Infrared shielding polyurethane glass film and preparation method thereof

Abstract

The present invention discloses an infrared-shielding polyurethane glass film and a preparation method thereof, relating to the field of polymer materials technology. When preparing the infrared-shielding polyurethane glass film, the present invention comprises reacting an organic nickel complex and 3-imidazole-1-propionic acid to produce a functionalized crosslinker; sequentially reacting 4-aminophenylacetonitrile with 3-hydroxypropyl acrylate and quinoline-4-carboxaldehyde to produce a UV-absorbing monomer; reacting polypropylene glycol, a UV-absorbing monomer, 1,4-butanediol, and 4-chloromethyl-1,3-phenylenediisocyanate to polymerize to produce polyurethane; reacting tungsten-doped titanium dioxide and chloropropyltriethoxysilane to produce modified titanium dioxide; and uniformly mixing the polyurethane, modified titanium dioxide, the functionalized crosslinker, and acetone, followed by coating and curing to produce the infrared-shielding polyurethane glass film. The infrared-shielding polyurethane glass film prepared by the present invention has excellent infrared shielding, anti-aging, antibacterial, and mechanical properties.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, in particular to an infrared shielding polyurethane glass film and a preparation method thereof. Background Art

[0002] With the accelerating pace of urbanization, the use of glass exterior walls and curtain walls in urban buildings is increasing. This influx of sunlight into indoor spaces has become a common phenomenon, causing rapid increases in room temperature. This prolonged exposure to high temperatures in indoor spaces also leads to increased air conditioning use, resulting in increased energy consumption. The energy distribution of the solar spectrum shows that solar radiation is primarily concentrated in the 200-2500nm band, with near-infrared light in the 780-2500nm band accounting for as much as 50%. Effectively blocking near-infrared light would significantly reduce the indoor temperature rise caused by the extensive use of architectural glass and reduce cooling energy consumption for air conditioners.

[0003] Resin-based glass films offer advantages such as low cost, simple processing, and high transparency, and have been used in the field of thermal insulation films for buildings. However, conventional resin-based glass films generally have low infrared rejection rates, failing to meet the growing demand for thermal insulation. Furthermore, when exposed to UV light for extended periods outdoors, resin-based glass films can yellow, powder, and harden, reducing the transparency of the glass and shortening the film's lifespan. Therefore, there is a need to improve existing technologies to enhance the infrared rejection and aging resistance of resin-based glass films, save energy, and extend the film's lifespan. Summary of the Invention

[0004] The object of the present invention is to provide an infrared shielding polyurethane glass film and a preparation method thereof, so as to solve the problems existing in the prior art.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0006] An infrared shielding polyurethane glass film is prepared by reacting an organic nickel complex and 3-imidazole-1-propionic acid to obtain a functional crosslinking agent; reacting and polymerizing polypropylene glycol, an ultraviolet absorbing monomer, 1,4-butanediol, and 4-chloromethyl-1,3-phenylenediisocyanate to obtain polyurethane; reacting tungsten-doped titanium dioxide and chloropropyltriethoxysilane to obtain modified titanium dioxide; and uniformly mixing the polyurethane, modified titanium dioxide, functional crosslinking agent, and acetone, followed by coating and curing.

[0007] The organic nickel complex is prepared by reacting 4,4'-dihydroxybenzil with phosphorus pentasulfide and nickel chloride in sequence;

[0008] The ultraviolet absorption monomer is prepared by reacting dihydroxyphenylacetonitrile and quinoline-4-carboxaldehyde;

[0009] The dihydroxybenzeneacetonitrile is prepared by reacting 4-aminobenzeneacetonitrile and 3-hydroxypropyl acrylate;

[0010] The tungsten-doped titanium dioxide is prepared by using tetraethyl titanate and tungsten chloride as raw materials through a temperature rising method.

[0011] A method for preparing an infrared shielding polyurethane glass film, comprising the following steps:

[0012] (1) Add the organic nickel complex and 3-imidazole-1-propionic acid in a molar ratio of 1:4 to m-xylene (10-12 times the mass of the organic nickel complex), add p-toluenesulfonic acid monohydrate (0.03-0.05 times the mass of the organic nickel complex), and stir the mixture at 78-82°C and 200-300 r / min for 20-30 min under nitrogen protection. Heat the mixture to 118-122°C at a heating rate of 10°C / h, continue stirring the mixture at 118-122°C for 30-40 min, and dry the mixture at 50-60°C under vacuum for 8-10 h to obtain a functional crosslinking agent.

[0013] (2) Polypropylene glycol, ultraviolet absorbing monomer, and N,N-dimethylformamide are mixed uniformly in a mass ratio of 1:(0.6~0.7):(8~9), stirred at 75~85℃ and 300~500r / min for 10~12min, 4-chloromethyl-1,3-phenylenediisocyanate (1.6~1.8 times the mass of polypropylene glycol) and dibutyltin dilaurate (0.02~0.03 times the mass of polypropylene glycol) are added, the temperature is raised to 90~92℃, the stirring reaction is continued for 2~3h, the temperature is lowered to 70~72℃, 1,4-butanediol (0.10~0.12 times the mass of polypropylene glycol) is added, the stirring is continued for 30~40min, and the polyurethane is dried at 60~70℃ under vacuum conditions for 9~11h to obtain polyurethane;

[0014] (3) Tungsten-doped titanium dioxide, silane hydrolyzate, and anhydrous ethanol were mixed uniformly in a mass ratio of 1:(12-14):(50-60), stirred at 55-65°C and 200-400 r / min for 2-3 h, filtered, washed with anhydrous ethanol 3-5 times, and dried at 55-65°C under vacuum conditions for 8-10 h to obtain modified titanium dioxide;

[0015] (4) Weigh 98-102 parts of polyurethane, 3-4 parts of modified titanium dioxide, 8-10 parts of functionalized crosslinking agent, and 200-220 parts of acetone by mass; mix the polyurethane, modified titanium dioxide, and acetone evenly, stir at 40-50°C and 100-200 r / min for 10-12 minutes, add the functionalized crosslinking agent, continue stirring for 2-3 minutes, and apply it on a glass plate with a coating thickness of 2-3 mm. Dry it at 60-70°C under vacuum conditions for 12-14 hours, and cool it to room temperature to obtain an infrared shielding polyurethane glass film.

[0016] As an optimization, the preparation method of the organic nickel complex in step (1) is as follows: 4,4'-dihydroxybenzil, phosphorus pentasulfide, ammonium sulfate, and 1,4-dioxane are mixed uniformly in a mass ratio of 1:(1.6~1.8):(0.4~0.6):(8~10), stirred and refluxed at 104~106℃ and 300~500r / min for 3~4h under nitrogen protection, cooled to room temperature, filtered, and the filtrate was heated to 90~ At 92°C, under a nitrogen atmosphere, add a nickel chloride aqueous solution (0.4-0.5 times the mass of 4,4'-dihydroxybenzil), stir and reflux at 104-106°C, 300-500 r / min for 1.8-2.2 hours, cool to room temperature, wash with an equal volume of deionized water and dimethyl carbonate, allow to stand and separate, take the organic phase, and dry it at 50-60°C under vacuum conditions for 8-10 hours to obtain an organic nickel complex. The reaction process is as follows:

[0017] .

