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

Abstract

The invention discloses a fluorescent functional monomer, a fluorinated polyacrylate soap-free emulsion and a preparation method of the fluorinated polyacrylate soap-free emulsion, and belongs to the technical field of high-performance resin coatings. The preparation method of the fluorescent functional monomer comprises the following steps: under an ice bath condition, taking ethylenediamine and perfluorobutyl sulfonyl fluoride as raw materials, and carrying out nucleophilic substitution reaction to obtain N-aminoethyl-perfluorobutyl sulfonamide; the preparation method comprises the following steps: adding 4-bromo-1, 8-naphthalic anhydride and allylamine hydrochloride into an alcohol organic solvent by taking sodium hydroxide as a neutralizing agent, and carrying out acylation reaction to obtain an intermediate product; in a sulfur-containing organic solvent, N-aminoethyl-perfluorobutyl sulfonamide and the intermediate product are subjected to an alkylation reaction, and the fluorescent functional monomer is obtained. The synthesized fluorescent functional monomer contains a rigid naphthalene ring and a low-surface-energy fluoroalkyl group, and has excellent hydrophobic stability and fluorescence performance.

Description

Technical Field

[0001] The present invention relates to the technical field of high-performance resin coatings, and more specifically to a fluorescent functional monomer, a fluorinated polyacrylate soap-free emulsion, and a preparation method thereof. Background Art

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

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

[0004] 。

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

[0006] 。

[0007] However, none of these products have anti-fouling ability and are prone to being contaminated.

[0008] The demand for fluorescent-based multifunctional fluorinated polyacrylate aqueous products in the market has shown explosive growth. Abrakhi et al. prepared fluorinated acrylate and fluorescent monomers by reacting acryloyl chloride with perfluorohexyl ethanol and 4-phenylazophenol respectively, and then carried out free radical polymerization reaction to prepare a series of fluorinated polyacrylate spin coatings with photo-controllable wettability [Langmuir, 2013, 29, 30, 9499–9509]. Zhou et al. prepared cellulose nanocrystal and coumarin-modified fluorinated polyacrylate emulsions by RAFT-assisted Pickering emulsion polymerization method. The latex film has self-healing properties, and the treated fabric has waterproof and oil-proof properties [Journal of Applied Polymer Science, 2023, 140(16), 10.1002 / app.53757.]. However, the waterproof and oil-proof stability is not ideal. Summary of the Invention

[0009] In view of the above problems, the present invention provides a fluorescent functional monomer, a soap-free emulsion of fluorinated polyacrylate and its preparation method. The fluorescent functional monomer synthesized in the present invention contains a rigid naphthalene ring and a low surface energy fluoroalkyl group, and has excellent hydrophobic stability and fluorescent properties.

[0010] The first object of the present invention is to provide a preparation method of a fluorescent functional monomer, which includes the following steps: Under ice bath conditions, using ethylenediamine and perfluorobutanesulfonyl fluoride as raw materials, a nucleophilic substitution reaction occurs to obtain N-aminoethyl-perfluorobutanesulfonamide.

[0011] In an alcohol organic solvent, with sodium hydroxide as a neutralizing agent, 4-bromo-1,8-naphthalic anhydride and allylamine hydrochloride are added, and an acylation reaction occurs to obtain an intermediate product.

[0012] In a sulfur-containing organic solvent, N-aminoethyl-perfluorobutanesulfonamide and the intermediate product undergo an alkylation reaction to obtain a fluorescent functional monomer.

[0013] In a preferred embodiment of the present invention, the reaction temperature of the nucleophilic substitution reaction is 0°C to 5°C, and the reaction time is 4h to 6h.

[0014] In a preferred embodiment of the present invention, the molar ratio of ethylenediamine to perfluorobutanesulfonyl fluoride is 3 to 7:1. More preferably, the molar ratio of ethylenediamine to perfluorobutanesulfonyl fluoride is 5:1.

[0015] In a preferred embodiment of the present invention, the reaction temperature of the acylation reaction is 80°C to 90°C, and the reaction time is 8h to 9h.

[0016] In a preferred embodiment of the present invention, the molar ratio of 4-bromo-1,8-naphthalic anhydride to allylamine hydrochloride is 1:2 to 5; more preferably, the molar ratio of 4-bromo-1,8-naphthalic anhydride to allylamine hydrochloride is 1:3.

[0017] The molar ratio of sodium hydroxide to allylamine hydrochloride is 1:1.

[0018] The addition amount of the alcohol organic solvent is 20 to 22 times the total mass of 4-bromo-1,8-naphthalic anhydride and allylamine hydrochloride.

[0019] In a preferred embodiment of the present invention, the reaction temperature of the alkylation reaction is 100°C to 110°C, and the reaction time is 7 h to 8 h.

