Heat-insulating film material for automobile and preparation method of heat-insulating film material

Abstract

The invention discloses a preparation method of a heat-insulating film material for an automobile, which comprises the following steps: uniformly mixing a photoinitiator and a modified filler in a solution formed by copolymerization of a modified monomer and a butadiene free radical so as to initiate a cross-linking reaction on a PET (Polyethylene Terephthalate) film in an ultraviolet irradiation stage to prepare the heat-insulating film material for the automobile. The weight part ratio of the modified monomer to butadiene to the modified filler is (60-70): (30-40): (25-35). A modified monomer molecule contains benzophenone, Schiff base and benzotriazole structures, and the three structures have a synergistic effect, so that ultraviolet rays are efficiently protected, infrared rays are absorbed, and the membrane material is promoted to maintain long-term heat insulation stability. The modified filler is formed by taking hollow microspheres as a framework and coating a titanium dioxide and antimony-doped tin oxide double-layer film on the outer layer, and the double-layer coating film has a synergistic effect and inhibits radiation heat transfer. The flexible polyethylene glycol chain segment easily induces crazing, and the rigid shell layer bears and disperses part of stress, so that the toughness of the membrane material is remarkably improved.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of preparation of heat insulation film materials, in particular to a heat insulation film material for automobiles and a preparation method thereof. BACKGROUND

[0002] The heat insulation film is generally composed of multiple layers and can be divided into a base film layer, a wear-resistant layer, a glue layer and a release layer. The base film commonly used in the base film layer is a metal-plated PET base film, that is, a metal is attached to the surface of the PET film by using a magnetron sputtering or vacuum evaporation process. Therefore, the film material with a metal plating layer can interfere with signals of electronic devices and has a metal oxidation risk, which shortens the service life of the heat insulation film. Water and plastic need to be scraped during film pasting, and the car window needs to be opened and closed daily, and foreign matter may be scraped, so the film material needs to have mechanical properties. Therefore, a heat insulation film material with stable heat insulation and excellent toughening capacity needs to be prepared to solve the problems in actual application. SUMMARY

[0003] The application aims to provide a heat insulation film material for automobiles, which solves the problems of poor toughness and weak heat insulation capacity of the heat insulation film material at the present stage.

[0004] The purpose of the application can be achieved by the following technical solutions. A preparation method of a heat insulation film material for automobiles, specifically comprising the following steps: Step S1: uniformly mix a modified monomer, butadiene and 2-methyltetrahydrofuran, and under the conditions of a rotation speed of 150-200 r / min and a temperature of 50-70 DEG C, stir and add potassium persulfate, 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide and modified fillers, and react for 8-10 h to obtain a polymer solution; Step S2: coat the polymer solution on a PET base material by using a doctor blade coater, and under the conditions of a temperature of 60-80 DEG C, irradiate the polymer solution with ultraviolet light for 20-30 s, and then turn off the ultraviolet lamp and continue drying for 30-50 min to obtain the heat insulation film material for automobiles.

[0005] Further, the weight ratio of the modified monomer, butadiene, 2-methyltetrahydrofuran, potassium persulfate, 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide and modified fillers in step S1 is 60-70:30-40:150-180:0.5-0.6:0.5-0.6:25-35.

[0006] Further, the modified monomer is prepared by the following steps: Step A1: Intermediate 1 was prepared by mixing phthalic anhydride and pyridine uniformly, stirring and adding ethanol at a rotation speed of 90-100 r / min and a temperature of 40-60℃, and reacting for 4-6 h; intermediate 1, 1-hydroxybenzotriazole and dichloromethane were mixed uniformly, stirring and adding 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide at a rotation speed of 100-110 r / min and a temperature of 0-5℃, and reacting for 30-50 min; the temperature was raised to 20-30℃, stirring and adding p-acetamidophenol and triethylamine, and reacting for 4-6 h; Step A2: Intermediate 3 was prepared by mixing polyphosphoric acid and intermediate 2 uniformly, reacting for 2-3 h at a rotation speed of 80-100 r / min and a temperature of 140-150℃; intermediate 3 and ethanol were mixed uniformly, stirring and adding sodium hydroxide solution and dimethyl sulfate under the condition of nitrogen at a rotation speed of 100-120 r / min and a temperature of 0-5℃, and the temperature was raised to 20-30℃, and reacting for 2-3 h; intermediate 4, toluene and allyl polyethylene glycol were mixed uniformly, stirring and adding p-toluenesulfonic acid under the condition of nitrogen at a rotation speed of 110-120 r / min and a temperature of 80-110℃, and reacting for 4-6 h, to obtain intermediate 5; Step A3: Intermediate 6 was prepared by mixing phosphorus oxychloride and dimethylformamide uniformly, raising the temperature to 20-30℃ at a rotation speed of 110-120 r / min and a temperature of 0-5℃, and reacting for 30-50 min; stirring and adding intermediate 5, raising the temperature to 75-90℃, and reacting for 4-6 h; intermediate 6 and tetrahydrofuran were mixed uniformly, stirring and adding 5-aminobenzotriazole and anhydrous magnesium sulfate under the condition of a rotation speed of 120-130 r / min and a temperature of 60-70℃, and reacting for 3-4 h, to obtain intermediate 7; intermediate 7 and acetonitrile were mixed uniformly, stirring and adding iodotrimethylsilane under the condition of a rotation speed of 100-110 r / min and a temperature of 0-20℃, to obtain the modified monomer.