[0018] As an optimization, the preparation method of the nickel chloride aqueous solution is: nickel chloride and deionized water are uniformly mixed in a mass ratio of 1: (9~10) to prepare the nickel chloride aqueous solution.

[0019] As an optimization, the preparation method of the ultraviolet absorbing monomer in step (2) is as follows: dihydroxybenzene acetonitrile and quinoline-4-carboxaldehyde are added in a molar ratio of 1:1 to ethanol with a mass of 20 to 24 times that of quinoline-4-carboxaldehyde, and sodium hydroxide with a mass of 0.03 to 0.05 times that of quinoline-4-carboxaldehyde is added, and the mixture is stirred at 20 to 30°C and 300 to 500 r / min for 20 to 24 hours, and dried at 50 to 60°C under vacuum conditions for 8 to 10 hours to obtain the ultraviolet absorbing monomer; the reaction process is as follows.

[0020] As an optimization, the preparation method of the dihydroxybenzeneacetonitrile is as follows: 4-aminobenzeneacetonitrile and 3-hydroxypropyl acrylate are added in a molar ratio of 1:2 to N,N-dimethylformamide with a mass of 8 to 10 times that of 4-aminobenzeneacetonitrile, and 1,5,7-triazabicyclo[4.4.0]dec-5-ene with a mass of 0.03 to 0.05 times that of 4-aminobenzeneacetonitrile is added, and the mixture is stirred at 45 to 55° C. and 300 to 500 r / min for 7 to 8 hours, and dried at 50 to 60° C. under vacuum conditions for 8 to 10 hours to obtain dihydroxybenzeneacetonitrile.

[0021] As an optimization, the model of the polypropylene glycol in step (2) is PPG-2000.

[0022] As an optimization, the preparation method of tungsten-doped titanium dioxide in step (3) is as follows: tetraethyl titanate, tungsten chloride, and anhydrous methanol are uniformly mixed in a mass ratio of 1: (0.1-0.12): (20-22), and stirred at 10-30°C and 300-500 r / min for 20-30 min to prepare a precursor solution; 1-octadecanol, oleic acid, and octadecene, which are 10-12 times the molar amount of tetraethyl titanate, are uniformly mixed in a mass ratio of 1: (0.7-0.8): (2-2.2), and stirred at 106-108°C and 300-400 r / min. , continue vacuuming for 18~22 minutes, under nitrogen atmosphere, heat to 128~132℃, continue stirring for 20~30 minutes, cool to 78~82℃, add precursor solution, continue stirring for 30~40 minutes, heat to 290~300℃ at a heating rate of 7℃ / min, continue stirring to react for 1~1.2 hours, cool to room temperature, filter, wash with acetone 3~5 times, dry at 60~70℃ under vacuum conditions for 10~12 hours, place in a ball mill, and ball mill at 280~320r / min for 10~12 hours to obtain tungsten-doped titanium dioxide.

[0023] As an optimization, the preparation method of the silane hydrolyzate in step (3) is as follows: chloropropyltriethoxysilane, an oxalic acid aqueous solution with a mass fraction of 4% to 6%, and anhydrous ethanol are uniformly mixed in a mass ratio of 1:(2~3):(20~30), and stirred at 10~30°C and 300~500r / min for 60~70min to prepare a silane hydrolyzate.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] When preparing the infrared shielding polyurethane glass film, the present invention comprises the following steps: reacting 4,4'-dihydroxybenzil with phosphorus pentasulfide and nickel chloride in sequence to obtain an organic nickel complex; reacting the organic nickel complex with 3-imidazole-1-propionic acid to obtain a functional crosslinking agent; reacting 4-aminobenzyl cyanide with 3-hydroxypropyl acrylate to obtain dihydroxybenzyl cyanide; reacting dihydroxybenzyl cyanide with quinoline-4-carboxaldehyde to obtain an ultraviolet absorption monomer; reacting polypropylene glycol, the ultraviolet absorption monomer, 1,4-butanediol and 4-chloromethyl-1,3-phenylenediisocyanate to obtain polyurethane; using tetraethyl titanate and tungsten chloride as raw materials, adopting a temperature rising method to obtain tungsten-doped titanium dioxide; reacting tungsten-doped titanium dioxide with chloropropyltriethoxysilane to obtain modified titanium dioxide; and uniformly mixing the polyurethane, modified titanium dioxide, the functional crosslinking agent and acetone, and coating and curing the mixture to obtain the infrared shielding polyurethane glass film.

[0026] First, 4,4'-dihydroxybenzil is reacted with phosphorus pentasulfide and nickel chloride in sequence to prepare an organic nickel complex, and four hydroxyl groups are introduced into the organic nickel complex; the organic nickel complex contains a thiodiene nickel complex structure, has strong absorption in the near-infrared region, and can improve the infrared shielding performance of the infrared shielding polyurethane glass film; the hydroxyl group on the organic nickel complex is reacted with the carboxyl group on 3-imidazole-1-propionic acid to prepare a functionalized cross-linker, and four alkylimidazole groups are introduced into the functionalized cross-linker; the alkylimidazole groups introduced into the functionalized cross-linker can react with the chlorine atoms on the side chains of the polyurethane molecules and the chlorine atoms on the modified titanium dioxide to generate imidazole salts, forming a cross-linked network structure, inhibiting the relative movement of the molecular chains, and giving the infrared shielding polyurethane glass film excellent mechanical properties; the generated imidazole salt is a cationic antibacterial agent, which can improve the antibacterial properties of the infrared shielding polyurethane glass film.

[0027] Secondly, the amino group on 4-aminophenylacetonitrile and the carbon-carbon double bond on 3-hydroxypropyl acrylate undergo Michael addition reaction to produce dihydroxyphenylacetonitrile; dihydroxyphenylacetonitrile and quinoline-4-carboxaldehyde react to produce a UV absorbing monomer; the UV absorbing monomer contains a phenyl-quinoline-acrylonitrile structure with hydroxyl groups at both ends; polypropylene glycol, the UV absorbing monomer, 1,4-butanediol and 4-chloromethyl-1,3-phenylenediisocyanate react and polymerize to produce polyurethane, introducing a phenyl-quinoline-acrylonitrile structure and a chlorine atom into the side chain of the polyurethane molecule; the phenyl-quinoline-acrylonitrile structure is naturally in the Z configuration, which is converted to the E configuration under the action of ultraviolet light and then returns to the Z configuration under light-proof conditions. This reversible cis-trans isomerization can absorb ultraviolet light and release the ultraviolet light energy in a harmless form, thereby improving the anti-aging performance of the infrared shielding polyurethane glass film. The mechanism of action is as follows:

[0028] ;

[0029] The chlorine atoms introduced on the side chains of the polyurethane molecules can react with the alkyl imidazole groups on the functionalized crosslinker to generate imidazole salts, forming a cross-linked network structure, inhibiting the relative slip between the polyurethane molecular chains, and improving the mechanical properties of the infrared shielding polyurethane glass film.

