Anti-ultraviolet automobile window film and preparation method thereof

Abstract

The invention discloses an anti-ultraviolet automobile window film and a preparation method thereof, and relates to the field of high polymer materials. When the anti-ultraviolet automobile window film is prepared, methylcyclotetrasiloxane, octamethylcyclotetrasiloxane, 3-glycidyl propyl (dimethoxy) methylsilane and 1, 3-bis (3-aminopropyl)-1, 1, 3, 3-tetramethyldisiloxane are subjected to a reaction, and modified polysiloxane is prepared; the preparation method comprises the following steps: reacting benzo [1, 2-d: 5, 4-d '] bis (oxazole)-2, 6-dithiol with 4-aminobenzoyl chloride to prepare a modified ultraviolet absorbent; isophorone diisocyanate, polytetrahydrofuran ether glycol, the modified polypyrrole particles, the modified polysiloxane and the modified ultraviolet absorbent are subjected to a reaction, and the reaction product is spread in a mold. The anti-ultraviolet automobile window film prepared by the invention has good anti-ultraviolet, heat-insulating, flame-retardant and anti-aging properties and good mechanical properties.

Description

Technical Field

[0001] The present invention relates to the field of polymer materials, and specifically to an ultraviolet-proof automotive window film and a preparation method thereof. Background Art

[0002] Automotive window film is a film-like object pasted on the front and rear windshield glass, side window glass, and sunroof of a vehicle. The main functions of automotive window film are to block ultraviolet rays, block part of the heat, prevent injury caused by flying glass, and prevent glare, etc.

[0003] With the improvement of living standards, people's requirements for the quality of life have gradually increased, and the requirements for window film have become more and more diverse. Long-term exposure to ultraviolet rays can cause skin burns, and there are great health risks in long-term exposure to ultraviolet rays. Moreover, ultraviolet radiation will accelerate the aging of interior trim and affect the long-term use of the vehicle. Infrared rays are the main source of heat. The irradiation of infrared rays will cause a significant increase in the temperature inside the car, which not only affects the comfort inside the car, but also has great potential safety hazards due to excessive temperature rise, affecting the use safety of the vehicle. The ultraviolet-proof automotive window film prepared by the present invention has good ultraviolet-proof, heat-insulating, flame-retardant, anti-aging properties and good mechanical properties, and has broad market prospects. Summary of the Invention

[0004] The purpose of the present invention is to provide a preparation method of a waterproof and anti-fouling wall cloth to solve the problems existing in the prior art.

[0005] To solve the above technical problems, the present invention provides the following technical solutions:

[0006] An ultraviolet-proof automotive window film, wherein the ultraviolet-proof automotive window film is prepared by reacting 1-H-pyrrole-3-methanol and pyrrole and then reacting with allylphosphine dichloride to obtain modified polypyrrole particles; reacting methylcyclotetrasiloxane, octamethylcyclotetrasiloxane, 3-glycidoxypropyl(dimethoxy)methylsilane, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane to obtain modified polysiloxane; reacting benz[1,2-d:5,4-d']bis(oxazole)-2,6-dithiol with 4-aminobenzoyl chloride to obtain modified ultraviolet absorber; reacting isophorone diisocyanate, polytetrahydrofuran ether diol, dibutyltin dilaurate, modified polypyrrole particles, modified polysiloxane, modified ultraviolet absorber, and chloroplatinic acid and paving them flat in a mold.

[0007] An ultraviolet-proof automotive window film and a preparation method thereof, including the following preparation steps:

[0008] (1) Mix polypyrrole particles and tetrahydrofuran at a mass ratio of 1:(40 - 60). Under a nitrogen atmosphere and in an ice bath, add a solution prepared by mixing allylphosphonous dichloride with a mass 0.2 - 0.4 times that of the polypyrrole particles and triethylamine with a mass 0.1 - 0.2 times that of the polypyrrole at a rate of 25 μL / min. Continue stirring for 6 - 8 h, centrifuge to separate the precipitate, wash the precipitate with deionized water 3 - 5 times, and freeze-dry for 7 - 9 h to obtain modified polypyrrole particles;

[0009] (2) Mix isophorone diisocyanate, polytetrahydrofuran ether glycol, N,N-dimethylformamide, and dibutyltin dilaurate, and stir at 400 - 600 r / min at 75 - 85 °C for 1.5 - 2.5 h. Add modified polypyrrole with a mass 0.4 - 0.6 times that of the isophorone diisocyanate, modified polysiloxane with a mass 0.2 - 0.4 times that of the isophorone diisocyanate, and modified ultraviolet absorber with a mass 0.1 - 0.3 times that of the isophorone diisocyanate. Continue stirring for 2 - 3 h, cool to room temperature, add chloroplatinic acid with a mass 0.7 - 0.9 times that of the isophorone diisocyanate, discharge the material, spread it flat in a mold, and let it stand at 80 - 90 °C for 8 - 10 h to obtain an ultraviolet-proof automotive window film.

