Antibacterial long-acting hydrophilic antifogging liquid as well as preparation method and application thereof

Abstract

The invention discloses antibacterial long-acting hydrophilic antifogging liquid as well as a preparation method and application thereof, and belongs to the field of functional coating materials. The antifogging liquid comprises the following raw materials in parts by mass: 4-15 parts of a compound A; 0.1-3 parts of a coalescing agent; 0.1 to 2 parts of a solubilizer; 80 to 93 parts of water; the special molecular structure compound A with siloxane at one end, a polyether chain segment at the other end and an amino group in the middle is introduced and has a synergistic effect with other components, so that the antifogging liquid has excellent antibacterial performance and lasting antifogging performance while having good film-forming property. Meanwhile, the surface of a transparent material or a metal base material is coated with the compound A, the molecular weight of the compound A can be controlled according to different base materials, the performance of the antifogging liquid is flexibly regulated and controlled, and diversified requirements are met.

Description

Technical Field

[0001] The present invention belongs to the field of functional coating materials, and in particular relates to an antibacterial long-lasting hydrophilic anti-fog liquid and a preparation method and application thereof. Background Art

[0002] In daily life and industrial production, the surfaces of transparent materials such as glass and plastic are easily fogged due to temperature differences, resulting in blurred vision and affecting the use effect. For example, the fogging problem of car windshields, bathroom mirrors, medical endoscopes, protective masks, etc. is not only inconvenient, but may also cause safety hazards in key areas such as medical care and transportation. At present, the common anti-fog liquids on the market are mostly based on surfactants to reduce surface tension to achieve anti-fog effect, but such anti-fog liquids have problems such as short anti-fog effect and single function. In actual use, the anti-fog effect of traditional surfactant-based anti-fog liquids can usually only last for a few hours.

[0003] Furthermore, in places like hospitals and food processing facilities, transparent surfaces pose a risk of bacterial growth, potentially leading to cross-infection. Therefore, developing anti-fog fluids that combine long-lasting anti-fog properties with hydrophilicity and antibacterial properties is crucial. Currently, few products effectively combine these functions, and some suffer from defects such as unstable ingredients and environmental unfriendliness. Furthermore, research into efficient synthesis methods for halogenated monomethoxylated polyethylene glycol and its derivatives, important intermediates, requires further refinement to meet the demands of multifunctional material preparation. Summary of the Invention

[0004] In response to the problems of poor time-efficiency of anti-fog liquid coatings in the prior art and the high probability of bacterial growth on the surface due to moisture absorption, the first objective of the present invention is to provide an antibacterial and long-lasting hydrophilic anti-fog liquid. By introducing a compound A with a specific structure to work synergistically with other components, the anti-fog liquid has good film-forming properties, as well as excellent antibacterial and long-lasting anti-fog properties.

[0005] The second object of the present invention is to provide a method for preparing an antibacterial long-lasting hydrophilic anti-fog liquid, which has the advantages of simple process and easy industrial production.

[0006] The third object of the present invention is to provide an application of an antibacterial, long-lasting hydrophilic anti-fog liquid, which is coated on the surface of a transparent material or a metal substrate. The molecular weight of compound A can be controlled according to different substrates, and the performance of the anti-fog liquid can be flexibly adjusted to meet diverse needs.

[0007] In order to achieve the above technical objectives, the present invention provides an antibacterial long-lasting hydrophilic anti-fog liquid, comprising the following raw materials in parts by weight: 4 to 15 parts of compound A; 0.1 to 3 parts of a film-forming aid; 0.1 to 2 parts of a solubilizer; and 80 to 93 parts of water; wherein the compound A has the structural formula 1:

[0008] ;

[0009] Formula 1;

[0010] wherein R1 is H or a C1-C6 alkyl group; m is an integer from 0 to 6, such as 0, 1, 2, 3, 4, 5 or 6; n is an integer from 4 to 227, such as 4, 11, 45, 51, 68, 117 or 227; R2, R3 and R4 are independently selected from one of substituted or unsubstituted phenyl, H and a C1-C30 alkyl group; R5 is selected from one of substituted or unsubstituted phenyl, a C1-C30 alkyl group and a C1-C30 alkyl group containing a heteroatom in the carbon chain; when the phenyl group is substituted, the substituent is selected from at least one of methyl, ethyl and methoxy, and the substitution may be monosubstituted or polysubstituted; and X is a halogen.

