Antistatic automobile window film and preparation method thereof

Abstract

The present invention discloses an antistatic automotive window film and a preparation method thereof, relating to the technical field of antistatic automotive window film. In the preparation of the antistatic automotive window film, the present invention comprises the following steps: polymerizing pyrrole and 1-ethylene-1H-pyrrole on the surface of fluorine-doped titanium dioxide and indium-doped copper sulfide to produce polypyrrole-coated nanoparticles; reacting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with itaconic acid to produce carboxylated DOPO; reacting carboxylated DOPO with 3-imidazole-1-ylpropane-1,2-diol, butanediol, and terephthalic acid to produce polyester; reacting polyester with 1,2-epoxy-7-octene to produce functionalized polyester; and finally, calendering the functionalized polyester, hydrogenated silicone oil, and polypyrrole-coated nanoparticles to produce the antistatic automotive window film. The antistatic automotive window film prepared by the present invention has excellent infrared blocking, flame retardancy, antistatic, and mechanical properties.

Description

Technical Field

[0001] The present invention relates to the technical field of automobile window films, in particular to an antistatic automobile window film and a preparation method thereof. Background Art

[0002] As an important part of the automotive functional system, automotive window film has been upgraded from basic optical protection to an intelligent interface that integrates multiple physical and chemical properties. Its technical value is reflected in the comprehensive optimization of optical performance, safety protection, energy efficiency and electronic compatibility.

[0003] The antistatic properties of automotive window film effectively reduce dust absorption and keep window surfaces clean. Static electricity attracts tiny particles in the air, and long-term accumulation can reduce light transmittance, creating visual disturbances and increasing driving risks, especially in backlit environments. Furthermore, antistatic design reduces static interference with in-car electronic devices, preventing signal anomalies in navigation systems and on-board displays, and improving device stability. In dry environments, antistatic film can also reduce static discomfort experienced by passengers when they touch the windows, improving the riding experience. Infrared radiation blocking is the core function of antistatic automotive window film in achieving effective heat insulation. Infrared radiation in sunlight carries a significant amount of heat energy, accounting for approximately 53% of the total solar radiation. High-quality window film uses a metal sputtering layer or ceramic nanoparticles to selectively absorb or reflect infrared radiation, significantly reducing the amount of heat entering the vehicle interior. In hot summer weather, window film with high infrared rejection can reduce the interior temperature by 5-15°C, reducing the load on the air conditioner. This can reduce fuel consumption in gasoline-powered vehicles and extend the range of electric vehicles. In addition, continuous high temperature will accelerate the aging of leather and plastic parts in the car, causing deformation of the dashboard or fading of the interior. The infrared absorption function can delay material degradation.

[0004] However, current automotive window film technology generally has performance imbalance problems in actual applications. Products with different technical routes can often only optimize some core functions while sacrificing other performance indicators. Metal films rely on high-reflectivity metal layers, but sacrifice electromagnetic compatibility; organic dye films are limited by the stability of the molecular structure and it is difficult to balance infrared absorption and anti-aging. A more complex challenge comes from multifunctional synergy: when the window film integrates conductive, flame-retardant, and optical control layers, the difference in thermal expansion coefficients of each layer of material will lead to interlayer peeling under high-temperature conditions. Therefore, in order to overcome these limitations, it is necessary to invent an automotive window film that has good infrared absorption and anti-static properties at the same time, breaking through the single-function optimization thinking and achieving multifunctional synergy. Summary of the Invention

[0005] The purpose of the present invention is to provide an antistatic automobile window film and a preparation method thereof, so as to solve the problems existing in the prior art.

[0006] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0007] An antistatic automotive window film is provided. The antistatic automotive window film is prepared by polymerizing pyrrole and 1-ethylene-1H-pyrrole on the surface of fluorine-doped titanium dioxide and indium-doped copper sulfide to produce polypyrrole-coated nanoparticles; reacting carboxylated DOPO, 3-imidazol-1-ylpropane-1,2-diol, butanediol, terephthalic acid, and 1,2-epoxy-7-octene to produce functionalized polyester; and calendering the functionalized polyester, hydrogenated silicone oil, and polypyrrole-coated nanoparticles to produce the antistatic automotive window film.

[0008] The fluorine-doped titanium dioxide is prepared by reacting tetraethyl titanate and ammonium fluoride;

[0009] The indium-doped copper sulfide is prepared by reacting indium acetylacetonate and copper nitrate hydrate;

[0010] The carboxylated DOPO is prepared by reacting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and itaconic acid.

[0011] A method for preparing an antistatic automobile window film, comprising the following steps:

[0012] (1) Tetraethyl titanate, ammonium fluoride, octadecyl alcohol, octadecene, oleic acid, and oleylamine were mixed uniformly in a mass ratio of 1:(0.04-0.06):(11-12):(25-26):(0.88-0.92):(0.88-0.92). Under nitrogen atmosphere, the temperature was raised from 10-30°C to 110-130°C at a rate of 5°C / min while stirring at 200-300 r / min. The temperature was kept constant and vacuum was applied for 18-22 minutes. Then, the mixture was introduced into the mixture. The mixture was heated to normal pressure at a rate of 5°C / min and heated to 290-310°C, followed by stirring for 55-65 minutes, and then naturally cooled to room temperature. The mixture was centrifuged and washed with acetone and anhydrous ethanol 2-4 times each. The mixture was dried at 55-65°C under vacuum for 11-13 hours, and ultrasonically crushed for 18-22 minutes to obtain fluorine-doped nano-titanium dioxide. The fluorine-doped nano-titanium dioxide and indium-doped nano-copper sulfide were uniformly mixed in a mass ratio of 1:(0.04-0.06) to obtain nanoparticles.

