A polyurethane-polyacrylate hybrid emulsion and a method for preparing the same

Abstract

The application discloses a polyurethane-polyacrylate hybrid emulsion and a preparation method thereof, and belongs to the technical field of high polymer functional materials. The preparation method of the polyurethane-polyacrylate hybrid emulsion is as follows: diisocyanate and an oligomer polyol are used as raw materials, and organic tin is used as a catalyst; after reaction, a hydrophilic chain extender and a fluorescent chain extender containing a naphthalene ring and a fluoroalkyl group are added; and a fluorescent polyurethane prepolymer terminated by -NCO is obtained through reaction; the fluorescent polyurethane prepolymer terminated by -NCO is modified by using hydroxyethyl acrylate as a modifier to obtain a polyurethane prepolymer terminated on both sides; after reaction with a neutralizing agent, water is added for dispersion and emulsification; then, after the acrylic ester and the fluorine-containing acrylic ester monomer are uniformly dispersed, an initiator solution is added; and the polyurethane-polyacrylate hybrid emulsion is obtained through reaction. The polyurethane-polyacrylate hybrid emulsion has excellent quality in terms of fluorescence performance, hydrophobic performance and mechanical performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high molecular functional materials, and more particularly to a polyurethane-polyacrylate hybrid emulsion and a preparation method thereof. BACKGROUND

[0002] Waterborne polyurethane is a new type of polymer material, which is a water-based dispersion prepared by reacting polyurethane resin with water-based solvent or water-based emulsifier. Compared with traditional organic solvent-based polyurethane, waterborne polyurethane has the advantages of environmental protection, non-toxicity, odorlessness, easy processing, convenience of use, and low cost, and therefore has 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 more need materials to have multiple functions, so materials with multiple functions have become the focus of people's research. Fluorescent waterborne polyurethane has good water resistance, weather resistance, chemical corrosion resistance and good flexibility, and also has fluorescent effect, which can improve the visibility of the material, making it easier to be found in dimly lit environments, and has important significance in night construction or occasions requiring high visibility. Therefore, it is widely used in anti-counterfeiting materials, architectural coatings, fluorescent coatings, waterproof coatings, sealing materials, ship coatings and other fields.

[0004] At present, there are various ways to make waterborne polyurethane have fluorescent properties and other properties, such as physically blending the fluorescent substance into the polyurethane emulsion or chemically bonding the fluorescent substance to the polyurethane molecular chain. In Chinese patent CN 115991854 A, product 1 and product 2 are prepared, and the two products are introduced into the reaction of polyurethane to modify the polyurethane, so that the polyurethane material has fluorescent and antibacterial properties. In Chinese patent CN 116478366 A, a borate compound M is prepared to modify polyurethane, so that the polyurethane has fluorescent and repairable functions. In Chinese patent CN 117586471 A, amino phenyl boronic acid is used to react to obtain a polyurethane emulsion, which is then blended with modified nano-silicon dioxide to obtain fluorescent and hydrophobic properties. In Chinese patent CN 116622045 A, curcumin is 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 study of the above documents, it can be found that the preparation of functional polyurethane often involves modifying the polyurethane with functional chain extenders, so that multiple functional polyurethane may require the addition of multiple chain extenders during preparation, which is complex and tedious, wasting manpower and resources. In addition, polyurethane is a high-cost film-forming material.

[0005] As a film-forming material, polyacrylate has low cost, good gloss, strong adhesion, flexibility and elasticity, and good weather resistance, but the tensile strength is not high. SUMMARY

[0006] In view of the above problems, the present application provides a polyurethane-polyacrylate hybrid emulsion and a preparation method thereof. The polyurethane-polyacrylate hybrid emulsion is prepared by modifying polyurethane with a fluorescent chain extender containing a rigid naphthalene ring and a fluorine alkyl group, and has excellent quality in terms of fluorescence, hydrophobicity and mechanical properties. It can be applied in the fields of anti-counterfeiting coating or film, anti-corrosion coating, photosensitive material, anti-counterfeiting mark, traffic sign, elastic material, chemical detection, fluorescent ink and fluorescent coating.

[0007] The first object of the present application is to provide a preparation method of a polyurethane-polyacrylate hybrid emulsion, comprising the following steps:

[0008] The pre-polymerization reaction is carried out with diisocyanate and oligomer polyol as raw materials and organic tin as catalyst, then the hydrophilic chain extender and the fluorescent chain extender containing naphthalene ring and fluorine alkyl group are added to carry out modification reaction, and the fluorescent polyurethane pre-polymer terminated by -NCO is obtained.

[0009] The fluorescent polyurethane pre-polymer terminated by -NCO is modified with hydroxyethyl acrylate as modifier to obtain the double-terminated polyurethane pre-polymer; after the neutralization reaction of the double-terminated polyurethane pre-polymer and the neutralizing agent at 40-50℃, water is added for dispersion and emulsification to obtain a mixed solution.

[0010] After the acrylic ester and fluorine-containing acrylic ester monomer are uniformly dispersed in the mixed solution, the initiator solution is added at 80-90℃ to carry out free radical polymerization reaction to obtain the polyurethane-polyacrylate hybrid emulsion.

