High-transmittance protective glass window coating and preparation method thereof

Abstract

The invention discloses a high-transmittance protective glass window coating and a preparation method thereof, and relates to the technical field of coating materials. When the high-transmittance protective glass window coating is prepared, polyether glycol, pyridine quaternary ammonium salt dihydric alcohol and isophorone diisocyanate are polymerized, and then 2, 5-furandimethanol is used for chain extension to prepare functional polyurethane; the preparation method comprises the following steps: reacting isoliquiritigenin with 3-maleimidopropionic acid to obtain functionalized isoliquiritigenin; the preparation method comprises the following steps: reacting nano titanium dioxide with an acylhydrazone salicylaldehyde ligand and diethyl tin chloride in sequence to prepare modified nano titanium dioxide; and uniformly mixing the functionalized polyurethane, the functionalized isoliquiritigenin, the modified nano titanium dioxide and butanone, coating and curing to obtain the high-transmittance protective glass window coating. The high-transmittance protective glass window coating prepared by the invention has excellent ultraviolet resistance, mildew resistance, bacteriostasis and self-repairing performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of coating materials, in particular to a high-transmittance protective glass window coating and a preparation method thereof. BACKGROUND

[0002] Glass windows, as multifunctional transparent components, are widely used in various fields such as buildings, automobiles, industries, consumer electronics, military and medical treatment. Glass window coating is a coating material coated on the surface of a glass window, which can play the roles of energy saving and heat insulation, UV blocking, hydrophobic self-cleaning, scratch resistance and delay of debris splashing, according to different application requirements. The coating material usually contains a large amount of organic matter. For glass window coatings used outdoors, yellowing and pulverization may occur under the long-term effect of sunlight, resulting in aging and performance degradation of the coating, and greatly reducing the service life of the coating. In addition, for glass window coatings used in some special fields such as medical devices, medical sites and food manufacturing plants, the requirements for hygiene and health are relatively high, so the coating material needs to have good mildew-proof and antibacterial properties. Based on the above problems, the present application provides a glass window coating material with the properties of anti-ultraviolet, self-repairing, mildew-proof and antibacterial, which improves the comprehensive performance of the coating material and prolongs the service life of the glass window coating. SUMMARY

[0003] The present application aims to provide a high-transmittance protective glass window coating and a preparation method thereof to solve the problems in the prior art.

[0004] To solve the above technical problems, the present application provides the following technical solutions: A high-transmittance protective glass window coating is prepared by polymerizing polyether diol, pyridine quaternary ammonium salt diol and isophorone diisocyanate, and then extending the chain with 2,5-furan dimethyl alcohol to obtain functionalized polyurethane; modified nano-titanium dioxide is prepared by sequentially reacting nano-titanium dioxide with acylhydrazone salicylaldehyde ligand and diethyltin chloride; and the functionalized polyurethane, functionalized glycyrrhizin, modified nano-titanium dioxide and butanone are mixed uniformly, coated and cured to obtain the high-transmittance protective glass window coating. The pyridine quaternary ammonium salt diol is prepared by reacting 3-(pyridin-4-yl) pentane-1,5-diol and 1-bromohexane. The functionalized glycyrrhizin is prepared by reacting glycyrrhizin and 3-maleimide propionic acid. The acylhydrazone salicylaldehyde ligand is prepared by reacting adipic acid-1-hydrazide and salicylaldehyde.