[0013] (2) Pyrrole and 1-vinyl-1H-pyrrole were added to a hydrochloric acid aqueous solution with a molar ratio of 1:(0.4-0.6) at a mass ratio of 18 to 22 times the mass of pyrrole, and mixed uniformly to obtain a pyrrole mixed solution; the pyrrole mixed solution and the nanoparticle dispersion were mixed uniformly at a mass ratio of 1:(4-6), ultrasonically shaken for 18 to 22 minutes, and an ammonium persulfate aqueous solution with a mass of 0.1 to 0.2 times the mass of pyrrole was added, stirred at 10 to 30°C and 250 to 350 r / min for 3 to 5 hours, filtered, washed with anhydrous ethanol and deionized water 3 to 5 times each, and dried at 55 to 65°C under vacuum conditions for 22 to 26 hours to obtain polypyrrole-coated nanoparticles;

[0014] (3) Carboxylated DOPO, 3-imidazole-1-ylpropane-1,2-diol, butanediol, and terephthalic acid were mixed uniformly in a molar ratio of 1:1.1:1.1:1, and tetrabutyl titanate (0.2 to 0.3 times the mass of terephthalic acid) was added. The mixture was stabilized at 140 to 150°C for 10 minutes under a nitrogen atmosphere, then heated to 170 to 180°C, stabilized for 20 minutes, and slowly heated to 220 to 240°C at a heating rate of 20°C / h. The temperature was kept constant until the water output reached 90% of the theoretical amount. The mixture was heated to 260 to 280°C under vacuum conditions. The polyester was reacted for 2 to 4 hours, and the material was discharged under a nitrogen atmosphere to obtain a polyester; the polyester, N,N-dimethylformamide, and phenol were mixed uniformly in a mass ratio of 1:(25 to 35):(15 to 25), stirred at 85 to 95°C and 450 to 550 r / min for 20 to 22 minutes, cooled to 65 to 75°C, 1,2-epoxy-7-octene (0.15 to 0.25 times the mass of the polyester) was added, stirred at 250 to 350 r / min for 3 to 4 hours, and dried at 75 to 85°C under vacuum conditions for 10 to 12 hours to obtain a functionalized polyester;

[0015] (4) According to the mass fraction, 100 parts of functionalized polyester, 18-22 parts of hydrogenated silicone oil, 3-5 parts of polypyrrole-coated nanoparticles, and 0.5-0.9 parts of platinum activated carbon catalyst were weighed; the functionalized polyester, hydrogenated silicone oil, and polypyrrole-coated nanoparticles were mixed, placed in an internal mixer, and plasticized at 260-280°C for 10-12 minutes, the platinum activated carbon catalyst was added and mixed, and plasticized for 10-12 minutes was continued, and calendered on an SK type double-roll open mill, placed at 260-280°C for 2-4 hours, and naturally cooled to room temperature to obtain an antistatic automobile window film.

[0016] As an optimization, the preparation method of indium-doped copper sulfide in step (1) is as follows: copper nitrate hydrate, indium acetylacetonate, and hexadecylamine are added in a mass ratio of 1:(0.03-0.05):(3.8-4.0) to n-hexane 65-75 times the volume of hexadecylamine, mixed evenly, stirred at 55-65°C and 350-450r / min for 18-22min, added with carbon disulfide 0.4-0.6 times the mass of hexadecylamine, reacted at 110-130°C for 22-26h, naturally cooled to room temperature, centrifuged, washed with anhydrous ethanol 3-5 times, dried at 55-65°C under vacuum conditions for 10-14h, and ultrasonically crushed for 18-22min to obtain indium-doped nano-copper sulfide.

[0017] As an optimization, the method for preparing the nanoparticle dispersion described in step (2) is: nanoparticles and toluene are uniformly mixed in a mass ratio of 1:(18-22) to prepare a nanoparticle dispersion; the concentration of the hydrochloric acid aqueous solution is 1 mol / L; and the mass fraction of the ammonium persulfate aqueous solution is 10%.

[0018] As an optimization, the preparation method of the carboxylated DOPO in step (3) is as follows: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and itaconic acid are added in a molar ratio of 1:1 to xylene with a mass 6 to 8 times that of itaconic acid, reacted at 115 to 125° C. for 4 to 6 hours under a nitrogen atmosphere, cooled to 90 to 110° C., filtered, washed with tetrahydrofuran 2 to 4 times, and dried at 65 to 75° C. under vacuum conditions for 10 to 14 hours to obtain the carboxylated DOPO.

[0019] As an optimization, the process parameters of the calendering process in step (4) are as follows: the roller mixing temperature is set to 260-280°C, the roller gap is set to 2.00mm, 1.00mm, 0.75mm, 0.50mm, and 0.25mm in sequence, and the calendering cycle is repeated 5 times.

[0020] As an optimization, the model of the hydrogen-containing silicone oil in step (4) is MHX-1107; the model of the platinum activated carbon catalyst is HS-101.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] When preparing the antistatic automobile window film, the present invention comprises the following steps: polymerizing pyrrole and 1-ethylene-1H-pyrrole on the surfaces of fluorine-doped titanium dioxide and indium-doped copper sulfide to prepare polypyrrole-coated nanoparticles; reacting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and itaconic acid to prepare carboxylated DOPO; reacting carboxylated DOPO, 3-imidazole-1-ylpropane-1,2-diol, butanediol, and terephthalic acid to prepare polyester; reacting polyester and 1,2-epoxy-7-octene to prepare functionalized polyester; and subjecting the functionalized polyester, hydrogen-containing silicone oil, and polypyrrole-coated nanoparticles to a calendering process to prepare the antistatic automobile window film.

[0023] First, tetraethyl titanate and ammonium fluoride are reacted to produce fluorine-doped titanium dioxide, and indium acetylacetonate and copper nitrate hydrate are reacted to produce indium-doped copper sulfide. This can increase the free carrier concentration of titanium dioxide and copper sulfide, thereby enabling them to exhibit a plasmon resonance effect. Fluorine-doped titanium dioxide can effectively absorb near-infrared light in the 1500-2500nm band, while indium-doped copper sulfide has strong absorption of near-infrared light in the 1000-1500nm wavelength band. Fluorine-doped titanium dioxide and indium-doped copper sulfide are mixed to prepare nanoparticles, thereby endowing the antistatic automotive window film with broadband infrared absorption and excellent infrared blocking properties. Pyrrole and 1-vinyl-1H-pyrrole are polymerized on the surface of the nanoparticles to produce polypyrrole-coated nanoparticles. Polypyrrole is generated on the nanoparticles and carbon-carbon double bonds are introduced. The polypyrrole has good conductivity and forms a conductive network in the antistatic automotive window film, thereby improving the antistatic properties of the antistatic automotive window film.