[0030] Finally, tungsten-doped titanium dioxide was prepared using tetraethyl titanate and tungsten chloride by a heating method; modified titanium dioxide was prepared by reacting tungsten-doped titanium dioxide with chloropropyltriethoxysilane; titanium dioxide has a large band gap and can only be excited by ultraviolet light, which only accounts for a very small amount of the energy of sunlight, but has no response to visible light and near-infrared light. After tungsten is doped into titanium dioxide, more electrons are released, forming free electrons, and the free electron content is significantly increased. Through the localized surface plasmon resonance effect, strong absorption is produced in the near-infrared region, thereby improving the infrared shielding performance of the infrared shielding polyurethane glass film; modified titanium dioxide was prepared by reacting tungsten-doped titanium dioxide with chloropropyltriethoxysilane, and chlorine atoms were introduced on the surface of the modified titanium dioxide; the chlorine atoms introduced on the surface of the modified titanium dioxide can react with the alkyl imidazole on the functionalized crosslinker to form an imidazole salt structure, increase the crosslinking sites, and further improve the mechanical properties of the infrared shielding polyurethane glass film. At the same time, the generated imidazole salt is a cationic antibacterial agent, which can improve the antibacterial performance of the infrared shielding polyurethane glass film. DETAILED DESCRIPTION

[0031] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0032] Example 1:

[0033] A method for preparing an infrared shielding polyurethane glass film, comprising the following steps:

[0034] (1) Nickel chloride and deionized water were mixed in a mass ratio of 1:9 to prepare a nickel chloride aqueous solution; 4,4'-dihydroxybenzil, phosphorus pentasulfide, ammonium sulfate, and 1,4-dioxane were mixed in a mass ratio of 1:1.6:0.4:8, stirred and refluxed at 104°C and 300 r / min for 4 hours under nitrogen protection, cooled to room temperature, filtered, and the filtrate was heated to 90°C. Under nitrogen atmosphere, 0.4 times the mass of nickel chloride aqueous solution of 4,4'-dihydroxybenzil was added, stirred and refluxed at 104°C and 300 r / min for 2.2 hours, cooled to room temperature, and washed with an equal volume of deionized water and carbon dioxide. The organic phase was washed with dimethyl ester and allowed to stand for stratification, and the organic phase was taken and dried at 50°C for 10 hours under vacuum conditions to obtain an organic nickel complex; the organic nickel complex and 3-imidazole-1-propionic acid were added in a molar ratio of 1:4 to m-xylene 10 times the mass of the organic nickel complex, and p-toluenesulfonic acid monohydrate 0.03 times the mass of the organic nickel complex was added, and under nitrogen protection, the mixture was stirred at 78°C and 200 r / min for 30 minutes, and the temperature was increased to 118°C at a heating rate of 10°C / h, and the stirring reaction was continued at 118°C for 40 minutes, and the mixture was dried at 50°C for 10 hours under vacuum conditions to obtain a functional cross-linking agent;

[0035] (2) 4-aminobenzeneacetonitrile and 3-hydroxypropyl acrylate were added in a molar ratio of 1:2 to N,N-dimethylformamide (8 times the mass of 4-aminobenzeneacetonitrile), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (0.03 times the mass of 4-aminobenzeneacetonitrile) was added, and the mixture was stirred at 45°C and 300 r / min for 8 hours. The mixture was dried at 50°C under vacuum for 10 hours to obtain dihydroxybenzeneacetonitrile. Dihydroxybenzeneacetonitrile and quinoline-4-carboxaldehyde were added in a molar ratio of 1:1 to ethanol (20 times the mass of quinoline-4-carboxaldehyde), and sodium hydroxide (0.03 times the mass of quinoline-4-carboxaldehyde) was added, and the mixture was stirred at 20°C and 300 r / min to obtain dihydroxybenzeneacetonitrile. The mixture was stirred and reacted for 24 hours, and dried at 50°C for 10 hours under vacuum conditions to obtain an ultraviolet absorbing monomer; polypropylene glycol, ultraviolet absorbing monomer, and N,N-dimethylformamide were uniformly mixed in a mass ratio of 1:0.6:8, stirred at 75°C and 300r / min for 12 minutes, 4-chloromethyl-1,3-phenylenediisocyanate (1.6 times the mass of polypropylene glycol) and dibutyltin dilaurate (0.02 times the mass of polypropylene glycol) were added, the temperature was raised to 90°C, the stirring reaction was continued for 3 hours, the temperature was lowered to 70°C, 1,4-butanediol (0.10 times the mass of polypropylene glycol) was added, the stirring was continued for 40 minutes, and the mixture was dried at 60°C for 11 hours under vacuum conditions to obtain a polyurethane;

[0036] (3) Tetraethyl titanate, tungsten chloride and anhydrous methanol were mixed in a mass ratio of 1:0.1:20, stirred at 10°C and 300 r / min for 30 minutes to prepare a precursor solution; 1-octadecanol, oleic acid and octadecene with a molar amount of 10 times that of tetraethyl titanate were mixed in a mass ratio of 1:0.7:2, stirred at 106°C and 300 r / min, and vacuumed for 18 minutes. In a nitrogen atmosphere, the temperature was raised to 128°C, stirred for 30 minutes, cooled to 78°C, and the precursor solution was added. The temperature was raised to 290°C at a heating rate of 7°C / min, and the reaction was stirred for 1.2 hours. The mixture was cooled to room temperature and allowed to stand for 18 minutes. The product was filtered, washed with acetone for 3 times, dried at 60°C for 12 hours under vacuum conditions, placed in a ball mill, and ball-milled at 280 r / min for 12 hours to obtain tungsten-doped titanium dioxide; chloropropyltriethoxysilane, a 4% oxalic acid aqueous solution, and anhydrous ethanol were mixed in a mass ratio of 1:2:20, stirred at 10°C and 300 r / min for 70 minutes to prepare a silane hydrolyzate; tungsten-doped titanium dioxide, silane hydrolyzate, and anhydrous ethanol were mixed in a mass ratio of 1:12:50, stirred at 55°C and 200 r / min for 3 hours, filtered, washed with anhydrous ethanol 3 times, and dried at 55°C for 10 hours under vacuum conditions to obtain modified titanium dioxide;

[0037] (4) Weigh 98 parts of polyurethane, 3 parts of modified titanium dioxide, 8 parts of functionalized crosslinking agent, and 200 parts of acetone by mass; mix the polyurethane, modified titanium dioxide, and acetone evenly, stir at 40°C and 100 r / min for 12 minutes, add the functionalized crosslinking agent, continue stirring for 3 minutes, and apply it on a glass plate with a coating thickness of 2 mm. Dry it at 60°C under vacuum conditions for 14 hours, and cool it to room temperature to obtain an infrared shielding polyurethane glass film.