[0005] A preparation method of a high-transmittance protective glass window coating, which comprises the following preparation steps: (1) mixing polyether diol, pyridine quaternary ammonium salt diol, N,N-dimethylformamide uniformly according to the mass ratio of 1: (0.5-0.6): (8-10), stirring at 70-80℃, 200-300r / min for 18-22min, adding isophorone diisocyanate with 2-2.2 times the mass of polyether diol, dibutyltin dilaurate with 0.04-0.06 times the mass of polyether diol, increasing the temperature to 88-92℃, continuing to stir for 3-4h, decreasing the temperature to 70-74℃, adding 2,5-furandimethanol with 0.5-0.6 times the mass of isophorone diisocyanate, continuing to stir for 60-70min, drying under vacuum condition at 60-70℃ for 13-15h, to obtain functional polyurethane; (2) adding glycyrrhizin and 3-maleimide propionic acid into dichloromethane with 10-12 times the mass of glycyrrhizin according to the molar ratio of 1:2, adding 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride with 0.4-0.5 times the mass of glycyrrhizin, adding 4-dimethylaminopyridine with 0.2-0.3 times the mass of glycyrrhizin, stirring at room temperature, 300-500r / min for 26-30h, drying under vacuum condition at 50-60℃ for 10-12h, to obtain functional glycyrrhizin; (3) mixing nano-titanium dioxide, acylhydrazone salicylaldehyde ligand and toluene uniformly according to the mass ratio of 1: (6-7): (30-34), stirring at 100-104℃, 300-500r / min for 1-2h, filtering, washing with anhydrous ethanol for 3 times, drying under vacuum condition at 50-60℃ for 10-12h, to obtain pre-modified nano-titanium dioxide; mixing pre-modified nano-titanium dioxide, diethyltin chloride, potassium hydroxide and anhydrous ethanol uniformly according to the mass ratio of 1: (4-5): (0.6-0.8): (28-30), stirring at room temperature, 300-500r / min for 2-3h, increasing the temperature to 78-80℃, continuing to stir for 2-3h, cooling to room temperature, filtering, washing with anhydrous ethanol for 3 times, drying under vacuum condition at 50-60℃ for 10-12h, to obtain modified nano-titanium dioxide; (4) mixing functional polyurethane, functional glycyrrhizin, modified nano-titanium dioxide and butanone uniformly, stirring at 50-60℃, 100-120r / min for 10-12min, to obtain polyurethane paint; uniformly coating the polyurethane paint on a glass plate, coating and curing, to obtain high-transparency protective glass window coating.

[0006] As optimization, the preparation method of the pyridine quaternary ammonium salt dihydric alcohol in step (1) is as follows: 3-(pyridin-4-yl) pentane-1, 5-diol and 1-bromohexane are added into 16-18 times the mass of 3-(pyridin-4-yl) pentane-1, 5-diol of tetrahydrofuran according to a molar ratio of 1:1, and then stirred at 300-500 r / min at 50-60 DEG C for 44-48 h; and then dried at 50-60 DEG C under vacuum for 10-12 h to obtain the pyridine quaternary ammonium salt dihydric alcohol; and the reaction process is as follows: .

[0007] As optimization, the reaction process of the functionalized isoliquiritigenin in step (2) is as follows: .

[0008] As optimization, the preparation method of the acylhydrazone salicylaldehyde ligand in step (3) is as follows: adipic acid-1-hydrazide and salicylaldehyde are added into 13-15 times the mass of adipic acid-1-hydrazide of anhydrous ethanol according to a molar ratio of 1:1, and then stirred at 300-500 r / min at room temperature for 2-3 h, and then heated to 78-80 DEG C, and then continuously stirred to reflux for 80-100 min; and then dried at 50-60 DEG C under vacuum for 8-10 h to obtain the acylhydrazone salicylaldehyde ligand; and the reaction process is as follows: .

[0009] As optimization, the CAS number of the adipic acid-1-hydrazide is 6292-67-7.

[0010] As optimization, the dosages of the functionalized polyurethane, the functionalized isoliquiritigenin, the modified nano titanium dioxide and the butanone in step (4) are as follows: the functionalized polyurethane is 70-80 parts, the functionalized isoliquiritigenin is 16-18 parts, the modified nano titanium dioxide is 4-5 parts, and the butanone is 140-150 parts.

[0011] As optimization, the process parameters of the coating and curing in step (4) are as follows: the coating thickness is 5 mm, and then dried at 60-70 DEG C for 20-24 h, and then placed at room temperature for 24 h.

[0012] Compared with the prior art, the present application has the following beneficial effects: In the preparation of the high-transparency protective glass window coating, first, 3-(pyridine-4-yl) pentane-1, 5-diol, 1-bromohexane is reacted to obtain a pyridine quaternary ammonium salt diol; the polyether diol, the pyridine quaternary ammonium salt diol and isophorone diisocyanate are polymerized, and then 2, 5-furan dimethyl alcohol is used for chain extension to obtain a functional polyurethane; the pyridine quaternary ammonium salt structure is introduced on the side chain of the polyurethane molecule, and the furan group is introduced on the main chain of the molecule; the pyridine quaternary ammonium salt structure introduced on the side chain of the polyurethane molecule can improve the mildew-proof and antibacterial performance of the high-transparency protective glass window coating.