[0007] Further, the amount of phthalic anhydride, pyridine and ethanol in step A1 is 1 mmol: 3-5 mL: 1.2 mmol, and the amount of intermediate 1, 1-hydroxybenzotriazole, dichloromethane, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, p-acetamidophenol and triethylamine is 1.2 mmol: 1.5 mmol: 5-10 mL: 1.5 mmol: 1 mmol: 3 mmol.

[0008] Furthermore, in step A2, the ratio of intermediate 2 to polyphosphoric acid is 1 mmol: 5-7 g, the ratio of intermediate 3 to dimethyl sulfate is 0.2 mol: 36.8 g, the molar concentration of sodium hydroxide solution is 2 mol / L, the molar ratio of intermediate 4 to allyl polyethylene glycol is 1:1.1, the average relative molecular mass of allyl polyethylene glycol is 2400, and the amount of p-toluenesulfonic acid is 1-3% of the mass of allyl polyethylene glycol.

[0009] Further, in step A3, the amounts of phosphorus oxychloride, dimethylformamide, and intermediate 5 are 1.5 mmol: 5-10 mL: 1 mmol, the molar ratio of intermediate 6 to 5-aminobenzotriazole is 1:1.2, the amount of anhydrous magnesium sulfate is 3-5% of the mass of 5-aminobenzotriazole, and the ratio of intermediate 7 to iodotrimethylsilane is 1 mmol: 1.5 mmol.

[0010] Furthermore, the modified filler is prepared by the following steps: Step B1: Mix hollow microspheres, deionized water and sodium dodecylbenzenesulfonate evenly, stir at 150-170 r / min and 90-100℃, add titanium sulfate solution and sodium hydroxide solution, adjust the pH to 2-2.5, react for 2-4 h, dry at 110-120℃ for 3-4 h, calcine at 500-600℃ for 1-2 h to obtain the pretreated filler; Step B2: Mix tin tetrachloride pentahydrate, antimony trichloride and anhydrous ethanol evenly, stir and add deionized water and hydrochloric acid at a speed of 180-200 r / min and a temperature of 50-60℃, and react for 2-3 hours to obtain ATO sol. Step B3: Disperse the pretreated filler in ethanol, and stir and add ATO sol and deionized water at a speed of 120-130 r / min, a temperature of 60-80℃, and a pH of 2-3. React for 4-5 h, add ammonia water, adjust the pH to 4-5, stir and add mercaptotriethoxysilane, and react for 3-4 h. Dry and heat treat at 350-450℃ to obtain the modified filler.

[0011] Furthermore, the hollow microspheres described in step B1 have an average particle size of 40-50 μm and an average specific surface area of ​​0.202-0.228 m². 2 / g, the ratio of hollow microspheres to titanium sulfate solution is 5g:125-160g, the amount of sodium dodecylbenzenesulfonate is 3-5% of the mass of hollow microspheres, the mass fraction of sodium hydroxide solution is 10%, and the mass fraction of titanium sulfate solution is 10%.

[0012] Furthermore, in step B2, the molar ratio of tin tetrachloride pentahydrate to antimony trichloride is 25 mmol: 1-3 mmol, the mass fraction of hydrochloric acid is 5%, and the volume ratio of hydrochloric acid to tin tetrachloride pentahydrate is 10 mL: 1.2 g.

[0013] Furthermore, in step B3, the ratio of the pretreatment filler to ATO sol is 10g:4-6g, and the amount of mercaptotriethoxysilane is 3-5% of the mass of the pretreatment filler.

[0014] The beneficial effects of this invention are as follows: Using 2-methyltetrahydrofuran as a solvent, under heating conditions, the sulfate anion radicals generated by the decomposition of potassium persulfate initiate the copolymerization of the modified monomer and butadiene. A polymer solution is prepared by adding a photoinitiator, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and a modified filler. During the ultraviolet irradiation stage, under the action of the photoinitiator, the thiol groups on the modified filler react with the carbon-carbon double bonds on the copolymer product to obtain an automotive heat insulation film material.