[0011] In the technical solution of the present invention, the molecular structure design of Compound A is key to the control of the anti-fog liquid. Specifically, the siloxy groups at the molecular ends of Compound A firmly bond to the substrate surface through hydrolysis and condensation, forming a stable chemical anchor, ensuring the durability of the anti-fog film. Meanwhile, the hydrophilic polyether segment at the other end extends toward the air interface, rapidly adsorbing water molecules from the environment and evenly spreading them into a hydrophilic film, thereby instantly eliminating fog droplets. Of particular importance is the antibacterial amino group located in the middle of the molecule, which not only spatially connects the hydrophilic and hydrophobic segments but also, after film formation, is distributed within the three-dimensional network constructed by the molecular chains. This enables sustained and long-term destruction of bacterial structure and inhibition of bacterial proliferation, thereby avoiding the attenuation of anti-fog performance caused by biofilm formation. This synergistic effect of "anchoring-hydrophilic-antibacterial" enables the anti-fog liquid to form an orderly molecular film on the substrate surface, significantly improving the service life and reliability of the anti-fog liquid in harsh environments such as high temperature and high humidity. Experiments have found that when the molecular weight of compound A is less than or equal to 4000, the anti-fog liquid has better adhesion performance, and when the molecular weight of compound A is higher than 4000, the anti-fog liquid has stronger hydrophilicity.

[0012] Experiments have also found that the coordination and dosage control of the various components in the anti-fog liquid also affect the performance of the anti-fog liquid. In the present invention, the addition of a film-forming aid can enhance the film-forming and adhesion of the anti-fog liquid on the material surface, while a solubilizer can improve the solubility and stability of each component in the system. Water mainly acts as a solvent to adjust the concentration and viscosity of the anti-fog liquid to ensure smooth spraying of the anti-fog liquid. When the dosage of compound A is too low, it will result in low hydrophilic group coverage, inability of droplets to spread, discontinuous coating, uneven anti-fog area, and poor anti-fog durability. When the dosage of compound A is too high, the anti-fog effect will no longer be improved or may even be reduced. Due to the limited adsorption sites on the substrate surface, excess derivative molecules cannot continue to adsorb and can only remain free in the solution or accumulate on the coating surface, and the coating contact angle cannot be further reduced. Excess molecules aggregate on the substrate surface to form a "thick film". Slight agglomeration of polyether chains or stacking of aminosiloxane chains will cause the coating to appear "slightly turbid", which in turn leads to a decrease in transmittance.

[0013] Furthermore, the antibacterial, long-lasting, hydrophilic, and anti-fog liquid comprises the following raw materials in parts by weight: 8-10 parts of compound A; 0.1-2 parts of a film-forming aid; 0.1-1.5 parts of a solubilizer; and 85-93 parts of water. The heteroatoms in the C1-C30 alkyl group containing heteroatoms are common heteroatoms, such as O, N, and S.

[0014] As a preferred solution, the film-forming aid includes at least one of polyvinyl alcohol and acrylic resin.

[0015] As a preferred solution, the solubilizer includes propylene glycol.

[0016] As a preferred solution, the compound A has a structural formula of Formula 2 or Formula 3:

[0017] ;

[0018] Formula 2;

[0019] ;

[0020] Formula 3;

[0021] wherein n is an integer from 4 to 227; R2, R3, and R4 are independently selected from one of monosubstituted phenyl, H, and a C1-C10 alkyl group; R5 is selected from one of monosubstituted phenyl, a C1-C30 alkyl group, and a C1-C10 alkyl group containing a heteroatom in the carbon chain; when the phenyl group is monosubstituted, the substituent is selected from one of methyl, ethyl, and methoxy; and X is a halogen.

[0022] As a preferred solution, the compound A is obtained by substitution reaction of aminosiloxane with a halogenated polyether compound. The reaction product after; the aminosiloxane has the structural formula 4:

[0023] ;

[0024] Formula 4;

[0025] The halogenated polyether compound has the structural formula 5:

[0026] ;

[0027] Formula 5;

[0028] wherein R1 is H or a C1-C6 alkyl group; m is an integer from 0 to 6; n is an integer from 4 to 227; X is a halogen, such as Br, Cl, F, etc.; R2, R3, and R4 are independently selected from one of substituted or unsubstituted phenyl, H, and a C1-C30 alkyl group; R5 is selected from one of substituted or unsubstituted phenyl, a C1-C30 alkyl group, and a C1-C30 alkyl group containing a heteroatom in the carbon chain; and when the phenyl group is substituted, the substituent is selected from at least one of methyl, ethyl, and methoxy.

