Antibacterial long-acting hydrophilic anti-fogging liquid, preparation method and application thereof

Abstract

The application discloses an antibacterial long-acting hydrophilic anti-fogging liquid as well as a preparation method and application thereof, and belongs to the field of functional coating materials. The anti-fogging liquid comprises the following raw materials in parts by mass: 4-15 parts of compound A; 0.1-3 parts of a film-forming aid; 0.1-2 parts of a solubilizer; and 80-93 parts of water. The application introduces a special molecular structure compound A with one end being a siloxane, the other end being a polyether chain segment and the middle being an amino group, and the compound A cooperates with other components to make the anti-fogging liquid have good film-forming property, excellent antibacterial property and long-lasting anti-fogging property. Meanwhile, the anti-fogging liquid is coated on the surface of a transparent material or a metal substrate, the molecular weight of the compound A can be controlled according to different substrates, the performance of the anti-fogging liquid can be flexibly regulated, and diversified requirements can be met.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of functional coating materials, and particularly relates to an antibacterial long-acting hydrophilic anti-fogging liquid as well as a preparation method and application thereof. BACKGROUND

[0002] In daily life and industrial production, the surface of transparent materials such as glass and plastic is prone to water fog due to temperature difference, which causes visual blurring and affects the use effect. For example, the windshield of a car, the mirror surface in a bathroom, a medical endoscope, a protective mask and the like, the fogging problem not only brings inconvenience, but also may cause safety hazards in key fields such as medical treatment and transportation. At present, the common anti-fogging liquid on the market is mostly based on surfactants to reduce the surface tension to achieve anti-fogging, but such anti-fogging liquid has problems such as short anti-fogging time and single function. In actual use, the anti-fogging effect of the traditional surfactant type anti-fogging liquid can usually only be maintained for several hours.

[0003] At the same time, in hospitals, food processing and other places, there is a risk of bacterial breeding on the surface of transparent materials, which may cause cross infection. Therefore, it is of great significance to develop an anti-fogging liquid with long-acting anti-fogging, hydrophilic performance and certain antibacterial ability. In the prior art, there are few products that effectively combine these functions, and some products have defects such as unstable composition and environmental unfriendliness. In addition, the efficient synthesis method of halogenated monomethoxylated polyethylene glycol and its derivatives as important intermediates still needs to be further improved to meet the needs of the preparation of multifunctional materials. SUMMARY

[0004] In view of the problems such as poor time efficiency of the anti-fogging liquid coating and easy breeding of bacteria on the surface due to moisture absorption in the prior art, a first object of the present application is to provide an antibacterial long-acting hydrophilic anti-fogging liquid, which has excellent antibacterial performance and long-lasting anti-fogging performance by introducing a compound A with a specific structure and other components to synergistically act, so that the anti-fogging liquid has good film-forming property.

[0005] A second object of the present application is to provide a preparation method of the antibacterial long-acting hydrophilic anti-fogging liquid, which has the advantages of simple process and easy industrial production.

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

[0007] In order to achieve the above technical objects, the present application provides an antibacterial long-acting hydrophilic anti-fogging liquid, which comprises the following raw materials by mass: 4-15 parts of compound A; 0.1-3 parts of film-forming aid; 0.1-2 parts of solubilizing agent; 80-93 parts of water; the compound A has a structural formula of formula 1:

[0008] ;

[0009] Formula 1

[0010] wherein, R1 is H or C1-C6 alkyl; 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, R4 are independently selected from one of substituted or unsubstituted phenyl, H and C1-C30 alkyl; R5 is selected from one of substituted or unsubstituted phenyl, C1-C30 alkyl and C1-C30 alkyl containing heteroatom in carbon chain; when phenyl is substituted, the substituent is selected from at least one of methyl, ethyl, methoxy, and when substituted, it can be either mono-substituted or multi-substituted, and X is halogen.