[0024] Secondly, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was carboxylated with itaconic acid to obtain carboxylated DOPO, which was then polymerized with 3-imidazol-1-ylpropane-1,2-diol, butanediol, and terephthalic acid to obtain polyester. DOPO and alkylimidazole were introduced into the polyester, resulting in DOPO with good flame retardant properties. Polyester and 1,2-epoxy-7-octene were reacted to obtain functionalized polyester, and the alkylimidazole on the polyester was reacted with the epoxy group to form an imidazole salt. At the same time, a carbon-carbon double bond was introduced into the side chain of the functionalized polyester. The imidazole salt carries a stable ammonium cation that can increase the charge density of the polymer, giving it an excellent antistatic effect.

[0025] Finally, functionalized polyester, hydrogenated silicone oil, and polypyrrole-coated nanoparticles are reacted to produce antistatic automotive window film. The carbon-carbon double bonds on the functionalized polyester and polypyrrole-coated nanoparticles undergo addition reaction with the silicon-hydrogen bonds on the hydrogenated silicone oil. The silicon-oxygen bonds on the hydrogenated silicone oil have high bond energy and excellent thermal stability, and are not easy to break at high temperatures, which improves the flame retardancy of the antistatic automotive window film. At the same time, a cross-linked network is formed between the three, which inhibits the relative slippage between the molecular chains and gives the antistatic automotive window film excellent mechanical properties. DETAILED DESCRIPTION

[0026] 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.

[0027] The types of raw materials used in the following examples and comparative examples are as follows:

[0028] The concentration of the hydrochloric acid aqueous solution is 1 mol / L.

[0029] The mass fraction of the ammonium persulfate aqueous solution is 10%.

[0030] The model of the hydrogen-containing silicone oil is MHX-1107.

[0031] The model of the platinum activated carbon catalyst is HS-101.

[0032] Example 1:

[0033] A method for preparing an antistatic automobile window film, comprising the following steps:

[0034] (1) Tetraethyl titanate, ammonium fluoride, octadecyl alcohol, octadecene, oleic acid, and oleylamine were mixed uniformly in a mass ratio of 1:0.04:11:25:0.88:0.88. Under nitrogen atmosphere, the mixture was heated from 10°C to 110°C at a heating rate of 5°C / min with stirring at 200 r / min. The temperature was kept constant and vacuumed for 18 minutes. Nitrogen was then introduced to atmospheric pressure and the mixture was heated to 290°C at a heating rate of 5°C / min. The mixture was stirred for 65 minutes, cooled naturally to room temperature, centrifuged, washed twice with acetone and anhydrous ethanol, dried at 55°C for 13 hours under vacuum conditions, and ultrasonically crushed for 18 minutes. Fluorine-doped nano-titanium dioxide was prepared; copper nitrate hydrate, indium acetylacetonate, and hexadecylamine were added in a mass ratio of 1:0.03:3.8 to n-hexane (65 times the volume of hexadecylamine), mixed evenly, reacted at 55°C and 350 r / min with stirring for 22 minutes, carbon disulfide (0.4 times the mass of hexadecylamine) was added, reacted at 110°C for 26 hours, naturally cooled to room temperature, centrifuged, washed three times with anhydrous ethanol, dried at 55°C under vacuum conditions for 14 hours, and ultrasonically crushed for 18 minutes to prepare indium-doped nano-copper sulfide; fluorine-doped nano-titanium dioxide and indium-doped nano-copper sulfide were evenly mixed in a mass ratio of 1:0.04 to prepare nanoparticles;

[0035] (2) Pyrrole and 1-vinyl-1H-pyrrole were added to a 1 mol / L hydrochloric acid aqueous solution (18 times the mass of pyrrole) in a molar ratio of 1:0.4, and mixed uniformly to obtain a pyrrole mixed solution; nanoparticles and toluene were mixed uniformly in a mass ratio of 1:18 to obtain a nanoparticle dispersion; the pyrrole mixed solution and the nanoparticle dispersion were mixed uniformly in a mass ratio of 1:4, ultrasonically shaken for 18 minutes, and a 10% ammonium persulfate aqueous solution (0.1 times the mass of pyrrole) was added, stirred at 10°C and 250 r / min for 5 hours, filtered, washed with anhydrous ethanol and deionized water 3 times each, and dried at 55°C under vacuum conditions for 26 hours to obtain polypyrrole-coated nanoparticles;

[0036] (3) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and itaconic acid were added to xylene (6 times the mass of itaconic acid) in a molar ratio of 1:1, and stirred at 115°C and 300 r / min for 6 h under nitrogen atmosphere, cooled to 90°C, filtered, washed twice with tetrahydrofuran, and dried at 65°C for 14 h under vacuum conditions to obtain carboxylated DOPO; carboxylated DOPO, 3-imidazole-1-ylpropane-1,2-diol, butanediol, and terephthalic acid were mixed in a molar ratio of 1:1.1:1.1:1, and tetrabutyl titanate (0.2 times the mass of terephthalic acid) was added, and dried at 140°C and 140°C under nitrogen atmosphere. The mixture was stirred at 95°C for 22 minutes, then heated to 170°C and stabilized for 20 minutes. The mixture was slowly heated to 220°C at a heating rate of 20°C / h, and kept constant at a constant temperature until the water output reached 90% of the theoretical amount. The mixture was heated to 260°C under vacuum conditions and reacted for 4 hours. The mixture was discharged under a nitrogen atmosphere to obtain polyester. The polyester, N,N-dimethylformamide, and phenol were uniformly mixed in a mass ratio of 1:25:15, stirred at 95°C and 450 r / min for 22 minutes, cooled to 65°C, 1,2-epoxy-7-octene (0.15 times the mass of the polyester) was added, stirred at 250 r / min for 4 hours, and dried at 75°C under vacuum conditions for 12 hours to obtain a functionalized polyester.