[0015] Modified monomers: Under the catalysis of pyridine, the hydroxyl oxygen atom of ethanol nucleophilically attacks a carbonyl carbon of phthalic anhydride, undergoing ring-opening esterification to generate a carboxyl group and an ester group structure, yielding intermediate 1. The carboxyl group on intermediate 1 is then activated and undergoes esterification with acetaminophen to yield intermediate 2. Under the action of polyphosphoric acid, the phenolic ester structure on intermediate 2 undergoes Fries rearrangement, and the resulting acyl cation migrates intramolecularly to the ortho position of the aromatic ring, yielding intermediate 3. Under the action of sodium hydroxide, intermediate 3 generates a phenoxy anion, which nucleophilically attacks the methyl carbide ion of dimethyl sulfate, undergoing a substitution reaction to generate a methoxy group, yielding intermediate 4. The ester group on intermediate 4 and the hydroxyl group on allyl polyethylene glycol undergo transesterification under the action of a catalyst to form a new ester group structure, yielding intermediate 5. At low temperature, phosphorus oxychloride and dimethylformamide generate Vilsmeier reagent and undergo Vilsmeier-Haack reaction. The position with the highest charge density on the aromatic ring of intermediate 5 is the ortho position of the methoxy group, i.e., the 3 position. An aldehyde group is generated at the 3 position to obtain intermediate 6.

[0016] The ester group on intermediate 6 forms a Schiff base structure with the amino group on 5-aminobenzotriazole to obtain intermediate 7. Iodotrimethylsilane can selectively convert methoxy groups into hydroxyl groups, allowing the hydroxyl groups to form intramolecular hydrogen bonds with carbonyl oxygen to obtain the modified monomer.

[0017] Modified filler: Under strongly acidic conditions, titanium sulfate hydrolyzes to form metatitanic acid precipitate, which is electrostatically adsorbed onto the surface of hollow microspheres. After calcination, the metatitanic acid is converted into well-crystallized titanium dioxide, yielding the pretreated filler. The added hydrochloric acid precisely controls the hydrolysis rates of tin and antimony ions, preventing precipitation and promoting co-hydrolysis to synthesize a uniformly doped antimony-doped tin oxide sol, yielding ATO sol. By adjusting the pH value, the ethanol solution of the pretreated filler is provided with an acidic environment matching the ATO sol, preventing the added ATO sol from becoming unstable and agglomerating. Instead, it is gradually adsorbed onto the surface of the pretreated filler through van der Waals forces, hydrogen bonds, and other interactions. Under heating conditions, the hydroxyl groups on the ATO sol surface undergo hydrolysis and condensation reactions with the hydroxyl groups on the titanium dioxide surface, forming Ti-O-Sn bonds. Under pH 4-5 conditions, the ethoxy groups on mercaptotriethoxysilane hydrolyze to form silanol bonds, which then condense with the hydroxyl groups on the coating layer surface, forming covalent bonds. After heat treatment, the modified filler is obtained.

[0018] The benzophenone structure on the modified monomer molecule allows the carbonyl oxygen to form a chelate ring with the hydroxyl group on the aromatic ring. When the heat-insulating membrane material is exposed to ultraviolet radiation, it generates a large amount of heat, causing thermal vibrations in the molecule, which in turn breaks the hydrogen bonds, opening the chelate ring and forming a less stable structure. Upon returning to its original state, the excess heat is released, thus achieving the purpose of UV protection. The Schiff base molecule itself contains carbon-nitrogen conjugated double bonds. On the modified monomer molecule, this imine group is connected to the benzene ring, forming a larger conjugated system. When infrared radiation from sunlight hits the membrane material, it is efficiently absorbed by the Schiff base molecule, expanding the ultraviolet absorption range of the membrane material and simultaneously protecting against both UVA and UVB ultraviolet rays. The benzotriazole structure has extremely high photostability and thermal stability, protecting the membrane structure and core functional materials from damage and ensuring long-term heat insulation stability. Flexible polyethylene glycol segments are prone to inducing crazes, while rigid benzene ring microregions can effectively terminate the expansion of crazes and transform them into harmless shear bands. The formation, intersection, and interaction of crazing and shear bands require significant energy, thus substantially improving toughness. The modified filler consists of a hollow microsphere framework coated with a double-layer film of titanium dioxide and antimony-doped tin oxide. The hollow microspheres have low thermal conductivity, effectively blocking heat transfer, while the titanium dioxide and antimony-doped tin oxide layers work synergistically to suppress radiative heat transfer. Both titanium dioxide and antimony-doped tin oxide are rigid materials; when the material is subjected to stress, these rigid shells bear and disperse some of the stress. If the shells undergo minor cracking or plastic deformation under strong stress, this process also absorbs energy, thereby improving the overall toughness of the membrane material. Detailed Implementation

[0019] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0020] Example 1: A method for preparing an automotive heat insulation film material, specifically including the following steps: Step S1: Mix the modified monomer, butadiene and 2-methyltetrahydrofuran evenly, stir at 150 r / min and 50 ℃, add potassium persulfate, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and modified filler, and react for 8 h to obtain polymer solution. Step S2: Apply the polymer solution to the PET substrate using a doctor blade coater, irradiate with ultraviolet light at 60°C for 20 seconds, turn off the ultraviolet light and continue drying for 30 minutes to obtain the automotive heat insulation film material.

[0021] The weight ratio of the modified monomer, butadiene, 2-methyltetrahydrofuran, potassium persulfate, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and modified filler in step S1 is 60:30:150:0.5:0.5:25.