[0011] In the technical solution of the present application, the molecular structure design of compound A is the key to the control of the anti-fog liquid. Specifically, the siloxyl group at the end of the molecule in compound A is firmly combined with the surface of the substrate through hydrolysis and condensation, forming a stable chemical anchor, which ensures the durability of the anti-fog film; and the hydrophilic polyether chain segment at the other end extends to the air interface, quickly adsorbing water molecules in the environment and making them evenly spread into a hydrophilic film, thereby instantly eliminating fog droplets. What is particularly key is that the antibacterial amino group located in the middle of the molecule not only connects the hydrophilic and hydrophobic segments in space, but also is distributed in the three-dimensional network constructed by the molecular chain after film formation, which can continuously and long-acting destroy the structure of bacteria and inhibit their proliferation, thereby avoiding the attenuation of anti-fog performance caused by the formation of biofilm. This synergistic effect of "anchoring-hydrophilic-antibacterial" enables the anti-fog liquid to form an ordered 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. It is found that when the molecular weight of compound A is less than or equal to 4000, the anti-fog liquid has more excellent adhesion performance, and when the molecular weight of compound A is higher than 4000, the anti-fog liquid has stronger hydrophilicity.

[0012] And the experiment found that the mutual cooperation and the dosage control of each component in the anti-fog liquid also affect the performance of the anti-fog liquid, and the film-forming aid can enhance the film-forming property and adhesion of the anti-fog liquid on the material surface, the solubilizing agent can improve the solubility and stability of each component in the system, and the water is mainly used as a solvent to adjust the concentration and viscosity of the anti-fog liquid, so that the anti-fog liquid can be smoothly sprayed. When the amount of compound A is too low, the hydrophilic group coverage is low, the droplets cannot spread, the coating is discontinuous, the anti-fog area is uneven, and the anti-fog durability is poor. When the amount of compound A is too high, the anti-fog effect no longer improves or even decreases, because the adsorption sites on the substrate surface are limited, the excess derivative molecules cannot continue to be adsorbed and can only be free in the solution or stacked on the coating surface, and the contact angle of the coating cannot be further reduced; the excess molecules are aggregated on the substrate surface to form a "thick film", and the slight aggregation of polyether chains or the stacking of amino siloxane chains can cause the coating to appear "micro-turbidity", thereby causing the light transmittance to decrease.

[0013] Further, the antibacterial long-acting hydrophilic anti-fog liquid is composed of the following raw materials in mass parts: 8-10 parts of compound A; 0.1-2 parts of film-forming aid; 0.1-1.5 parts of solubilizing agent; 85-93 parts of water. The heteroatom in the C1-C30 alkyl containing a heteroatom in the present application is a common heteroatom, such as O, N, S, etc.

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

[0015] As a preferred scheme, the solubilizing agent includes propylene glycol.

[0016] As a preferred scheme, 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 of 4-227; R2, R3, R4 are independently selected from one of monosubstituted phenyl, H and C1-C10 alkyl; R5 is selected from one of monosubstituted phenyl, C1-C30 alkyl and C1-C10 alkyl containing a heteroatom in the carbon chain; the phenyl is monosubstituted, and the substituent is selected from one of methyl, ethyl and methoxy, and X is halogen.

[0022] As a preferred scheme, the compound A is obtained by substitution reaction of amino siloxane and halogenated polyether compound a reaction product of the amino siloxane and a halogenated polyether compound; the amino siloxane has a structural formula of Formula 4:

[0023] ;

[0024] Formula 4;

[0025] the halogenated polyether compound has a structural formula of Formula 5:

[0026] ;

[0027] Formula 5;

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

[0029] The preparation of the compound A of the present application is by the interaction of the halogen X in Formula 5 with the active amino group of Formula 4, thereby obtaining the special molecular structure of the present application with one end of siloxane, the other end of polyether segment and the middle of amino group, which has the advantages of simple operation and strong repeatability.