[0020] In a preferred embodiment of the present invention, the molar ratio of the intermediate product to N-aminoethyl-perfluorobutanesulfonamide is 1:2 to 5; more preferably, the molar ratio of the intermediate product to N-aminoethyl-perfluorobutanesulfonamide is 1:3.

[0021] The addition amount of the sulfur-containing organic solvent is 15 to 17 times the total mass of the intermediate product and N-aminoethyl-perfluorobutanesulfonamide.

[0022] The second object of the present invention is to provide the fluorescent functional monomer prepared by the above preparation method.

[0023] The third object of the present invention is to provide a preparation method of a fluorinated polyacrylate soap-free emulsion, comprising the following steps: Stir the above fluorescent functional monomer, the first polymerizable non-fluorinated monomer, the first emulsifier and the first chain transfer agent evenly to obtain a first mixed solution; under the protection of nitrogen, at 75 - 80°C, add a first initiator to the first mixed solution to carry out a polymerization reaction to obtain a second mixed solution.

[0024] Among them, the mass ratio of the fluorescent functional monomer to the first polymerizable non-fluorinated monomer is 0.5 - 5:90 - 95; the addition amount of the first chain transfer agent accounts for 0.5% - 2% of the mass of the fluorescent functional monomer and the first polymerizable non-fluorinated monomer; the addition amount of the first emulsifier accounts for 0.5% - 5% of the mass of the fluorescent functional monomer and the first polymerizable non-fluorinated monomer; the addition amount of the first initiator accounts for 0.5% - 3% of the mass of the fluorescent functional monomer and the first polymerizable non-fluorinated monomer.

[0025] Mix the polymerizable fluorinated monomer, the second polymerizable non-fluorinated monomer, the self-crosslinking monomer, the second emulsifier and the second chain transfer agent evenly to obtain a third mixed solution.

[0026] Among them, the mass ratio of the polymerizable fluorinated monomer to the second polymerizable non-fluorinated monomer is 50-70:10-30; the addition amount of the second chain transfer agent accounts for 0.5%-2% of the mass of the polymerizable fluorinated monomer, the second polymerizable non-fluorinated monomer and the self-crosslinking monomer; the addition amount of the second emulsifier accounts for 0.5%-5% of the mass of the polymerizable fluorinated monomer, the second polymerizable non-fluorinated monomer and the self-crosslinking monomer; the addition amount of the second initiator accounts for 0.5%-3% of the mass of the polymerizable fluorinated monomer, the second polymerizable non-fluorinated monomer and the self-crosslinking monomer.

[0027] Add the third mixed solution and the second initiator solution to the second mixed solution to carry out a polymerization reaction to obtain a soap-free fluorinated polyacrylate emulsion. Among them, the reaction time of the polymerization reaction is 2h-6h.

[0028] Furthermore, the polymerizable fluorinated monomer is one of trifluoroethyl methacrylate, hexafluorobutyl methacrylate and dodecafluorooctyl methacrylate.

[0029] The self-crosslinking monomer is one of N-methylolacrylamide and γ-(methacryloyloxy)propyltrimethoxysilane.

[0030] The emulsifier is ammonium 1-allyloxy-3-(4-nonylphenol)-2-propanol polyoxyethylene (10) ether sulfate (DNS-86) The chain transfer agent is dodecyl mercaptan.

[0031] The first initiator is one of ammonium persulfate and potassium persulfate.

[0032] The second initiator is one of ammonium persulfate and potassium persulfate.

[0033] The fourth object of the present invention is to provide the soap-free fluorinated polyacrylate emulsion prepared by the above preparation method. The prepared soap-free fluorinated polyacrylate emulsion has excellent fluorescence, anti-fouling and mechanical properties, and can be used in the fields of anti-counterfeiting coatings or films, anti-corrosion coatings, light-sensitive materials, anti-counterfeiting marks, traffic signs, elastic materials, building materials, fluorescent inks, fluorescent coatings, etc., with wide applications.

[0034] Compared with the prior art, the present invention has the following beneficial effects: 1. The fluorescent multifunctional monomer BANA-F synthesized by the present invention contains a fluorescent rigid group in its molecular structure. By connecting the fluorinated group through it, it is beneficial to the structural stability of the fluorinated chain segment at the two-phase interface, and it is not easy to occur structural rearrangement phenomena, and it has excellent hydrophobic stability and fluorescence performance.

[0035] 2. The present invention utilizes the "hinging" effect of the rigid centers (naphthalene rings) in the side chains of the molecular chains and the chemical bond cross-linking effect between the self-crosslinking groups of the self-crosslinking monomers (the nitrogen-containing hydroxymethyl in N-hydroxymethylacrylamide or the siloxy group in γ-(methacryloyloxy)propyltrimethoxysilane), enabling the polyacrylate film to have high mechanical properties.