[0011] In a preferred embodiment of the present application, the preparation of the fluorescent chain extender containing naphthalene ring and fluorine alkyl group comprises the following steps:

[0012] Under ice bath condition, the first acylation reaction is carried out with ethylenediamine and perfluorobutylsulfonyl fluoride as raw materials to obtain N-aminoethyl-perfluorobutylsulfonamide.

[0013] In an alcohol organic solution, the second acylation reaction is carried out between 4-bromo-1,8-naphthalic anhydride and 2-amino-1,3-propanediol to obtain 4-bromo-N-(2-hydroxy-1-hydroxymethylethyl)-1,8-naphthalene dicarboxamide.

[0014] In the sulfur-containing organic solvent, N-aminoethyl-perfluorobutyl sulfonamide and 4-bromo-N-(2-hydroxy-1-hydroxymethyl ethyl)-1,8-naphthalene dicarboxamide undergo alkylation reaction to obtain a fluorescent chain extender containing naphthalene ring and fluorine alkyl.

[0015] In a preferred embodiment of the present application, the molar ratio of ethylenediamine and perfluorobutylsulfonyl fluoride is 3-7:1; more preferably, the molar ratio of ethylenediamine and perfluorobutylsulfonyl fluoride is 5:1.

[0016] The reaction temperature of the first acylation reaction is 0-5°C, and the reaction time is 5-6h.

[0017] In a preferred embodiment of the present application, the molar ratio of 4-bromo-1,8-naphthalene dicarboxylic anhydride and 2-amino-1,3-propanediol is 1:2-5; more preferably, the molar ratio of 4-bromo-1,8-naphthalene dicarboxylic anhydride and 2-amino-1,3-propanediol is 1:3.

[0018] The reaction temperature of the second acylation reaction is 80-90°C, and the reaction time is 8-9h.

[0019] In a preferred embodiment of the present application, the addition amount of the alcohol organic solution is 20-22 times of the total mass of 4-bromo-1,8-naphthalene dicarboxylic anhydride and 2-amino-1,3-propanediol.

[0020] In a preferred embodiment of the present application, the molar ratio of 4-bromo-N-(2-hydroxy-1-hydroxymethyl ethyl)-1,8-naphthalene dicarboxamide and N-aminoethyl-perfluorobutyl sulfonamide is 1:2-5, and more preferably, the molar ratio of 4-bromo-N-(2-hydroxy-1-hydroxymethyl ethyl)-1,8-naphthalene dicarboxamide and N-aminoethyl-perfluorobutyl sulfonamide is 1:3.

[0021] The reaction temperature of the alkylation reaction is 100-110°C, and the reaction time is 7-8h.

[0022] In a preferred embodiment of the present application, the addition amount of the sulfur-containing organic solvent is 15-17 times of the total mass of 4-bromo-N-(2-hydroxy-1-hydroxymethyl ethyl)-1,8-naphthalene dicarboxamide and N-aminoethyl-perfluorobutyl sulfonamide.

[0023] In a preferred embodiment of the present application, the molar ratio of the diisocyanate and the oligomer polyol is 1:0.2-0.4; further, the diisocyanate is one of isophorone diisocyanate or 2,4-toluene diisocyanate. The oligomer polyol is one of polyethylene glycol, polytetrahydrofuran diol, polybutylene adipate, polycarbonate diol. The molecular weight of the oligomer polyol is 1000; the organotin is dibutyltin dilaurate (DBTDL).

[0024] The molar ratio of the diisocyanate and the hydrophilic chain extender is 1:0.4-0.6; further, the hydrophilic chain extender is dimethylolpropionic acid (DMPA) or dihydroxymethyl butyric acid.

[0025] The molar ratio of the diisocyanate and the fluorescent chain extender containing naphthalene ring and fluorine alkyl is 1:0.04-0.05.

[0026] The molar ratio of the diisocyanate and the hydroxyethyl acrylate is 1:0.2-0.3.

[0027] The molar ratio of the diisocyanate and the neutralizer is 1:0.4-0.6; further, the neutralizer is triethylamine (Et3N).

[0028] The reaction time of the neutralization reaction is 30min-40min.

[0029] In a preferred embodiment of the present application, the ratio of the total mass of the acrylate and the fluorine-containing acrylate to the total mass of the diisocyanate, the oligomer polyol, the hydrophilic chain extender, the fluorescent chain extender containing naphthalene ring and fluorine alkyl, the hydroxyethyl acrylate and the neutralizer is 1 / 4-2 / 3.

[0030] The mass ratio of the acrylate and the fluorine-containing acrylate is 1-2.4:1; further, the acrylate is butyl acrylate (BA), and the fluorine-containing acrylate is one of dodecafluoroheptylmethacrylate (DFMA), trifluoroethyl methacrylate and hexafluorobutyl methacrylate (HFBA).

[0031] The reaction time of the free radical polymerization reaction is 6h-8h.

[0032] Further, the initiator is one of ammonium persulfate and potassium persulfate.

[0033] The second object of the present application is to provide a polyurethane-polyacrylate hybrid emulsion prepared by the above preparation method.

