized water and filtered. Then, it was washed repeatedly with deionized water 3 times and dried in vacuo at 50 °C for 12 h to obtain a yellow powder. Finally, the dried yellow powder was purified by silica gel chromatography to obtain a brown solid product, which is the fluorescent chain extender BA-F.

[0079] 2) Synthesis of fluorescent antifouling self-healing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion: In a three-necked flask equipped with a stirring device, 11.11 g of isophorone diisocyanate and 20 g of polybutylene adipate were added. Dibutyltin dilaurate was used as a catalyst, and the addition amount of dibutyltin dilaurate was 0.03% of the total mass of isophorone diisocyanate and polybutylene adipate. The reaction was carried out at 90 °C for 1 h. Subsequently, 4.02 g of dimethylolpropionic acid and 1.37 g of the fluorescent multifunctional chain extender BA-F obtained in step 1) were added to the system, and the reaction was carried out for 2 hours to obtain an -NCO-terminated fluorescent polyurethane prepolymer; at a temperature of 90 °C, 1.74 g of hydroxyethyl acrylate was added to the above reaction system, and the mixture was heated and stirred for 3 h to perform double-sided capping on the polyurethane prepolymer; the temperature of the system was lowered to 45 °C, 3.04 g of triethylamine was added to neutralize the reaction for 0.5 h, and then under the condition of high-speed stirring, 125 g of deionized water was slowly added and dispersed and emulsified for 1 h. Subsequently, 11.66 g of butyl acrylate and 4.85 g of dodecafluoroheptyl methacrylate were added to the reaction system and stirred and dispersed for half an hour; the temperature was raised to 85 °C, and then 0.51 g of ammonium persulfate dissolved in 10 g of deionized water was slowly dropped into the reaction system, and then the mixture was kept warm and polymerized for 6 hours to obtain a fluorescent antifouling self-healing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion.

[0080] The structures and properties of the fluorescent multifunctional chain extenders prepared in Examples 1 to 5 and the polyurethane-polyacrylate hybrid emulsions prepared were tested, and the results are as follows: Figure 3 This is the infrared spectrum of 4-bromo-1,8-naphthalic anhydride BA, its intermediate products BAA, PFSF-E and the fluorescent chain extender BA-F in Example 1 of the present invention. As Figure 3 shown, the absorption peaks of 4-bromo-1,8-naphthalic anhydride BA at 1782, 1731 and 1020 cm -1 are the stretching vibration absorption peaks of C=O and C-O of the anhydride group, and there are characteristic absorption peaks belonging to the aromatic ring at positions such as 1402, 1502, 1585 and 779 cm -1 ; the absorption peak at 555 cm -1 is attributed to the stretching vibration absorption peak of C-Br; in comparison, the characteristic peaks of C=O and C-O of the anhydride group of the intermediate BAA disappear, and new stretching vibration absorption peaks belonging to amide C=O and C-N appear at 1697, 1649 and 1043 cm -1 , and the new absorption peak at 3388 cm -1 is the stretching vibration absorption peak of -OH, and the new peak at 426 cm -1 is the characteristic peak of the cyclic amide structure; the intermediate PFAS-E has an absorption peak at 3222 cm -1The absorption peak at [specific location] belongs to the stretching vibration absorption peak of -NH2, at 524, 580, 1083, and 1137 cm -1 The absorption peak at [specific location] is attributed to the bending and stretching vibration absorption peaks of -C-F, at 1353 cm -1 The characteristic absorption peak of -SO2-NH- appears at [specific location], at 2991 and 2891 cm -1 The absorption peak at [specific location] is the stretching vibration absorption peak of C-H; compared with BAA, the stretching vibration peak of C-Br at 555 cm -1 for BA-F disappears, and, for BA-F, the newly emerged absorption peaks at 524, 582, 1083, and 1137 cm -1 are the bending and stretching vibration absorption peaks of -C-F, and the newly emerged characteristic absorption peak of -SO2-NH- appears at 1355 cm -1 In summary, it indicates that the fluorescent chain extender BA-F was successfully synthesized.