[0036] 3. The present invention uses a polymerizable emulsifier to prepare a fluorinated polyacrylate soap-free emulsion with fluorescence, antifouling, and high mechanical properties. The emulsifier molecules are copolymerized into the polymer molecular chains, and there are no free emulsifier molecules in the emulsion, which is thus beneficial to environmental protection and the hydrophobicity of the product. Description of the Drawings

[0037] Figure 1 It is a reaction mechanism diagram of the fluorescent functional monomer.

[0038] Figure 2 It is a reaction mechanism diagram for synthesizing the fluorinated polyacrylate soap-free emulsion.

[0039] Figure 3 It is an ultraviolet absorption spectrum diagram of the intermediate and the fluorescent multifunctional monomer A.

[0040] Figure 4 It is a fluorescence emission spectrum diagram of the intermediate and the fluorescent multifunctional monomer A.

[0041] Figure 5 It is a fluorescence picture of different fluorescent multifunctional fluorinated polyacrylate emulsions.

[0042] Figure 6 It is the result of the change in the contact angle over time of the surface of the fabric treated with different fluorescent multifunctional fluorinated polyacrylates.

[0043] Figure 7 It is a stress-strain curve diagram of the latex films of the emulsions obtained in Examples 1 to 3. Detailed Embodiments

[0044] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts shall fall within the scope of protection of the present invention.

[0045] The present invention provides a preparation method for a fluorescent functional monomer, including the following steps: Under ice bath conditions, using ethylenediamine and perfluorobutanesulfonyl fluoride as raw materials, a nucleophilic substitution reaction occurs to obtain N-aminoethyl-perfluorobutanesulfonamide.

[0046] In an alcoholic organic solvent, using sodium hydroxide as a neutralizing agent, 4-bromo-1,8-naphthalic anhydride and allylamine hydrochloride undergo an acylation reaction to obtain an intermediate product, 4-bromo-N-allyl-1,8-naphthalenedicarboxamide.

[0047] In a sulfur-containing organic solvent, N-aminoethyl-perfluorobutanesulfonamide and the intermediate product undergo an alkylation reaction to obtain a fluorescent functional monomer; the reaction mechanism diagram is as Figure 1 shown.

[0048] The fluorescent functional monomer prepared by the present invention contains a rigid naphthalene ring connecting fluorine-containing groups in its molecule. When copolymerized with other monomers, on the one hand, the fluorine-containing chain segments are not prone to rearrangement at the two-phase interface, showing structural stability; on the other hand, the riveting or physical cross-linking effect of this fluorescent rigid center between polymer molecular chains can endow the fluorinated polyacrylate soap-free emulsion with stable anti-fouling properties, high mechanical properties, and fluorescent functions.

[0049] The present invention provides a method for preparing a fluorinated polyacrylate soap-free emulsion, comprising the following steps: The fluorescent functional monomer, the first polymerizable non-fluorine monomer, the first emulsifier, and the first chain transfer agent are stirred evenly to obtain a first mixed solution; under the protection of nitrogen, at 75 °C to 80 °C, a first initiator is added to the first mixed solution to carry out a polymerization reaction to obtain a second mixed solution.

[0050] The polymerizable fluorine-containing monomer, the second polymerizable non-fluorine monomer, the self-crosslinking monomer, the second emulsifier, and the second chain transfer agent are mixed evenly to obtain a third mixed solution.

[0051] The third mixed solution and the second initiator solution are added to the second mixed solution to carry out a polymerization reaction to obtain a fluorinated polyacrylate soap-free emulsion. The reaction mechanism diagram is as Figure 2 shown.

[0052] When preparing the fluorinated polyacrylate soap-free emulsion, the present invention is prepared by a semi-continuous seed emulsion polymerization reaction. The first mixed solution is a pre-emulsion. After polymerization is initiated by an initiator, the third mixed solution and the second initiator are respectively dropped into the core phase (the second mixed solution) for polymerization to obtain a fluorinated polyacrylate soap-free emulsion.

[0053] In order to make the objectives, technical solutions, and advantages of the present invention clearer, the following further details the present invention 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.

[0054] Example 1 A method for preparing a fluorinated polyacrylate soap-free emulsion, comprising the following steps: Step 1) Preparation of the fluorescent multifunctional monomer: Under ice bath conditions (0 °C), 3 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 maintained at 0 °C 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.

[0055] In a new three-necked flask equipped with a stir bar and a condenser, 2 g (7.22 mmol) of 4-bromo-1,8-naphthalic anhydride, 3.38 g (21.66 mmol) of allylamine hydrochloride, and 0.87 g (21.66 mmol) of sodium hydroxide were successively added. Then, 90 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 repeatedly with deionized water 3 times and vacuum dried at 50 °C for 12 h to obtain a light yellow powder, denoted as intermediate BANA.

[0056] In a new three-necked flask equipped with a stir bar and a condenser, 1 g (3.16 mmol) of BANA and 3.24 g (9.48 mmol) of PFSF-E were successively added. Then, 50 ml of DMSO was added and stirred to dissolve. 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 multifunctional monomer (BANA-F).