[0034] Compared with the prior art, the present application has the following beneficial effects:

[0035] 1. The fluorescent chain extender with rigid naphthalene ring and low surface energy fluoroalkyl structure is used to modify polyurethane, and then free radical polymerization is carried out with polyacrylate to prepare polyurethane-polyacrylate hybrid material, which can increase the hydrogen bonding in the molecular chain of the hybrid material, the mechanical hinge action of the rigid naphthalene ring, the fluorescence and hydrophobic properties, so as to endow the hybrid material with the properties of fluorescence, antifouling, high mechanical strength and self-repairing.

[0036] 2. The multifunctional polyurethane-polyacrylate hybrid material designed and synthesized in the application combines the advantages of polyurethane and polyacrylate materials, reduces the cost, and improves the comprehensive performance of the material.

[0037] 3. The multifunctional polyurethane-polyacrylate hybrid material prepared in the application has strong fluorescence effect, hydrophobic property, mechanical and self-repairing property, so the application has wide application fields, such as anti-fake identification, fluorescent ink and fluorescent coating, antifouling, waterproof and corrosion-resistant coating or film, building materials, elastic materials and the like. BRIEF DESCRIPTION OF DRAWINGS

[0038] Figure 1 The reaction equation of the fluorescent chain extender containing naphthalene ring and fluoroalkyl.

[0039] Figure 2 The reaction equation of the polyurethane-polyacrylate hybrid emulsion.

[0040] Figure 3 The infrared spectrum of the reactant BA and the intermediate products BAA, PFSF-E and the fluorescent chain extender BA-F.

[0041] Figure 4 The optical photos of the fluorescent multifunctional polyurethane-polyacrylate hybrid emulsion of Example 1 under different concentrations: (A) visible light, (B) ultraviolet light.

[0042] Figure 5 The photo of the water contact angle of the surface of the fluorescent multifunctional polyurethane-polyacrylate hybrid emulsion film of Example 1.

[0043] Figure 6 The self-repairing diagram of the fluorescent multifunctional polyurethane-polyacrylate hybrid emulsion film of Example 1, wherein (a) is 0h, (b) is 3h, (c) is 6h, and (d) is 9h.

[0044] Figure 7 The stress-strain curve of the fluorescent multifunctional polyurethane-polyacrylate hybrid emulsion film DETAILED DESCRIPTION

[0045] Clearly and completely, the technical solutions in the embodiments of the present application will be described in combination with the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0046] The present application first provides a preparation method of a fluorescent chain extender containing a naphthalene ring and a fluoroalkyl group, as shown in the following formula (I): Figure 1 The preparation method comprises the following steps:

[0047] Under ice bath conditions, a first acylation reaction is performed on ethylenediamine and perfluorobutylsulfonyl fluoride to obtain N-aminoethyl-perfluorobutylsulfonamide.

[0048] In an alcoholic organic solution, a second acylation reaction is performed on 4-bromo-1,8-naphthalic anhydride and 2-amino-1,3-propanediol to obtain 4-bromo-N-(2-hydroxy-1-hydroxymethylethyl)-1,8-naphthalene dicarboxamide; further, the alcoholic organic solution is ethanol.

[0049] In a sulfur-containing organic solvent, an alkylation reaction is performed on N-aminoethyl-perfluorobutylsulfonamide and 4-bromo-N-(2-hydroxy-1-hydroxymethylethyl)-1,8-naphthalene dicarboxamide to obtain a fluorescent chain extender; further, the sulfur-containing organic solvent is dimethyl sulfoxide (DMSO).

[0050] The fluorescent chain extender prepared by the present application is a fluorescent chain extender containing a rigid naphthalene ring and a low-surface-energy fluoroalkyl group in the molecule. It is used for preparing a polyurethane-polyacrylate hybrid emulsion, as shown in the following formula (II): Figure 2 The specific preparation method is as follows:

[0051] With diisocyanate and oligomeric polyol as raw materials and organic tin as a catalyst, a prepolymerization reaction is performed, then a hydrophilic chain extender and a fluorescent chain extender containing a naphthalene ring and a fluoroalkyl group are added, and a polyaddition reaction is performed to obtain a fluorescent polyurethane prepolymer terminated by -NCO.

[0052] With hydroxyethyl acrylate as a modifier, an addition reaction is performed on the fluorescent polyurethane prepolymer terminated by -NCO to end-cap both sides of the polyurethane macromolecular chain with hydroxyl acrylate, thereby obtaining a double-side end-capped polyurethane prepolymer; after the temperature of the system is reduced to 40-50°C, a neutralizing agent is added for neutralization reaction, then water is added for dispersion and emulsification to obtain a mixed solution.

[0053] After the acrylic ester and fluorine-containing acrylic ester monomer are uniformly dispersed in the mixed solution, an initiator solution is added at 80-90°C for a free radical polymerization reaction to obtain a polyurethane-polyacrylate hybrid emulsion.

[0054] The polyurethane-polyacrylate hybrid emulsion prepared by the method can synergistically exert the "hinge" effect of the rigid naphthalene ring center in the fluorescent multifunctional chain extender in the molecular chain, the hydrophobic effect of the fluorescence and low surface energy perfluoroalkyl, the hydrogen bonding effect between the soft and hard segments of the polyurethane, and the advantages of combining polyurethane and polyacrylate materials, thereby endowing the hybrid material with multiple functions such as fluorescence, hydrophobicity, self-repairing, and high mechanical properties.