[0037] (4) According to the mass fraction, 100 parts of functionalized polyester, 18 parts of hydrogenated silicone oil, 3 parts of polypyrrole-coated nanoparticles, and 0.5 parts of platinum activated carbon catalyst were weighed; the functionalized polyester, hydrogenated silicone oil, and polypyrrole-coated nanoparticles were mixed and placed in an internal mixer, and plasticized at 260°C for 12 minutes. The platinum activated carbon catalyst was added and mixed, and plasticized for 12 minutes. The mixture was then rolled on an SK type double-roll mill, with the roller mixing temperature set to 260°C and the roller gaps set to 2.00 mm, 1.00 mm, 0.75 mm, 0.50 mm, and 0.25 mm, respectively. The mixture was rolled 5 times in a cycle, and the mixture was kept at 260°C for 4 hours. The mixture was naturally cooled to room temperature to obtain an antistatic automotive window film.

[0038] Example 2:

[0039] A method for preparing an antistatic automobile window film, comprising the following steps:

[0040] (1) Tetraethyl titanate, ammonium fluoride, octadecyl alcohol, octadecene, oleic acid, and oleylamine were mixed uniformly in a mass ratio of 1:0.05:11.5:25.5:0.9:0.9. Under a nitrogen atmosphere, the mixture was stirred at 250 r / min and heated from 20°C to 120°C at a heating rate of 5°C / min. The temperature was kept constant and vacuumed for 20 min. Nitrogen was then introduced to atmospheric pressure and the mixture was heated to 300°C at a heating rate of 5°C / min. The mixture was stirred for 60 min, cooled to room temperature naturally, centrifuged, washed with acetone and anhydrous ethanol three times each, dried at 60°C under vacuum for 12 h, and ultrasonically crushed for 2 min. 0min to prepare fluorine-doped titanium dioxide; copper nitrate hydrate, indium acetylacetonate, and hexadecylamine were added to n-hexane with a mass ratio of 1:0.04:3.9, mixed evenly, and reacted at 60°C and 400r / min with stirring for 20min, and carbon disulfide with a mass of 0.5 times that of hexadecylamine was added, reacted at 120°C for 24h, naturally cooled to room temperature, centrifuged, washed with anhydrous ethanol 4 times, dried at 60°C for 12h under vacuum conditions, and ultrasonically crushed for 20min to prepare indium-doped copper sulfide; fluorine-doped titanium dioxide and indium-doped copper sulfide were mixed evenly with a mass ratio of 1:0.05 to prepare nanoparticles;

[0041] (2) Pyrrole and 1-vinyl-1H-pyrrole were added to a 1 mol / L hydrochloric acid aqueous solution with a molar ratio of 1:0.5, and mixed evenly to obtain a pyrrole mixed solution; nanoparticles and toluene were mixed evenly with a mass ratio of 1:20 to obtain a nanoparticle dispersion; the pyrrole mixed solution and the nanoparticle dispersion were mixed evenly with a mass ratio of 1:5, ultrasonically shaken for 20 minutes, and a 10% ammonium persulfate aqueous solution with a mass fraction of 0.15 times the mass of pyrrole was added, stirred at 20°C and 300 r / min for 4 hours, filtered, washed with anhydrous ethanol and deionized water 4 times each, and dried at 60°C under vacuum conditions for 24 hours to obtain polypyrrole-coated nanoparticles;

[0042] (3) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and itaconic acid were added to xylene (7 times the mass of itaconic acid) in a molar ratio of 1:1, stirred at 120°C and 350 r / min for 5 h under nitrogen atmosphere, cooled to 100°C, filtered, washed with tetrahydrofuran 3 times, and dried at 70°C for 12 h under vacuum conditions to obtain carboxylated DOPO; carboxylated DOPO, 3-imidazole-1-ylpropane-1,2-diol, butanediol, and terephthalic acid were mixed in a molar ratio of 1:1.1:1.1:1, and tetrabutyl titanate (0.25 times the mass of terephthalic acid) was added. Under nitrogen atmosphere, 14 The mixture was stabilized at 5°C for 10 minutes, heated to 175°C, stabilized for 20 minutes, and slowly heated to 230°C at a heating rate of 20°C / h. The temperature was kept constant until the water output reached 90% of the theoretical amount. Under vacuum conditions, the mixture was heated to 270°C for reaction for 3 hours, and discharged under a nitrogen atmosphere to obtain polyester. The polyester, N,N-dimethylformamide, and phenol were uniformly mixed in a mass ratio of 1:30:20, stirred at 90°C and 500 r / min for 21 minutes, cooled to 70°C, 1,2-epoxy-7-octene (0.2 times the mass of the polyester) was added, stirred at 300 r / min for reaction for 3.5 hours, and dried at 80°C for 11 hours under vacuum conditions to obtain functionalized polyester.

[0043] (4) According to the mass fraction, 100 parts of functionalized polyester, 20 parts of hydrogenated silicone oil, 4 parts of polypyrrole-coated nanoparticles, and 0.7 parts of platinum activated carbon catalyst were weighed; the functionalized polyester, hydrogenated silicone oil, and polypyrrole-coated nanoparticles were mixed and placed in an internal mixer, and plasticized at 270°C for 11 minutes. The platinum activated carbon catalyst was added and mixed, and plasticized for 11 minutes. The mixture was calendered on an SK type double-roll mill, and the roller mixing temperature was set to 270°C. The roller gap was set to 2.00 mm, 1.00 mm, 0.75 mm, 0.50 mm, and 0.25 mm in sequence. The mixture was calendered 5 times in a cycle, and the mixture was kept at 270°C for 3 hours. The mixture was naturally cooled to room temperature to obtain an antistatic automotive window film.