[0029] The preparation of compound A of the present invention is achieved through the interaction between the halogen X in formula 5 and the active amino group in formula 4, thereby obtaining a unique molecular structure of the present invention having a siloxane at one end, a polyether segment at the other end, and an amino group in the middle. This preparation method has the advantages of simple operation and strong reproducibility.

[0030] As a preferred solution, the halogenated polyether compound has a structural formula of Formula 6 or Formula 7:

[0031] ;

[0032] Formula 6;

[0033] ;

[0034] Formula 7;

[0035] Wherein, n is an integer ranging from 4 to 227.

[0036] As a preferred solution, the substitution reaction The conditions are: temperature of 50~150℃, time of 1~12h, and addition of alkaline catalyst and reaction solvent.

[0037] As a preferred solution, the amount of the alkaline catalyst is 0.1-5 wt% of the total mass of the aminosiloxane and the halogenated polyether compound; the reaction solvent is selected from at least one of toluene, xylene, tetrahydrofuran, and N,N-dimethylformamide (DMF); the alkaline catalyst can be selected from a strong inorganic base or an organic base; wherein the strong inorganic base includes one of sodium hydroxide, potassium hydroxide, and sodium carbonate; and the organic base is selected from one of triethylamine and pyridine.

[0038] As a preferred solution, the halogenated polyether compound is prepared by: performing a base-catalyzed reaction between compound B and a dihalogenated alkane in an organic solvent;

[0039] Compound B has the structural formula 8:

[0040] ;

[0041] Formula 8;

[0042] The dihaloalkane has the structural formula 9:

[0043] ;

[0044] Formula 9;

[0045] Wherein, R1 is H or a C1-C6 alkyl group; m is an integer from 0 to 6; n is an integer from 4 to 227; and X is a halogen.

[0046] In the present invention, compound B with different molecular weights is subjected to a base-catalyzed reaction with a dihalogenated alkane to obtain halogenated polyether compounds with different molecular weights, thereby controlling the molecular weight of compound A and ultimately controlling the performance of the anti-fog liquid.

[0047] As a preferred solution, the molecular weight of the compound B is 200 to 10,000, and has a structural formula of Formula 10 or Formula 11:

[0048] ;

[0049] Formula 10;

[0050] ;

[0051] Formula 11;

[0052] Wherein, n is an integer ranging from 4 to 227.

[0053] As a preferred embodiment, the organic solvent is selected from at least one of dichloromethane, chloroform, tetrahydrofuran, and N,N-dimethylformamide, more preferably N,N-dimethylformamide. The amount of the organic solvent used is controlled to achieve a concentration of compound B in the reaction system of 0.5 to 1 mol / L.

[0054] As a preferred solution, the base-catalyzed reaction uses at least one of potassium carbonate, sodium carbonate, sodium hydroxide, and potassium hydroxide as a catalyst; potassium carbonate is more preferred.

[0055] As a preferred solution, the molar ratio of the catalyst to compound B is (1.2-2.0):1. More preferably, it is 1.8:1.

[0056] As a preferred embodiment, the base-catalyzed reaction conditions are: a temperature of 40-70°C, a reaction time of 12-24 hours, and a molar ratio of compound B to dihaloalkane of 1:(0.5-3). Within the reaction temperature and time range of the present invention, the reaction yield is guaranteed while reducing the formation of by-products. More preferably, the temperature is 60-70°C and the reaction time is 16-20 hours.

[0057] As a preferred embodiment, after the base-catalyzed reaction is completed, the reaction solution is cooled to room temperature, the solid precipitate is filtered to remove, the reaction solution is washed with a saturated sodium bicarbonate solution to remove acidic impurities, then washed with deionized water until neutral, and finally dried over anhydrous sodium sulfate. After filtration, the solvent is distilled off under reduced pressure, and the crude product is purified by column chromatography. Furthermore, elution is performed using a mixed solution of petroleum ether and ethyl acetate.

[0058] The present invention also provides a method for preparing an antibacterial, long-lasting hydrophilic anti-fog liquid, which is prepared by sequentially adding compound A, a film-forming aid, and a solubilizer to water, mixing the mixture under stirring, and filtering. The method of the present invention has the advantages of being simple and easy to industrialize.