[0055] In order to make the purpose, technical scheme and advantages of the present application clearer and more apparent, the present application will be further described in detail below in combination with examples. It should be understood that the specific examples described herein are only used to explain the present application and not to limit the present application. In the following examples, the oligomeric polyol used is polybutylene adipate with a molecular weight of 1000.

[0056] Example 1:

[0057] A preparation method of a fluorescent antifouling self-repairing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion, comprising the following steps:

[0058] 1) Synthesis of fluorescent multifunctional chain extender BA-F:

[0059] Under ice bath conditions (0℃), 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 perfluorobutylsulfonyl fluoride was weighed into a constant pressure funnel and slowly added 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 the product was filtered to obtain a white solid, which was denoted as N-aminoethyl-perfluorobutylsulfonamide, denoted as PFSF-E.

[0060] A new three-necked flask equipped with a stirring rod and a condenser tube was first charged with 2.77 g (10 mmol) of 4-bromo-1,8-naphthalic anhydride and 2.73 g (30 mmol) of 2-amino-1,3-propanediol, followed by the addition of 110 ml of ethanol for stirring and dissolution. The reaction was continuously stirred at 80℃ for 9 h. After the reaction was completed, the excess ethanol was removed using a rotary evaporator, the sample was washed with deionized water for 3 times, and vacuum dried at 50℃ for 12 h to obtain a light gray powder, denoted as intermediate product BAA.

[0061] In a new three-necked flask equipped with a stirring rod and a condenser, 1.75 g (5 mmol) of BAA and 5.13 g (15 mmol) of PFSF-E were sequentially added, and then 100 ml of DMSO was added to stir and dissolve, and the three-necked flask was placed in a 100 ℃ heating reflux reactor for 8 h. After the reaction was completed, the solution was poured into 150 mL of deionized water and filtered, then washed with deionized water for 3 times, and vacuum dried at 50 ℃ 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.

[0062] 2) Synthesis of fluorescent antifouling self-repairing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion:

[0063] 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, and dibutyltin dilaurate was used as a catalyst, and the amount of dibutyltin dilaurate was 0.01% of the total mass of isophorone diisocyanate and polybutylene adipate, and the reaction was carried out at 90 ℃ for 1 h. Subsequently, 3.35 g of dimethylol propionic 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 hours to prepare a fluorescent polyurethane prepolymer terminated by -NCO; 1.45 g of hydroxyethyl acrylate was added to the above reaction system at a temperature of 90 ℃, and the polyurethane prepolymer was double-terminated by heating and stirring for 3 h; the temperature of the system was reduced to 40 ℃, 2.53 g of triethylamine was added for neutralization reaction for 0.5 h, and then 132 g of deionized water was slowly added under high-speed stirring, and dispersed and emulsified for 1 h. Subsequently, 16.98 g of butyl acrylate and 7.28 g of methacrylic acid dodecafluoroheptyl ester were added to the reaction system and stirred and dispersed for half an hour; the temperature was raised to 80 ℃, 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 polymerization was carried out at constant temperature for 6 hours to prepare a fluorescent antifouling self-repairing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion.

[0064] Example 2

[0065] A method for preparing a fluorescent antifouling self-repairing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion, comprising the following steps:

[0066] 1) Synthesis of fluorescent multifunctional chain extender BA-F:

[0067] Under ice bath conditions (0°C), 3.00 g (50 mmol) of ethylenediamine was first added to a three-necked flask equipped with a stirrer. Then, 3.02 g (10 mmol) of perfluorobutylsulfonyl fluoride was weighed into a constant pressure funnel and slowly added dropwise to the three-necked flask. After the addition was completed, the reaction was allowed to proceed for another 5 h. After the reaction was completed, excess ethylenediamine was removed using a rotary evaporator, yielding a small amount of yellow viscous liquid. This liquid was washed with a large amount of deionized water and filtered to obtain a white solid product, N-aminoethyl-perfluorobutylsulfonamide, denoted as PFSF-E.

[0068] In a new three-necked flask equipped with a stir bar and a condenser, 2.77 g (10 mmol) of 4-bromo-1,8-naphthalenedicarboxylic anhydride and 2.73 g (30 mmol) of 2-amino-1,3-propanediol were added sequentially. Then, 110 mL of ethanol was added and stirred to dissolve the product. The reaction was carried out at 80 °C for 9 h with continuous stirring. After the reaction was complete, excess ethanol was removed using a rotary evaporator. The sample was washed three times with deionized water and dried under vacuum at 50 °C for 12 h to obtain a light gray powder, which was designated as the intermediate product BAA.

[0069] 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 sequentially, followed by 100 mL of DMSO and stirred until dissolved. The flask was then heated under reflux at 100 °C for 8 h. After the reaction was complete, the solution was poured into 150 mL of deionized water and filtered. The solution was then washed three times with deionized water and dried under vacuum 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.