[0010] As an optimization, the preparation method of the polypyrrole particles in step (1) is as follows: Mix 1-H-pyrrole-3-methanol and pyrrole at a mass ratio of 1:6 to obtain a pyrrole monomer mixed solution; mix ferric chloride hexahydrate, polyvinyl alcohol, and deionized water at a mass ratio of 1:(1.2 - 1.4):(40 - 60), stir at 200 - 300 r / min at room temperature for 1 h, cool in an ice bath, add the pyrrole monomer mixed solution with a mass 0.1 - 0.2 times that of the ferric chloride hexahydrate, continue stirring for 3 - 5 h, centrifuge to separate the precipitate, wash the precipitate with hot water 3 - 5 times, and freeze-dry for 7 - 9 h to obtain the product.

[0011] As an optimization, the preparation method of the modified polysiloxane in step (2) is as follows: Mix tetramethylammonium hydroxide and octamethylcyclotetrasiloxane at a mass ratio of 1:(0.2 - 0.4), and stir at 200 - 300 r / min at 75 - 85 °C for 1.5 - 2.5 h under vacuum conditions to obtain a catalyst; mix tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, 3-glycidoxypropyl(dimethoxy)methylsilane, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane at a molar ratio of 1:(1 - 2):(0.2 - 0.4):(1 - 1.2) to obtain a mixed siloxane; mix the mixed siloxane and the catalyst at a mass ratio of 1:(0.006 - 0.009), stir at 200 - 300 r / min at 105 - 115 °C in a nitrogen atmosphere for 6 - 8 h, raise the temperature to 140 °C, continue reacting for 1 - 2 h, and remove low-boiling substances under vacuum at 150 °C to obtain the product.

[0012] As an optimization, the preparation method of the modified ultraviolet absorber described in step (2) is as follows: Mix benz

[0013] [1,2-d:5,4-d']bis(oxazole)-2,6-dithiol, triethylamine, and tetrahydrofuran in a mass ratio of 1:(1.2 - 1.4):(30 - 40). Under a nitrogen atmosphere, in an ice bath, stir at 200 - 300 r / min, and add 4-aminobenzoyl chloride in an amount 2 - 3 times the molar amount of benz[1,2-d:5,4-d']bis(oxazole)-2,6-dithiol at a rate of 1 - 2 mL / min. After the addition is complete, raise the temperature to 45 - 55 °C and continue stirring for 7 - 9 h. Extract and separate layers with ethyl acetate, dry the organic phase with anhydrous sodium sulfate overnight, rotary evaporate at 30 - 40 °C for 0.5 - 1 h, and then purify by column chromatography using petroleum ether:ethyl acetate 12:1 as the eluent to obtain it.

[0014] As an optimization, the structural formula of the benz[1,2-d:5,4-d']bis(oxazole)-2,6-dithiol is:

[0015]

[0016] As an optimization, the mass ratio of the isophorone diisocyanate, polytetrahydrofuran ether glycol, N,N-dimethylformamide, and dibutyltin dilaurate described in step (2) is 1:(4 - 6):(20 - 30):(0.4 - 0.6).

[0017] As an optimization, the polytetrahydrofuran ether glycol described in step (2) is polytetrahydrofuran ether glycol with a molecular weight of 2000.

[0018] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0019] When preparing the ultraviolet-proof automotive window film, the present invention reacts 1-H-pyrrole-3-methanol and pyrrole and then reacts with allylphosphine dichloride to obtain modified polypyrrole particles; reacts methylcyclotetrasiloxane, octamethylcyclotetrasiloxane, 3-glycidoxypropyl(dimethoxy)methylsilane, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane to obtain modified polysiloxane; reacts benz[1,2-d:5,4-d']bis(oxazole)-2,6-dithiol with 4-aminobenzoyl chloride to obtain a modified ultraviolet absorber; reacts isophorone diisocyanate, polytetrahydrofuran ether glycol, dibutyltin dilaurate, modified polypyrrole particles, modified polysiloxane, modified ultraviolet absorber, and chloroplatinic acid and spreads them flat in a mold to obtain the ultraviolet-proof automotive window film.

[0020] First, 1-H-pyrrole-3-methanol and pyrrole react and then react with allylphosphonous dichloride to obtain modified polypyrrole particles. Allylphosphonous dichloride introduces double bonds onto the polypyrrole particles, which can react and crosslink with the Si-H bonds on the modified polysiloxane, improving the crosslinking density and effectively enhancing the tensile strength of the ultraviolet-resistant automotive window film. Moreover, polypyrrole is an organic conjugated polymer with good near-infrared absorption performance, thus endowing the ultraviolet-resistant automotive window film with good heat insulation performance.