[0057] Step 2) Preparation of fluorinated polyacrylate soap-free emulsion: Take 0.4 g of the fluorescent multifunctional monomer, 10 g of butyl acrylate, 0.3 g of DNS-86, and 1.03 g of the chain transfer agent dodecyl mercaptan. After mixing, 18 g of deionized water was added and stirred at high speed for 30 min. The resulting mixture was denoted as the first mixed solution. Under the protection of nitrogen, the first mixed solution was heated to 78 °C, and an aqueous solution of 0.1236 g of ammonium persulfate dissolved in 5 g of deionized water was added. The polymerization reaction was started at 78 °C for 1 h to obtain the second mixed solution.

[0058] Take 6 g of dodecafluoroheptyl methacrylate, 2 g of butyl acrylate, 1 g of N-hydroxymethyl acrylamide, 0.28 g of DNS-86, and 0.97 g of chain transfer agent dodecyl mercaptan. After mixing, add 13 g of deionized water and stir at high speed for 30 min. The resulting mixture is denoted as the third mixed solution.

[0059] Then, the third mixed solution and the initiator solution prepared by dissolving 0.0363 g of ammonium persulfate in 10 g of deionized water are slowly added dropwise to the reaction system of the second mixed solution above, and it is approximately controlled to be added dropwise within 1 h. The reaction is carried out under heat preservation at 78 °C for 4 h to obtain the fluorescent antifouling high-strength "three-in-one" functional fluorinated polyacrylate soap-free emulsion.

[0060] Example 2 A preparation method of a fluorinated polyacrylate soap-free emulsion, comprising the following steps: Step 1) Preparation of a fluorescent multifunctional monomer: Under ice bath conditions (0 °C), first add 3 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, keep the reaction at 0 °C for 6 h. After the reaction is completed, use a rotary evaporator to remove the excess ethylenediamine, 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.

[0061] In a new three-necked flask equipped with a stirrer and a condenser, first add 2 g (7.22 mmol) of 4-bromo-1,8-naphthalic anhydride, 3.38 g (21.66 mmol) of allylamine hydrochloride, and 0.87 g (21.66 mmol) of sodium hydroxide, and then add 90 ml of ethanol and stir to dissolve. Stir and react continuously 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 dry it under vacuum at 50 °C for 12 h to obtain a light yellow powder, denoted as the intermediate BANA.

[0062] In a new three-necked flask equipped with a stir bar and a condenser, 1 g (3.16 mmol) of BANA and 3.24 g (9.48 mmol) of PFSF-E were successively added, and then 50 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 multifunctional monomer (BANA-F).

[0063] Step 2) Preparation of fluorinated polyacrylate soap-free emulsion: Take 0.4 g of the fluorescent multifunctional monomer, 10 g of isooctyl acrylate, 0.3 g of DNS-86, and 1.03 g of the chain transfer agent dodecyl mercaptan. After mixing, 18 g of deionized water was added and stirred at high speed for 30 min. The resulting mixture was designated as the first mixture. Under the protection of nitrogen, the first mixture was heated to 78 °C, and 0.1236 g of ammonium persulfate dissolved in 5 g of deionized water was added, and the polymerization reaction was started at 78 °C for 1 h to obtain the second mixture.

[0064] Take 6 g of dodecafluoroheptyl methacrylate, 2 g of isooctyl acrylate, 1 g of N-methylolacrylamide, 0.28 g of DNS-86, and 0.97 g of the chain transfer agent dodecyl mercaptan. After mixing, 13 g of deionized water was added and stirred at high speed for 30 min. The resulting mixture was designated as the third mixture. Then, the third mixture and the initiator solution prepared by dissolving 0.0363 g of ammonium persulfate in 10 g of deionized water were slowly added dropwise to the reaction system of the second mixture respectively, and it was approximately controlled to be added dropwise within 1 h, and the reaction was carried out at 78 °C for 4 h to obtain the fluorescent antifouling high-strength "three-in-one" functional fluorinated polyacrylate soap-free emulsion.

[0065] Example 3 A method for preparing a fluorinated polyacrylate soap-free emulsion, comprising the following steps: Step 1) Preparation of fluorescent multifunctional monomer: Under ice bath conditions (0 °C), 3 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 maintained at 0 °C for 4 - 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, which was washed with a large amount of deionized water, filtered, and finally a white solid product N-aminoethyl-perfluorobutanesulfonamide was obtained, designated as PFSF-E.

[0066] In a new three-necked flask equipped with a stir bar and a condenser, 2 g (7.22 mmol) of 4-bromo-1,8-naphthalic anhydride, 3.38 g (21.66 mmol) of allylamine hydrochloride, and 0.87 g (21.66 mmol) of sodium hydroxide were successively added. Then, 90 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 yellow powder, denoted as intermediate BANA.