[0059] As a preferred solution, the stirring speed is 350-500 r / min, the time is 40-60 min, and the mixture is filtered through a 0.45 μm filter membrane to remove impurities, and then the mixture is dispensed into sealed containers.

[0060] Finally, the present invention provides an application of an antibacterial, long-lasting hydrophilic antifog liquid for preparing antibacterial and antifog coatings. The molecular weight of compound A can be controlled based on the substrate, flexibly regulating the performance of the antifog liquid to meet diverse needs and effectively extending the service life of transparent materials and metal substrates.

[0061] As a preferred solution, the application process is achieved by coating on the surface of a transparent material or a metal substrate, and the coating methods include but are not limited to spray coating, flow coating and dipping.

[0062] As a preferred solution, the coating is followed by heating and curing to form a film, and the heating temperature is 100°C to 140°C.

[0063] Compared with the prior art, the present invention has the following beneficial effects:

[0064] (1) The halogenated polyether compound of the present invention is simple to operate and has strong repeatability by reacting compound B with different molecular weights with dihaloalkane. The optimized separation and purification steps can effectively improve the purity of the product and provide high-quality raw materials for the preparation of the core component of the anti-fog liquid.

[0065] (2) The anti-fog liquid provided by the present invention firmly bonds to the surface of the substrate through hydrolysis and condensation by introducing a specific silanol group at the end of the molecule of compound A, forming a stable chemical anchor, thereby ensuring the durability of the anti-fog film. The hydrophilic polyether segment at the other end extends to the air interface, quickly adsorbs water molecules in the environment and evenly spreads them into a hydrophilic film, thereby instantly eliminating fog droplets. At the same time, together with the amino group in the middle segment, a synergistic effect of "anchoring-hydrophilicity-antibacterial" is produced, allowing the anti-fog liquid to form an orderly molecular film on the surface of the substrate, significantly improving the service life and reliability of the anti-fog liquid in harsh environments such as high temperature and high humidity.

[0066] (3) The anti-fog liquid of the present invention has an anti-fog effect of more than 72 hours, which is significantly better than traditional anti-fog liquids. It also has a certain inhibitory effect on common bacteria such as Escherichia coli and Staphylococcus aureus, meeting the antibacterial needs of general scenarios. After testing, the minimum inhibitory concentration of the anti-fog liquid against Escherichia coli is 27μg / mL, and the minimum inhibitory concentration against Staphylococcus aureus is 24μg / mL.

[0067] (4) The anti-fog liquid of the present invention forms a uniform, firm film layer on the surface of the material through the synergistic effect of compound A, film-forming aid and solubilizer, which is not easy to fall off. At the same time, the stability and storage life of the anti-fog liquid are improved, and the anti-fog liquid has good comprehensive performance.

[0068] (5) The preparation method of the present invention is simple to operate, has low equipment requirements, is suitable for large-scale industrial production, and reduces production costs. At the same time, by selecting compound A with different molecular weights, the performance of the anti-fog liquid can be flexibly adjusted to meet diverse needs. BRIEF DESCRIPTION OF THE DRAWINGS

[0069] Figure 1 Comparison of the anti-fog effects of the antibacterial long-lasting hydrophilic anti-fog liquid prepared in Example 1 of the present invention: without anti-fog liquid (a); with anti-fog liquid (b).

[0070] Figure 2 CH3-(CH2CH2O) prepared in Example 1 of the present invention 11 -OCH2CH2Br NMR spectrum. DETAILED DESCRIPTION

[0071] The present invention is further described below with reference to specific embodiments, but the scope of protection of the present invention is not limited to the following specific embodiments. Obviously, the embodiments described below are only a part of the embodiments, and all other embodiments obtained by professionals in this field without making creative efforts are still within the scope of protection of the present invention.

[0072] Unless otherwise specified, all raw materials, reagents, instruments, and equipment used in the present invention can be purchased from the market or prepared by existing methods. Polyvinyl alcohol used in the Examples and Comparative Examples of the present invention was purchased from a chemical reagent platform with CAS number: 9002-89-5, and acrylic resin was purchased from a chemical reagent platform with CAS number: 9003-01-4.

[0073] Example 1

[0074] An antibacterial, long-lasting hydrophilic anti-fog liquid is composed of the following raw material components, calculated by mass percentage: 5% of compound A, 2% of polyvinyl alcohol, 1.5% of propylene glycol, and the balance being deionized water.