[0044] Example 3:

[0045] A method for preparing an antistatic automobile window film, comprising the following steps:

[0046] (1) Tetraethyl titanate, ammonium fluoride, octadecyl alcohol, octadecene, oleic acid, and oleylamine were mixed uniformly in a mass ratio of 1:0.06:12:26:0.92:0.92. Under nitrogen atmosphere, the mixture was stirred at 300 r / min and heated from 30°C to 130°C at a heating rate of 5°C / min. The temperature was kept constant and vacuumed for 18 min. Nitrogen was then introduced to atmospheric pressure and the mixture was heated to 310°C at a heating rate of 5°C / min. The mixture was stirred for 55 min, cooled to room temperature naturally, centrifuged, washed with acetone and anhydrous ethanol 4 times each, dried at 65°C under vacuum for 11 h, and ultrasonically crushed for 22 min. min to prepare fluorine-doped titanium dioxide; copper nitrate hydrate, indium acetylacetonate, and hexadecylamine were added in a mass ratio of 1:0.04:4.0 to n-hexane (75 times the volume of hexadecylamine), mixed evenly, and reacted at 65°C and 450r / min with stirring for 18 minutes; carbon disulfide (0.6 times the mass of hexadecylamine) was added, reacted at 130°C for 22 hours, naturally cooled to room temperature, centrifuged, washed with anhydrous ethanol 5 times, dried at 65°C for 10 hours under vacuum conditions, and ultrasonically crushed for 22 minutes to prepare indium-doped copper sulfide; fluorine-doped titanium dioxide and indium-doped copper sulfide were evenly mixed in a mass ratio of 1:0.06 to prepare nanoparticles;

[0047] (2) Pyrrole and 1-vinyl-1H-pyrrole were added to a 1 mol / L hydrochloric acid aqueous solution with a molar ratio of 1:0.6, and mixed evenly to obtain a pyrrole mixed solution; nanoparticles and toluene were mixed evenly with a mass ratio of 1:22 to obtain a nanoparticle dispersion; the pyrrole mixed solution and the nanoparticle dispersion were mixed evenly with a mass ratio of 1:6, ultrasonically shaken for 22 minutes, and a 10% ammonium persulfate aqueous solution with a mass fraction of 0.2 times the mass of pyrrole was added, stirred at 30°C and 350 r / min for 3 hours, filtered, washed with anhydrous ethanol and deionized water 5 times each, and dried at 65°C under vacuum conditions for 22 hours to obtain polypyrrole-coated nanoparticles;

[0048] (3) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and itaconic acid were added to xylene with a molar ratio of 1:1, and stirred at 125°C and 400 r / min for 4 h under nitrogen atmosphere, cooled to 110°C, filtered, washed with tetrahydrofuran 4 times, and dried at 75°C for 10 h under vacuum conditions to obtain carboxylated DOPO; carboxylated DOPO, 3-imidazole-1-ylpropane-1,2-diol, butanediol, and terephthalic acid were mixed at a molar ratio of 1:1.1:1.1:1, and tetrabutyl titanate with a mass of 0.3 times that of terephthalic acid was added, and dried at 15 The mixture was stabilized at 0°C for 10 minutes, heated to 180°C, stabilized for 20 minutes, and slowly heated to 240°C at a heating rate of 20°C / h. The temperature was kept constant until the water output reached 90% of the theoretical amount. Under vacuum conditions, the temperature was raised to 280°C for reaction for 2 hours, and the material was discharged under a nitrogen atmosphere to obtain polyester. The polyester, N,N-dimethylformamide, and phenol were uniformly mixed in a mass ratio of 1:35:25, stirred at 95°C and 550 r / min for 20 minutes, cooled to 75°C, 1,2-epoxy-7-octene (0.25 times the mass of the polyester) was added, stirred at 350 r / min for reaction for 3 hours, and dried at 85°C for 10 hours under vacuum conditions to obtain functionalized polyester.

[0049] (4) According to the mass fraction, 100 parts of functionalized polyester, 22 parts of hydrogenated silicone oil, 5 parts of polypyrrole-coated nanoparticles, and 0.9 parts of platinum activated carbon catalyst were weighed; the functionalized polyester, hydrogenated silicone oil, and polypyrrole-coated nanoparticles were mixed and placed in an internal mixer, and plasticized at 280°C for 10 minutes. The platinum activated carbon catalyst was added and mixed, and plasticized for 10 minutes. The mixture was then rolled on an SK type double-roll mill, with the roller mixing temperature set to 280°C and the roller gaps set to 2.00 mm, 1.00 mm, 0.75 mm, 0.50 mm, and 0.25 mm, respectively. The mixture was rolled 5 times in a cycle, and the mixture was kept at 280°C for 2 hours. The mixture was naturally cooled to room temperature to obtain an antistatic automotive window film.

[0050] Comparative Example 1:

[0051] The preparation method of the antistatic automotive window film of Comparative Example 1 differs from that of Example 2 only in step (1). Step (1) is modified as follows: copper nitrate hydrate, indium acetylacetonate, and hexadecylamine are added in a mass ratio of 1:0.04:3.9 to n-hexane (70 times the volume of hexadecylamine), mixed uniformly, stirred at 60°C and 400 rpm for 20 minutes, carbon disulfide (0.5 times the mass of hexadecylamine) is added, reacted at 120°C for 24 hours, cooled naturally to room temperature, centrifuged, washed four times with anhydrous ethanol, dried at 60°C for 12 hours under vacuum conditions, and ultrasonically crushed for 20 minutes to prepare indium-doped copper sulfide; titanium dioxide and indium-doped copper sulfide are mixed uniformly in a mass ratio of 1:0.05 to prepare nanoparticles; the particle size of the titanium dioxide is 10 nm. The remaining steps are the same as those of Example 2.

[0052] Comparative Example 2:

[0053] The preparation method of the antistatic automotive window film of Comparative Example 2 differs from that of Example 2 only in step (1). Step (1) is modified as follows: tetraethyl titanate, ammonium fluoride, octadecanol, octadecene, oleic acid, and oleylamine are uniformly mixed in a mass ratio of 1:0.05:11.5:25.5:0.9:0.9, and the mixture is heated from 20°C to 120°C at a heating rate of 5°C / min under a nitrogen atmosphere with stirring at 250 r / min. The temperature is maintained constant and vacuumed for 20 min. Nitrogen is then introduced to atmospheric pressure, and the mixture is heated to 300°C at a heating rate of 5°C / min. The mixture is stirred and reacted for 60 min. The mixture is naturally cooled to room temperature, centrifuged, washed with acetone and anhydrous ethanol three times each, dried at 60°C under vacuum for 12 h, and ultrasonically crushed for 20 min to obtain nanoparticles. The remaining steps are the same as those of Example 2.