[0030] As a preferred scheme, 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 from 4 to 227.

[0036] As a preferred scheme, the substitution reaction is under the conditions of temperature from 50 to 150℃, time from 1 to 12h, and adding basic catalyst and reaction solvent.

[0037] As a preferred embodiment, the amount of alkaline catalyst is 0.1-5 wt% of the total mass of aminosiloxane and halogenated polyether compound, and 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 inorganic strong base or organic base; wherein, the inorganic strong 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 embodiment, the halopolyether compound is prepared by reacting compound B with a dihaloalkane in an organic solvent under alkaline catalysis.

[0039] Compound B has the structural formula of Formula 8:

[0040] ;

[0041] Formula 8;

[0042] Dihaloalkanes have the structural formula of formula 9:

[0043] ;

[0044] Equation 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 this invention, compounds B with different molecular weights are subjected to alkaline catalytic reactions with dihaloalkanes to obtain halogenated polyether compounds with different molecular weights, thereby controlling the molecular weight of compound A and ultimately controlling the performance of the antifogging liquid.

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

[0048] ;

[0049] Formula 10;

[0050] ;

[0051] Formula 11;

[0052] Where n is an integer 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 solvent used is controlled to ensure that the concentration of compound B in the reaction system is 0.5~1 mol / L.

[0054] As a preferred embodiment, the alkaline catalytic reaction uses at least one of potassium carbonate, sodium carbonate, sodium hydroxide, and potassium hydroxide as a catalyst; more preferably, potassium carbonate.

[0055] As a preferred embodiment, 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 h, and a molar ratio of compound B to dihaloalkane of 1:(0.5-3). Within the reaction temperature and time range of this invention, both the reaction yield and the generation of byproducts can be guaranteed. More preferably, the temperature is 60-70°C and the time is 16-20 h.

[0057] As a preferred embodiment, after the alkaline catalytic reaction is completed, the reaction solution is cooled to room temperature, filtered to remove the solid precipitate, washed with saturated sodium bicarbonate solution to remove acidic impurities, washed with deionized water until neutral, and finally dried with anhydrous sodium sulfate. After filtration, the solvent is removed by vacuum distillation, and the crude product is purified by column chromatography. Further, a mixed solution of petroleum ether and ethyl acetate is used for elution.

[0058] This invention also provides a method for preparing an antibacterial, long-lasting, hydrophilic, and anti-fogging liquid. The liquid is prepared by sequentially adding compound A, a film-forming aid, and a solubilizer to water, mixing them under stirring, and then filtering. The method of this invention has advantages such as simple process and ease of industrial production.

[0059] As a preferred embodiment, the stirring speed is 350~500 r / min, the time is 40~60 min, the filter is made with a 0.45 μm filter membrane to remove impurities, and then it is dispensed into sealed containers.

[0060] Finally, this invention also provides an application of an antibacterial, long-lasting, hydrophilic anti-fogging liquid, which is used to prepare antibacterial and anti-fogging functional coatings. This invention allows for flexible adjustment of the anti-fogging liquid's performance by controlling the molecular weight of compound A according to different substrates, meeting diverse needs, and effectively extending the service life of transparent materials and metal substrates.

[0061] As a preferred embodiment, the application process is achieved by coating on the surface of a transparent material or a metal substrate, and the coating method includes, but is not limited to, spraying, curtain coating and dip coating.

[0062] As a preferred option, the coating is cured by heating to form a film at a temperature of 100℃~140℃.

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

[0064] (1) The halogenated polyether compounds of the present invention are simple to operate and highly reproducible by reacting compound B with dihaloalkanes of different molecular weights. Through optimized separation and purification steps, the purity of the product can be effectively improved, providing high-quality raw materials for the preparation of the core components of antifogging liquid.