[0075] The preparation process for the antibacterial, long-lasting hydrophilic anti-fog liquid is as follows: polyvinyl alcohol and propylene glycol are first added to deionized water and stirred to dissolve at a stirring speed of 300 r / min. Compound A is then added and stirring is continued for 40 minutes. The mixed solution is filtered through a 0.45 μm filter membrane and dispensed into sealed containers.

[0076] Wherein, compound A has the following structural formula, and n is 11:

[0077] ;

[0078] Formula 12;

[0079] The preparation process of compound A is as follows: using CH3-(CH2CH2O) 11 The halogenated polyether compound of -OCH2CH2Br is reacted with an aminosiloxane having formula 13, wherein the reaction uses a catalyst sodium hydroxide in an amount of 1wt% of the total mass of the reactants; the reaction solvent is N,N-dimethylformamide (DMF); the reaction temperature is 60°C; and the reaction time is 5h.

[0080] ;

[0081] Formula 13;

[0082] Among them, R2, R3, and R4 are all methyl groups; and R5 is -(CH2)3OCH2-.

[0083] CH3-(CH2CH2O) 11The synthesis of -OCH2CH2Br is carried out according to the following steps:

[0084] S1 weighs 0.1 mol of CH3-(CH2CH2O) with a number average molecular weight of 500 11 -OH and 0.15 mol of dibromoethane.

[0085] S2 will (CH3-(CH2CH2O) 11 -OH) was added into 150 mL of dichloromethane to make its concentration in the reaction system 0.67 mol / L.

[0086] S3: Add 0.13 mol of potassium carbonate to the reaction system, and stir the reaction at 50° C. under nitrogen protection for 18 h.

[0087] After the reaction in step S4 is completed, the reaction solution is cooled to room temperature, the solid precipitate is removed by filtration, the reaction solution is washed with a saturated sodium bicarbonate solution, and then washed with deionized water until neutral, and dried over anhydrous sodium sulfate. After filtration, the solvent is removed by distillation under reduced pressure, and the crude product is purified by column chromatography using a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 4:1 as the eluent to obtain a halogenated polyether compound (CH3-(CH2CH2O) 11 -OCH2CH2Br), the yield was 82% and the purity was 94%.

[0088] Figure 1 To compare the anti-fog effect of the anti-fog liquid prepared in this example, it was spray-coated on a transparent PC board and the bottom was heated in a water bath to test the anti-fog effect. (a) shows the board without anti-fog liquid, and (b) shows the board with the anti-fog liquid of this example. It can be clearly seen that the present invention has a good anti-fog effect.

[0089] Figure 2 CH3-(CH2CH2O) prepared in this example 11 -OCH2CH2Br NMR spectrum, such as Figure 2 As shown, the compound structure: CH3-(CH2CH2O) 11-OCH2CH2Br, a total of 5 hydrogen environments (labeled as H1~H5): H1: terminal methyl hydrogen (-CH3), chemical shift of 3.34PPM; H2: methylene hydrogen directly connected to ether oxygen in the polyether chain (-OCH2-), chemical shift of 3.55-3.63PPM; H3: methylene hydrogen away from ether oxygen in the polyether chain (-CH2O-), chemical shift of 3.43-3.51PPM; H4: methylene hydrogen connected to ether oxygen at the bromoethyl end (-OCH2-), chemical shift of 3.69-3.75PPM; H5: methylene hydrogen connected to bromine at the bromoethyl end (-CH2Br), chemical shift of 3.47-3.53PPM; the peak integration ratio is H1:H2:H3:H4:H5≈3:22:22:2:2, which is consistent with the theoretical hydrogen atom number ratio (3:22:22 The results were completely consistent with those of the previous studies (n: 2: 2), confirming the number of repeating units in the polyether chain. The absence of hydroxyl peaks (no broad peak in the 3.0-5.0 range) ruled out unreacted hydroxyl impurities. The peak patterns (quartet + triplet) and chemical shifts of H4 and H5 at the bromoethyl end confirmed the presence of the -OCH2CH2Br structure. The H2 and H3 multiplet peaks (3.4-3.7) of the polyether chain were consistent with the methylene group characteristic of the ether bond, confirming the structure and chain length characteristics of the target compound.

[0090] Example 2

[0091] An antibacterial, long-lasting hydrophilic anti-fog liquid is composed of the following raw material components, calculated by mass percentage: 7% of compound A, 2.5% of acrylic resin, 1.8% of propylene glycol, and the balance being deionized water.