[0022] The modified monomer is prepared by the following steps: Step A1: Phthalic anhydride and pyridine are mixed evenly, stirred and ethanol is added at 90 r / min and 40 °C, and the reaction is carried out for 4 h to obtain intermediate 1. Intermediate 1, 1-hydroxybenzotriazole and dichloromethane are mixed evenly, stirred and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide is added at 100 r / min and 0 °C, and the reaction is carried out for 30 min. The temperature is raised to 20 °C, stirred and acetaminophen and triethylamine are added, and the reaction is carried out for 4 h to obtain intermediate 2. Step A2: Mix polyphosphoric acid and intermediate 2 evenly, and react for 2 hours at 80 r / min and 140℃ to obtain intermediate 3. Mix intermediate 3 and ethanol evenly, and stir at 100 r / min, 0℃, and nitrogen gas, while adding sodium hydroxide solution and dimethyl sulfate. Heat to 20℃ and react for 2 hours to obtain intermediate 4. Mix intermediate 4, toluene and allyl polyethylene glycol evenly, and stir at 110 r / min, 80℃, and nitrogen gas, while adding p-toluenesulfonic acid. React for 4 hours to obtain intermediate 5. Step A3: Phosphorus oxychloride and dimethylformamide are mixed evenly. Under conditions of 110 r / min and 0℃, the temperature is raised to 20℃ and reacted for 30 min. Intermediate 5 is added while stirring, and the temperature is raised to 75℃ and reacted for 4 h to obtain intermediate 6. Intermediate 6 and tetrahydrofuran are mixed evenly. Under conditions of 120 r / min and 60℃, 5-aminobenzotriazole and anhydrous magnesium sulfate are added while stirring and reacted for 3 h to obtain intermediate 7. Intermediate 7 and acetonitrile are mixed evenly. Under conditions of 100 r / min and 0℃, iodotrimethylsilane is added while stirring to obtain the modified monomer.

[0023] In step A1, the ratio of phthalic anhydride, pyridine, and ethanol is 1 mmol: 3 mL: 1.2 mmol, and the ratio of intermediate 1, 1-hydroxybenzotriazole, dichloromethane, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, acetaminophen, and triethylamine is 1.2 mmol: 1.5 mmol: 5 mL: 1.5 mmol: 1 mmol: 3 mmol.

[0024] In step A2, the ratio of intermediate 2 to polyphosphoric acid is 1 mmol: 5 g, the ratio of intermediate 3 to dimethyl sulfate is 0.2 mol: 36.8 g, the molar concentration of sodium hydroxide solution is 2 mol / L, the molar ratio of intermediate 4 to allyl polyethylene glycol is 1:1.1, the average relative molecular mass of allyl polyethylene glycol is 2400, and the amount of p-toluenesulfonic acid is 1% of the mass of allyl polyethylene glycol.

[0025] In step A3, the amounts of phosphorus oxychloride, dimethylformamide, and intermediate 5 are 1.5 mmol: 5 mL: 1 mmol, the molar ratio of intermediate 6 to 5-aminobenzotriazole is 1:1.2, the amount of anhydrous magnesium sulfate is 3% of the mass of 5-aminobenzotriazole, and the ratio of intermediate 7 to iodotrimethylsilane is 1 mmol: 1.5 mmol.

[0026] The modified filler is prepared by the following steps: Step B1: Hollow microspheres, deionized water and sodium dodecylbenzenesulfonate are mixed evenly. Under the conditions of 150 r / min and 90℃, titanium sulfate solution and sodium hydroxide solution are added and the pH value is adjusted to 2. The reaction is carried out for 2 hours, dried at 110℃ for 3 hours, and calcined at 500℃ for 1 hour to obtain the pretreated filler. Step B2: Mix tin tetrachloride pentahydrate, antimony trichloride and anhydrous ethanol evenly, stir at 180 r / min and 50 ℃, add deionized water and hydrochloric acid, and react for 2 h to obtain ATO sol. Step B3: Disperse the pretreatment filler in ethanol, stir and add ATO sol and deionized water at a speed of 120 r / min, a temperature of 60℃ and a pH of 2, and react for 4 h. Add ammonia water to adjust the pH to 4, stir and add mercaptotriethoxysilane, and react for 3 h. Dry and heat treat at 350℃ to obtain the modified filler.

[0027] The hollow microspheres described in step B1 have an average particle size of 40 μm and an average specific surface area of ​​0.202 m². 2 / g, the ratio of hollow microspheres to titanium sulfate solution is 5g:125g, the amount of sodium dodecylbenzenesulfonate is 3% of the mass of hollow microspheres, the mass fraction of sodium hydroxide solution is 10%, and the mass fraction of titanium sulfate solution is 10%.

[0028] In step B2, the molar ratio of tin tetrachloride pentahydrate to antimony trichloride is 25 mmol: 1 mmol, the mass fraction of hydrochloric acid is 5%, and the volume ratio of hydrochloric acid to tin tetrachloride pentahydrate is 10 mL: 1.2 g.