[0054] Comparative Example 3:

[0055] The method for preparing the antistatic automotive window film of Comparative Example 3 differs from that of Example 2 in that step (2) is omitted and step (4) is modified as follows: 100 parts of functionalized polyester, 20 parts of hydrogenated silicone oil, 4 parts of nanoparticles, and 0.7 parts of platinum activated carbon catalyst are weighed, by mass; the functionalized polyester, hydrogenated silicone oil, and nanoparticles are mixed and placed in an internal mixer, and plasticized at 270° C. for 11 minutes. The platinum activated carbon catalyst is added and mixed, and plasticized for another 11 minutes. The mixture is then rolled on an SK two-roll mill, with the roller mixing temperature set to 270° C. and the roller gaps set to 2.00 mm, 1.00 mm, 0.75 mm, 0.50 mm, and 0.25 mm, in a cycle of five times, and the mixture is kept at 270° C. for 3 hours and naturally cooled to room temperature to produce the antistatic automotive window film. The remaining steps are the same as those of Example 2.

[0056] Comparative Example 4:

[0057] The preparation method of the antistatic automobile window film of Comparative Example 4 differs from that of Example 2 only in step (3). Step (3) is modified as follows: 3-imidazole-1-ylpropane-1,2-diol, butanediol, and terephthalic acid are mixed uniformly in a molar ratio of 1.1:1.1:2, and tetrabutyl titanate (0.125 times the mass of terephthalic acid) is added. In a nitrogen atmosphere, the mixture is stabilized at 145°C for 10 minutes, heated to 175°C, stabilized for 20 minutes, and slowly heated to 230°C at a heating rate of 20°C / h. The temperature was maintained constant until the water output reached 90% of the theoretical amount. The reaction was then heated to 270°C under vacuum for 3 hours, and the mixture was discharged under a nitrogen atmosphere to produce polyester. Polyester, N,N-dimethylformamide, and phenol were uniformly mixed in a mass ratio of 1:30:20, stirred at 90°C and 500 rpm for 21 minutes, cooled to 70°C, and 1,2-epoxy-7-octene (0.2 times the mass of the polyester) was added. The mixture was stirred at 300 rpm for 3.5 hours, and dried at 80°C under vacuum for 11 hours to produce functionalized polyester. The remaining steps were the same as in Example 2.

[0058] Comparative Example 5:

[0059] The preparation method of the antistatic automobile window film of Comparative Example 5 is different from that of Example 2 only in step (3). Step (3) is modified as follows: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and itaconic acid are added to xylene with a molar ratio of 1:1 at 7 times the mass of itaconic acid, and the mixture is stirred at 120°C and 350r / min under a nitrogen atmosphere for 5h, cooled to 100°C, filtered, washed with tetrahydrofuran 3 times, and dried at 70°C under vacuum for 12h to obtain carboxylated DOPO; the carboxylated DOPO is obtained. DOPO, 3-imidazol-1-ylpropane-1,2-diol, butanediol, and terephthalic acid were uniformly mixed in a molar ratio of 1:1.1:1.1:1. Then, tetrabutyl titanate (0.25 times the mass of the terephthalic acid) was added. Under a nitrogen atmosphere, the mixture was stabilized at 145°C for 10 minutes. The temperature was then raised to 175°C and stabilized for 20 minutes. The temperature was then slowly raised to 230°C at a rate of 20°C / h and maintained until the water output reached 90% of the theoretical amount. The mixture was then heated to 270°C under vacuum for 3 hours. The mixture was discharged under a nitrogen atmosphere to produce a functionalized polyester. The remaining steps were the same as in Example 2.

[0060] Comparative Example 6:

[0061] The preparation method of the antistatic automotive window film of Comparative Example 6 differs from that of Example 2 only in step (4), which is modified as follows: 100 parts by mass of functionalized polyester, 4 parts of polypyrrole-coated nanoparticles, and 0.7 parts of platinum activated carbon catalyst are weighed; the functionalized polyester and polypyrrole-coated nanoparticles are mixed, placed in an internal mixer, and plasticized at 270°C for 11 minutes. The platinum activated carbon catalyst is added and mixed, and plasticized for another 11 minutes. The mixture is then rolled on an SK two-roll mill, with the roller mixing temperature set to 270°C and the roller gaps set to 2.00 mm, 1.00 mm, 0.75 mm, 0.50 mm, and 0.25 mm, in a cycle of five times, and the mixture is kept at 270°C for 3 hours and naturally cooled to room temperature to produce the antistatic automotive window film. The remaining steps are the same as those of Example 2.

[0062] Test Example 1

[0063] Antistatic performance test

[0064] Test Method: The test voltage was set at 500V. Before testing, the samples were conditioned at 23°C and 50% relative humidity for 24 hours. The surface resistivity of the examples and comparative examples was measured using a ZC36 high resistance meter at 23°C and 50% relative humidity. 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 antistatic automobile window film prepared by the present invention has good antistatic performance.

[0068] By comparison, the surface resistivity of Examples 1 to 3 is lower than that of Comparative Example 3, indicating that pyrrole and 1-vinyl-1H-pyrrole are polymerized on the surface of nanoparticles to prepare polypyrrole-wrapped nanoparticles, and polypyrrole is generated on the nanoparticles. Polypyrrole has good conductivity and forms a conductive network on the antistatic automobile window film, thereby improving the antistatic properties of the antistatic automobile window film.

[0069] By comparison, the surface resistivity of Examples 1 to 3 is lower than that of Comparative Example 5, indicating that the alkyl imidazole on the polyester reacts with the epoxy group to form an imidazole salt, and the imidazole salt carries a stable ammonium cation, which can increase the charge density of the polymer and give it an excellent antistatic effect.

[0070] Test Example 2

[0071] Infrared blocking performance test

[0072] Test Method: The transmittance of the antistatic automotive window film was tested using a spectrophotometer, and the near-infrared blocking rates of the examples and comparative examples were calculated. The results are shown in Table 2.

[0073] Table 2

[0074] Near infrared blocking rate (%) Near infrared blocking rate (%) Example 1 81.3 Comparative Example 1 51.9 Example 2 84.0 Comparative Example 2 37.1 Example 3 80.7 Comparative Example 3 79.4 Comparative Example 4 78.2 Comparative Example 5 80.1 Comparative Example 6 78.6

[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 antistatic automobile window film prepared by the present invention has good infrared blocking performance.