[0092] The preparation process for the antibacterial, long-lasting hydrophilic anti-fog liquid is as follows: acrylic resin and propylene glycol are first added to deionized water and stirred to dissolve at a stirring speed of 300 r / min. Compound A is then added and stirring is continued for 50 minutes. The mixed solution is filtered through a 0.45 μm filter membrane and dispensed into sealed containers.

[0093] Wherein, the structural formula of compound A is the same as formula 12, R2 and R3 are both methyl groups, R4 is phenyl, R5 is -(CH2)3OCH2-; and n is 45.

[0094] The preparation process of compound A is the same as that of Example 1, but CH3-(CH2CH2O) is used. 45 The synthesis of -OCH2CH2Br is carried out according to the following steps:

[0095] S1 weighs 0.1 mol of CH3-(CH2CH2O) with a number average molecular weight of 2000 45 -OH and 0.15 mol of dibromoethane.

[0096] S2 will CH3-(CH2CH2O) 45 -OH was added to 180 mL of N,N-dimethylformamide to make its concentration in the reaction system 0.56 mol / L.

[0097] S3: Add 0.18 mol of potassium carbonate to the reaction system, and stir the reaction at 60°C under nitrogen protection for 16 hours.

[0098] After the reaction in step S4 is completed, the mixture is cooled to room temperature and the subsequent treatment is the same as in Example 1 to obtain a halogenated polyether compound (CH3-(CH2CH2O) 45 -OCH2CH2Br), the yield was 80%, and the purity was 93%.

[0099] Example 3

[0100] An antibacterial, long-lasting hydrophilic anti-fog liquid is composed of the following raw material components, calculated by mass percentage: 10% of compound A, 2.2% of polyvinyl alcohol, 1.6% of propylene glycol, and the balance being deionized water.

[0101] The preparation process for the antibacterial, long-lasting hydrophilic anti-fog liquid is as follows: polyvinyl alcohol and propylene glycol are first added to deionized water and stirred to dissolve at a stirring speed of 400 r / min. Compound A is then added and stirred for 45 minutes. The mixed solution is filtered through a 0.45 μm filter membrane and dispensed into sealed containers.

[0102] Wherein, the structural formula of compound A is the same as formula 12, and R2 and R3 are , R4 is ethyl, R5 is -(CH2)3OCH2-, and n is 117.

[0103] The preparation process of compound A is the same as that of Example 1, but CH3-(CH2CH2O) is used. n The synthesis of -OCH2CH2Br is carried out according to the following steps:

[0104] S1 weighs 0.1 mol of CH3-(CH2CH2O) with a number average molecular weight of 5000 n -OH and 0.15 mol of dibromoethane.

[0105] S2 will CH3-(CH2CH2O) n -OH was added to 200 mL of N,N-dimethylformamide to make its concentration in the reaction system 0.5 mol / L.

[0106] S3: Add 0.18 mol of potassium carbonate to the reaction system, and stir the reaction at 70° C. under nitrogen protection for 12 h.

[0107] After the reaction in step S4 is completed, the mixture is cooled to room temperature and the subsequent treatment is the same as in Example 1 to obtain a halogenated polyether compound (CH3-(CH2CH2O) n -OCH2CH2Br), the yield was 84% ​​and the purity was 95%.

[0108] Example 4

[0109] An antibacterial, long-lasting hydrophilic anti-fog liquid is composed of the following raw material components, calculated by mass percentage: 4% of compound A, 2.2% of polyvinyl alcohol, 1.6% of propylene glycol, and the balance being deionized water.

[0110] The preparation process for the antibacterial, long-lasting hydrophilic anti-fog liquid is as follows: polyvinyl alcohol and propylene glycol are first added to deionized water and stirred to dissolve at a stirring speed of 450 r / min. Compound A is then added and stirred for 30 minutes. The mixed solution is filtered through a 0.45 μm filter membrane and dispensed into sealed containers.

[0111] Among them, the structural formula of compound A is the same as formula 12, R2 and R3 are both ethyl, R4 is methyl, R5 is -(CH2)3OCH2-, and n is 68.

[0112] The preparation process of compound A is the same as that of Example 1, but CH3-(CH2CH2O) is used. 68 The synthesis of -OCH2CH2Br is carried out according to the following steps:

[0113] S1 weighs 0.1 mol of CH3-(CH2CH2O) with a number average molecular weight of 3000 68 -OH and 0.2 mol of dibromoethane.