[0038] Example 2:

[0039] A method for preparing an infrared shielding polyurethane glass film, comprising the following steps:

[0040] (1) Nickel chloride and deionized water were mixed at a mass ratio of 1:9.5 to prepare a nickel chloride aqueous solution; 4,4'-dihydroxybenzil, phosphorus pentasulfide, ammonium sulfate, and 1,4-dioxane were mixed at a mass ratio of 1:1.7:0.5:9, stirred and refluxed at 105°C and 400 r / min for 3.5 h under nitrogen protection, cooled to room temperature, filtered, and the filtrate was heated to 91°C. Under nitrogen atmosphere, a nickel chloride aqueous solution with a mass of 0.45 times that of 4,4'-dihydroxybenzil was added, stirred and refluxed at 105°C and 400 r / min for 2 h, cooled to room temperature, and washed with an equal volume of deionized water. The organic phase was mixed and washed with dimethyl carbonate, allowed to stand for stratification, and the organic phase was taken and dried at 55°C for 9 hours under vacuum conditions to obtain an organic nickel complex; the organic nickel complex and 3-imidazole-1-propionic acid were added in a molar ratio of 1:4 to m-xylene with a mass 11 times that of the organic nickel complex, and p-toluenesulfonic acid monohydrate with a mass 0.04 times that of the organic nickel complex was added, and under nitrogen protection, the mixture was stirred at 80°C and 250 r / min for 25 minutes, and the temperature was increased to 120°C at a heating rate of 10°C / h, and the stirring reaction was continued at 120°C for 35 minutes, and the mixture was dried at 55°C for 9 hours under vacuum conditions to obtain a functional cross-linking agent;

[0041] (2) Add 4-aminobenzeneacetonitrile and 3-hydroxypropyl acrylate in a molar ratio of 1:2 to N,N-dimethylformamide (9 times the mass of 4-aminobenzeneacetonitrile), add 1,5,7-triazabicyclo[4.4.0]dec-5-ene (0.04 times the mass of 4-aminobenzeneacetonitrile), stir at 50°C, 400 r / min for 7.5 h, and dry at 55°C under vacuum for 9 h to obtain dihydroxybenzeneacetonitrile; add dihydroxybenzeneacetonitrile and quinoline-4-carboxaldehyde in a molar ratio of 1:1 to ethanol (22 times the mass of quinoline-4-carboxaldehyde), add sodium hydroxide (0.04 times the mass of quinoline-4-carboxaldehyde), stir at 25°C, 400 r / min for 9 h, and obtain dihydroxybenzeneacetonitrile; The mixture was stirred for 22 hours, dried at 55°C under vacuum for 9 hours to obtain an ultraviolet absorbing monomer; polypropylene glycol, ultraviolet absorbing monomer and N,N-dimethylformamide were uniformly mixed in a mass ratio of 1:0.65:8.5, stirred at 80°C and 400r / min for 11 minutes, 4-chloromethyl-1,3-phenylenediisocyanate (1.7 times the mass of polypropylene glycol) and dibutyltin dilaurate (0.025 times the mass of polypropylene glycol) were added, the temperature was raised to 91°C, the stirring reaction was continued for 2.5 hours, the temperature was lowered to 71°C, 1,4-butanediol (0.11 times the mass of polypropylene glycol) was added, the stirring was continued for 35 minutes, and the polyurethane was dried at 65°C under vacuum for 10 hours to obtain the polyurethane;

[0042] (3) Tetraethyl titanate, tungsten chloride, and anhydrous methanol were mixed in a mass ratio of 1:0.11:21, stirred at 20°C and 400 r / min for 25 minutes to prepare a precursor solution; 1-octadecanol, oleic acid, and octadecene (11 times the molar amount of tetraethyl titanate) were mixed in a mass ratio of 1:0.75:2.1, stirred at 107°C and 350 r / min, and vacuumed for 20 minutes. In a nitrogen atmosphere, the temperature was raised to 130°C, stirred for 25 minutes, cooled to 80°C, and the precursor solution was added. The temperature was stirred for 35 minutes. The temperature was raised to 295°C at a heating rate of 7°C / min, and the reaction was stirred for 1.1 hours. The mixture was cooled to room temperature. The mixture was filtered, washed with acetone 4 times, dried at 65°C for 11 hours under vacuum conditions, placed in a ball mill, and ball-milled at 300 r / min for 11 hours to obtain tungsten-doped titanium dioxide; chloropropyltriethoxysilane, a 5% oxalic acid aqueous solution, and anhydrous ethanol were mixed in a mass ratio of 1:2.5:25, stirred at 20°C and 400 r / min for 65 minutes to prepare a silane hydrolyzate; tungsten-doped titanium dioxide, silane hydrolyzate, and anhydrous ethanol were mixed in a mass ratio of 1:13:55, stirred at 60°C and 300 r / min for 2.5 hours, filtered, washed with anhydrous ethanol 4 times, and dried at 60°C under vacuum conditions for 9 hours to obtain modified titanium dioxide;

[0043] (4) Weigh 100 parts of polyurethane, 3.5 parts of modified titanium dioxide, 9 parts of functionalized crosslinking agent, and 210 parts of acetone by mass; mix the polyurethane, modified titanium dioxide, and acetone evenly, stir at 45°C and 150 r / min for 11 minutes, add the functionalized crosslinking agent, continue stirring for 2.5 minutes, and apply it on a glass plate with a coating thickness of 2.5 mm. Dry it at 65°C under vacuum conditions for 13 hours, and cool it to room temperature to obtain an infrared shielding polyurethane glass film.

[0044] Example 3:

[0045] A method for preparing an infrared shielding polyurethane glass film, comprising the following steps:

[0046] (1) Nickel chloride and deionized water were mixed at a mass ratio of 1:10 to prepare a nickel chloride aqueous solution; 4,4'-dihydroxybenzil, phosphorus pentasulfide, ammonium sulfate, and 1,4-dioxane were mixed at a mass ratio of 1:1.8:0.6:10, stirred and refluxed at 106°C and 500 r / min for 3 h under nitrogen protection, cooled to room temperature, filtered, and the filtrate was heated to 92°C. Under nitrogen atmosphere, a nickel chloride aqueous solution 0.5 times the mass of 4,4'-dihydroxybenzil was added, stirred and refluxed at 106°C and 500 r / min for 1.8 h, cooled to room temperature, and washed with an equal volume of deionized water. The organic phase was mixed and washed with dimethyl carbonate, allowed to stand for stratification, and the organic phase was taken and dried at 60°C for 8 hours under vacuum conditions to obtain an organic nickel complex; the organic nickel complex and 3-imidazole-1-propionic acid were added in a molar ratio of 1:4 to m-xylene 12 times the mass of the organic nickel complex, and p-toluenesulfonic acid monohydrate 0.05 times the mass of the organic nickel complex was added, and under nitrogen protection, the mixture was stirred at 82°C and 300 r / min for 20 minutes, and the temperature was increased to 122°C at a heating rate of 10°C / h, and the stirring reaction was continued at 122°C for 30 minutes, and the mixture was dried at 60°C for 8 hours under vacuum conditions to obtain a functional cross-linking agent;