[0076] By comparison, the near-infrared blocking rates of Examples 1 to 3 are greater than that of Comparative Example 1, indicating that the fluorine-doped titanium dioxide prepared by reacting tetraethyl titanate and ammonium fluoride can increase its free carrier concentration so that the titanium dioxide has a plasma resonance effect. The fluorine-doped titanium dioxide can effectively absorb near-infrared light in the 1500-2500nm band, giving the nanoparticles the ability to absorb near-infrared light in the 1500-2500nm band, thereby improving the infrared absorption performance of the antistatic automotive window film and giving the antistatic automotive window film good infrared blocking performance.

[0077] By comparison, the near-infrared blocking rates of Examples 1 to 3 are greater than that of Comparative Example 2, indicating that by reacting indium acetylacetonate and copper nitrate hydrate to prepare indium-doped copper sulfide, the free carrier concentration thereof is increased, and the copper sulfide has a plasma resonance effect. By mixing indium-doped copper sulfide and fluorine-doped titanium dioxide to prepare nanoparticles, the nanoparticles can be endowed with the ability to absorb infrared light in the 1000-1500nm band, thereby improving the infrared absorption performance of the antistatic automotive window film, and the antistatic automotive window film has good infrared blocking performance.

[0078] Test Example 3

[0079] Flame retardant performance test

[0080] Test method: The examples and comparative examples were prepared into standard specimens according to GB / T 2406.2, and the limiting oxygen index of the standard specimens was tested. The results are shown in Table 3.

[0081] Table 3

[0082] Limiting oxygen index (%) Limiting oxygen index (%) Example 1 28.8 Comparative Example 1 28.4 Example 2 29.3 Comparative Example 2 28.6 Example 3 29.0 Comparative Example 3 29.0 Comparative Example 4 24.3 Comparative Example 5 29.2 Comparative Example 6 25.1

[0083] 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 antistatic automobile window film prepared by the present invention has good flame retardant properties.

[0084] By comparison, the limiting oxygen index of Examples 1 to 3 is greater than that of Comparative Example 4, indicating that carboxylated DOPO, 3-imidazole-1-ylpropane-1,2-diol, butanediol, and terephthalic acid are polymerized to prepare polyester, and DOPO is introduced into the polyester. DOPO has good flame retardant properties, thereby improving the good flame retardant properties of the antistatic automotive window film.

[0085] By comparison, the limiting oxygen index of Examples 1 to 3 is greater than that of Comparative Example 6, indicating that the antistatic automotive window film is prepared by reacting functionalized polyester, hydrogenated silicone oil, and polypyrrole-wrapped nanoparticles. The silicon-oxygen bond on the hydrogenated silicone oil has high bond energy and excellent thermal stability, and is not easily broken at high temperatures, thereby improving the flame retardancy of the antistatic automotive window film.

[0086] Test Example 4

[0087] Mechanical properties testing

[0088] Test Method: The examples and comparative examples were cut into dumbbell-shaped strips 6 mm long and 4 mm wide. The strips were tested on a universal electronic testing machine at a tensile rate of 50 mm / min at 23°C and 50% relative humidity. The results are shown in Table 4.

[0089] Table 4

[0090] Tensile strength (MPa) Tensile strength (MPa) Example 1 178.16 Comparative Example 1 178.06 Example 2 182.40 Comparative Example 2 177.49 Example 3 179.74 Comparative Example 3 160.72 Comparative Example 4 178.42 Comparative Example 5 166.84 Comparative Example 6 145.81

[0091] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 6 in Table 4, it can be found that the antistatic automobile window film prepared by the present invention has good mechanical properties.

[0092] By comparison, the tensile strengths of Examples 1 to 3 are greater than that of Comparative Example 3, indicating that pyrrole and 1-vinyl-1H-pyrrole are polymerized on the surface of nanoparticles to prepare polypyrrole-coated nanoparticles, carbon-carbon double bonds are introduced into the nanoparticles, and the carbon-carbon double bonds on the polypyrrole-coated nanoparticles react with the silicon-hydrogen bonds on the hydrogen-containing silicone oil to form a cross-linked network, which inhibits the relative slip between the molecular chains and imparts excellent mechanical properties to the antistatic automotive window film.

[0093] By comparison, the tensile strength of Examples 1 to 3 is greater than that of Comparative Example 5, indicating that the functionalized polyester is prepared by reacting polyester and 1,2-epoxy-7-octene, and a carbon-carbon double bond is introduced into the side chain of the functionalized polyester. The carbon-carbon double bond on the polyester and the silicon-hydrogen bond on the hydrogen-containing silicone oil undergo an addition reaction to form a cross-linked network, which inhibits the relative slip between the molecular chains and imparts excellent mechanical properties to the antistatic automotive window film.

[0094] By comparison, the tensile strength of Examples 1 to 3 is greater than that of Comparative Example 6, indicating that the antistatic automotive window film is prepared by reacting the functionalized polyester, hydrogen-containing silicone oil, and polypyrrole-coated nanoparticles. The carbon-carbon double bonds on the functionalized polyester and polypyrrole-coated nanoparticles and the silicon-hydrogen bonds on the hydrogen-containing silicone oil undergo an addition reaction to form a cross-linked network, which inhibits the relative slip between the molecular chains and imparts excellent mechanical properties to the antistatic automotive window film.

[0095] 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 antistatic car window film, characterized in that: The antistatic automobile window film comprises the following steps: polymerizing pyrrole and 1-ethylene-1H-pyrrole on the surface of fluorine-doped nano-titanium dioxide and indium-doped nano-copper sulfide to produce polypyrrole-coated nanoparticles; reacting carboxylated DOPO, 3-imidazol-1-ylpropane-1,2-diol, butanediol, and terephthalic acid to produce polyester; reacting polyester and 1,2-epoxy-7-octene to produce functionalized polyester; and calendering the functionalized polyester, hydrogenated silicone oil, polypyrrole-coated nanoparticles, and a platinum activated carbon catalyst to produce the antistatic automobile window film. The fluorine-doped nano-titanium dioxide is prepared by reacting tetraethyl titanate and ammonium fluoride; The indium-doped nano-copper sulfide is prepared by reacting indium acetylacetonate, copper nitrate hydrate and carbon disulfide; The carboxylated DOPO is prepared by reacting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and itaconic acid.