[0013] Secondly, glycyrrhizin and 3-maleimide propionic acid are reacted to obtain functional glycyrrhizin; glycyrrhizin is a natural chalcone compound, which widely exists in safflower and licorice, is a precursor of flavonoids synthesized in plants, and has certain antibacterial performance; meanwhile, the skeleton structure of glycyrrhizin contains alternating single and double bonds, the hydroxyl group and the adjacent carbonyl group in the molecular structure of glycyrrhizin can form intramolecular hydrogen bond, which can achieve the purpose of ultraviolet protection through the excited state intramolecular proton transfer and trans-cis photoisomerization double-channel relaxation energy, and endow the high-transparency protective glass window coating with excellent ultraviolet resistance; the C-4 and C-4' positions of glycyrrhizin are modified by 3-maleimide propionic acid, two maleimide groups are introduced into the functional glycyrrhizin, and the maleimide groups can occur reversible Diels Alder reaction with the furan group on the main chain of the polyurethane molecule, thereby endowing the high-transparency protective glass window coating with self-repairing performance.

[0014] Finally, adipic acid-1-hydrazide and salicylaldehyde are reacted to obtain an acylhydrazone salicylaldehyde ligand; the nano titanium dioxide and the acylhydrazone salicylaldehyde ligand are reacted to obtain pre-modified nano titanium dioxide; the hydroxyl group on the nano titanium dioxide and the carboxyl group on the acylhydrazone salicylaldehyde ligand occur esterification reaction similar to that of acid and alcohol, thereby grafting the acylhydrazone salicylaldehyde ligand structure on the pre-modified nano titanium dioxide; the pre-modified nano titanium dioxide and diethyl tin chloride are reacted to obtain modified nano titanium dioxide; the acylhydrazone salicylaldehyde ligand structure on the pre-modified nano titanium dioxide reacts with diethyl tin chloride to generate an organotin complex, the organotin complex has excellent bactericidal capacity, and can further improve the mildew-proof and antibacterial performance of the high-transparency protective glass window coating; meanwhile, the introduction of nano titanium dioxide can further improve the ultraviolet resistance of the high-transparency protective glass window coating. DETAILED DESCRIPTION

[0015] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0016] Example 1 A preparation method of a high-transmittance protective glass window coating, the preparation method of the high-transmittance protective glass window coating comprising the following preparation steps: (1) 3-(pyridin-4-yl)pentane-1,5-diol and 1-bromohexane are added to 16 times the mass of 3-(pyridin-4-yl)pentane-1,5-diol tetrahydrofuran at a molar ratio of 1:1, stirred at 50°C and 300 r / min for 48 h, and dried at 50°C under vacuum for 12 h to obtain a pyridine quaternary ammonium salt diol; polyether diol, pyridine quaternary ammonium salt diol, and N,N-dimethylformamide are uniformly mixed at a mass ratio of 1:0.5:8, stirred at 70°C and 200 r / min for 22 min, 2 times the mass of isophorone diisocyanate is added to the polyether diol, 0.04 times the mass of dibutyltin dilaurate is added to the polyether diol, the temperature is raised to 88°C, and the stirring is continued for 4 h, the temperature is lowered to 70°C, 0.5 times the mass of 2,5-furandimethanol is added to the isophorone diisocyanate, and the stirring is continued for 70 min, and the mixture is dried at 60°C under vacuum for 15 h to obtain a functional polyurethane; (2) glycyrrhizin and 3-maleimide propionic acid are added to 10 times the mass of glycyrrhizin dichloromethane at a molar ratio of 1:2, 0.4 times the mass of 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride is added to the glycyrrhizin, 0.2 times the mass of 4-dimethylaminopyridine is added to the glycyrrhizin, the mixture is stirred at room temperature and 300 r / min for 26 h, and the mixture is dried at 50°C under vacuum for 12 h to obtain a functional glycyrrhizin; (3) adipic acid-1-hydrazide and salicylaldehyde are added to 13 times the mass of anhydrous ethanol at a molar ratio of 1:1, the mixture is stirred at room temperature and 300 r / min for 2 h, the temperature is raised to 78°C, the stirring is continued for 100 min, and the mixture is dried at 50°C under vacuum for 10 h to obtain an acylhydrazone salicylaldehyde ligand; nano-titanium dioxide, the acylhydrazone salicylaldehyde ligand, and toluene are uniformly mixed at a mass ratio of 1:6:30, the mixture is stirred at 100°C and 300 r / min for 2 h, the mixture is filtered, washed with anhydrous ethanol for 3 times, and dried at 50°C under vacuum for 12 h to obtain a pre-modified nano-titanium dioxide; the pre-modified nano-titanium dioxide, diethyltin chloride, potassium hydroxide, and anhydrous ethanol are uniformly mixed at a mass ratio of 1:4:0.6:28, the mixture is stirred at room temperature and 300 r / min for 2 h, the temperature is raised to 78°C, the stirring is continued for 3 h, the mixture is cooled to room temperature, the mixture is filtered, washed with anhydrous ethanol for 3 times, and dried at 50°C under vacuum for 12 h to obtain a modified nano-titanium dioxide; (4) by mass fraction, take 70 parts of functional polyurethane, 16 parts of functional glycyrrhizin, 4 parts of modified nano titanium dioxide, 140 parts of butanone; the functional polyurethane, the functional glycyrrhizin, the modified nano titanium dioxide, the butanone are mixed uniformly, stirred at 50℃, 10r / min for 12min, and the polyurethane paint is prepared; the polyurethane paint is uniformly coated on the glass plate, and the coating thickness is 5mm; dried at 60℃ for 24h, and placed at room temperature for 24h, and the high-transparency protective glass window coating is prepared.