[0065] (2) The antifog liquid provided by the present invention introduces the silanoxy group at the end of the specific compound A molecule and binds firmly to the substrate surface through hydrolysis and condensation to form a stable chemical anchor, which ensures the durability of the antifog film. The hydrophilic polyether chain segment at the other end extends to the air interface, quickly adsorbs water molecules in the environment and spreads them evenly into a hydrophilic film, thereby eliminating fog droplets in time. At the same time, together with the amino group in the middle segment, it produces a synergistic effect of "anchoring-hydrophilic-antibacterial", which makes the antifog liquid form an ordered molecular film on the substrate surface, significantly improving the service life and reliability of the antifog liquid in harsh environments such as high temperature and high humidity.

[0066] (3) The anti-fogging liquid of the present invention has an anti-fogging time of more than 72 hours, which is significantly better than traditional anti-fogging 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. According to the test, the minimum inhibitory concentration of the anti-fogging liquid against Escherichia coli is 27 μg / mL, and the minimum inhibitory concentration against Staphylococcus aureus is 24 μg / mL.

[0067] (4) The anti-fogging liquid of the present invention, through the synergistic effect of compound A, film-forming aid and solubilizer, makes the film layer formed by the anti-fogging liquid on the material surface uniform, firm and not easy to fall off, while improving the stability and storage life of the anti-fogging liquid, and has good comprehensive performance.

[0068] (5) The preparation method of the present invention is simple to operate, requires little equipment, is suitable for large-scale industrial production, and reduces production costs. At the same time, the performance of the anti-fogging liquid can be flexibly adjusted by selecting compound A with different molecular weights to meet diverse needs. Attached Figure Description

[0069] Figure 1 Comparison of anti-fogging effects of the antibacterial long-lasting hydrophilic anti-fogging liquid prepared in Example 1 of the present invention: no anti-fogging liquid applied (a); anti-fogging liquid applied (b).

[0070] Figure 2 CH3-(CH2CH2O) prepared in Example 1 of this invention 11 The NMR spectrum of -OCH2CH2Br. Detailed Implementation

[0071] The present invention will be 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 those skilled in the art without creative effort are still within the scope of protection of the present invention.

[0072] Unless otherwise specified, all raw materials, reagents, instruments, and equipment used in this invention can be purchased commercially or prepared using existing methods. The polyvinyl alcohol used in the embodiments and comparative examples of this invention was purchased from a chemical reagent platform, CAS number: 9002-89-5, and the acrylic resin was purchased from the same platform, CAS number: 9003-01-4.

[0073] Example 1

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

[0075] The preparation process of the antibacterial long-lasting hydrophilic anti-fogging liquid is as follows: Polyvinyl alcohol and propylene glycol are first added to deionized water and stirred until dissolved, then compound A is added, and stirring continues for 40 minutes. The mixed solution is then filtered through a 0.45 μm filter membrane and dispensed into sealed containers.

[0076] Compound A has the following structural formula, where n is 11:

[0077] ;

[0078] Equation 12;

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

[0080] ;

[0081] Equation 13;

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

[0083] CH3-(CH2CH2O) 11The synthesis of -OCH2CH2Br was 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 dibromoethane.

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

[0086] S3 added 0.13 mol of potassium carbonate to the reaction system and stirred the mixture at 50°C for 18 h under nitrogen protection.