[0067] In a new three-necked flask equipped with a stir bar and a condenser, 1 g (3.16 mmol) of BANA and 3.24 g (9.48 mmol) of PFSF-E were successively added. Then, 50 ml of DMSO was added and stirred until dissolved. The three-necked flask was heated under 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 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 multifunctional monomer (BANA-F).

[0068] Step 2) Preparation of the fluorinated polyacrylate soap-free emulsion: 0.4 g of the fluorescent multifunctional monomer, 10 g of lauryl methacrylate, 0.3 g of DNS-86, and 1.03 g of the chain transfer agent dodecyl mercaptan were taken. After mixing, 18 g of deionized water was added and stirred at high speed for 30 min. The resulting mixture was denoted as the first mixture. Under the protection of nitrogen, the first mixture was heated to 78 °C, and an aqueous solution of 0.1236 g of potassium persulfate dissolved in 5 g of deionized water was added. Polymerization reaction was started at 78 °C for 1 h to obtain the second mixture.

[0069] 6 g of dodecafluoroheptyl methacrylate, 2 g of lauryl methacrylate, 1 g of γ-(methacryloyloxy)propyltrimethoxysilane, 0.28 g of DNS-86, and 0.97 g of the chain transfer agent dodecyl mercaptan were taken. After mixing, 13 g of deionized water was added and stirred at high speed for 30 min. The resulting mixture was denoted as the third mixture.

[0070] Then, the third mixture and the initiator solution of 0.0363 g of potassium persulfate dissolved in 10 g of deionized water were slowly added dropwise to the reaction system of the above second mixture, and it was approximately controlled to finish dropping in 1 h. The reaction was kept at 78 °C for 4 h to obtain the fluorescent antifouling high-strength "three-in-one" functional fluorinated polyacrylate soap-free emulsion.

[0071] Example 4 A preparation method of a fluorinated polyacrylate soap-free emulsion, comprising the following steps: Step 1) Preparation of a fluorescent multifunctional monomer: Under ice bath conditions (0 °C), first add 3 g (50 mmol) of ethylenediamine to a three-necked flask equipped with a stirring device, 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, keep the reaction at 0 °C for 6 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.

[0072] In a new three-necked flask equipped with a stirrer and a condenser, successively add 2 g (7.22 mmol) of 4-bromo-1,8-naphthalic anhydride, 3.38 g (21.66 mmol) of allylamine hydrochloride, and 0.87 g (21.66 mmol) of sodium hydroxide, then add 90 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 dry it in vacuo at 50 °C for 12 h to obtain a light yellow powder, denoted as intermediate BANA.

[0073] In a new three-necked flask equipped with a stirrer and a condenser, successively add 1 g (3.16 mmol) of BANA and 3.24 g (9.48 mmol) of PFSF-E, then add 50 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 it with deionized water repeatedly 3 times, and dry it in vacuo 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 multifunctional monomer (BANA-F).

[0074] Step 2) Preparation of the fluorinated polyacrylate soap-free emulsion: Take 0.4 g of the fluorescent multifunctional monomer, 8 g of butyl acrylate, 0.24 g of DNS-86, 0.82 g of the chain transfer agent dodecyl mercaptan, mix them and then add 18 g of deionized water and stir at high speed for 30 min. The resulting mixture is denoted as the first mixture. Under the protection of nitrogen, the first mixture is heated to 78 °C and an aqueous solution of 0.0989 g of ammonium persulfate dissolved in 5 g of deionized water is added, and polymerization reaction is carried out at 78 °C for 1 h to obtain the second mixture.

[0075] Take 8 g of hexafluorobutyl methacrylate, 2 g of butyl acrylate, 1 g of N-hydroxymethyl acrylamide, 0.34 g of DNS-86, and 1.17 g of the chain transfer agent dodecyl mercaptan. After mixing, add 13 g of deionized water and stir at high speed for 30 min. The resulting mixture is denoted as the third mixed solution.

[0076] Then, the third mixed solution and the initiator solution prepared by dissolving 0.061 g of ammonium persulfate in 10 g of deionized water are slowly added dropwise to the reaction system of the second mixed solution described above, and it is approximately controlled to finish dropping in 1 h. Keep the reaction at 78 °C for 4 h to obtain the fluorescent antifouling high-strength "three-in-one" functional fluorinated polyacrylate soap-free emulsion.

[0077] Example 5 A method for preparing a fluorinated polyacrylate soap-free emulsion, comprising the following steps: Step 1) Preparation of the fluorescent multifunctional monomer: Under ice bath conditions (0 °C), first add 3 g (50 mmol) of ethylenediamine to a three-necked flask equipped with a stirring device. Then, weigh 3.02 g (10 mmol) of perfluorobutylsulfonyl fluoride in a constant pressure funnel and slowly add it dropwise to the above three-necked flask. After the dropping is completed, keep the reaction at 0 °C for 6 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.