[0047] (2) 4-aminobenzeneacetonitrile and 3-hydroxypropyl acrylate were added to N,N-dimethylformamide (10 times the mass of 4-aminobenzeneacetonitrile) in a molar ratio of 1:2, and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (0.05 times the mass of 4-aminobenzeneacetonitrile) was added, and the mixture was stirred at 55°C and 500 r / min for 7 hours, and dried at 60°C under vacuum conditions for 8 hours to obtain dihydroxybenzeneacetonitrile; dihydroxybenzeneacetonitrile and quinoline-4-carboxaldehyde were added to ethanol (24 times the mass of quinoline-4-carboxaldehyde) in a molar ratio of 1:1, and sodium hydroxide (0.05 times the mass of quinoline-4-carboxaldehyde) was added, and the mixture was stirred at 30°C and 500 r / min .... The mixture was stirred and reacted for 20 hours, and dried at 60°C under vacuum conditions for 8 hours to obtain an ultraviolet absorbing monomer; polypropylene glycol, ultraviolet absorbing monomer, and N,N-dimethylformamide were uniformly mixed in a mass ratio of 1:0.7:9, stirred at 85°C and 500 r / min for 10 minutes, 4-chloromethyl-1,3-phenylenediisocyanate (1.8 times the mass of polypropylene glycol) and dibutyltin dilaurate (0.03 times the mass of polypropylene glycol) were added, the temperature was raised to 92°C, the mixture was stirred and reacted for 2 hours, the temperature was lowered to 72°C, 1,4-butanediol (0.12 times the mass of polypropylene glycol) was added, the mixture was stirred for 30 minutes, and the mixture was dried at 70°C under vacuum conditions for 9 hours to obtain a polyurethane;

[0048] (3) Tetraethyl titanate, tungsten chloride, and anhydrous methanol were mixed in a mass ratio of 1:0.12:22, stirred at 30°C and 500 r / min for 20 min to prepare a precursor solution; 1-octadecanol, oleic acid, and octadecene, which were 12 times the molar amount of tetraethyl titanate, were mixed in a mass ratio of 1:0.8:2.2, stirred at 108°C and 400 r / min, and vacuumed for 22 min. In a nitrogen atmosphere, the temperature was raised to 132°C, stirred for 20 min, cooled to 82°C, and the precursor solution was added. The temperature was stirred for 30 min, and the temperature was raised to 300°C at a heating rate of 7°C / min. The reaction was stirred for 1 h, and cooled to room temperature. The mixture was filtered, washed with acetone for 5 times, dried at 70°C for 10 h under vacuum conditions, placed in a ball mill, and ball-milled at 320 r / min for 10 h to obtain tungsten-doped titanium dioxide; chloropropyltriethoxysilane, a 6% oxalic acid aqueous solution, and anhydrous ethanol were mixed in a mass ratio of 1:3:30, stirred at 30°C and 500 r / min for 60 min to prepare a silane hydrolyzate; tungsten-doped titanium dioxide, silane hydrolyzate, and anhydrous ethanol were mixed in a mass ratio of 1:14:60, stirred at 65°C and 400 r / min for 2 h, filtered, washed with anhydrous ethanol 5 times, and dried at 65°C under vacuum conditions for 8 h to obtain modified titanium dioxide;

[0049] (4) Weigh 102 parts of polyurethane, 4 parts of modified titanium dioxide, 10 parts of functionalized crosslinking agent, and 220 parts of acetone by mass; mix the polyurethane, modified titanium dioxide, and acetone evenly, stir at 50°C and 200 r / min for 10 minutes, add the functionalized crosslinking agent, continue stirring for 2 minutes, and apply it on a glass plate with a coating thickness of 2 mm. Dry it at 70°C under vacuum for 12 hours, and cool it to room temperature to obtain an infrared shielding polyurethane glass film.

[0050] Comparative Example 1:

[0051] The preparation method of the infrared shielding polyurethane glass film of Comparative Example 1 differs from that of Example 2 in that step (1) is different. Step (1) is modified as follows: nickel chloride and deionized water are mixed uniformly in a mass ratio of 1:9.5 to prepare a nickel chloride aqueous solution; benzil, phosphorus pentasulfide, ammonium sulfate, and 1,4-dioxane are mixed uniformly in a mass ratio of 1:1.7:0.5:9, stirred and refluxed at 105°C and 400 r / min for 3.5 hours under nitrogen protection, cooled to room temperature, filtered, and the filtrate is heated to 91°C. Under nitrogen atmosphere, a nickel chloride aqueous solution 0.45 times the mass of benzil is added, stirred and refluxed at 105°C and 400 r / min for 2 hours, cooled to room temperature, washed with an equal volume of deionized water and dimethyl carbonate, allowed to stand for stratification, and the organic phase is taken and dried at 55°C under vacuum conditions for 9 hours to prepare a functionalized crosslinking agent. The remaining steps are the same as those of Example 2.

[0052] Comparative Example 2:

[0053] The preparation method of the infrared shielding polyurethane glass film of Comparative Example 2 differs from that of Example 2 in that step (1) is omitted and step (4) is modified as follows: 100 parts of polyurethane, 3.5 parts of modified titanium dioxide, and 210 parts of acetone are weighed, by mass; the polyurethane, modified titanium dioxide, and acetone are uniformly mixed, stirred at 45°C and 150 r / min for 13.5 minutes, coated on a glass plate to a coating thickness of 2.5 mm, dried at 65°C under vacuum conditions for 13 hours, and cooled to room temperature to obtain an infrared shielding polyurethane glass film. The remaining steps are the same as those of Example 2.

[0054] Comparative Example 3:

[0055] The preparation method of the infrared shielding polyurethane glass film of Comparative Example 3 differs from that of Example 2 only in step (2). Step (2) is modified as follows: polypropylene glycol, 1,6-hexanediol, and N,N-dimethylformamide are uniformly mixed in a mass ratio of 1:0.65:8.5, stirred at 80°C and 400 r / min for 11 min, 4-chloromethyl-1,3-phenylenediisocyanate (1.7 times the mass of the polypropylene glycol) and dibutyltin dilaurate (0.025 times the mass of the polypropylene glycol) are added, the temperature is raised to 91°C, the stirring reaction is continued for 2.5 h, the temperature is lowered to 71°C, 1,4-butanediol (0.11 times the mass of the polypropylene glycol) is added, the stirring is continued for 35 min, and the polyurethane is dried at 65°C under vacuum conditions for 10 h to obtain the polyurethane. The remaining steps are the same as those of Example 2.