[0021] Second, methylcyclotetrasiloxane, octamethylcyclotetrasiloxane, 3-glycidoxypropyl(dimethoxy)methylsilane, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane react to obtain modified polysiloxane. The modified polysiloxane introduces a rich Si-O-Si structure and has good anti-aging effects, thereby improving the aging resistance of the ultraviolet-resistant automotive window film. Additionally, the Si-H bonds on the modified polysiloxane can undergo chemical crosslinking with the double bonds on the modified polypyrrole particles, increasing the crosslinking density and thus enhancing the tensile strength of the ultraviolet-resistant automotive window film.

[0022] Finally, benz[1,2-d:5,4-d']bis(oxazole)-2,6-dithiol reacts with 4-aminobenzoyl chloride to obtain a modified ultraviolet absorber. The obtained ultraviolet absorber is a mercaptoester benzoxazole ultraviolet absorber with good ultraviolet absorption performance, which can effectively absorb ultraviolet rays in light, thereby improving the aging resistance and ultraviolet resistance of the ultraviolet-resistant automotive window film. Specific embodiments

[0023] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0024] Example 1:

[0025] An ultraviolet-resistant automotive window film and its preparation method include the following preparation steps:

[0026] (1) Mix 1-H-pyrrole-3-methanol and pyrrole in a mass ratio of 1:6 to obtain a pyrrole monomer mixed solution; mix ferric chloride hexahydrate, polyvinyl alcohol, and deionized water in a mass ratio of 1:1.2:40, stir at 200 r / min at room temperature for 1 h, cool in an ice bath, add a pyrrole monomer mixed solution that is 0.1 times the mass of ferric chloride hexahydrate, continue stirring for 3 h, centrifuge to separate the precipitate, wash the precipitate with hot water 3 times, and freeze-dry for 7 h to obtain polypyrrole particles;

[0027] (2) Mix polypyrrole particles and tetrahydrofuran in a mass ratio of 1:40. Under a nitrogen atmosphere, in an ice bath, add a solution prepared by mixing allylphosphonous dichloride 0.2 times the mass of the polypyrrole particles and triethylamine 0.1 times the mass of the polypyrrole at a rate of 25 μL / min, and continue stirring for 6 h. Centrifuge to separate the precipitate, wash the precipitate 3 times with deionized water, and freeze-dry for 7 h to obtain modified polypyrrole particles;

[0028] (3) Mix tetramethylammonium hydroxide and octamethylcyclotetrasiloxane in a mass ratio of 1:0.2. Under vacuum conditions, stir at 75 °C and 200 r / min for 1.5 h to obtain a catalyst; Mix tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, 3-glycidoxypropyl(dimethoxy)methylsilane, 1,3-bis(3-aminopropyl)

[0029] -1,1,3,3-tetramethyldisiloxane in a molar ratio of 1:1:0.2:1 to obtain a mixed siloxane; Mix the mixed siloxane and the catalyst in a mass ratio of 1:0.006. Under a nitrogen atmosphere, stir at 105 °C and 200 r / min for 6 h, raise the temperature to 140 °C, continue the reaction for 1 h, and remove low-boiling substances under vacuum at 150 °C to obtain modified polysiloxane;

[0030] (4) Mix benz[1,2-d:5,4-d']bis(oxazole)-2,6-dithiol, triethylamine, and tetrahydrofuran in a mass ratio of 1:1.2:30. Under a nitrogen atmosphere, in an ice bath, stir at 200 r / min and add 4-aminobenzoyl chloride 2 times the molar amount of benz[1,2-d:5,4-d']bis(oxazole)-2,6-dithiol at a rate of 1 mL / min. After adding, raise the temperature to 45 °C and continue stirring for 7 h. Extract and separate layers with ethyl acetate, dry the organic phase with anhydrous sodium sulfate overnight, rotary evaporate at 30 °C for 0.5 h, and then separate and purify by column chromatography using petroleum ether:ethyl acetate 12:1 as the eluent to obtain modified ultraviolet absorber;

[0031] (5) Mix isophorone diisocyanate, polytetrahydrofuran ether glycol, N,N-dimethylformamide, and dibutyltin dilaurate in a mass ratio of 1:4:20:0.4. Stir at 75 °C and 400 r / min for 1.5 h, add modified polypyrrole 0.4 times the mass of isophorone diisocyanate, modified polysiloxane 0.2 times the mass of isophorone diisocyanate, and modified ultraviolet absorber 0.1 times the mass of isophorone diisocyanate, continue stirring for 2 h, cool to room temperature, add chloroplatinic acid 0.7 times the mass of isophorone diisocyanate, discharge, spread evenly in a mold, and stand at 80 °C for 8 h to obtain an anti-ultraviolet automotive window film.