[0070] 2) Synthesis of fluorescent, antifouling, self-healing, high-strength, multifunctional polyurethane-polyacrylate hybrid emulsion:

[0071] 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, 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, and the reaction was carried out at 90 ℃ for 1 h. Subsequently, 3.7 g of dimethylol butyric acid, 1.28 g of the fluorescent multifunctional chain extender BA-F obtained in step 1) was added to the system, and the reaction was carried out for 2 h to obtain a fluorescent polyurethane prepolymer terminated by -NCO; 1.45 g of hydroxyethyl acrylate was added to the above reaction system at a temperature of 90 ℃, and heating and stirring were carried out for 3 h to terminate the polyurethane prepolymer on both sides; the temperature of the system was reduced to 40 ℃, 2.53 g of triethylamine was added for neutralization for 0.5 h, and then 105 g of deionized water was slowly added under high-speed stirring, 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 increased to 80 ℃, 0.32 g of ammonium persulfate dissolved in 10 g of deionized water was slowly dropped into the reaction system, and then the polymerization was carried out for 6 h to obtain a fluorescent antifouling self-repairing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion.

[0072] Example 3

[0073] A method for preparing a fluorescent antifouling self-repairing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion, comprising the following steps:

[0074] 1) Synthesis of fluorescent multifunctional chain extender BA-F:

[0075] Under ice bath conditions (0 ℃), 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 perfluorobutylsulfonyl fluoride was weighed into a constant pressure funnel and slowly added to the above three-necked flask, and after the addition was completed, the reaction was carried out 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, which was washed with a large amount of deionized water and filtered to obtain a white solid product N-aminoethyl-perfluorobutylsulfonamide, denoted as PFSF-E.

[0076] 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 sequentially added, then 110 ml of ethanol was added to stir and dissolve, and the reaction was continuously stirred at 80 ℃ for 9 h. After the reaction was completed, the excess ethanol was removed using a rotary evaporator, the sample was washed with deionized water for 3 times, and vacuum dried at 50 ℃ for 12 h to obtain a light gray powder, which was recorded as intermediate product BAA.

[0077] In a new three-necked flask equipped with a stirring rod and a condenser, 1.75 g (5 mmol) of BAA and 5.13 g (15 mmol) of PFSF-E were sequentially added, then 100 ml of DMSO was added to stir and dissolve, and the three-necked flask was placed in a heating reflux reactor at 100 ℃ for 8 h. After the reaction was completed, the solution was poured into 150 mL of deionized water and filtered, then washed with deionized water for 3 times, and vacuum dried at 50 ℃ 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.

[0078] 2) Synthesis of fluorescent antifouling self-repairing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion:

[0079] 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, 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 polytetramethylene adipate, and the reaction was carried out at 90 ℃ for 1 h. Subsequently, 3.35 g of dimethylol propionic acid, 1.28 g of 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 prepare a fluorescent polyurethane prepolymer terminated by -NCO; 0.7 g of hydroxyethyl acrylate was added to the above reaction system at a temperature of 90 ℃, and the polyurethane prepolymer was double-end capped by heating and stirring for 3 h; the temperature of the system was reduced to 40 ℃, 2.53 g of triethylamine was added for neutralization reaction for 0.5 h, then deionized water was slowly added under high-speed stirring conditions, and the dispersion was carried out 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 ℃, and 0.32 g of ammonium persulfate dissolved in 10 g of deionized water was slowly dropped into the reaction system, and then the polymerization was carried out for 6 hours to prepare a fluorescent antifouling self-repairing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion.

[0080] Example 4

[0081] A method for preparing a fluorescent antifouling self-repairing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion, comprising the following steps:

[0082] 1) Synthesis of fluorescent multifunctional chain extender BA-F:

[0083] 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 perfluorobutylsulfonyl fluoride was weighed into a constant pressure funnel and slowly added 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 performed. Finally, the white solid product N-aminoethyl-perfluorobutylsulfonamide was obtained, which was denoted as PFSF-E.

[0084] 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 first added, followed by the addition of 110 ml of ethanol for stirring and dissolution. 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 repeatedly washed with deionized water for 3 times, and then vacuum dried at 50°C for 12 h to obtain a light gray powder, which was denoted as intermediate product BAA.

[0085] In a new three-necked flask equipped with a stirring rod and a condenser, 1.75 g (5 mmol) of BAA and 5.13 g (15 mmol) of PFSF-E were first added, followed by the addition of 100 ml of DMSO for stirring and dissolution. The three-necked flask was placed in a heating reflux reactor at 100°C for 8 h. After the reaction was completed, the solution was poured into 150 mL of deionized water and filtered. Then the sample was repeatedly washed with deionized water for 3 times, and then 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 was the fluorescent chain extender BA-F.

[0086] 2) Synthesis of fluorescent antifouling self-repairing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion:

[0087] 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, the addition amount of dibutyltin dilaurate was 0.01% of the total mass of isophorone diisocyanate and polybutylene adipate, and the reaction was carried out at 90 ℃ for 1 h. Subsequently, 3.35 g of dimethylol propionic 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 a fluorescent polyurethane prepolymer terminated by -NCO; 1.45 g of hydroxyethyl acrylate was added to the above reaction system at a temperature of 90 ℃, and the polyurethane prepolymer was terminated on both sides by heating and stirring for 3 h; the temperature of the system was reduced to 40 ℃, 2.53 g of triethylamine was added for neutralization reaction for 0.5 h, and then 110 g of deionized water was slowly added under high-speed stirring, 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 increased to 80 ℃, 0.33 g of ammonium persulfate dissolved in 10 g of deionized water was slowly dropped into the reaction system, and then the polymerization was carried out for 6 h to obtain a fluorescent antifouling self-repairing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion.