[0056] Comparative Example 4:

[0057] The preparation method of the infrared shielding polyurethane glass film of Comparative Example 4 is different from that of Example 2 only in step (2). Step (2) is modified as follows: 4-aminobenzeneacetonitrile and 3-hydroxypropyl acrylate are added in a molar ratio of 1:2 to N,N-dimethylformamide with a mass of 9 times that of 4-aminobenzeneacetonitrile, 1,5,7-triazabicyclo[4.4.0]dec-5-ene with a mass of 0.04 times that of 4-aminobenzeneacetonitrile is added, the mixture is stirred at 50°C and 400r / min for 7.5h, and dried at 55°C under vacuum for 9h to obtain dihydroxybenzeneacetonitrile; dihydroxybenzeneacetonitrile and quinoline-4-carboxaldehyde are added in a molar ratio of 1:1 to ethanol with a mass of 22 times that of quinoline-4-carboxaldehyde, and quinoline-4-carboxaldehyde is added to obtain dihydroxybenzeneacetonitrile. A 0.04-fold sodium hydroxide solution was stirred at 25°C and 400 rpm for 22 hours, and then dried at 55°C under vacuum for 9 hours to produce a UV absorbing monomer. Polypropylene glycol, a UV absorbing monomer, and N,N-dimethylformamide were uniformly mixed in a mass ratio of 1:0.65:8.5, stirred at 80°C and 400 rpm for 11 minutes, 1,3-phenylenediisocyanate (1.7 times the mass of the polypropylene glycol) and dibutyltin dilaurate (0.025 times the mass of the polypropylene glycol) were added, the temperature was raised to 91°C, the stirring reaction continued for 2.5 hours, the temperature was lowered to 71°C, 1,4-butanediol (0.11 times the mass of the polypropylene glycol) was added, the stirring continued for 35 minutes, and the polyurethane was dried at 65°C under vacuum for 10 hours to produce the polyurethane. The remaining steps were the same as in Example 2.

[0058] Comparative Example 5:

[0059] The preparation method of the infrared shielding polyurethane glass film of Comparative Example 5 is different from that of Example 2 only in step (3). Step (3) is modified as follows: tetraethyl titanate, tungsten chloride, and anhydrous methanol are mixed uniformly in a mass ratio of 1:0.11:21, stirred at 20°C, 400r / min for 25min, and prepared into a precursor solution; 1-octadecanol (11 times the molar amount of tetraethyl titanate), oleic acid, and octadecene are mixed uniformly in a mass ratio of 1:0.75:2.1, stirred at 107°C, 35 0 r / min stirring condition, continue to vacuum for 20 minutes, under nitrogen atmosphere, heat to 130 ° C, continue stirring for 25 minutes, cool to 80 ° C, add the precursor solution, continue stirring for 35 minutes, heat to 295 ° C at a heating rate of 7 ° C / min, continue stirring and react for 1.1 hours, cool to room temperature, filter, wash with acetone 4 times, dry at 65 ° C under vacuum conditions for 11 hours, place in a ball mill, and ball mill at 300 r / min for 11 hours to obtain modified titanium dioxide. The remaining steps are the same as in Example 2.

[0060] Comparative Example 6:

[0061] The preparation method of the infrared shielding polyurethane glass film of Comparative Example 6 differs from that of Example 2 only in step (3). Step (3) is modified as follows: chloropropyltriethoxysilane, a 5% oxalic acid aqueous solution, and anhydrous ethanol are uniformly mixed in a mass ratio of 1:2.5:25, and stirred at 20°C and 400 r / min for 65 min to prepare a silane hydrolyzate; nano-titanium dioxide, the silane hydrolyzate, and anhydrous ethanol are uniformly mixed in a mass ratio of 1:13:55, stirred at 60°C and 300 r / min for 2.5 h, filtered, washed with anhydrous ethanol four times, and dried at 60°C under vacuum for 9 h to prepare modified titanium dioxide. The remaining steps are the same as those of Example 2.

[0062] Test Example 1

[0063] Infrared shielding performance test

[0064] Test Method: The transmittance of the examples and comparative examples was tested using a Shimadzu UV-3600i Plus UV-visible near-infrared spectrophotometer, and the near-infrared rejection was calculated. The results are shown in Table 1.

[0065] Table 1

[0066]

[0067] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 6 in Table 1, it can be found that the infrared shielding polyurethane glass film prepared in the present invention has good infrared shielding performance.

[0068] By comparison, the near-infrared blocking rates of Examples 1 to 3 are greater than that of Comparative Example 2, indicating that an organic nickel complex is prepared by reacting 4,4'-dihydroxybenzil with phosphorus pentasulfide and nickel chloride in sequence; the organic nickel complex contains a thiodiolefin nickel complex structure, has strong absorption in the near-infrared region, and can improve the infrared shielding performance of the infrared shielding polyurethane glass film.

[0069] By comparison, the near-infrared blocking rates of Examples 1 to 3 are greater than that of Comparative Example 6, indicating that tungsten-doped titanium dioxide was prepared using tetraethyl titanate and tungsten chloride as raw materials by a temperature rising method; titanium dioxide has a large band gap and can only be excited by ultraviolet light, which accounts for only a very small amount of the energy of sunlight, but has no response to visible light and near-infrared light. After tungsten is doped into titanium dioxide, more electrons are released to form free electrons, and the free electron content is significantly improved. Through the localized surface plasmon resonance effect, strong absorption is generated in the near-infrared region, thereby improving the infrared shielding performance of the infrared shielding polyurethane glass film.

[0070] Test Example 2

[0071] Testing of mechanical properties and anti-aging properties

[0072] Test Method: The examples and comparative examples were prepared into standard bars according to GB / T 1040.3. The tensile strength (M) of the standard bars was measured using an electronic universal testing machine. The standard bars were then placed in a bulb-type yellowing test chamber for accelerated aging. The light source was a red flame lamp with a wavelength of 320 nm to 400 nm and a maximum intensity wavelength of 360 nm. The standard bars were held 15 cm from the UVA lamp for 7 days. The tensile strength (N) of the standard bars after UV aging was measured, and the tensile strength change rate was calculated: tensile strength change rate = (MN) / M × 100%. The results are shown in Table 2.

[0073] Table 2

[0074]

[0075] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 6 in Table 2, it can be found that the infrared shielding polyurethane glass film prepared in the present invention has good mechanical properties and anti-aging properties.

[0076] By comparison, the tensile strength of Examples 1 to 3 is greater than that of Comparative Examples 1 to 2, indicating that 4,4'-dihydroxybenzil is reacted with phosphorus pentasulfide and nickel chloride in sequence to prepare an organic nickel complex, and four hydroxyl groups are introduced into the organic nickel complex; the hydroxyl groups on the organic nickel complex are reacted with the carboxyl groups on 3-imidazole-1-propionic acid to prepare a functionalized cross-linker, and four alkylimidazole groups are introduced into the functionalized cross-linker; the alkylimidazole groups introduced into the functionalized cross-linker can react with the chlorine atoms on the side chains of the polyurethane molecules and the chlorine atoms on the modified titanium dioxide to generate imidazole salts, forming a cross-linked network structure, inhibiting the relative movement of the molecular chains, and giving the infrared shielding polyurethane glass film excellent mechanical properties.