[0032] Example 2:

[0033] An anti-ultraviolet automotive window film and its preparation method, including the following preparation steps:

[0034] (1) Mix 1-H-pyrrole-3-methanol and pyrrole in a mass ratio of 1:6 to obtain a pyrrole monomer mixed solution; mix ferric chloride hexahydrate, polyvinyl alcohol, and deionized water in a mass ratio of 1:1.3:50, stir at 250 r / min at room temperature for 1 h, cool in an ice bath, add a pyrrole monomer mixed solution 0.15 times the mass of ferric chloride hexahydrate, continue stirring for 4 h, centrifuge to separate the precipitate, wash the precipitate with hot water 4 times, and freeze-dry for 8 h to obtain polypyrrole particles;

[0035] (2) Mix the polypyrrole particles and tetrahydrofuran in a mass ratio of 1:50. Under a nitrogen atmosphere and in an ice bath, add a solution prepared by mixing allyl dichlorophosphine 0.3 times the mass of the polypyrrole particles and triethylamine 0.15 times the mass of the polypyrrole at a rate of 25 μL / min, continue stirring for 7 h, centrifuge to separate the precipitate, wash the precipitate with deionized water 4 times, and freeze-dry for 8 h to obtain modified polypyrrole particles;

[0036] (3) Mix tetramethylammonium hydroxide and octamethylcyclotetrasiloxane in a mass ratio of 1:0.3. Under vacuum conditions, stir at 80 °C and 250 r / min for 2 h to obtain a catalyst; mix tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, 3-glycidoxypropyl(dimethoxy)methylsilane, 1,3-bis(3-aminopropyl)

[0037] -1,1,3,3-tetramethyldisiloxane in a molar ratio of 1:1.5:0.3:1.1 to obtain a mixed siloxane; mix the mixed siloxane and the catalyst in a mass ratio of 1:0.007. Under a nitrogen atmosphere, stir at 110 °C and 250 r / min for 7 h, raise the temperature to 140 °C, continue reacting for 1.5 h, and remove low-boiling substances under vacuum at 150 °C to obtain modified polysiloxane;

[0038] (4) Mix benz[1,2-d:5,4-d']bis(oxazole)-2,6-dithiol, triethylamine, and tetrahydrofuran in a mass ratio of 1:1.3:35. Under a nitrogen atmosphere and in an ice bath, stir at 250 r / min and add 4-aminobenzoyl chloride 2.5 times the molar amount of benz[1,2-d:5,4-d']bis(oxazole)-2,6-dithiol at a rate of 1.5 mL / min. After adding, raise the temperature to 50 °C and continue stirring for 8 h. Extract and layer with ethyl acetate, dry the organic phase with anhydrous sodium sulfate overnight, rotary evaporate at 35 °C for 0.75 h, and then separate and purify by column chromatography using petroleum ether:ethyl acetate 12:1 as the eluent to obtain a modified ultraviolet absorber;

[0039] (5) Mix isophorone diisocyanate, polytetrahydrofuran glycol, N,N-dimethylformamide, and dibutyltin dilaurate in a mass ratio of 1:5:25:0.5, stir at 500 r / min for 2 h at 80 °C, add modified polypyrrole with a mass 0.5 times that of isophorone diisocyanate, modified polysiloxane with a mass 0.5 times that of isophorone diisocyanate, and modified ultraviolet absorber with a mass 0.2 times that of isophorone diisocyanate, continue stirring for 2.5 h, cool to room temperature, add chloroplatinic acid with a mass 0.8 times that of isophorone diisocyanate, discharge, spread it flat in a mold, and stand at 85 °C for 9 h to obtain an ultraviolet-proof automotive window film.

[0040] Example 3:

[0041] An ultraviolet-proof automotive window film and its preparation method, including the following preparation steps:

[0042] (1) Mix 1-H-pyrrole-3-methanol and pyrrole in a mass ratio of 1:6 to obtain a pyrrole monomer mixed solution; mix ferric chloride hexahydrate, polyvinyl alcohol, and deionized water in a mass ratio of 1:1.4:60, stir at 300 r / min for 1 h at room temperature, cool in an ice bath, add the pyrrole monomer mixed solution with a mass 0.2 times that of ferric chloride hexahydrate, continue stirring for 5 h, centrifuge to separate the precipitate, wash the precipitate with hot water 5 times, and freeze-dry for 9 h to obtain polypyrrole particles;

[0043] (2) Mix the polypyrrole particles and tetrahydrofuran in a mass ratio of 1:60, under a nitrogen atmosphere, cool in an ice bath, and add a solution prepared by mixing allylphosphine dichloride with a mass 0.4 times that of the polypyrrole particles and triethylamine with a mass 0.2 times that of the polypyrrole at a rate of 25 μL / min, continue stirring for 8 h, centrifuge to separate the precipitate, wash the precipitate with deionized water 5 times, and freeze-dry for 9 h to obtain modified polypyrrole particles;