[0114] S2 will CH3-(CH2CH2O) 51 -OH was added to 150 mL of tetrahydrofuran to make its concentration in the reaction system 0.67 mol / L.

[0115] S3: Add 0.18 mol of potassium carbonate to the reaction system, and stir the reaction at 60° C. under nitrogen protection for 16 h.

[0116] After the reaction in step S4 is completed, the mixture is cooled to room temperature and the subsequent treatment is the same as in Example 1 to obtain a halogenated polyether compound (CH3-(CH2CH2O) 68 -OCH2CH2Br), the yield was 80%, and the purity was 90%.

[0117] Example 5

[0118] An antibacterial long-lasting hydrophilic anti-fog liquid is composed of the following raw material components, calculated by mass percentage: 7% of compound A, 2.2% of polyvinyl alcohol, 1.6% of propylene glycol, and the balance being deionized water.

[0119] The preparation process for the antibacterial, long-lasting hydrophilic anti-fog liquid is as follows: polyvinyl alcohol and propylene glycol are first added to deionized water and stirred to dissolve at a stirring speed of 450 r / min. Compound A is then added and stirred for 30 minutes. The mixed solution is filtered through a 0.45 μm filter membrane and dispensed into sealed containers.

[0120] Wherein, compound A has the following structural formula, and n is 51:

[0121] ;

[0122] Formula 14;

[0123] R2 and R3 are both butyl, R4 is ethyl, and R5 is -(CH2)3OCH2-.

[0124] The preparation process of compound A is the same as that of Example 1, but CH3-(CH2CH2CH2O) is used. 51 The synthesis of -OCH2CH2Br is carried out according to the following steps:

[0125] S1 weigh 0.1 mol of CH3-(CH2CH2CH2O) with a number average molecular weight of 3000 51 -OH and 0.2 mol of dibromoethane.

[0126] S2 will CH3-(CH2CH2CH2O) 51 -OH was added to 180 mL of N,N-dimethylformamide to make its concentration in the reaction system 0.55 mol / L.

[0127] S3: Add 0.18 mol of sodium carbonate to the reaction system, and stir the reaction at 65° C. under nitrogen protection for 18 h.

[0128] After the reaction in step S4 is completed, the mixture is cooled to room temperature and the subsequent treatment is the same as in Example 1 to obtain a halogenated polyether compound (CH3-(CH2CH2CH2O) 51 -OCH2CH2Br), the yield was 82% and the purity was 89%.

[0129] Comparative Example 1

[0130] The difference between this comparative example and Example 4 is that the same amount of halogenated polyether compound CH3-(CH2CH2O) is used. 51 -OCH2CH2Br replaced compound A, and the other steps and conditions were the same.

[0131] Among them, halogenated polyether compounds CH3-(CH2CH2O) 51 The synthesis of -OCH2CH2Br is the same as that in Example 4.

[0132] Comparative Example 2

[0133] The only difference between this comparative example and Example 3 is that an equal amount of aminosilicone is used to replace compound A, and the remaining steps and conditions are the same.

[0134] The structural formula of aminosiloxane is the same as that of formula 13, and R2 and R3 are , R4 is ethyl, and R5 is -(CH2)3OCH2-.

[0135] Comparative Example 3

[0136] The only difference between this comparative example and Example 4 is that the amount of compound A is changed to 20 wt %, and the other steps and conditions are the same.

[0137] Comparative Example 4

[0138] The only difference between this comparative example and Example 4 is that the amount of compound A is changed to 2 wt %, and the other steps and conditions are the same.

[0139] The antibacterial and long-lasting hydrophilic antifogging liquids of the examples and comparative examples were applied to the glass surface and cured to form films (at a temperature of 110° C.). The antifogging and antibacterial properties were tested, and the results are shown in Table 1.

[0140]

[0141] Note: The anti-fog performance test is carried out according to GB / T 31726-2015; the antibacterial performance test is carried out according to GB / T 31402-2015; the adhesion test method is the 100-grid method, and the test is carried out according to GB / T 9286-2021.