[0078] In a new three-necked flask equipped with a stirrer and a condenser, successively add 2 g (7.22 mmol) of 4-bromo-1,8-naphthalic anhydride, 3.38 g (21.66 mmol) of allylamine hydrochloride, and 0.87 g (21.66 mmol) of sodium hydroxide. Then add 90 ml of ethanol and stir to dissolve. Keep stirring and reacting 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 dry it under vacuum at 50 °C for 12 h to obtain a light yellow powder, denoted as the intermediate BANA.

[0079] In a new three-necked flask equipped with a stir bar and a condenser, 1 g (3.16 mmol) of BANA and 3.24 g (9.48 mmol) of PFSF-E were successively added, and then 50 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 three 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 multifunctional monomer (BANA-F).

[0080] Step 2) Preparation of fluorinated polyacrylate soap-free emulsion: Take 0.4 g of the fluorescent multifunctional monomer, 6 g of butyl acrylate, 0.18 g of DNS-86, and 0.62 g of the chain transfer agent dodecyl mercaptan. After mixing, 18 g of deionized water was added and stirred at high speed for 30 min. The resulting mixture was designated as the first mixed solution. Under the protection of nitrogen, the first mixed solution was heated to 78 °C, and an aqueous solution of 0.0742 g of ammonium persulfate dissolved in 5 g of deionized water was added, and the polymerization reaction was started at 78 °C for 1 h to obtain the second mixed solution.

[0081] Take 10 g of trifluoroethyl methacrylate, 2 g of butyl acrylate, 1 g of N-methylolacrylamide, 0.4 g of DNS-86, and 1.38 g of the chain transfer agent dodecyl mercaptan. After mixing, 13 g of deionized water was added and stirred at high speed for 30 min. The resulting mixture was designated as the third mixed solution.

[0082] Then, the third mixed solution and the initiator solution of 0.0857 g of ammonium persulfate dissolved in 10 g of deionized water were slowly added dropwise to the above second mixed solution reaction system, and it was approximately controlled to finish dropping in 1 h, and the reaction was kept at 78 °C for 4 h to obtain the fluorescent antifouling high-strength "three-in-one" functional fluorinated polyacrylate soap-free emulsion.

[0083] Example 6 A preparation method of a fluorinated polyacrylate soap-free emulsion, comprising the following steps: Step 1) Preparation of the fluorescent multifunctional monomer: 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 maintained at 5 °C for 4 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 was obtained, designated as PFSF-E.

[0084] In a new three-necked flask equipped with a stir bar and a condenser, 2 g (7.22 mmol) of 4-bromo-1,8-naphthalic anhydride, 2.25 g (14.44 mmol) of allylamine hydrochloride and 0.58 g (14.44 mmol) of sodium hydroxide were successively added. Then, 93.5 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 three times and dried in vacuo at 50 °C for 12 h to obtain a light yellow powder, denoted as intermediate BANA.

[0085] In a new three-necked flask equipped with a stir bar and a condenser, 1 g (3.16 mmol) of BANA and 5.4 g (15.8 mmol) of PFSF-E were successively added. Then, 108.8 ml of DMSO was added and stirred until dissolved. The three-necked flask was heated under reflux at 110 °C 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 three 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 multifunctional monomer (BANA-F).

[0086] Step 2) Preparation of the fluorinated polyacrylate soap-free emulsion: 0.4 g of the fluorescent multifunctional monomer, 10 g of butyl acrylate, 0.3 g of DNS-86, and 1.03 g of the chain transfer agent dodecyl mercaptan were taken. After mixing, 18 g of deionized water was added and stirred at high speed for 10 min. The resulting mixture was denoted as the first mixture. Under the protection of nitrogen, the first mixture was heated to 75 °C, and an aqueous solution of 0.1236 g of ammonium persulfate dissolved in 5 g of deionized water was added. Polymerization reaction was carried out at 75 °C for 0.5 h to obtain the second mixture.

[0087] 6 g of dodecafluoroheptyl methacrylate, 2 g of butyl acrylate, 1 g of N-methylolacrylamide, 0.28 g of DNS-86, and 0.97 g of the chain transfer agent dodecyl mercaptan were taken. After mixing, 13 g of deionized water was added and stirred at high speed for 10 min. The resulting mixture was denoted as the third mixture.

[0088] Then, the third mixture and the initiator solution of 0.0363 g of ammonium persulfate dissolved in 10 g of deionized water were slowly added dropwise to the above second mixture reaction system, and it was approximately controlled to be added dropwise within 2 h. The reaction was carried out at 75 °C for 4 h to obtain the fluorescent antifouling high-strength "three-in-one" functional fluorinated polyacrylate soap-free emulsion.

[0089] Example 7 A preparation method of a fluorinated polyacrylate soap-free emulsion, comprising the following steps: Step 1) Preparation of a fluorescent multifunctional monomer: Under ice bath conditions (3 °C), first add 4.2 g (70 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 dropwise addition, keep the reaction at 3 °C for 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.