[0029] In step B3, the ratio of pretreatment filler to ATO sol is 10g:4g, and the amount of mercaptotriethoxysilane is 3% of the mass of the pretreatment filler.

[0030] Example 2, a method for preparing an automotive heat insulation film material, specifically includes the following steps: Step S1: Mix the modified monomer, butadiene and 2-methyltetrahydrofuran evenly, stir at 160 r / min and 65 ℃, add potassium persulfate, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and modified filler, and react for 9 h to obtain a polymer solution. Step S2: Apply the polymer solution to the PET substrate using a doctor blade coater, irradiate with ultraviolet light at 70°C for 25 seconds, turn off the ultraviolet light and continue drying for 40 minutes to obtain the automotive heat insulation film material.

[0031] The weight ratio of the modified monomer, butadiene, 2-methyltetrahydrofuran, potassium persulfate, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and modified filler in step S1 is 65:35:160:0.5:0.5:30.

[0032] The modified monomer is prepared by the following steps: Step A1: Phthalic anhydride and pyridine are mixed evenly, stirred and ethanol is added at 50°C and the mixture is stirred for 5 hours to obtain intermediate 1. Intermediate 1, 1-hydroxybenzotriazole and dichloromethane are mixed evenly, stirred and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide is added at 2°C and the mixture is stirred for 40 minutes. The mixture is then heated to 25°C, stirred and acetaminophen and triethylamine are added, and the mixture is stirred for 5 hours to obtain intermediate 2. Step A2: Mix polyphosphoric acid and intermediate 2 evenly, and react for 2 hours at 90 r / min and 145℃ to obtain intermediate 3. Mix intermediate 3 and ethanol evenly, and stir at 110 r / min and 2℃ with nitrogen gas, add sodium hydroxide solution and dimethyl sulfate, raise the temperature to 25℃ and react for 2 hours to obtain intermediate 4. Mix intermediate 4, toluene and allyl polyethylene glycol evenly, and stir at 115 r / min and 100℃ with nitrogen gas, add p-toluenesulfonic acid and react for 5 hours to obtain intermediate 5. Step A3: Phosphorus oxychloride and dimethylformamide are mixed evenly. The mixture is heated to 25°C at 115 r / min and 2°C and reacted for 40 min. Intermediate 5 is added while stirring, and the mixture is heated to 80°C and reacted for 5 h to obtain intermediate 6. Intermediate 6 and tetrahydrofuran are mixed evenly. The mixture is stirred at 125 r / min and 65°C and 5-aminobenzotriazole and anhydrous magnesium sulfate are added and reacted for 3 h to obtain intermediate 7. Intermediate 7 and acetonitrile are mixed evenly. The mixture is stirred at 105 r / min and 10°C and iodotrimethylsilane is added to obtain the modified monomer.

[0033] In step A1, the ratio of phthalic anhydride, pyridine, and ethanol is 1 mmol: 4 mL: 1.2 mmol, and the ratio of intermediate 1, 1-hydroxybenzotriazole, dichloromethane, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, acetaminophen, and triethylamine is 1.2 mmol: 1.5 mmol: 6 mL: 1.5 mmol: 1 mmol: 3 mmol.

[0034] In step A2, the ratio of intermediate 2 to polyphosphoric acid is 1 mmol: 6 g, the ratio of intermediate 3 to dimethyl sulfate is 0.2 mol: 36.8 g, the molar concentration of sodium hydroxide solution is 2 mol / L, the molar ratio of intermediate 4 to allyl polyethylene glycol is 1:1.1, the average relative molecular mass of allyl polyethylene glycol is 2400, and the amount of p-toluenesulfonic acid is 2% of the mass of allyl polyethylene glycol.

[0035] In step A3, the amounts of phosphorus oxychloride, dimethylformamide, and intermediate 5 are 1.5 mmol: 8 mL: 1 mmol, the molar ratio of intermediate 6 to 5-aminobenzotriazole is 1:1.2, the amount of anhydrous magnesium sulfate is 4% of the mass of 5-aminobenzotriazole, and the ratio of intermediate 7 to iodotrimethylsilane is 1 mmol: 1.5 mmol.

[0036] The modified filler is prepared by the following steps: Step B1: Hollow microspheres, deionized water and sodium dodecylbenzenesulfonate are mixed evenly. Under the conditions of 160 r / min and 95℃, titanium sulfate solution and sodium hydroxide solution are added and the pH value is adjusted to 2. The reaction is carried out for 3 h, dried at 110℃ for 3 h, and calcined at 550℃ for 1 h to obtain the pretreated filler. Step B2: Mix tin tetrachloride pentahydrate, antimony trichloride and anhydrous ethanol evenly, stir at 190 r / min and 55 ℃, add deionized water and hydrochloric acid, and react for 2 h to obtain ATO sol. Step B3: Disperse the pretreatment filler in ethanol, stir and add ATO sol and deionized water at a speed of 125 r / min, a temperature of 70℃ and a pH of 2, and react for 4 h. Add ammonia water to adjust the pH to 4, stir and add mercaptotriethoxysilane, and react for 3 h. Dry and heat treat at 400℃ to obtain the modified filler.