[0077] By comparison, the tensile strength of Examples 1 to 3 is greater than that of Comparative Example 4, indicating that polypropylene glycol, ultraviolet absorbing monomer, 1,4-butanediol and 4-chloromethyl-1,3-phenylenediisocyanate are reacted and polymerized to prepare polyurethane, and chlorine atoms are introduced into the side chains of the polyurethane molecules; the chlorine atoms introduced into the side chains of the polyurethane molecules can react with the alkyl imidazole groups on the functionalized cross-linking agent to generate imidazole salts, forming a cross-linked network structure, inhibiting the relative slip between the polyurethane molecular chains, and improving the mechanical properties of the infrared shielding polyurethane glass film.

[0078] By comparison, the tensile strength of Examples 1 to 3 is greater than that of Comparative Example 5, indicating that tungsten-doped titanium dioxide and chloropropyltriethoxysilane are reacted to prepare modified titanium dioxide, and chlorine atoms are introduced on the surface of the modified titanium dioxide; the chlorine atoms introduced on the surface of the modified titanium dioxide can react with the alkyl imidazole on the functionalized cross-linker to generate an imidazole salt structure, increase the cross-linking sites, and further improve the mechanical properties of the infrared shielding polyurethane glass film.

[0079] By comparison, the change rate of tensile strength of Examples 1 to 3 is less than the change rate of tensile strength of Comparative Example 3, indicating that the amino group on 4-aminobenzeneacetonitrile and the carbon-carbon double bond on 3-hydroxypropyl acrylate undergo Michael addition reaction to prepare dihydroxybenzeneacetonitrile; dihydroxybenzeneacetonitrile and quinoline-4-carboxaldehyde are reacted to prepare an ultraviolet absorbing monomer; the ultraviolet absorbing monomer contains a phenyl-quinoline-acrylonitrile structure and hydroxyl groups at both ends; polypropylene glycol, the ultraviolet absorbing monomer, 1,4-butanediol and 4-chloromethyl-1,3-phenylenediisocyanate are reacted and polymerized to prepare polyurethane, and a phenyl-quinoline-acrylonitrile structure is introduced into the side chain of the polyurethane molecule; the phenyl-quinoline-acrylonitrile structure is in the Z configuration in its natural state, and is converted to the E configuration under the action of ultraviolet light, and then returns to the Z configuration under light-proof conditions. This reversible cis-trans isomerization change can absorb ultraviolet light and release ultraviolet light energy in a harmless form, thereby improving the anti-aging performance of the infrared shielding polyurethane glass film.

[0080] Test Example 3

[0081] Antibacterial performance testing

[0082] Test method: Use a puncher to take a 6 mm diameter circular slice from the embodiment and the comparative example; use Staphylococcus aureus as the experimental strain, activate the experimental strain at 37°C for 24 hours, and prepare a concentration of 1×10 7 cfu / mL bacterial suspension; 0.2 ml of the bacterial suspension was evenly coated on the surface of beef extract peptone agar medium. A circular thin slice was then placed upside down on the surface of the medium and incubated in a constant temperature incubator at 37°C for 24 hours. The diameter of the inhibition zone was measured. The results are shown in Table 3.

[0083] Table 3

[0084]

[0085] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 6 in Table 3, it can be found that the infrared shielding polyurethane glass film prepared by the present invention has good antibacterial properties.

[0086] By comparison, the diameters of the inhibition zones of Examples 1 to 3 are larger than those of Comparative Examples 1 to 2, indicating that 4,4'-dihydroxybenzil is reacted with phosphorus pentasulfide and nickel chloride in sequence to prepare an organic nickel complex, and four hydroxyl groups are introduced into the organic nickel complex; the hydroxyl groups on the organic nickel complex are reacted with the carboxyl groups on 3-imidazole-1-propionic acid to prepare a functionalized cross-linker, and four alkylimidazole groups are introduced into the functionalized cross-linker; the alkylimidazole groups introduced into the functionalized cross-linker can react with the chlorine atoms on the side chains of the polyurethane molecules and the chlorine atoms on the modified titanium dioxide to generate imidazole salts. The generated imidazole salts are cationic antibacterial agents that can improve the antibacterial properties of infrared shielding polyurethane glass films.

[0087] By comparison, the diameters of the inhibition zones of Examples 1 to 3 are larger than that of Comparative Example 4, indicating that polypropylene glycol, an ultraviolet absorbing monomer, 1,4-butanediol and 4-chloromethyl-1,3-phenylenediisocyanate are reacted and polymerized to prepare polyurethane, and chlorine atoms are introduced into the side chains of the polyurethane molecules; the chlorine atoms introduced into the side chains of the polyurethane molecules can react with the alkyl imidazole groups on the functionalized cross-linking agent to form imidazole salts. The generated imidazole salts are cationic antibacterial agents and can enhance the antibacterial properties of the infrared shielding polyurethane glass film.

[0088] By comparison, the diameters of the inhibition zones of Examples 1 to 3 are larger than that of Comparative Example 5, indicating that tungsten-doped titanium dioxide and chloropropyltriethoxysilane are reacted to prepare modified titanium dioxide, and chlorine atoms are introduced on the surface of the modified titanium dioxide; the chlorine atoms introduced on the surface of the modified titanium dioxide can react with the alkyl imidazole on the functionalized cross-linker to form imidazole salts. The generated imidazole salts are cationic antibacterial agents and can enhance the antibacterial properties of infrared-shielding polyurethane glass films.

[0089] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. 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 infrared shielding polyurethane glass film, characterized in that: The infrared shielding polyurethane glass film is prepared by reacting an organic nickel complex and 3-imidazole-1-propionic acid to obtain a functional crosslinking agent; reacting and polymerizing polypropylene glycol, an ultraviolet absorbing monomer, 1,4-butanediol, and 4-chloromethyl-1,3-phenylenediisocyanate to obtain polyurethane; reacting tungsten-doped titanium dioxide and chloropropyltriethoxysilane to obtain modified titanium dioxide; and uniformly mixing the polyurethane, modified titanium dioxide, functional crosslinking agent, and acetone, followed by coating and curing. The organic nickel complex is prepared by reacting 4,4'-dihydroxybenzil with phosphorus pentasulfide and nickel chloride in sequence; The ultraviolet absorption monomer is prepared by reacting dihydroxyphenylacetonitrile and quinoline-4-carboxaldehyde; The dihydroxybenzeneacetonitrile is prepared by reacting 4-aminobenzeneacetonitrile and 3-hydroxypropyl acrylate; The tungsten-doped titanium dioxide is prepared by using tetraethyl titanate and tungsten chloride as raw materials through a temperature rising method.