[0090] In a new three-necked flask equipped with a stirrer and a condenser, successively add 2 g (7.22 mmol) of 4-bromo-1,8-naphthalic anhydride, 5.63 g (36.1 mmol) of allylamine hydrochloride, and 1.45 g (36.1 mmol) of sodium hydroxide, then add 160 ml of ethanol and stir to dissolve. Stir and react at 85 °C for 8.5 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 yellow powder, denoted as intermediate product BANA.

[0091] In a new three-necked flask equipped with a stirrer and a condenser, successively add 1 g (3.16 mmol) of BANA and 2.16 g (6.352 mmol) of PFSF-E, then add 50 ml of DMSO and stir to dissolve. Place the three-necked flask in a heating reflux reaction at 105 °C for 7.5 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 multifunctional monomer (BANA-F).

[0092] Step 2) Preparation of the fluorinated polyacrylate soap-free emulsion: Take 0.4 g of the fluorescent multifunctional monomer, 10 g of butyl acrylate, 0.3 g of DNS-86, 1.03 g of the chain transfer agent dodecyl mercaptan, mix them and then add 18 g of deionized water and stir at high speed for 20 min. The resulting mixture is denoted as the first mixture. Under the protection of nitrogen, the first mixture is heated to 80 °C, and an aqueous solution of 0.1236 g of ammonium persulfate dissolved in 5 g of deionized water is added, and the polymerization reaction starts at 80 °C for 40 min to obtain the second mixture.

[0093] Take 6 g of dodecafluoroheptyl methacrylate, 2 g of butyl acrylate, 1 g of N-hydroxymethyl acrylamide, 0.28 g of DNS-86, and 0.97 g of chain transfer agent dodecyl mercaptan. After mixing, add 13 g of deionized water and stir at high speed for 20 min. The resulting mixture is denoted as the third mixture.

[0094] Then, the third mixture and the initiator solution prepared by dissolving 0.0363 g of ammonium persulfate in 10 g of deionized water are slowly added dropwise to the reaction system of the second mixture above, and it is approximately controlled to finish dropping in 1.5 h. Keep the reaction at 80 °C for 4 h to obtain the fluorescent antifouling high-strength "three-in-one" functional fluorinated polyacrylate soap-free emulsion.

[0095] Figure 3 This is the UV-Vis absorption spectrum of the fluorescent multifunctional monomer and its intermediate prepared in Example 1 of the present invention. As Figure 3 shown, the intermediate product BANA has two absorption peaks at 253 nm and 342 nm; the UV absorption peak of the fluorescent multifunctional monomer BANA-F at 342 nm has no obvious change, but the UV absorption peak at 253 nm is red-shifted to 261 nm. This is because the electron-donating group connected to the 4th position of BANA-F increases the conjugated system, reduces the energy gap of the molecular orbitals, and lowers the electron transition energy, resulting in the absorption peak shifting to a lower wavenumber. In addition, the UV absorption peak formed at 435 nm belongs to the sulfonamide group. The above results illustrate the successful synthesis of the fluorescent multifunctional monomer BANA-F.

[0096] Figure 4 This is the fluorescence emission spectrum of the reaction raw materials 4-bromo-1,8-naphthalic anhydride (BA), the intermediate product 4-bromo-N-allyl-1,8-naphthalenedicarboxamide (BANA), and the fluorescent multifunctional monomer (BANA-F). As Figure 4 shown, the maximum emission wavelengths of BA and BANA are at 515 nm, while the maximum emission wavelength of BANA-F is at 535 nm, with a red shift of 20 nm. This is attributed to the increased conjugation degree in the structure of BANA-F, the increase in the π→π* conjugated plane, which leads to enhanced delocalization of π electrons in the system and a decrease in energy, thus making the emission wavelength longer. The above results illustrate that the synthesized monomer BANA-F has fluorescence function.

[0097] Figure 5 From left to right are the optical photos of the emulsions obtained in Examples 1 to 3 under a 365 nm ultraviolet lamp. From Figure 5 it can be seen that several emulsions show blue-green to green under ultraviolet lamp irradiation, indicating that the synthesized emulsions have fluorescence properties.

[0098] The soap-free emulsion of fluorescent multifunctional fluorinated polyacrylate prepared in Examples 1 to 3 was used for fabric finishing, which specifically included the following steps: 100% twill cotton fabric with a density size (warp × weft, roots per inch): 133×72 was cut into specimens with a length × width of 2 cm × 1 cm. Under the temperature condition of 25±2°C, it was ultrasonically washed with acetone and distilled water in sequence for 15 min, and then dried at 80°C. Take 1 g of the soap-free emulsion of fluorescent multifunctional fluorinated polyacrylate, dilute it with 100 parts of water and prepare a working bath solution at 40°C. The fabric sample was finished by a small experimental padding mangle in a one-dip-one-roll manner, and the liquor pickup was controlled at 70%. Then the fabric sample was dried at 100°C for 5 min and then heat-set and baked at 170°C for 3 min.