[0017] Example 2: A preparation method of a high-transparency protective glass window coating, the preparation method of the high-transparency protective glass window coating comprises the following preparation steps: (1) 3-(pyridine-4-yl)pentane-1,5-diol, 1-bromohexane are added to 3-(pyridine-4-yl)pentane-1,5-diol mass 17 times of tetrahydrofuran in a molar ratio of 1:1, stirred at 55℃, 400r / min for 46h, dried at 55℃ under vacuum for 11h, and the pyridine quaternary ammonium salt diol is prepared; the polyether diol, the pyridine quaternary ammonium salt diol, the N,N-dimethylformamide are mixed uniformly according to the mass ratio of 1:0.55:9, stirred at 75℃, 250r / min for 20min, 2.1 times of isophorone diisocyanate of polyether diol, 0.05 times of dibutyltin dilaurate of polyether diol are added, heated to 90℃, continue to stir for 3.5h, cooled to 72℃, 0.55 times of 2,5-furan dimethyl alcohol of isophorone diisocyanate is added, continue to stir for 65min, dried at 65℃ under vacuum for 14h, and the functional polyurethane is prepared; (2) glycyrrhizin, 3-maleimide propionic acid are added to glycyrrhizin mass 11 times of dichloromethane in a molar ratio of 1:2, 0.45 times of 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride of glycyrrhizin, 0.25 times of 4-dimethylamino pyridine of glycyrrhizin are added, stirred at room temperature, 400r / min for 28h, dried at 55℃ under vacuum for 11h, and the functional glycyrrhizin is prepared; (3) adipic acid-1-hydrazide, salicylaldehyde were added into anhydrous ethanol with 14 times of the mass of adipic acid-1-hydrazide at a molar ratio of 1:1, stirred at 400 r / min for 2.5 h at room temperature, continued to stir for 90 min at 79 ℃ under reflux, dried for 9 h at 55 ℃ under vacuum, to obtain acylhydrazone salicylaldehyde ligand; nano-titanium dioxide, acylhydrazone salicylaldehyde ligand, toluene were mixed uniformly at a mass ratio of 1:6.5:32, stirred at 400 r / min for 1.5 h at 102 ℃, filtered, washed with anhydrous ethanol for 3 times, dried for 11 h at 55 ℃ under vacuum, to obtain pre-modified nano-titanium dioxide; the pre-modified nano-titanium dioxide, diethyl tin chloride, potassium hydroxide, anhydrous ethanol were mixed uniformly at a mass ratio of 1:4.5:0.7:29, stirred at 400 r / min for 2.5 h at room temperature, continued to stir for 2.5 h at 79 ℃ under reflux, cooled to room temperature, filtered, washed with anhydrous ethanol for 3 times, dried for 11 h at 55 ℃ under vacuum, to obtain modified nano-titanium dioxide; (4) functionalized polyurethane 75 parts, functionalized glycyrrhetin 17 parts, modified nano-titanium dioxide 4.5 parts, butanone 145 parts were weighed according to the mass fraction; the functionalized polyurethane, the functionalized glycyrrhetin, the modified nano-titanium dioxide and the butanone were mixed uniformly, stirred at 110 r / min for 11 min at 55 ℃, to obtain polyurethane paint; the polyurethane paint was uniformly coated on a glass plate with a coating thickness of 5 mm; dried for 22 h at 65 ℃, and stood for 24 h at room temperature, to obtain a high-transmittance protective glass window coating.