[0081] Figure 4 This is the optical photograph of the polyurethane-polyacrylate hybrid emulsion prepared in Example 1 of the present invention at different mass concentrations. The mass concentrations from left to right are 30%, 3%, and 0.3% in turn. Figure 4 In (a) is the optical photograph under visible light, and (b) is the optical photograph under ultraviolet light. As Figure 4 shown, the polyurethane-polyacrylate hybrid emulsions with different concentrations prepared in Example 1 appear blue-yellow, light yellow, and yellow respectively under visible light; while under ultraviolet light irradiation, their colors change to blue-green, green, and bright green respectively, indicating that the synthesized polyurethane-polyacrylate hybrid emulsion has fluorescence.

[0082] Figure 5 This is the photograph of the water contact angle on the surface of the film formed by the polyurethane-polyacrylate hybrid emulsion prepared in Example 1 of the present invention. As Figure 5 shown, the size of the static water contact angle on the surface of the hybrid latex film is 115.3°, indicating that it has good hydrophobicity.

[0083] Figure 6 This is the self-repair diagram of the film formed by the polyurethane-polyacrylate hybrid emulsion prepared in Example 1 of the invention. Figure 6 In (a) is 0 h, (b) is 3 h, (c) is 6 h, and (d) is 9 h. As Figure 6As shown, when the two membranes just come into contact with each other after being cut, a large black gap can be clearly observed between them; after 3 hours, the two membranes have clearly re-bonded together, presenting a black band; after 6 hours, the two membranes are almost bonded together, and only a light line can be observed; after 9 hours, the two membranes have become an integral whole and completed the repair, indicating that the polyurethane-polyacrylate hybrid membrane has good self-repair performance.

[0084] Pour the polyurethane-polyacrylate hybrid emulsions prepared in Examples 1 to 5 into a polytetrafluoroethylene plate and dry them into films at 50 °C to obtain polyurethane-polyacrylate hybrid membranes with a thickness of 0.5 mm. Test the mechanical properties of the hybrid membranes prepared in Examples 1 to 5. Figure 7 This is the stress-strain curve graph of the hybrid membranes prepared in Examples 1 to 5 of the present invention. As Figure 7 shown, the stress of the hybrid membrane is approximately 32 - 44 MPa and the strain is 450% - 700%, having good mechanical properties.

[0085] 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 learn the basic creative concept. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications falling within the scope of the present invention.

[0086] 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 preparation method of a polyurethane-polyacrylate hybrid emulsion, characterized in that It includes the following steps: Using diisocyanate and oligomeric polyol as raw materials and organotin as a catalyst, a prepolymerization reaction occurs. Then, a hydrophilic chain extender and a fluorescent chain extender containing a naphthalene ring and a fluoroalkyl group are added to carry out a modification reaction to obtain an -NCO-terminated fluorescent polyurethane prepolymer; Using hydroxyethyl acrylate as a modifier, the -NCO-terminated fluorescent polyurethane prepolymer is modified to obtain a double-ended polyurethane prepolymer; after the double-ended polyurethane prepolymer and a neutralizing agent undergo a neutralization reaction at 40°C to 50°C, water is added for dispersion and emulsification to obtain a mixture; After adding acrylate and fluoroacrylate monomers to the mixture and dispersing them evenly, an initiator solution is added at 80°C to 90°C to carry out a free radical polymerization reaction to obtain a polyurethane-polyacrylate hybrid emulsion.