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

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

[0089] Figure 2 CH3-(CH2CH2O) prepared in this embodiment 11 The NMR spectrum of -OCH2CH2Br, as shown Figure 2 As shown, the compound structure is: CH3-(CH2CH2O) 11-OCH2CH2Br, with 5 hydrogen environments (labeled H1~H5): H1: terminal methyl hydrogen (-CH3), chemical shift 3.34 PPM; H2: methylene hydrogen directly bonded to the ether oxygen in the polyether chain (-OCH2-), chemical shift 3.55-3.63 PPM; H3: methylene hydrogen far from the ether oxygen in the polyether chain (-CH2O-), chemical shift 3.43-3.51 PPM; H4: methylene hydrogen with the bromoethyl end bonded to the ether oxygen (-OCH2-), chemical shift 3.69-3.75 PPM; H5: methylene hydrogen with the bromoethyl end bonded to bromine (-CH2Br), chemical shift 3.47-3.53 PPM; the peak integral ratio is H1 : H2 : H3 : H4 : H5 ≈ 3 : 22 : 22 : 2, which is similar to the theoretical hydrogen atom ratio (3 : 22 : 22). :2 :2) Completely consistent, proving the number of repeating units n in the polyether chain. No hydroxyl peak (no broad peak in the 3.0-5.0 range), eliminating unreacted hydroxyl impurities; the H4 and H5 peak types (quartet + triplet) and chemical shifts at the bromoethyl end confirm the existence of the -OCH2CH2Br structure; the H2 and H3 multiplet range (3.4-3.7) of the polyether chain conforms to the methylene characteristics of the ether bond, proving the structural and chain length characteristics of the target compound.

[0090] Example 2

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

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

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

[0094] The preparation process of compound A is the same as in Example 1, but CH3-(CH2CH2O) is used. 45 The synthesis of -OCH2CH2Br was 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 dibromoethane.

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

[0097] S3 added 0.18 mol of potassium carbonate to the reaction system and stirred the mixture at 60°C for 16 h under nitrogen protection.

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

[0099] Example 3

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

[0101] The preparation process of the antibacterial long-lasting hydrophilic anti-fogging liquid is as follows: Polyvinyl alcohol and propylene glycol are first added to deionized water and stirred until dissolved. Then, compound A is added, and stirring continues for 45 minutes. The mixed solution is filtered through a 0.45 μm filter membrane and dispensed into sealed containers.

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

[0103] The preparation process of compound A is the same as in Example 1, but CH3-(CH2CH2O) is used. n The synthesis of -OCH2CH2Br was 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 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 added 0.18 mol of potassium carbonate to the reaction system and stirred the mixture for 12 h under nitrogen protection at 70 °C.

[0107] After the S4 reaction was completed, the mixture was cooled to room temperature, and subsequent processing was the same as in Example 1 to obtain a halopolyether compound (CH3-(CH2CH2O). n -OCH2CH2Br), with a yield of 84% and a purity of 95%.

[0108] Example 4

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

[0110] The preparation process of the antibacterial long-lasting hydrophilic anti-fogging liquid is as follows: Polyvinyl alcohol and propylene glycol are first added to deionized water and stirred until dissolved. Then, compound A is added, and stirring continues for 30 minutes. The mixed solution is filtered through a 0.45 μm filter membrane and dispensed into sealed containers.

[0111] In this compound, the structural formula of compound A is the same as that of 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 in Example 1, but CH3-(CH2CH2O) is used. 68 The synthesis of -OCH2CH2Br was 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, bringing its concentration in the reaction system to 0.67 mol / L.

[0115] S3 added 0.18 mol of potassium carbonate to the reaction system and stirred the mixture for 16 h under nitrogen protection at 60 °C.

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

[0117] Example 5

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

[0119] The preparation process of the antibacterial long-lasting hydrophilic anti-fogging liquid is as follows: Polyvinyl alcohol and propylene glycol are first added to deionized water and stirred until dissolved. Then, compound A is added, and stirring continues for 30 minutes. The mixed solution is filtered through a 0.45 μm filter membrane and dispensed into sealed containers.

[0120] Compound A has the following structural formula, where n is 51:

[0121] ;

[0122] Equation 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 in Example 1, but CH3-(CH2CH2CH2O) is used. 51 The synthesis of -OCH2CH2Br was carried out according to the following steps:

[0125] S1 weighs 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 added 0.18 mol of sodium carbonate to the reaction system and stirred the mixture for 18 h under nitrogen protection at 65 °C.