2. A method for preparing the infrared shielding polyurethane glass film according to claim 1, characterized in that: The preparation method of the infrared shielding polyurethane glass film comprises the following preparation steps: (1) Add the organic nickel complex and 3-imidazole-1-propionic acid in a molar ratio of 1:4 to m-xylene (10-12 times the mass of the organic nickel complex), add p-toluenesulfonic acid monohydrate (0.03-0.05 times the mass of the organic nickel complex), and stir the mixture at 78-82°C and 200-300 r / min for 20-30 min under nitrogen protection. Heat the mixture to 118-122°C at a heating rate of 10°C / h, continue stirring the mixture at 118-122°C for 30-40 min, and dry the mixture at 50-60°C under vacuum for 8-10 h to obtain a functional crosslinking agent. (2) Polypropylene glycol, ultraviolet absorbing monomer, and N,N-dimethylformamide are mixed uniformly in a mass ratio of 1:(0.6~0.7):(8~9), stirred at 75~85℃ and 300~500r / min for 10~12min, 4-chloromethyl-1,3-phenylenediisocyanate (1.6~1.8 times the mass of polypropylene glycol) and dibutyltin dilaurate (0.02~0.03 times the mass of polypropylene glycol) are added, the temperature is raised to 90~92℃, the stirring reaction is continued for 2~3h, the temperature is lowered to 70~72℃, 1,4-butanediol (0.10~0.12 times the mass of polypropylene glycol) is added, the stirring is continued for 30~40min, and the polyurethane is dried at 60~70℃ under vacuum conditions for 9~11h to obtain polyurethane; (3) Tungsten-doped titanium dioxide, silane hydrolyzate, and anhydrous ethanol were mixed uniformly in a mass ratio of 1:(12-14):(50-60), stirred at 55-65°C and 200-400 r / min for 2-3 h, filtered, washed with anhydrous ethanol 3-5 times, and dried at 55-65°C under vacuum conditions for 8-10 h to obtain modified titanium dioxide; (4) Weigh 98-102 parts of polyurethane, 3-4 parts of modified titanium dioxide, 8-10 parts of functionalized crosslinking agent, and 200-220 parts of acetone by mass; mix the polyurethane, modified titanium dioxide, and acetone evenly, stir at 40-50°C and 100-200 r / min for 10-12 minutes, add the functionalized crosslinking agent, continue stirring for 2-3 minutes, and apply it on a glass plate with a coating thickness of 2-3 mm. Dry it at 60-70°C under vacuum conditions for 12-14 hours, and cool it to room temperature to obtain an infrared shielding polyurethane glass film.

3. The method for preparing an infrared shielding polyurethane glass film according to claim 2, characterized in that: The preparation method of the organic nickel complex in step (1) is as follows: 4,4'-dihydroxybenzil, phosphorus pentasulfide, ammonium sulfate, and 1,4-dioxane are mixed uniformly in a mass ratio of 1:(1.6~1.8):(0.4~0.6):(8~10), stirred and refluxed at 104~106°C and 300~500r / min for 3~4h under nitrogen protection, cooled to room temperature, filtered, and the filtrate is heated to 90~92°C. Under nitrogen atmosphere, a nickel chloride aqueous solution with a mass of 0.4~0.5 times that of 4,4'-dihydroxybenzil is added, stirred and refluxed at 104~106°C and 300~500r / min for 1.8~2.2h, cooled to room temperature, washed with an equal volume of deionized water and dimethyl carbonate, allowed to stand for stratification, and the organic phase is taken and dried at 50~60°C under vacuum conditions for 8~10h to obtain the organic nickel complex.

4. The method for preparing an infrared shielding polyurethane glass film according to claim 3, characterized in that: The nickel chloride aqueous solution is prepared by uniformly mixing nickel chloride and deionized water in a mass ratio of 1:(9-10) to prepare the nickel chloride aqueous solution.

5. The method for preparing an infrared shielding polyurethane glass film according to claim 2, wherein: The preparation method of the ultraviolet absorbing monomer in step (2) is as follows: dihydroxybenzene acetonitrile and quinoline-4-carboxaldehyde are added in a molar ratio of 1:1 to ethanol with a mass of 20 to 24 times that of quinoline-4-carboxaldehyde, and sodium hydroxide with a mass of 0.03 to 0.05 times that of quinoline-4-carboxaldehyde is added, and the mixture is stirred at 20 to 30°C and 300 to 500 r / min for 20 to 24 hours, and dried at 50 to 60°C under vacuum conditions for 8 to 10 hours to obtain the ultraviolet absorbing monomer.

6. The method for preparing an infrared shielding polyurethane glass film according to claim 5, characterized in that: The preparation method of the dihydroxybenzyl acetonitrile comprises: adding 4-aminobenzyl acetonitrile and 3-hydroxypropyl acrylate in a molar ratio of 1:2 to N,N-dimethylformamide (8 to 10 times the mass of 4-aminobenzyl acetonitrile), adding 1,5,7-triazabicyclo[4.4.0]dec-5-ene (0.03 to 0.05 times the mass of 4-aminobenzyl acetonitrile), stirring at 45 to 55° C. and 300 to 500 r / min for reaction for 7 to 8 hours, and drying at 50 to 60° C. under vacuum conditions for 8 to 10 hours to obtain the dihydroxybenzyl acetonitrile.

7. The method for preparing an infrared shielding polyurethane glass film according to claim 2, characterized in that: The model of the polypropylene glycol in step (2) is PPG-2000.

8. The method for preparing an infrared shielding polyurethane glass film according to claim 2, characterized in that: The preparation method of tungsten-doped titanium dioxide in step (3) is as follows: tetraethyl titanate, tungsten chloride, and anhydrous methanol are mixed uniformly in a mass ratio of 1: (0.1-0.12): (20-22), stirred at 10-30°C and 300-500r / min for 20-30min to prepare a precursor solution; 1-octadecanol, oleic acid, and octadecene, which are 10-12 times the molar amount of tetraethyl titanate, are mixed uniformly in a mass ratio of 1: (0.7-0.8): (2-2.2), stirred at 106-108°C and 300-400r / min for 20-30min. Continue to vacuum for 18~22 minutes, raise the temperature to 128~132℃ under nitrogen atmosphere, continue stirring for 20~30 minutes, cool to 78~82℃, add the precursor solution, continue stirring for 30~40 minutes, raise the temperature to 290~300℃ at a heating rate of 7℃ / min, continue stirring and react for 1~1.2 hours, cool to room temperature, filter, wash with acetone 3~5 times, dry at 60~70℃ under vacuum conditions for 10~12 hours, place in a ball mill, and ball mill at 280~320r / min for 10~12 hours to obtain tungsten-doped titanium dioxide.

9. The method for preparing an infrared shielding polyurethane glass film according to claim 2, wherein: The preparation method of the silane hydrolyzate in step (3) is as follows: chloropropyltriethoxysilane, an oxalic acid aqueous solution with a mass fraction of 4% to 6%, and anhydrous ethanol are uniformly mixed in a mass ratio of 1:(2-3):(20-30), and stirred at 10-30° C. and 300-500 r / min for 60-70 min to prepare a silane hydrolyzate.

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