[0018] Example 3: A preparation method of a high-transmittance protective glass window coating, the preparation method of the high-transmittance protective glass window coating comprises the following preparation steps: (1) 3-(pyridin-4-yl)pentane-1,5-diol, 1-bromohexane were added into tetrahydrofuran with 18 times of the mass of 3-(pyridin-4-yl)pentane-1,5-diol at a molar ratio of 1:1, stirred at 500 r / min for 44 h at 60 ℃, dried for 10 h at 60 ℃ under vacuum, to obtain pyridine quaternary ammonium salt diol; polyether diol, pyridine quaternary ammonium salt diol, N,N-dimethylformamide were mixed uniformly at a mass ratio of 1:0.6:10, stirred at 300 r / min for 18 min at 80 ℃, polyether diol 2.2 times of isophorone diisocyanate was added, polyether diol 0.06 times of dibutyltin dilaurate was added, heated to 92 ℃, continued to stir for 3 h, cooled to 74 ℃, isophorone diisocyanate 0.6 times of 2,5-furandimethanol was added, continued to stir for 60 min, dried for 13 h at 70 ℃ under vacuum, to obtain functionalized polyurethane; (2) isoamyrin, 3-maleimide propionic acid are added to dichloromethane in a molar ratio of 1:2, 0.5 times the mass of isoamyrin of 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride is added, 0.3 times the mass of isoamyrin of 4-dimethylaminopyridine is added, stirring at room temperature at 500 r / min for 30 h, drying at 60℃ under vacuum for 10 h, to obtain functionalized isoamyrin; (3) adipic acid-1-hydrazide and salicylaldehyde are added to anhydrous ethanol in a molar ratio of 1:1, stirring at room temperature at 500 r / min for 3 h, heating to 80℃, continuing to stir for 80 min, drying at 50℃ under vacuum for 10 h, to obtain acylhydrazone salicylaldehyde ligand; nano-titanium dioxide, acylhydrazone salicylaldehyde ligand and toluene are mixed in a mass ratio of 1:7:34, stirring at 104℃ at 500 r / min for 1 h, filtering, washing with anhydrous ethanol for 3 times, drying at 60℃ under vacuum for 10 h, to obtain pre-modified nano-titanium dioxide; pre-modified nano-titanium dioxide, diethyl tin chloride, potassium hydroxide and anhydrous ethanol are mixed in a mass ratio of 1:5:0.8:30, stirring at room temperature at 500 r / min for 3 h, heating to 80℃, continuing to stir for 2 h, cooling to room temperature, filtering, washing with anhydrous ethanol for 3 times, drying at 60℃ under vacuum for 10 h, to obtain modified nano-titanium dioxide; (4) 80 parts of functionalized polyurethane, 18 parts of functionalized isoamyrin, 5 parts of modified nano-titanium dioxide and 150 parts of butanone are mixed, stirring at 60℃ at 120 r / min for 10 min, to obtain polyurethane paint; the polyurethane paint is uniformly coated on a glass plate with a coating thickness of 5 mm, drying at 70℃ for 20 h, standing at room temperature for 24 h, to obtain a high-transparency protective glass window coating.

[0019] Comparative Example 1 The preparation method of the high-transparency protective glass window coating of Comparative Example 1 is different from that of Example 2 in step (1), which is modified as follows: polyether diol, 1,5-pentanediol and N,N-dimethylformamide are mixed in a mass ratio of 1:0.55:9, stirring at 75℃ at 250 r / min for 20 min, adding 2.1 times the mass of polyether diol of isophorone diisocyanate and 0.05 times the mass of polyether diol of dibutyltin dilaurate, heating to 90℃, continuing to stir for 3.5 h, cooling to 72℃, adding 0.55 times the mass of isophorone diisocyanate of 2,5-furandimethanol, continuing to stir for 65 min, drying at 65℃ under vacuum for 14 h, to obtain functionalized polyurethane. The remaining steps are the same as those of Example 2.

[0020] Comparative Example 2: The preparation method of the high-transmittance protective glass window coating of Comparative Example 2 is different from that of Example 2 only in that step (2) is not performed, and step (4) is modified as follows: by mass fraction, 75 parts of functionalized polyurethane, 17 parts of glycyrrhizin, and 4.5 parts of modified nano-titanium dioxide, and 145 parts of butanone are weighed and uniformly mixed to prepare a polyurethane paint under stirring at 55°C and 110 r / min for 11 min; the polyurethane paint is uniformly coated on a glass plate with a coating thickness of 5 mm; and the high-transmittance protective glass window coating is prepared by drying at 65°C for 22 h and standing at room temperature for 24 h. The remaining steps are the same as those of Example 2.