[0037] The hollow microspheres described in step B1 have an average particle size of 45 μm and an average specific surface area of ​​0.210 m². 2 / g, the ratio of hollow microspheres to titanium sulfate solution is 5g:140g, the amount of sodium dodecylbenzenesulfonate is 4% of the mass of hollow microspheres, the mass fraction of sodium hydroxide solution is 10%, and the mass fraction of titanium sulfate solution is 10%.

[0038] In step B2, the molar ratio of tin tetrachloride pentahydrate to antimony trichloride is 25 mmol: 2 mmol, the mass fraction of hydrochloric acid is 5%, and the volume ratio of hydrochloric acid to tin tetrachloride pentahydrate is 10 mL: 1.2 g.

[0039] In step B3, the ratio of pretreatment filler to ATO sol is 10g:4-6g, and the amount of mercaptotriethoxysilane is 4% of the mass of the pretreatment filler.

[0040] Example 3: A method for preparing an automotive heat insulation film material, specifically including the following steps: Step S1: Mix the modified monomer, butadiene and 2-methyltetrahydrofuran evenly, stir at 200 r / min and 70 ℃, add potassium persulfate, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and modified filler, and react for 10 h to obtain a polymer solution. Step S2: Apply the polymer solution to the PET substrate using a doctor blade coater, irradiate with ultraviolet light at 80°C for 30 seconds, turn off the ultraviolet light and continue drying for 50 minutes to obtain the automotive heat insulation film material.

[0041] The weight ratio of the modified monomer, butadiene, 2-methyltetrahydrofuran, potassium persulfate, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and modified filler in step S1 is 70:40:180:0.6:0.6:35.

[0042] The modified monomer is prepared by the following steps: Step A1: Phthalic anhydride and pyridine are mixed evenly, stirred and ethanol is added at 100 r / min and 60 °C, and the reaction is carried out for 6 h to obtain intermediate 1. Intermediate 1, 1-hydroxybenzotriazole and dichloromethane are mixed evenly, stirred and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide is added at 110 r / min and 5 °C, and the reaction is carried out for 50 min. The temperature is raised to 30 °C, stirred and acetaminophen and triethylamine are added, and the reaction is carried out for 6 h to obtain intermediate 2. Step A2: Mix polyphosphoric acid and intermediate 2 evenly, and react for 3 hours at 100 r / min and 150°C to obtain intermediate 3. Mix intermediate 3 and ethanol evenly, and stir at 120 r / min and 5°C with nitrogen purging. Add sodium hydroxide solution and dimethyl sulfate, heat to 30°C, and react for 3 hours to obtain intermediate 4. Mix intermediate 4, toluene, and allyl polyethylene glycol evenly, and stir at 120 r / min and 110°C with nitrogen purging. Add p-toluenesulfonic acid and react for 6 hours to obtain intermediate 5. Step A3: Phosphorus oxychloride and dimethylformamide are mixed evenly. The mixture is heated to 30°C at 120 r / min and 5°C for 50 min, and stirred. Intermediate 5 is added, and the mixture is heated to 90°C for 6 h to obtain intermediate 6. Intermediate 6 is mixed evenly with tetrahydrofuran. The mixture is stirred at 130 r / min and 70°C for 7 h, and 5-aminobenzotriazole and anhydrous magnesium sulfate are added to obtain intermediate 7. Intermediate 7 is mixed evenly with acetonitrile. The mixture is stirred at 110 r / min and 20°C for 20°C for 20 h, and iodotrimethylsilane is added to obtain the modified monomer.

[0043] In step A1, the ratio of phthalic anhydride, pyridine, and ethanol is 1 mmol: 5 mL: 1.2 mmol, and the ratio of intermediate 1, 1-hydroxybenzotriazole, dichloromethane, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, acetaminophen, and triethylamine is 1.2 mmol: 1.5 mmol: 10 mL: 1.5 mmol: 1 mmol: 3 mmol.

[0044] In step A2, the ratio of intermediate 2 to polyphosphoric acid is 1 mmol: 7 g, the ratio of intermediate 3 to dimethyl sulfate is 0.2 mol: 36.8 g, the molar concentration of sodium hydroxide solution is 2 mol / L, the molar ratio of intermediate 4 to allyl polyethylene glycol is 1:1.1, the average relative molecular mass of allyl polyethylene glycol is 2400, and the amount of p-toluenesulfonic acid is 3% of the mass of allyl polyethylene glycol.

[0045] In step A3, the amounts of phosphorus oxychloride, dimethylformamide, and intermediate 5 are 1.5 mmol:10 mL:1 mmol, the molar ratio of intermediate 6 to 5-aminobenzotriazole is 1:1.2, the amount of anhydrous magnesium sulfate is 5% of the mass of 5-aminobenzotriazole, and the ratio of intermediate 7 to iodotrimethylsilane is 1 mmol:1.5 mmol.