[0044] (3) Mix tetramethylammonium hydroxide and octamethylcyclotetrasiloxane in a mass ratio of 1:0.4, stir at 300 r / min for 2.5 h at 85 °C under vacuum conditions to obtain a catalyst; mix tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, 3-glycidoxypropyl(dimethoxy)methylsilane, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane in a molar ratio of 1:2:0.4:1.2 to obtain a mixed siloxane; mix the mixed siloxane and the catalyst in a mass ratio of 1:0.009, under a nitrogen atmosphere, stir at 300 r / min for 8 h at 115 °C, raise the temperature to 140 °C, continue reacting for 2 h, and remove low-boiling substances under vacuum at 150 °C to obtain modified polysiloxane;

[0045] (4) Mix benzol[1,2-d:5,4-d']bis(oxazole)-2,6-dithiol, triethylamine, and tetrahydrofuran in a mass ratio of 1:1.4:40. Under a nitrogen atmosphere, cool in an ice bath and stir at 300 r / min. Add 4-aminobenzoyl chloride in an amount three times the molar amount of benzol[1,2-d:5,4-d']bis(oxazole)-2,6-dithiol at a rate of 2 mL / min. After the addition, raise the temperature to 55 °C and continue stirring for 9 h. Extract and separate the layers with ethyl acetate. Dry the organic phase with anhydrous sodium sulfate overnight, rotary evaporate at 40 °C for 1 h, and then purify by column chromatography using petroleum ether:ethyl acetate 12:1 as the eluent to obtain a modified ultraviolet absorber;

[0046] (5) Mix isophorone diisocyanate, polytetrahydrofuran ether glycol, N,N-dimethylformamide, and dibutyltin dilaurate in a mass ratio of 1:6:30:0.6. Stir at 600 r / min at 85 °C for 2.5 h. Add modified polypyrrole in an amount 0.6 times the mass of isophorone diisocyanate, modified polysiloxane in an amount 0.4 times the mass of isophorone diisocyanate, and modified ultraviolet absorber in an amount 0.3 times the mass of isophorone diisocyanate. Continue stirring for 3 h, cool to room temperature, add chloroplatinic acid in an amount 0.9 times the mass of isophorone diisocyanate, discharge, spread evenly in a mold, and stand at 90 °C for 10 h to obtain an anti-ultraviolet automotive window film.

[0047] Comparative Example 1:

[0048] The preparation method of the anti-ultraviolet automotive window film in Comparative Example 1 is different from that in Example 2 in that step (2) is not carried out, and step (5) is modified as follows: Mix isophorone diisocyanate, polytetrahydrofuran ether glycol, N,N-dimethylformamide, and dibutyltin dilaurate in a mass ratio of 1:(4 - 6):(20 - 30):(0.4 - 0.6). Stir at 400 - 600 r / min at 75 - 85 °C for 1.5 - 2.5 h. Add polypyrrole particles in an amount 0.4 - 0.6 times the mass of isophorone diisocyanate, modified polysiloxane in an amount 0.2 - 0.4 times the mass of isophorone diisocyanate, and modified ultraviolet absorber in an amount 0.1 - 0.3 times the mass of isophorone diisocyanate. Continue stirring for 2 - 3 h, cool to room temperature, add chloroplatinic acid in an amount 0.7 - 0.9 times the mass of isophorone diisocyanate, discharge, spread evenly in a mold, and stand at 80 - 90 °C for 8 - 10 h to obtain an anti-ultraviolet automotive window film. The remaining steps are the same as those in Example 2.

[0049] Comparative Example 2:

[0050] The preparation method of the ultraviolet-proof automotive window film of Comparative Example 2 is different from that of Example 2 in that steps (1) and (2) are not carried out, and step (5) is modified as follows: Mix isophorone diisocyanate, polytetrahydrofuran ether glycol, N,N-dimethylformamide, and dibutyltin dilaurate according to a mass ratio of 1:(4-6):(20-30):(0.4-0.6), stir at 400-600 r / min at 75-85 °C for 1.5-2.5 h, add a modified polysiloxane that is 0.2-0.4 times the mass of isophorone diisocyanate and a modified ultraviolet absorber that is 0.1-0.3 times the mass of isophorone diisocyanate, continue to stir for 2-3 h, cool to room temperature, add chloroplatinic acid that is 0.7-0.9 times the mass of isophorone diisocyanate, discharge, spread it in a mold, and stand at 80-90 °C for 8-10 h to obtain the ultraviolet-proof automotive window film. The remaining steps are the same as those in Example 2.