[0088] Example 5:

[0089] A method for preparing a fluorescent antifouling self-repairing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion, comprising the following steps:

[0090] 1) Synthesis of fluorescent multifunctional chain extender BA-F:

[0091] Under ice bath conditions (0 ℃), 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 perfluorobutylsulfonyl fluoride was weighed into a constant pressure funnel and slowly added to the above three-necked flask. After the addition was completed, the reaction was carried out 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 to finally obtain a white solid product N-aminoethyl-perfluorobutylsulfonamide, which is denoted as PFSF-E.

[0092] In a new three-necked flask equipped with a stirring rod and a condenser tube, 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 in sequence, and then 110 ml of ethanol was added for stirring and dissolution. The reaction was continuously stirred at 80 ℃ for 9 h. After the reaction was completed, the excess ethanol was removed using a rotary evaporator. The sample was repeatedly washed with deionized water for 3 times, and then vacuum dried at 50 ℃ for 12 h to obtain a light gray powder, which is denoted as intermediate product BAA.

[0093] In a new three-necked flask equipped with a stirring rod and a condenser, 1.75 g (5 mmol) of BAA and 5.13 g (15 mmol) of PFSF-E were added successively, and then 100 ml of DMSO was added to stir and dissolve. The three-necked flask was placed in a 100 ℃ heating reflux reactor for 8 h. After the reaction was completed, the solution was poured into 150 mL of deionized water and filtered, then washed with deionized water for 3 times, and dried at 50 ℃ under vacuum 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.

[0094] 2) Synthesis of fluorescent antifouling self-repairing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion:

[0095] 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, and dibutyltin dilaurate was used as a catalyst. The amount of dibutyltin dilaurate added was 0.01% of the total mass of isophorone diisocyanate and polybutylene adipate. The reaction was carried out at 90 ℃ for 1 h. Subsequently, 3.35 g of dimethylol propionic 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 prepare a fluorescent polyurethane prepolymer terminated with -NCO. At a temperature of 90 ℃, 1.45 g of hydroxyethyl acrylate was added to the above reaction system, and the polyurethane prepolymer was double-terminated by heating and stirring for 3 h. The temperature of the system was reduced to 40 ℃, 2.53 g of triethylamine was added for neutralization reaction for 0.5 h, and then 109 g of deionized water was slowly added under high-speed stirring for 1 h of dispersion and emulsification. Subsequently, 10.8 g of butyl acrylate and 4.59 g of dodecafluoroheptyl methacrylate were added to the reaction system and stirred for half an hour; the temperature was raised to 80 ℃, and then 0.34 g of ammonium persulfate dissolved in 10 g of deionized water was slowly dropped into the reaction system, and then the polymerization was carried out at constant temperature for 6 h to prepare a fluorescent antifouling self-repairing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion.

[0096] Example 6:

[0097] A method for preparing a fluorescent antifouling self-repairing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion, comprising the following steps:

[0098] 1) Synthesis of fluorescent multifunctional chain extender BA-F:

[0099] Under ice bath conditions (5°C), 1.8 g (30 mmol) of ethylenediamine was first added to a three-necked flask equipped with a stirrer. Then, 3.02 g (10 mmol) of perfluorobutylsulfonyl fluoride was weighed into a constant pressure funnel and slowly added dropwise to the three-necked flask. After the addition was completed, the reaction was allowed to proceed for 5.5 h. After the reaction was completed, excess ethylenediamine was removed using a rotary evaporator, yielding a small amount of yellow viscous liquid. This liquid was washed with a large amount of deionized water and filtered to obtain a white solid product, N-aminoethyl-perfluorobutylsulfonamide, denoted as PFSF-E.

[0100] In a new three-necked flask equipped with a stir bar and a condenser, 2.77 g (10 mmol) of 4-bromo-1,8-naphthalenedicarboxylic anhydride and 1.82 g (20 mmol) of 2-amino-1,3-propanediol were added sequentially. Then, 100 ml of ethanol was added and stirred to dissolve the product. The reaction was carried out at 85 °C for 8.5 h with continuous stirring. After the reaction was complete, excess ethanol was removed using a rotary evaporator. The sample was washed three times with deionized water and dried under vacuum at 50 °C for 12 h to obtain a light gray powder, which was designated as the intermediate product BAA.

[0101] 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 added sequentially, followed by 90 mL of DMSO and stirred until dissolved. The flask was then heated under reflux at 105 °C for 7.5 h. After the reaction was complete, the solution was poured into 150 mL of deionized water and filtered. The solution was then washed three times with deionized water and dried under vacuum 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.

[0102] 2) Synthesis of fluorescent, antifouling, self-healing, high-strength, multifunctional polyurethane-polyacrylate hybrid emulsion:

[0103] 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 catalyst, the addition amount of dibutyltin dilaurate was 0.02% of the total mass of isophorone diisocyanate and polybutylene adipate, and the reaction was carried out at 90 ℃ for 1 h. Subsequently, 2.68 g of dimethylol propionic 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 obtain a fluorescent polyurethane prepolymer terminated by -NCO; 1.16 g of hydroxyethyl acrylate was added to the above reaction system at a temperature of 90 ℃, and the polyurethane prepolymer was terminated on both sides by heating and stirring for 3 h; the temperature of the system was reduced to 50 ℃, 2.02 g of triethylamine was added for neutralization reaction for 0.5 h, and then 73 g of deionized water was slowly added under high-speed stirring, 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 ℃, 0.51 g of ammonium persulfate was dissolved in 10 g of deionized water and slowly dropped into the reaction system, and then the polymerization was carried out for 6 h to obtain a fluorescent antifouling self-repairing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion.