[0021] Comparative Example 3: The preparation method of the high-transmittance protective glass window coating of Comparative Example 3 is different from that of Example 2 only in that step (2) is not performed, and step (4) is modified as follows: by mass fraction, 75 parts of functionalized polyurethane, 4.5 parts of modified nano-titanium dioxide, and 145 parts of butanone are weighed and uniformly mixed to prepare a polyurethane paint under stirring at 55°C and 110 r / min for 11 min; the polyurethane paint is uniformly coated on a glass plate with a coating thickness of 5 mm; and the high-transmittance protective glass window coating is prepared by drying at 65°C for 22 h and standing at room temperature for 24 h. The remaining steps are the same as those of Example 2.

[0022] Comparative Example 4: The preparation method of the high-transmittance protective glass window coating of Comparative Example 4 is different from that of Example 2 only in that step (3) is different, and step (3) is modified as follows: adipic acid-1-hydrazide and salicylaldehyde are added to anhydrous ethanol in an amount of 14 times the mass of adipic acid-1-hydrazide, and stirred at 400 r / min at room temperature for 2.5 h, and then heated to 79°C and stirred under reflux for 90 min; and the high-transmittance protective glass window coating is prepared by drying at 55°C under vacuum for 9 h. The remaining steps are the same as those of Example 2.

[0023] Comparative Example 5: The preparation method of the high-transmittance protective glass window coating of Comparative Example 5 is different from that of Example 2 only in that step (3) is not performed, and step (4) is modified as follows: 75 parts of functionalized polyurethane, 17 parts of functionalized glycyrrhizin, and 145 parts of butanone are weighed out by mass fraction; the functionalized polyurethane, the functionalized glycyrrhizin, and the butanone are mixed uniformly, stirred at 55°C and 110 r / min for 11 min, and a polyurethane paint is prepared; the polyurethane paint is uniformly coated on a glass plate, and the coating thickness is 5 mm; the coating is dried at 65°C for 22 h, and is left to stand at room temperature for 24 h, and a high-transmittance protective glass window coating is prepared.

[0024] Test Example 1 Test of ultraviolet resistance and self-repairing performance Test method: The polyurethane paint prepared in the examples and comparative examples is poured into a polytetrafluoroethylene mold, dried at 65°C for 22 h, left to stand at room temperature for 24 h, and prepared into a standard sample bar according to GB / T1040, and the tensile strength M thereof is tested at a tensile rate of 50 mm / min; Test method of ultraviolet resistance: the standard sample bar is subjected to irradiation experiment under a 200 W ultraviolet lamp with a wavelength of 365 nm, the distance between the standard sample bar and the ultraviolet irradiation lamp is 10 cm, the environmental temperature is 25°C, the irradiation time is 20 days, and after the irradiation experiment is completed, the tensile strength N of the standard sample bar is tested, and the performance decline rate of the standard sample bar before and after irradiation is calculated; the performance decline rate = (M-N) / M×100%.

[0025] Test of self-repairing performance: a clean blade is used to draw a 20 mm long scratch in the middle of the standard sample bar, the sample is kept at 120°C for 20 min, cooled to 60°C for 3 h, and cooled to room temperature for 12 h to obtain a repaired sample, the tensile strength P of the repaired sample is tested, and the self-repairing rate is calculated; the self-repairing rate = (P / M)×100%. The results are shown in Table 1.

[0026] Table 1 ; From the experimental data of Examples 1-3 and Comparative Examples 1-5 in Table 1, it can be found that the high-transmittance protective glass window coating prepared by the present application has good ultraviolet resistance and self-repairing performance.

[0027] By comparison, the performance decline rate of examples 1-3 is less than that of comparative example 3, which shows that isoliquiritigenin is a natural chalcone compound, widely exists in safflower and licorice, is a precursor of flavonoids synthesized in plants, and has certain antibacterial performance; meanwhile, the skeleton structure of isoliquiritigenin contains alternating single bond and double bond, the hydroxyl group and adjacent carbonyl group in the molecular structure of isoliquiritigenin can form intramolecular hydrogen bond, and the energy can be relaxed through the double channels of excited state intramolecular proton transfer and trans-cis photoisomerization, so as to achieve the purpose of ultraviolet protection, and excellent ultraviolet resistance of the high-transmission protective glass window coating is obtained.

[0028] By comparison, the performance decline rate of examples 1-3 is less than that of comparative example 5, which shows that the introduction of nano-titanium dioxide can further improve the ultraviolet resistance of the high-transmission protective glass window coating.