[0051] Comparative Example 3:

[0052] The preparation method of the ultraviolet-proof automotive window film of Comparative Example 3 is different from that of Example 2 in that step (3) is not carried out, and step (5) is modified as follows: Mix isophorone diisocyanate, polytetrahydrofuran ether glycol, N,N-dimethylformamide, and dibutyltin dilaurate according to a mass ratio of 1:(4-6):(20-30):(0.4-0.6), stir at 400-600 r / min at 75-85 °C for 1.5-2.5 h, add modified polypyrrole particles that are 0.4-0.6 times the mass of isophorone diisocyanate and a modified ultraviolet absorber that is 0.1-0.3 times the mass of isophorone diisocyanate, continue to stir for 2-3 h, cool to room temperature, add chloroplatinic acid that is 0.7-0.9 times the mass of isophorone diisocyanate, discharge, spread it in a mold, and stand at 80-90 °C for 8-10 h to obtain the ultraviolet-proof automotive window film. The remaining steps are the same as those in Example 2.

[0053] Comparative Example 4:

[0054] The preparation method of the ultraviolet-proof automotive window film of Comparative Example 4 is different from that of Example 2 in that step (4) is not carried out, and step (5) is modified as follows: Mix isophorone diisocyanate, polytetrahydrofuran ether glycol, N,N-dimethylformamide, and dibutyltin dilaurate according to a mass ratio of 1:(4-6):(20-30):(0.4-0.6), stir at 400-600 r / min at 75-85 °C for 1.5-2.5 h, add modified polypyrrole particles 0.4-0.6 times the mass of isophorone diisocyanate and modified polysiloxane 0.2-0.4 times the mass of isophorone diisocyanate, continue to stir for 2-3 h, cool to room temperature, add chloroplatinic acid 0.7-0.9 times the mass of isophorone diisocyanate, discharge, spread it flat in a mold, and stand at 80-90 °C for 8-10 h to obtain the ultraviolet-proof automotive window film. The remaining steps are the same as those in Example 2.

[0055] Test Example 1:

[0056] Mechanical property test: According to the test method in the national standard GB / T 1040.3-2006, cut the composite material into dumbbell-shaped specimens, measure the thickness and width of each specimen with a vernier caliper, and use an electronic universal testing machine to measure the tensile strength of the specimen. Before the test, input the data of the specimens to be measured into the computer, the tensile rate is 500 mm / min, and take the average value after multiple measurements. The results are shown in Table 1.

[0057] Aging resistance test: Use a xenon lamp to simulate sunlight, put the specimen into a xenon lamp accelerated aging test chamber, the aging time is 360 h, the experimental atmosphere condition is air, the temperature is 65 °C, the distance between the lamp source and the specimen is 25 cm, and the radiation intensity is 550 W / m 2 , measure the tensile strength again, and calculate the tensile strength loss rate = 1 - tensile strength after aging / initial tensile strength. The results are shown in Table 1.

[0058] Table 1

[0059] Tensile strength (MPa) Tensile strength loss rate Example 1 47.35 0.7 Example 2 47.11 0.8 Example 3 47.19 0.8 Comparative Example 1 31.37 0.8 Comparative Example 2 43.83 0.9 Comparative Example 3 33.94 14.1 Comparative Example 4 47.07 27.6

[0060] From the comparison of the experimental data of Examples 1-3 and Comparative Examples 1-4 in Table 1, it can be found that the ultraviolet-proof automotive window film prepared by the present invention has good mechanical properties and aging resistance.

[0061] The difference between Comparative Example 1 and Example 2 is that the polypyrrole particles were not modified with allylphosphorus dichloride. By comparison, the tensile strength of Examples 1-3 is greater than that of Comparative Example 1, indicating that allylphosphorus dichloride introduced double bonds onto the polypyrrole particles, which can react and crosslink with the Si-H bonds on the modified polysiloxane, increasing the crosslinking density and effectively improving the tensile strength of the ultraviolet-resistant automotive window film. The difference between Comparative Example 3 and Example 2 is that the modified polysiloxane was not added. By comparison, the tensile strength of Examples 1-3 is greater than that of Comparative Example 3, indicating that the Si-H bonds on the modified polysiloxane can chemically crosslink with the double bonds on the modified polypyrrole particles, increasing the crosslinking density and thus improving the tensile strength of the ultraviolet-resistant automotive window film.

[0062] The difference between Comparative Example 3 and Example 2 is that the modified polysiloxane was not added. By comparison, the tensile strength loss rate of Examples 1-3 is less than that of Comparative Example 1, indicating that the modified polysiloxane introduced rich Si-O-Si structures, having good anti-aging effects and thus improving the aging resistance of the ultraviolet-resistant automotive window film. The difference between Comparative Example 4 and Example 2 is that the modified ultraviolet absorber was not added. By comparison, the tensile strength loss rate of Examples 1-3 is less than that of Comparative Example 4, indicating that the modified ultraviolet absorber has good ultraviolet absorption effects, can effectively absorb ultraviolet rays in light, and thus improves the aging resistance of the ultraviolet-resistant automotive window film.