[0104] Example 7:

[0105] A method for preparing a fluorescent antifouling self-repairing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion, comprising the following steps:

[0106] 1) Synthesis of fluorescent multifunctional chain extender BA-F:

[0107] Under ice bath conditions (3 ℃), 4.2 g (70 mmol) of ethylenediamine was first added to a three-necked flask equipped with a stirring device, and then 3.02 g (10 mmol) of perfluorobutylsulfonyl fluoride was weighed into a constant pressure funnel and slowly added to the above three-necked flask. After the addition was completed, the reaction was carried out for another 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 to finally obtain a white solid product N-aminoethyl-perfluorobutylsulfonamide, which is denoted as PFSF-E.

[0108] In a new three-necked flask equipped with a stirring rod and a condenser tube, 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 in sequence, and then 160 ml of ethanol was added for stirring and dissolution. The reaction was continuously stirred at 90 ℃ for 8 h. After the reaction was completed, the excess ethanol was removed using a rotary evaporator, the sample was repeatedly washed with deionized water for 3 times, and vacuum drying was carried out at 50 ℃ for 12 h to obtain a light gray powder, which is denoted as intermediate product BAA.

[0109] In a new three-necked flask equipped with a stirring rod and a condenser, 1.75 g (5 mmol) of BAA and 8.55 g (25 mmol) of PFSF-E were added successively, and then 175 ml of DMSO was added to stir and dissolve, and the three-necked flask was placed under heating reflux at 110 ℃ for 7 h. After the reaction was completed, the solution was poured into 150 mL of deionized water and filtered, then washed with deionized water for 3 times, and dried at 50 ℃ under vacuum 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.

[0110] 2) Synthesis of fluorescent antifouling self-repairing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion:

[0111] In a three-necked flask equipped with a stirring device, 11.11 g of isophorone diisocyanate and 20 g of polybutylene adipate were added, and 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, and the reaction was carried out at 90 ℃ for 1 h. Subsequently, 4.02 g of dimethylol propionic 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 prepare a fluorescent polyurethane prepolymer terminated by -NCO; 1.74 g of hydroxyethyl acrylate was added to the above-mentioned reaction system under the condition that the temperature was 90 ℃, and the polyurethane prepolymer was double-terminated by heating and stirring for 3 h; the temperature of the system was reduced to 45 ℃, 3.04 g of triethylamine was added for neutralization reaction for 0.5 h, and then 125 g of deionized water was slowly added under the condition of high-speed stirring, 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 increased to 85 ℃, 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 polymerization was carried out for 6 hours to prepare a fluorescent antifouling self-repairing high-strength multifunctional polyurethane-polyacrylate hybrid emulsion.

[0112] The structure and performance of the fluorescent multifunctional chain extender and the polyurethane-polyacrylate hybrid emulsion prepared in examples 1-5 were tested, and the results were as follows:

[0113] Figure 3 The infrared spectrum of 4-bromo-1,8-naphthalic anhydride BA, intermediate products BAA and PFSF-E and fluorescent chain extender BA-F in example 1 of the present application is shown in Figure 3 Fig. 1, and as shown in Fig. 1, 4-bromo-1,8-naphthalic anhydride BA has absorption peaks at 1782, 1731 and 1020 cm -1The absorption peaks at 1402, 1502, 1585 and 779 cm -1 The absorption peaks at 1402, 1502, 1585 and 779 cm -1 The absorption peaks at 1402, 1502, 1585 and 779 cm -1 The absorption peaks at 1402, 1502, 1585 and 779 cm -1 The absorption peaks at 1402, 1502, 1585 and 779 cm -1 The absorption peaks at 1402, 1502, 1585 and 779 cm -1 The absorption peaks at 1402, 1502, 1585 and 779 cm -1 The absorption peaks at 1402, 1502, 1585 and 779 cm -1 The absorption peaks at 1402, 1502, 1585 and 779 cm -1 The absorption peaks at 1402, 1502, 1585 and 779 cm -1 The absorption peaks at 1402, 1502, 1585 and 779 cm -1 The absorption peaks at 1402, 1502, 1585 and 779 cm -1 The absorption peaks at 1402, 1502, 1585 and 779 cm

[0114] Figure 4 The optical photographs of the polyurethane-polyacrylate hybrid emulsion prepared in Example 1 at different mass concentrations, from left to right, the mass concentrations are 30%, 3% and 0.3% respectively. Figure 4 (a) is the optical photograph under visible light, (b) is the optical photograph under ultraviolet light. As shown in Figure 4 , the polyurethane-polyacrylate hybrid emulsion prepared in Example 1 at different concentrations respectively appears blue yellow, light yellow and yellow under visible light; and under ultraviolet light, their colors correspondingly change to blue green, green and bright green, which shows that the synthesized polyurethane-polyacrylate hybrid emulsion has fluorescence.