[0029] By comparison, the self-repairing rate of examples 1-3 is greater than that of comparative examples 2-3, which shows that the functionalized isoliquiritigenin is prepared by reacting isoliquiritigenin and 3-maleimide propionic acid; the C-4 and C-4' positions of isoliquiritigenin are modified by 3-maleimide propionic acid, two maleimide groups are introduced into the functionalized isoliquiritigenin, the maleimide groups can occur reversible Diels Alder reaction with furan groups on the polyurethane molecular backbone, and the high-transmission protective glass window coating is endowed with self-repairing performance.

[0030] Test example 2 Test of mildew-proof and antibacterial performance Test method: the polyurethane paint prepared from examples and comparative examples is poured into a polytetrafluoroethylene mold, dried at 65℃ for 22h, placed at room temperature for 24h, cut into a sample with a size of 10mmx10mmx5mm, sterilized by ultraviolet irradiation for 3h; the escherichia coli strain is activated and prepared into a bacterial suspension with a concentration of 3x10 4 cfu / ml; the sample is placed in 50ml of bacterial suspension and cultured at 37℃ for 24h, after the culture is completed, the bacteria are fully dispersed by shaking at 500r / min for 3min, 1ml of the diluted bacterial suspension is taken and diluted to 100 times, 1ml of the diluted bacterial suspension is inoculated into agar culture medium and cultured at 37℃ for 24h, the colony count is carried out according to the method in GB / T15979, and the antibacterial rate is calculated. The results are shown in table 2.

[0031] Table 2 ; From the experimental data comparison of examples 1-3 and comparative examples 1-5 in table 2, it can be found that the high-transmission protective glass window coating prepared by the present application has good mildew-proof and antibacterial performance.

[0032] By comparison, the bacteriostatic rates of examples 1~3 are greater than that of comparative example 1, which indicates that the pyridine quaternary ammonium salt diol is prepared by reacting 3-(pyridin-4-yl)pentane-1,5-diol and 1-bromohexane; the functional polyurethane is prepared by polymerizing polyether diol, pyridine quaternary ammonium salt diol and isophorone diisocyanate, and then chain extending with 2,5-furandimethanol; the pyridine quaternary ammonium salt structure is introduced into the side chain of the polyurethane molecule, and the furan group is introduced into the main chain of the molecule; the pyridine quaternary ammonium salt structure introduced into the side chain of the polyurethane molecule can improve the mildew and bacteriostatic performance of the high-transmittance protective glass window coating.

[0033] By comparison, the bacteriostatic rates of examples 1~3 are greater than that of comparative examples 4~5, which indicates that the acylhydrazone salicylaldehyde ligand is prepared by reacting adipic acid-1-hydrazide and salicylaldehyde; the pre-modified nano-titanium dioxide is prepared by reacting nano-titanium dioxide and acylhydrazone salicylaldehyde ligand; the esterification reaction similar to that of acid and alcohol occurs between the hydroxyl group on the nano-titanium dioxide and the carboxyl group on the acylhydrazone salicylaldehyde ligand, and the acylhydrazone salicylaldehyde ligand structure is grafted on the pre-modified nano-titanium dioxide; the modified nano-titanium dioxide is prepared by reacting the pre-modified nano-titanium dioxide and diethyl tin chloride; the acylhydrazone salicylaldehyde ligand structure on the pre-modified nano-titanium dioxide reacts with diethyl tin chloride to form organotin complex, and the organotin complex has excellent bactericidal ability, which can further improve the mildew and bacteriostatic performance of the high-transmittance protective glass window coating.

[0034] The above specific embodiments further illustrate the purpose, technical solutions and beneficial effects of the present application, and it should be understood that the above description is only a specific embodiment of the present application and is not intended to limit the protection scope of the present application, and any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A high-transmission, high-protection glass glazing coating, characterized in that, The high-transmittance protective glass window coating is prepared by polymerizing polyether diol, pyridine quaternary ammonium salt diol and isophorone diisocyanate, and then extending the chain with 2, 5-furan dimethyl alcohol to obtain functional polyurethane; the modified nano titanium dioxide is prepared by sequentially reacting nano titanium dioxide with acylhydrazone salicylaldehyde ligand and diethyl tin chloride; the functional polyurethane, functional glycyrrhizin, modified nano titanium dioxide and butanone are uniformly mixed, coated and cured to obtain the high-transmittance protective glass window coating. The pyridine quaternary ammonium salt diol is prepared by reacting 3-(pyridine-4-yl) pentane-1, 5-diol and 1-bromohexane. The functional glycyrrhizin is prepared by reacting glycyrrhizin and 3-maleimide propionic acid. The acylhydrazone salicylaldehyde ligand is prepared by reacting adipic acid-1-hydrazide and salicylaldehyde.