[0099] Figure 6 It is a graph showing the change of the static contact angle of surface water on the fabric treated with the emulsions obtained in Examples 1 to 3 over time. As Figure 6 shown, the initial contact angles on the surfaces of the fabrics finished in Examples 1 to 3 were approximately 130°. After 30 s, it was about 125°, and it only dropped to about 120° after 120 s, indicating that the fabrics finished with the soap-free emulsion of fluorescent multifunctional fluorinated polyacrylate had good hydrophobic stability.

[0100] Figure 7 It is a stress-strain curve graph of the latex films of the emulsions obtained in Examples 1 to 3. As Figure 7 shown, the stresses of the latex films of the emulsions prepared in Examples 1 to 3 were all about 18 MPa, and the strains were in the range of 268% - 332%. For polyacrylate films, they had very good mechanical properties, which benefited from the riveting cross-linking effect of the rigid naphthalene ring centers in the polymer chains and the chemical cross-linking effect formed by the self-crosslinking groups containing nitrogen hydroxymethyl or silane oxy groups between the molecular chains.

[0101] Although the preferred embodiments of the present invention have been described, those skilled in the art can make additional changes and modifications to these embodiments once they know the basic creative concepts. Therefore, the appended claims are intended to be construed to include the preferred embodiments as well as all changes and modifications falling within the scope of the present invention.

[0102] 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 also intends to include these modifications and variations.

Claims

1. A preparation method of a fluorescent functional monomer, characterized in that It includes the following steps: Under ice bath conditions, using ethylenediamine and perfluorobutanesulfonyl fluoride as raw materials, a nucleophilic substitution reaction occurs to obtain N-aminoethyl-perfluorobutanesulfonamide; In an alcoholic organic solvent, with sodium hydroxide as a neutralizing agent, 4-bromo-1,8-naphthalic anhydride and allylamine hydrochloride are added, and an acylation reaction occurs to obtain an intermediate product; In a sulfur-containing organic solvent, N-aminoethyl-perfluorobutanesulfonamide and the intermediate product undergo an alkylation reaction to obtain a fluorescent functional monomer.

2. The preparation method of a soap-free fluorinated polyacrylate emulsion according to claim 1, characterized in that, The reaction temperature of the nucleophilic substitution reaction is 0°C to 5°C, and the reaction time is 4h to 6h.

3. The preparation method of a soap-free fluorinated polyacrylate emulsion according to claim 1, characterized in that, The molar ratio of ethylenediamine to perfluorobutanesulfonyl fluoride is 3 to 7:

1.

4. The preparation method of a soap-free fluorinated polyacrylate emulsion according to claim 1, characterized in that, The reaction temperature of the acylation reaction is 80°C to 90°C, and the reaction time is 8h to 9h.

5. The preparation method of a soap-free fluorinated polyacrylate emulsion according to claim 1, characterized in that, The molar ratio of 4-bromo-1,8-naphthalic anhydride to allylamine hydrochloride is 1:2 to 5; The molar ratio of sodium hydroxide to allylamine hydrochloride is 1:1; The addition amount of the alcoholic organic solvent is 20 to 22 times the total mass of 4-bromo-1,8-naphthalic anhydride and allylamine hydrochloride.

6. The preparation method of a soap-free fluorinated polyacrylate emulsion according to claim 1, characterized in that, 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 soap-free fluorinated polyacrylate emulsion according to claim 1, characterized in that, The molar ratio of the intermediate product to N-aminoethyl-perfluorobutanesulfonamide is 1:2 to 5; The addition amount of the sulfur-containing organic solvent is 15 to 17 times the total mass of the intermediate product and N-aminoethyl-perfluorobutanesulfonamide.

8. A fluorescent functional monomer prepared by the preparation method according to any one of claims 1 to 7.

9. A preparation method of a fluorinated polyacrylate soap-free emulsion, characterized in that, It includes the following steps: Stir the fluorescent functional monomer, the first polymerizable non-fluorine monomer, the first emulsifier and the first chain transfer agent according to claim 8 evenly to obtain a first mixed solution; under the protection of nitrogen, at 75 - 80°C, add a first initiator to the first mixed solution, and a polymerization reaction occurs to obtain a second mixed solution; Mix the polymerizable fluorine-containing monomer, the second polymerizable non-fluorine monomer, the self-crosslinking monomer, the second emulsifier and the second chain transfer agent evenly to obtain a third mixed solution; Add the third mixed solution and the second initiator solution to the second mixed solution, and a polymerization reaction occurs to obtain a fluorinated polyacrylate soap-free emulsion.

10. A fluorinated polyacrylate soap-free emulsion prepared by the preparation method according to claim 9.

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