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

[0129] Comparative Example 1

[0130] The only difference between this comparative example and Example 4 is the use of equal amounts of the halopolyether compound CH3-(CH2CH2O). 51 -OCH2CH2Br replaces compound A, and the remaining steps and conditions are the same.

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

[0132] Comparative Example 2

[0133] The only difference between this comparative example and Example 3 is that compound A is replaced with an equal amount of aminosiloxane; all other steps and conditions are the same.

[0134] Among them, the structural formula of aminosiloxane is the same as that of formula 13, and R2 and R3 are both... 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%, while 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%, while the other steps and conditions are the same.

[0139] The antibacterial long-lasting hydrophilic antifog liquids of the examples and comparative examples were applied to the glass surface and cured into a film (temperature 110℃). Their antifog performance and antibacterial performance were tested, and the results are shown in Table 1.

[0140]

[0141] Note: The standard for anti-fog performance testing is GB / T 31726-2015; the standard for antibacterial performance testing is GB / T31402-2015; the adhesion test method is the cross-cut adhesion test, and the standard for testing is 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 within the protection scope of the present invention.

Claims

1. An antibacterial, long-lasting, hydrophilic, anti-fogging liquid, characterized in that: The raw materials include the following parts by weight: 4-15 parts of compound A; 0.1-3 parts of film-forming aid; 0.1-2 parts of solubilizer; 80-93 parts of water; The compound A has the structural formula of 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 substituted or unsubstituted phenyl groups, H groups, and C1~C30 alkyl groups, 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 a phenyl group is substituted, the substituent is selected from at least one of methyl, ethyl, and methoxy groups.

2. The antibacterial, long-lasting, hydrophilic, and anti-fogging liquid according to claim 1, characterized in that: The film-forming aid includes at least one of polyvinyl alcohol and acrylic resins; The solubilizer 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 monosubstituted phenyl, H, and C1 to C10 alkyl groups; R5 is selected from one of monosubstituted phenyl, C1-C30 alkyl, and C1-C10 alkyl containing heteroatoms in the carbon chain; When a phenyl group is monosubstituted, the substituent is selected from methyl, ethyl, or methoxy, and X is a halogen.

3. The antibacterial, long-lasting, hydrophilic, and anti-fogging liquid according to claim 1, characterized in that: Compound A is formed by a substitution reaction between an aminosiloxane and a halogenated polyether compound. The reaction products afterward; The aminosiloxane has the structural formula of Formula 4: ； Equation 4; The halogenated polyether compound has the structural formula of 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 C1~C30 alkyl groups; R5 is selected from one of substituted or unsubstituted phenyl groups, C1-C30 alkyl groups, and C1-C30 alkyl groups containing heteroatoms in the carbon chain; when the phenyl group is substituted, the substituent is selected from at least one of methyl, ethyl, and methoxy groups.

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

5. The antibacterial, long-lasting, hydrophilic, anti-fogging 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 the addition of alkaline catalyst and reaction solvent.

6. The antibacterial, long-lasting, hydrophilic, and anti-fogging liquid according to claim 3, characterized in that: The halopolyether compound is prepared by reacting compound B with a dihaloalkane in an organic solvent under alkaline catalysis. Compound B has the structural formula of Formula 8: ； Formula 8; Dihaloalkanes have the structural formula of formula 9: ; Equation 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, and anti-fogging liquid according to claim 6, characterized in that: The molecular weight of compound B is 200-10000, and it has the structural formula of formula 10 or formula 11: ； Formula 10; ； Formula 11; Where n is an integer from 4 to 227.

8. The antibacterial, long-lasting, hydrophilic, and anti-fogging 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 alkaline catalytic 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℃, reaction time of 12~24h, and molar ratio of compound B to dihaloalkane of 1:(0.5~3).

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

10. The application of the antibacterial, long-lasting, hydrophilic, and anti-fogging liquid according to any one of claims 1 to 8, characterized in that: It is used to prepare antibacterial and anti-fogging functional coatings.

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