2. A method of making a high-transmission, high-protective glass glazing coating, characterized in that, The preparation method of the high-transmittance protective glass window coating comprises the following preparation steps: (1) uniformly mixing polyether diol, pyridine quaternary ammonium salt diol and N, N-dimethylformamide, stirring at 70-80℃ for 18-22 min, adding isophorone diisocyanate and dibutyltin dilaurate, increasing the temperature to 88-92℃, continuing to stir for 3-4 h, decreasing the temperature to 70-74℃, adding 2, 5-furan dimethyl alcohol, continuing to stir for 60-70 min, and vacuum drying to obtain functional polyurethane; (2) adding glycyrrhizin and 3-maleimide propionic acid into dichloromethane, adding 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine, stirring at room temperature for 26-30 h, and vacuum drying to obtain functional glycyrrhizin; (3) uniformly mixing nano titanium dioxide, acylhydrazone salicylaldehyde ligand and toluene, stirring at 100-104℃ for 1-2 h, filtering, washing and drying to obtain pre-modified nano titanium dioxide; uniformly mixing the pre-modified nano titanium dioxide, diethyl tin chloride, potassium hydroxide and anhydrous ethanol, stirring at room temperature for 2-3 h, increasing the temperature to 78-80℃, continuing to stir for 2-3 h, cooling to room temperature, filtering, washing and drying to obtain modified nano titanium dioxide; (4) uniformly mixing the functional polyurethane, functional glycyrrhizin, modified nano titanium dioxide and butanone, stirring at 50-60℃ for 10-12 min to obtain polyurethane paint; uniformly coating the polyurethane paint on a glass plate, coating and curing to obtain the high-transmittance protective glass window coating.

3. The method of claim 2, wherein the coating is applied by a method selected from the group consisting of sputtering, vacuum deposition, and chemical vapor deposition. In step (1), the polyether diol is PPG-1000.

4. The method of claim 2, wherein the coating is applied by a method selected from the group consisting of sputtering, vacuum deposition, and ion plating. In step (1), the preparation method of the pyridine quaternary ammonium salt diol is as follows: adding 3-(pyridine-4-yl) pentane-1, 5-diol and 1-bromohexane into tetrahydrofuran according to a molar ratio of 1:1, reacting at 50-60℃ for 44-48 h, and vacuum drying to obtain the pyridine quaternary ammonium salt diol.

5. The method of claim 2, wherein the coating is applied by a method selected from the group consisting of sputtering, vacuum deposition, and ion plating. In step (2), the molar ratio of glycyrrhizin to 3-maleimide propionic acid is 1:

2.

6. The method for preparing a high-transparency protective glass window coating according to claim 2, characterized in that, The preparation method of the acylhydrazone salicylaldehyde ligand in step (3) is as follows: adipic acid-1-hydrazide and salicylaldehyde are added into anhydrous ethanol, stirred and reacted at room temperature for 2-3 h, heated to 78-80 DEG C, continuously stirred and refluxed for 80-100 min, vacuum dried, and the acylhydrazone salicylaldehyde ligand is prepared.

7. The method of claim 2, wherein the coating is applied by a method selected from the group consisting of sputtering, vacuum deposition, and ion plating. The preparation method of the acylhydrazone salicylaldehyde ligand in step (3) is as follows: adipic acid-1-hydrazide and salicylaldehyde are added into anhydrous ethanol, stirred and reacted at room temperature for 2-3 h, heated to 78-80 DEG C, continuously stirred and refluxed for 80-100 min, vacuum dried, and the acylhydrazone salicylaldehyde ligand is prepared.

8. The method of claim 2, wherein the coating is prepared by a method comprising: depositing a first layer of a first material on a glass substrate; depositing a second layer of a second material on the first layer; and depositing a third layer of a third material on the second layer. The dosages of the functionalized polyurethane, the functionalized glycyrrhizin, the modified nano titanium dioxide and butanone in step (4) are as follows: the functionalized polyurethane is 70-80 parts, the functionalized glycyrrhizin is 16-18 parts, the modified nano titanium dioxide is 4-5 parts, and butanone is 140-150 parts.

9. The method for preparing a high-transparency protective glass window coating according to claim 2, characterized in that, The process parameters of the coating and curing in step (4) are as follows: the coating thickness is 5 mm, drying is carried out at 60-70 DEG C for 20-24 h, and standing is carried out at room temperature for 24 h.