[0046] The modified filler is prepared by the following steps: Step B1: Hollow microspheres, deionized water and sodium dodecylbenzenesulfonate are mixed evenly. Under the conditions of 170 r / min and 100℃, titanium sulfate solution and sodium hydroxide solution are added and the pH value is adjusted to 2.5. The reaction is carried out for 4 h, dried at 120℃ for 4 h, and calcined at 600℃ for 2 h to obtain the pretreated filler. Step B2: Mix tin tetrachloride pentahydrate, antimony trichloride and anhydrous ethanol evenly, stir at 200 r / min and 60℃, add deionized water and hydrochloric acid, and react for 3 h to obtain ATO sol. Step B3: Disperse the pretreatment filler in ethanol, stir and add ATO sol and deionized water at a speed of 130 r / min, a temperature of 80℃ and a pH of 3, and react for 5 h. Add ammonia water to adjust the pH to 5, stir and add mercaptotriethoxysilane, and react for 4 h. Dry and heat treat at 450℃ to obtain the modified filler.

[0047] The hollow microspheres described in step B1 have an average particle size of 50 μm and an average specific surface area of ​​0.228 m². 2 / g, the ratio of hollow microspheres to titanium sulfate solution is 5g:160g, the amount of sodium dodecylbenzenesulfonate is 5% of the mass of hollow microspheres, the mass fraction of sodium hydroxide solution is 10%, and the mass fraction of titanium sulfate solution is 10%.

[0048] In step B2, the molar ratio of tin tetrachloride pentahydrate to antimony trichloride is 25 mmol:3 mmol, the mass fraction of hydrochloric acid is 5%, and the volume ratio of hydrochloric acid to tin tetrachloride pentahydrate is 10 mL:1.2 g.

[0049] In step B3, the ratio of pretreatment filler to ATO sol is 10g:6g, and the amount of mercaptotriethoxysilane is 5% of the mass of the pretreatment filler.

[0050] Comparative Example 1: This comparative example uses allyl polyethylene glycol instead of allyl alcohol, while the other steps are the same as in Example 1.

[0051] Comparative Example 2: In this comparative example, intermediate 7 is replaced by intermediate 5, while the other steps are the same as in Example 1.

[0052] Comparative Example 3: This comparative example uses pretreatment filler instead of modified filler, but the other steps are the same as in Example 1.

[0053] The automotive heat insulation film materials prepared in Examples 1-3 and Comparative Examples 1-3 were applied to ordinary flat glass. The ultraviolet transmittance and infrared transmittance were tested according to GB / T5137.4-2020 "Test Methods for Automotive Safety Glass Part 4: Solar Energy Characteristics Test". The test results are shown in Table 1. A flat test piece measuring 20cm × 20cm × 6mm was selected, with the test piece perpendicular to the incident light beam. The test was performed three times, and the average value was taken.

[0054] The automotive heat-insulating film materials prepared in Examples 1-3 and Comparative Examples 1-3 were applied to ordinary flat glass. The heat insulation performance was tested using the testing equipment specified in GB / T29501-2013 "Heat-Insulating Coated Glass". The test results are shown in Table 1. The sample size was 380mm × 380mm × 6mm, and the specimen was installed in a specimen frame with the coated side facing outwards. Double-sided adhesive was used to fill the lower part of the inner surface of the specimen to ensure that the outer surface of the specimen and the outer surface of the specimen frame were on the same horizontal plane, with no obvious gaps between the specimen and the specimen frame. Continuous irradiation was performed, and the temperature inside the chamber was recorded every 1 minute until the temperature inside the chamber stabilized.

[0055] The automotive heat insulation film materials prepared in Examples 1-3 and Comparative Examples 1-3 were tested for impact resistance according to GB / T8809-2015 "Plastic Films - Test Method for Pendulum Impact Resistance". The test results are shown in Table 1. The sample size was 100mm × 100mm, and a type A punch was selected.

[0056] Table 1

[0057] Table 1 shows that the ultraviolet transmittance of the automotive heat insulation film materials prepared in Examples 1-3 ranges from 0.35% to 0.51%, the infrared transmittance ranges from 8.55% to 10.24%, and the impact resistance ranges from 2.204 to 2.613 J. When the infrared device is turned on, the temperature inside the heat insulation box rises, and gradually approaches an equilibrium state over time. The lower the equilibrium temperature, the better the heat insulation effect. The test results show that the present invention has excellent heat insulation effect and toughening ability.

[0058] The above description is merely an example and illustration of the concept of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the concept of the invention or exceed the scope defined in the claims, they should all fall within the protection scope of the present invention.

Claims

1. A method for preparing an automotive heat insulation film material, characterized in that: Specifically comprising the following steps: Step S1: the modified monomer, butadiene and 2-methyltetrahydrofuran are mixed and stirred, and potassium persulfate, 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide and modified filler are added, and the reaction is carried out to obtain a polymer solution; Step S2: the polymer solution is coated on the PET substrate by using a doctor blade coater, and is irradiated by ultraviolet light, and then the drying process is continued after the ultraviolet lamp is turned off to obtain the heat insulation film material for automobile; The weight ratio of the modified monomer, butadiene, 2-methyltetrahydrofuran, potassium persulfate, 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide and modified filler in step S1 is 60-70:30-40:150-180:0.5-0.6:0.5-0.6:25-35.