[0063] Test Example 2:

[0064] Ultraviolet resistance test: Use a UV spectrophotometer (UV-1800 Shimadzu) to test the ultraviolet transmittance of the film material. Cut the film to be tested into rectangular slices of 1 cm * 5 cm in advance, and then use tweezers to place the film in the spectrophotometer to block the light port for testing. Convert the obtained curve results into csv format to obtain the final data and record the ultraviolet blocking rate. The results are shown in Table 2.

[0065] Table 2

[0066]

[0067]

[0068] From the comparison of the experimental data of Examples 1-3 and Comparative Examples 1-4 in Table 2, it can be found that the ultraviolet-resistant automotive window film prepared by the present invention has good ultraviolet resistance.

[0069] The difference between Comparative Example 4 and Example 2 is that the modified ultraviolet absorber was not added. By comparison, the ultraviolet blocking rate of Examples 1-3 is greater than that of Comparative Example 1, indicating that the introduction of the mercaptoester benzoxazole ultraviolet absorber makes the ultraviolet-resistant automotive window film have good ultraviolet resistance.

[0070] Test Example 3:

[0071] Heat insulation performance test: In this experiment, an NS-11 type heat insulation performance tester was used to test the heat insulation performance of the prepared nano-composite heat insulation film material. The blank glass was placed on the left side of the area to be tested, and the ultraviolet-proof automotive window film was used to keep the initial temperatures on both sides the same. Then the switch was turned on for testing. The temperature difference after 1 minute was recorded. The results are shown in Table 3.

[0072] Table 3

[0073] Temperature difference (°C) Temperature difference (°C) Example 1 1.8 Comparative Example 1 1.9 Example 2 1.7 Comparative Example 2 5.2 Example 3 1.9 Comparative Example 3 1.8 Comparative Example 4 2.0

[0074] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 4 in Table 3, it can be found that the ultraviolet-proof automotive window film prepared by the present invention has good heat insulation performance.

[0075] The difference between Comparative Example 2 and Example 2 is that modified polypyrrole particles were not added. By comparison, the temperature differences in Examples 1 to 3 are significantly smaller than those in Comparative Example 2, indicating that the modified polypyrrole particles introduce polypyrrole into the ultraviolet-proof automotive window film. Polypyrrole is an organic conjugated polymer with good near-infrared absorption performance, thus enabling the ultraviolet-proof automotive window film to have good heat insulation performance.

[0076] Test Example 4:

[0077] Flame retardancy performance test: Samples of the ultraviolet-proof automotive window films obtained in each example and test example were prepared according to GB / T2406 and the limiting oxygen index was tested. The results are shown in Table 4.

[0078] Table 4

[0079] Limiting oxygen index (%) Limiting oxygen index (%) Example 1 37.2 Comparative Example 1 24.7 Example 2 37.5 Comparative Example 2 24.1 Example 3 37.4 Comparative Example 3 31.8 Comparative Example 4 37.2

[0080] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 4 in Table 4, it can be found that the ultraviolet-proof automotive window film prepared by the present invention has good flame retardancy performance.

[0081] The difference between Comparative Example 1 and Example 2 is that the polypyrrole particles were not modified with allylphosphorus dichloride. By comparison, the limiting oxygen indexes of Examples 1 to 3 are significantly greater than those of Comparative Example 1, indicating that allylphosphorus dichloride introduces rich phosphorus elements into the ultraviolet-proof automotive film, which can play a role in promoting carbon formation during combustion and effectively improve the flame retardancy performance of the ultraviolet-proof automotive film.

[0082] The specific embodiments described above further elaborate on the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only the specific embodiments of the present invention and is not used to limit the protection scope of the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. An anti-ultraviolet automotive window film, characterized in that, The anti-UV automotive window film is prepared by reacting isophorone diisocyanate, polytetrahydrofuran ether glycol, dibutyltin dilaurate, modified polypyrrole particles, modified polysiloxane, modified UV absorber, and chloroplatinic acid and spreading them flat in a mold. The modified polypyrrole particles are prepared by reacting 1-H-pyrrole-3-methanol and pyrrole and then reacting with allylphosphine dichloride. The modified polysiloxane is prepared by reacting methylcyclotetrasiloxane, octamethylcyclotetrasiloxane, 3-glycidoxypropyl(dimethoxy)methylsilane, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane. The modified UV absorber is prepared by reacting benz[1,2-d:5,4-d']bis(oxazole)-2,6-dithiol with 4-aminobenzoyl chloride.