2. A method for preparing an antistatic automobile window film, characterized in that: The preparation method of the antistatic automobile window film comprises the following preparation steps: (1) Tetraethyl titanate, ammonium fluoride, octadecyl alcohol, octadecene, oleic acid, and oleylamine were mixed uniformly in a mass ratio of 1:(0.04~0.06):(11~12):(25~26):(0.88~0.92):(0.88~0.92). Under nitrogen atmosphere, the temperature was raised from 10~30℃ to 110~130℃ at a rate of 5℃ / min while stirring at 200~300r / min. The temperature was kept constant and vacuum was applied for 18~22min. Then, the mixture was introduced into the mixture. The mixture was cooled to normal pressure by nitrogen and heated to 290-310°C at a heating rate of 5°C / min, and the reaction was continued with stirring for 55-65 minutes. The mixture was naturally cooled to room temperature, centrifuged, washed with acetone and anhydrous ethanol 2-4 times each, dried at 55-65°C under vacuum for 11-13 hours, and ultrasonically crushed for 18-22 minutes to obtain fluorine-doped nano-titanium dioxide; the fluorine-doped nano-titanium dioxide and indium-doped nano-copper sulfide were uniformly mixed in a mass ratio of 1:(0.04-0.06) to prepare nanoparticles; (2) Pyrrole and 1-vinyl-1H-pyrrole were added to a hydrochloric acid aqueous solution with a molar ratio of 1:(0.4~0.6) at 18~22 times the mass of pyrrole, and mixed evenly to obtain a pyrrole mixed solution; the pyrrole mixed solution and the nanoparticle dispersion were mixed evenly at a mass ratio of 1:(4~6), ultrasonically shaken for 18~22 minutes, and an ammonium persulfate aqueous solution with a mass of 0.1~0.2 times the mass of pyrrole was added, stirred at 10~30℃, 250~350r / min for 3~5 hours, filtered, washed with anhydrous ethanol and deionized water 3~5 times each, and dried at 55~65℃ under vacuum conditions for 22~26 hours to obtain polypyrrole-coated nanoparticles; (3) Carboxylated DOPO, 3-imidazole-1-ylpropane-1,2-diol, butanediol, and terephthalic acid were mixed in a molar ratio of 1:1.1:1.1:1, and tetrabutyl titanate (0.2-0.3 times the mass of terephthalic acid) was added. The mixture was stabilized at 140-150°C for 10 min under a nitrogen atmosphere, then heated to 170-180°C and stabilized for 20 min. The mixture was then slowly heated to 220-240°C at a heating rate of 20°C / h, and the temperature was kept constant until the water output reached 90% of the theoretical amount. The mixture was then heated to 260-280°C under vacuum conditions. The polyester was reacted for 2 to 4 hours, and the material was discharged under a nitrogen atmosphere to obtain a polyester; the polyester, N,N-dimethylformamide, and phenol were uniformly mixed in a mass ratio of 1:(25 to 35):(15 to 25), stirred at 85 to 95°C and 450 to 550 r / min for 20 to 22 minutes, cooled to 65 to 75°C, 1,2-epoxy-7-octene (0.15 to 0.25 times the mass of the polyester) was added, stirred at 250 to 350 r / min for 3 to 4 hours, and dried at 75 to 85°C under vacuum conditions for 10 to 12 hours to obtain a functionalized polyester; (4) According to the mass fraction, 100 parts of functionalized polyester, 18-22 parts of hydrogenated silicone oil, 3-5 parts of polypyrrole-coated nanoparticles, and 0.5-0.9 parts of platinum activated carbon catalyst were weighed; the functionalized polyester, hydrogenated silicone oil, and polypyrrole-coated nanoparticles were mixed, placed in an internal mixer, and plasticized at 260-280°C for 10-12 minutes, the platinum activated carbon catalyst was added and mixed, and the plasticization was continued for 10-12 minutes, and the mixture was rolled on an SK type double-roll mill, kept at 260-280°C for 2-4 hours, and naturally cooled to room temperature to obtain an antistatic automobile window film; The preparation method of indium-doped nano-copper sulfide in step (1) is as follows: copper nitrate hydrate, indium acetylacetonate, and hexadecylamine are added to n-hexane with a mass ratio of 1:(0.03-0.05):(3.8-4.0) in a volume ratio of 1:(0.03-0.05):(3.8-4.0), mixed evenly, stirred at 55-65°C and 350-450 r / min for 18-22 minutes, added with carbon disulfide with a mass of 0.4-0.6 times that of the hexadecylamine, reacted at 110-130°C for 22-26 hours, naturally cooled to room temperature, centrifuged, washed with anhydrous ethanol for 3-5 times, dried at 55-65°C under vacuum conditions for 10-14 hours, and ultrasonically crushed for 18-22 minutes to obtain indium-doped nano-copper sulfide; The method for preparing the nanoparticle dispersion in step (2) is as follows: nanoparticles and toluene are uniformly mixed in a mass ratio of 1:(18-22) to prepare a nanoparticle dispersion; the concentration of the hydrochloric acid aqueous solution is 1 mol / L; the mass fraction of the ammonium persulfate aqueous solution is 10%; The preparation method of the carboxylated DOPO in step (3) is as follows: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and itaconic acid are added in a molar ratio of 1:1 to xylene with a mass 6 to 8 times that of itaconic acid, reacted at 115 to 125° C. for 4 to 6 hours under a nitrogen atmosphere, cooled to 90 to 110° C., filtered, washed with tetrahydrofuran 2 to 4 times, and dried at 65 to 75° C. under vacuum conditions for 10 to 14 hours to obtain the carboxylated DOPO.

3. The method for preparing an antistatic automobile window film according to claim 2, wherein: The calendering process parameters of step (4) are as follows: the roller mixing temperature is set to 260-280°C, the roller gap is set to 2.00mm, 1.00mm, 0.75mm, 0.50mm, and 0.25mm in sequence, and the calendering cycle is repeated 5 times.

4. The method for preparing an antistatic automobile window film according to claim 2, wherein: The model of the hydrogen-containing silicone oil in step (4) is MHX-1107; the model of the platinum activated carbon catalyst is HS-101.

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