2. The method of claim 1, wherein the method further comprises: The modified monomer is prepared by the following steps: Step A1: phthalic anhydride and pyridine are mixed and stirred, and ethanol is added, and the reaction is carried out to obtain intermediate 1, intermediate 1, 1-hydroxybenzotriazole and dichloromethane are mixed and stirred, and 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide is added, and the reaction is carried out, and then heated, stirred, and p-acetamidophenol and triethylamine are added, and the reaction is carried out to obtain intermediate 2; Step A2: polyphosphoric acid and intermediate 2 are mixed and stirred, and the reaction is carried out to obtain intermediate 3, intermediate 3 and ethanol are mixed and stirred, and sodium hydroxide solution and dimethyl sulfate are added, and the reaction is carried out to obtain intermediate 4, intermediate 4, toluene and allyl polyethylene glycol are mixed and stirred, and p-toluenesulfonic acid is added, and the reaction is carried out to obtain intermediate 5; Step A3: phosphorus oxychloride and dimethylformamide are mixed and stirred, and the reaction is carried out, and then heated, and intermediate 5 is added, and the reaction is carried out to obtain intermediate 6, intermediate 6 and tetrahydrofuran are mixed and stirred, and 5-aminobenzotriazole and anhydrous magnesium sulfate are added, and the reaction is carried out to obtain intermediate 7, intermediate 7 and acetonitrile are mixed and stirred, and iodotrimethylsilane is added to obtain the modified monomer.

3. The method of claim 2, wherein the method further comprises: The amount ratio of phthalic anhydride, pyridine and ethanol in step A1 is 1 mmol:3-5 mL:1.2 mmol, and the amount ratio of intermediate 1, 1-hydroxybenzotriazole, dichloromethane, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide, p-acetamidophenol and triethylamine is 1.2 mmol:1.5 mmol:5-10 mL:1.5 mmol:1 mmol:3 mmol.

4. The method of claim 2, wherein the method further comprises: The amount ratio of intermediate 2 and polyphosphoric acid in step A2 is 1 mmol:5-7 g, the amount ratio of intermediate 3 and dimethyl sulfate is 0.2 mol:36.8 g, the molar ratio of intermediate 4 and allyl polyethylene glycol is 1:1.1, and the amount of p-toluenesulfonic acid is 1-3% of the mass of allyl polyethylene glycol.

5. The method of claim 2, wherein the film material is prepared by the steps of: a) preparing a solution of the polymer and the additive; b) coating the solution on a substrate; c) drying the coated solution; and d) removing the substrate. The amount of phosphorus oxychloride, dimethylformamide and intermediate 5 in step A3 is 1.5 mmol:5-10 mL:1 mmol, the molar ratio of intermediate 6 and 5-aminobenzotriazole is 1:1.2, the amount of anhydrous magnesium sulfate is 3-5% of the mass of 5-aminobenzotriazole, and the amount ratio of intermediate 7 and iodotrimethylsilane is 1 mmol:1.5 mmol.

6. The method for preparing an automotive heat insulation film material according to claim 1, characterized in that: The modified filler is prepared by the following steps: Step B1: mixing hollow microspheres, deionized water and sodium dodecyl benzene sulfonate, stirring and adding titanium sulfate solution, adding sodium hydroxide solution, adjusting pH value, reacting, drying and calcining to prepare pretreated filler; Step B2: mixing tin tetrachloride pentahydrate and antimony trichloride, stirring and adding deionized water and hydrochloric acid, and reacting to prepare ATO sol; Step B3: dispersing the pretreated filler in ethanol, stirring and adding ATO sol and deionized water, reacting, adding ammonia water, adjusting pH, stirring and adding mercapto triethoxysilane, reacting, drying, and heat treating to prepare the modified filler.

7. The method of claim 6, wherein the method further comprises the step of: The amount ratio of hollow microspheres to titanium sulfate solution in step B1 is 5g:125-160g, and the amount of sodium dodecyl benzene sulfonate is 3-5% of the mass of hollow microspheres. ​ 8. The method of claim 6, wherein the method further comprises the step of: The molar ratio of tin tetrachloride pentahydrate to antimony trichloride in step B2 is 25mmol:1-3mmol, and the amount ratio of hydrochloric acid to tin tetrachloride pentahydrate is 10mL:1.2g. ​ 9. The method for preparing an automotive heat insulation film material according to claim 6, characterized in that: The amount ratio of pretreated filler to ATO sol in step B3 is 10g:4-6g, and the amount of mercapto triethoxysilane is 3-5% of the mass of pretreated filler.

10. A heat shield film material for an automobile, characterized by: Prepared according to the preparation method of any one of claims 1-9. Prepared according to the preparation method of any one of claims 1-9.

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