2. An ultraviolet-proof automotive window film and a preparation method thereof, characterized in that, It includes the following preparation steps: (1) Mix polypyrrole particles and tetrahydrofuran at a mass ratio of 1:(40 - 60), under a nitrogen atmosphere, in an ice bath, add a solution prepared by mixing allylphosphine dichloride at 0.2 - 0.4 times the mass of the polypyrrole particles and triethylamine at 0.1 - 0.2 times the mass of the polypyrrole at a rate of 25 μL / min, continue stirring for 6 - 8 h, centrifuge to separate the precipitate, wash the precipitate with deionized water 3 - 5 times, and freeze-dry for 7 - 9 h to obtain the modified polypyrrole particles. (2) Mix isophorone diisocyanate, polytetrahydrofuran ether glycol, N,N-dimethylformamide, and dibutyltin dilaurate, stir at 400 - 600 r / min at 75 - 85 °C for 1.5 - 2.5 h, add modified polypyrrole at 0.4 - 0.6 times the mass of the isophorone diisocyanate, modified polysiloxane at 0.2 - 0.4 times the mass of the isophorone diisocyanate, and modified UV absorber at 0.1 - 0.3 times the mass of the isophorone diisocyanate, continue stirring for 2 - 3 h, cool to room temperature, add chloroplatinic acid at 0.7 - 0.9 times the mass of the isophorone diisocyanate, discharge, spread it flat in a mold, and let it stand at 80 - 90 °C for 8 - 10 h to obtain the anti-UV automotive window film.

3. The anti-ultraviolet automotive window film according to claim 2 and its preparation method are characterized in that, The preparation method of the polypyrrole particles in step (1) is: Mix 1-H-pyrrole-3-methanol and pyrrole at a mass ratio of 1:6 to obtain a pyrrole monomer mixed solution; mix ferric chloride hexahydrate, polyvinyl alcohol, and deionized water at a mass ratio of 1:(1.2 - 1.4):(40 - 60), stir at 200 - 300 r / min at room temperature for 1 h, in an ice bath, add the pyrrole monomer mixed solution at 0.1 - 0.2 times the mass of the ferric chloride hexahydrate, continue stirring for 3 - 5 h, centrifuge to separate the precipitate, wash the precipitate with hot water 3 - 5 times, and freeze-dry for 7 - 9 h to obtain.

4. The anti-ultraviolet automotive window film according to claim 2 and its preparation method are characterized in that, The preparation method of the modified polysiloxane described in step (2) is as follows: Mix tetramethylammonium hydroxide and octamethylcyclotetrasiloxane at a mass ratio of 1:(0.2 - 0.4), under vacuum conditions, stir at 200 - 300 r / min at 75 - 85 °C for 1.5 - 2.5 h to obtain a catalyst; Mix tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, 3-glycidylpropyl(dimethoxy)methylsilane, and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane at a molar ratio of 1:(1 - 2):(0.2 - 0.4):(1 - 1.2) to obtain a mixed siloxane; Mix the mixed siloxane and the catalyst at a mass ratio of 1:(0.006 - 0.009), under a nitrogen atmosphere, stir at 200 - 300 r / min at 105 - 115 °C for 6 - 8 h, raise the temperature to 140 °C, continue the reaction for 1 - 2 h, and remove low-boiling substances under vacuum at 150 °C to obtain it.

5. The anti-ultraviolet automotive window film according to claim 2 and its preparation method are characterized in that, The preparation method of the modified ultraviolet absorber described in step (2) is as follows: Mix benz[1,2-d:5,4-d']bis(oxazole)-2,6-dithiol, triethylamine, and tetrahydrofuran at a mass ratio of 1:(1.2 - 1.4):(30 - 40), under a nitrogen atmosphere, in an ice bath, stir at 200 - 300 r / min, and add 4-aminobenzoyl chloride which is 2 - 3 times the molar amount of benz[1,2-d:5,4-d']bis(oxazole)-2,6-dithiol at a rate of 1 - 2 mL / min. After the addition is complete, raise the temperature to 45 - 55 °C and continue stirring for 7 - 9 h. Extract and separate layers with ethyl acetate, dry the organic phase with anhydrous sodium sulfate overnight, rotary evaporate at 30 - 40 °C for 0.5 - 1 h, and then purify by column chromatography using petroleum ether:ethyl acetate 12:1 as the eluent to obtain it.

6. The anti-ultraviolet automotive window film according to claim 2 and its preparation method are characterized in that, The mass ratio of isophorone diisocyanate, polytetrahydrofuran ether glycol, N,N-dimethylformamide, and dibutyltin dilaurate described in step (2) is 1:(4 - 6):(20 - 30):(0.4 - 0.6).

7. A UV-proof automotive window film and its preparation method according to claim 2, characterized in that, The polytetrahydrofuran ether glycol described in step (2) is polytetrahydrofuran ether glycol with a molecular weight of 2000.

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