2. The preparation method of a polyurethane-polyacrylate hybrid emulsion according to claim 1, characterized in that, The preparation of the fluorescent chain extender containing a naphthalene ring and a fluoroalkyl group includes the following steps: Under ice bath conditions, using ethylenediamine and perfluorobutanesulfonyl fluoride as raw materials, a first acylation reaction occurs to obtain N-aminoethyl-perfluorobutanesulfonamide; In an alcoholic organic solution, 4-bromo-1,8-naphthalic anhydride and 2-amino-1,3-propanediol undergo a second acylation reaction to obtain 4-bromo-N-(2-hydroxy-1-hydroxymethylethyl)-1,8-naphthalenedicarboxamide; In a sulfur-containing organic solvent, N-aminoethyl-perfluorobutanesulfonamide and 4-bromo-N-(2-hydroxy-1-hydroxymethylethyl)-1,8-naphthalenedicarboxamide undergo an alkylation reaction to obtain a fluorescent chain extender containing a naphthalene ring and a fluoroalkyl group.

3. The preparation method of a polyurethane-polyacrylate hybrid emulsion according to claim 2, characterized in that, The molar ratio of ethylenediamine to perfluorobutanesulfonyl fluoride is 3 to 7:1; the reaction temperature of the first acylation reaction is 0°C to 5°C, and the reaction time is 5h to 6h.

4. The preparation method of a polyurethane-polyacrylate hybrid emulsion according to claim 2, characterized in that, The molar ratio of 4-bromo-1,8-naphthalic anhydride to 2-amino-1,3-propanediol is 1:2 to 5; the reaction temperature of the second acylation reaction is 80°C to 90°C, and the reaction time is 8h to 9h.

5. The preparation method of a polyurethane-polyacrylate hybrid emulsion according to claim 2, characterized in that, The addition amount of the alcoholic organic solution is 20 to 22 times the total mass of 4-bromo-1,8-naphthalic anhydride and 2-amino-1,3-propanediol.

6. The preparation method of a polyurethane-polyacrylate hybrid emulsion according to claim 2, wherein, The molar ratio of 4-bromo-N-(2-hydroxy-1-hydroxymethylethyl)-1,8-naphthalenedicarboxamide to N-aminoethyl-perfluorobutanesulfonamide is 1:2 to 5, the reaction temperature of the alkylation reaction is 100°C to 110°C, and the reaction time is 7h to 8h.

7. The preparation method of a polyurethane-polyacrylate hybrid emulsion according to claim 2, wherein, The addition amount of DMSO is 15 to 17 times the total mass of 4-bromo-N-(2-hydroxy-1-hydroxymethylethyl)-1,8-naphthalenedicarboxamide and N-aminoethyl-perfluorobutanesulfonamide.

8. The preparation method of a polyurethane-polyacrylate hybrid emulsion according to claim 1, characterized in that, The molar ratio of diisocyanate to oligomeric polyol is 1:0.2 - 0.4; The molar ratio of diisocyanate to hydrophilic chain extender is 1:0.4 - 0.6; The molar ratio of diisocyanate to the fluorescent chain extender containing a naphthalene ring and a fluoroalkyl group is 1:0.04 - 0.05; The molar ratio of diisocyanate to hydroxyethyl acrylate is 1:0.2 - 0.3; The molar ratio of diisocyanate to neutralizing agent is 1:0.4 - 0.6; The reaction time of the neutralization reaction is 30min to 40min.

9. The preparation method of a polyurethane-polyacrylate hybrid emulsion according to claim 1, characterized in that, The ratio of the total mass of acrylate and fluorinated acrylate to the total mass of diisocyanate, oligomeric polyol, hydrophilic chain extender, fluorescent chain extender containing naphthalene ring and fluoroalkyl, 2-hydroxyethyl acrylate and neutralizing agent is 1 / 4 to 2 / 3; The mass ratio of acrylate to fluorinated acrylate is 1 to 2.4:1; The reaction time of the free radical polymerization reaction is 6 h to 8 h.

10. A polyurethane-polyacrylate hybrid emulsion prepared by the preparation method according to any one of claims 1 to 9.

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