[0142] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. An antibacterial, long-lasting hydrophilic anti-fog liquid, characterized by: The method comprises the following raw materials in parts by weight: 4 to 15 parts of compound A; 0.1 to 3 parts of a film-forming aid; 0.1 to 2 parts of a solubilizer; and 80 to 93 parts of water. The compound A has the structural formula 1: ； Formula 1; wherein R1 is H or a C1-C6 alkyl group; m is an integer from 0 to 6; n is an integer from 4 to 227; R2, R3, and R4 are independently selected from one of substituted or unsubstituted phenyl, H, and a C1-C30 alkyl group; and X is a halogen; R5 is selected from one of substituted or unsubstituted phenyl, C1-C30 alkyl and C1-C30 alkyl containing heteroatoms in the carbon chain; When the phenyl group is substituted, the substituent is at least one selected from the group consisting of methyl, ethyl, and methoxy.

2. The antibacterial, long-lasting hydrophilic anti-fog liquid according to claim 1, characterized in that: The film-forming aid comprises at least one of polyvinyl alcohol and acrylic resin; The solubilizing agent includes propylene glycol; The compound A has a structural formula of Formula 2 or Formula 3: ； Formula 2; ； Formula 3; wherein n is an integer from 4 to 227; R2, R3, and R4 are independently selected from a monosubstituted phenyl group, H, and a C1-C10 alkyl group; R5 is selected from one of a monosubstituted phenyl group, a C1-C30 alkyl group, and a C1-C10 alkyl group containing a heteroatom in the carbon chain; When the phenyl group is monosubstituted, the substituent is selected from methyl, ethyl and methoxy, and X is halogen.

3. The antibacterial, long-lasting hydrophilic anti-fog liquid according to claim 1, characterized in that: The compound A is formed by a substitution reaction between aminosiloxane and a halogenated polyether compound. The reaction product after The aminosiloxane has the structural formula 4: ； Formula 4; The halogenated polyether compound has the structural formula 5: ； Formula 5; wherein R1 is H or a C1-C6 alkyl group; m is an integer from 0 to 6; n is an integer from 4 to 227; X is a halogen; R2, R3, and R4 are independently selected from one of substituted or unsubstituted phenyl, H, and a C1-C30 alkyl group; R5 is selected from one of substituted or unsubstituted phenyl, C1-C30 alkyl and C1-C30 alkyl containing heteroatoms in the carbon chain; when the phenyl is substituted, the substituent is selected from at least one of methyl, ethyl and methoxy.

4. The antibacterial, long-lasting hydrophilic anti-fog liquid according to claim 3, characterized in that: The halogenated polyether compound has a structural formula of Formula 6 or Formula 7: ； Formula 6; ； Formula 7; Wherein, n is an integer ranging from 4 to 227.

5. The antibacterial, long-lasting hydrophilic anti-fog liquid according to claim 3 or 4, characterized in that: The substitution reaction The conditions are: temperature of 50~150℃, time of 1~12h, and addition of alkaline catalyst and reaction solvent.

6. The antibacterial, long-lasting hydrophilic anti-fog liquid according to claim 3, characterized in that: The halogenated polyether compound is prepared by: performing a base-catalyzed reaction between compound B and dihalogenated alkane in an organic solvent; Compound B has the structural formula 8: ； Formula 8; The dihaloalkane has the structural formula 9: ; Formula 9; Wherein, R1 is H or a C1-C6 alkyl group; m is an integer from 0 to 6; n is an integer from 4 to 227; and X is a halogen.

7. The antibacterial, long-lasting hydrophilic anti-fog liquid according to claim 6, characterized in that: The compound B has a molecular weight of 200 to 10,000 and has a structural formula of Formula 10 or Formula 11: ； Formula 10; ； Formula 11; Wherein, n is an integer ranging from 4 to 227.

8. The antibacterial, long-lasting hydrophilic anti-fog liquid according to claim 6, characterized in that: The organic solvent is selected from at least one of dichloromethane, chloroform, tetrahydrofuran, and N,N-dimethylformamide; The base-catalyzed reaction uses at least one of potassium carbonate, sodium carbonate, sodium hydroxide, and potassium hydroxide as a catalyst; The conditions for the base-catalyzed reaction are: temperature of 40-70° C., reaction time of 12-24 h, and a molar ratio of compound B to dihalogenated alkane of 1:(0.5-3).

9. The method for preparing an antibacterial long-lasting hydrophilic anti-fog liquid according to any one of claims 1 to 8, characterized in that: Compound A, a film-forming aid and a solubilizer are sequentially added into water, mixed under stirring, and filtered to obtain the product.

10. Use of the antibacterial, long-lasting hydrophilic anti-fog liquid according to any one of claims 1 to 8, characterized in that: Used to prepare antibacterial and anti-fog functional coatings.

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