[0115] Figure 5 The film surface water contact angle photograph of the polyurethane-polyacrylate hybrid emulsion prepared in Example 1 after film formation. As shown in Figure 5The static water contact angle of the surface of the hybrid latex film is 115.3°, which indicates that the film has good hydrophobicity.

[0116] Figure 6 The self-repairing diagram of the polyurethane-polyacrylate hybrid film prepared in Example 1 after film formation. Figure 6 (a) is 0h, (b) is 3h, (c) is 6h, and (d) is 9h. Figure 6 As shown in the figure, a large black gap between the two films can be obviously observed when the two films just begin to contact together after being cut; after 3 hours, the two films have been obviously re-bonded together, showing a black band; after 6 hours, the two films have almost been bonded together, only a light line can be observed; after 9 hours, the two films have become a whole, and the repair is completed, which indicates that the polyurethane-polyacrylate hybrid film has good self-repairing performance.

[0117] The polyurethane-polyacrylate hybrid emulsion prepared in Example 1 to Example 5 is poured into a polytetrafluoroethylene plate and dried at 50℃ to form a film, to obtain a polyurethane-polyacrylate hybrid film with a thickness of 0.5mm. Figure 7 The stress-strain curve of the hybrid film prepared in Example 1 to Example 5 of the application is shown in the figure. Figure 7 As shown in the figure, the stress of the hybrid film is about 32~44MPa, and the strain is about 450%~700%, which indicates that the hybrid film has good mechanical properties.

[0118] Although the preferred embodiments of the application have been described, those skilled in the art can make further changes and modifications to the embodiments once they know the basic inventive concept. Therefore, the appended claims are intended to be interpreted as including all the preferred embodiments and all the changes and modifications falling within the scope of the application.

[0119] Obviously, those skilled in the art can make various modifications and variations to the application without departing from the spirit and scope of the application. Thus, if these modifications and variations of the application fall within the scope of the claims of the application and their equivalent technologies, the application also intends to include these modifications and variations.

Claims

1. A process for the preparation of a polyurethane-polyacrylate hybrid emulsion, characterized in that, Includes the following steps: Using diisocyanate and oligomeric polyol as raw materials and organotin as catalyst, a prepolymerization reaction is carried out. Then, a hydrophilic chain extender and a fluorescent chain extender containing naphthalene ring and fluoroalkyl group are added to carry out a modification reaction to obtain -NCO-terminated fluorescent polyurethane prepolymer. Hydroxyethyl acrylate was used as a modifier to modify the -NCO-terminated fluorescent polyurethane prepolymer to obtain a double-terminated polyurethane prepolymer. After the double-terminated polyurethane prepolymer and the neutralizing agent were neutralized at 40℃~50℃, water was added for dispersion and emulsification to obtain a mixture. After adding acrylate and fluorinated acrylate monomers to the mixture and dispersing them evenly, an initiator solution is added at 80℃~90℃ to carry out a free radical polymerization reaction to obtain a polyurethane-polyacrylate hybrid emulsion.

2. The process for the preparation of a polyurethane-polyacrylate hybrid emulsion according to claim 1, characterized in that, The preparation of fluorescent chain extenders containing naphthalene rings and fluoroalkyl groups includes the following steps: N-aminoethyl-perfluorobutylsulfonamide was obtained by a primary acylation reaction using ethylenediamine and perfluorobutylsulfonyl fluoride as raw materials under ice bath conditions. In an alcoholic organic solution, 4-bromo-1,8-naphthalenedicarboxylic anhydride and 2-amino-1,3-propanediol undergo a second acylation reaction to give 4-bromo-N-(2-hydroxy-1-hydroxymethylethyl)-1,8-naphthalenedicarboxylic anhydride; In a sulfur-containing organic solvent, N-aminoethyl-perfluorobutylsulfonamide and 4-bromo-N-(2-hydroxy-1-hydroxymethylethyl)-1,8-naphthalenediamide undergo an alkylation reaction to obtain a fluorescent chain extender containing a naphthalene ring and a fluoroalkyl group.

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

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

5. The process for the preparation of polyurethane-polyacrylate hybrid emulsion as claimed in claim 2, wherein, The amount of alcohol organic solution added is 20 to 22 times the total mass of 4-bromo-1,8-naphthalenedicarboxylic anhydride and 2-amino-1,3-propanediol.

6. The process for the preparation of polyurethane-polyacrylate hybrid emulsion as claimed in claim 2, wherein, The molar ratio of 4-bromo-N-(2-hydroxy-1-hydroxymethylethyl)-1,8-naphthalenedicarboxylamide and N-aminoethyl-perfluorobutylsulfonamide is 1:2~5. The alkylation reaction temperature is 100℃~110℃ and the reaction time is 7h~8h.

7. The process for the preparation of polyurethane-polyacrylate hybrid emulsion as claimed in claim 2, wherein, The amount of sulfur-containing organic solvent added is 15 to 17 times the total mass of 4-bromo-N-(2-hydroxy-1-hydroxymethylethyl)-1,8-naphthalenedicarboxylamide and N-aminoethyl-perfluorobutylsulfonamide.

8. The method for preparing 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 fluorescent chain extender containing naphthalene ring and 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 neutralization reaction takes 30 to 40 minutes.

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

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

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