Anti-aging organic silicon modified polyimide film

Abstract

Polyamic acid and a modifier react and then are mixed with N-methyl pyrrolidone to prepare coating liquid, a glass plate is coated with the coating liquid, high-temperature heat preservation is conducted, the anti-aging organic silicon modified polyimide film is prepared, a benzimidazole structure is grafted to the side chain of a polyimide molecule, and the anti-aging organic silicon modified polyimide film is obtained. Nitrogen atoms in benzimidazole have lone pair electrons and can be used as a free radical trapping agent to interrupt an autocatalytic oxidation chain reaction of polyimide in a high-temperature aerobic environment, meanwhile, a side chain contains a fluoropolysiloxane chain segment, and the strong electronegativity and hydrophobicity of fluorine atoms can inhibit formation of a charge transfer complex, so that aging of polyimide is reduced, and the polyimide film is prepared. The larger atomic radius can increase the molecular chain spacing and reduce the molecular chain stacking density, and is matched with the polysiloxane chain segment, so that aging media such as water vapor and oxygen are more difficult to permeate and diffuse, and the anti-aging effect of the polyimide film is further improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of polyimide film preparation, and particularly relates to an aging-resistant organic silicon modified polyimide film. BACKGROUND

[0002] In the modern electronic information industry, the requirements for high-performance insulating materials are increasingly high, especially in electronic components working under the influence of high temperature, humidity and ultraviolet light, etc. The ideal insulating material not only needs to have good electrical insulation performance, but also needs to exhibit excellent heat resistance, corrosion resistance and mechanical strength. Although the traditional polyimide film can maintain good electrical properties at high temperatures, it will gradually show aging phenomena in long-term use as the environmental conditions change, especially under sunlight exposure and high humidity conditions, which not only reduces its own performance, but also may cause material peeling and electrical short circuit, leading to equipment failure or safety problems. SUMMARY

[0003] The present application relates to the technical field of polyimide film preparation, and particularly relates to an aging-resistant organic silicon modified polyimide film.

[0004] The object of the present application can be achieved by the following technical solutions:

[0005] An aging-resistant organic silicon modified polyimide film, specifically comprising the following steps:

[0006] Step A1: uniformly mix o-phenylenediamine, acrylic acid, p-hydroquinone and dimethylbenzene, stir and add concentrated hydrochloric acid under the conditions of a rotation speed of 150-200 r / min and a temperature of 20-25 DEG C, heat to 120-130 DEG C, and react for 3-5 h, adjust the pH value to 9, and prepare a modifier;

[0007] Step A2: uniformly mix 4,4'-diamino diphenyl ether, a modified monomer and N-methyl pyrrolidone, stir and add pyromellitic anhydride under the conditions of a rotation speed of 200-300 r / min and a temperature of 20-25 DEG C, and react for 5-7 h to prepare a polyamide acid;

[0008] Step A3: mix the polyamide acid, the modifier, chloroplatinic acid and N-methyl pyrrolidone, protect with nitrogen, and react for 6-8 h under the conditions of a rotation speed of 120-150 r / min and a temperature of 60-70 DEG C to prepare a coating liquid;

[0009] Step A4: The coating solution is coated on a glass plate, and then aged at 80℃ for 2h, at 100℃ for 1h, at 150℃ for 1h, at 200℃ for 1h, and at 250℃ for 1h to obtain an aging-resistant silicone-modified polyimide film.

[0010] Further, the o-phenylenediamine, acrylic acid and concentrated hydrochloric acid in step A1 are used in a ratio of 30mmol:60mmol:15mL, and the mass fraction of the concentrated hydrochloric acid is 36%, and the amount of hydroquinone is 1% of the mass of the acrylic acid.

[0011] Further, the molar ratio of the 4,4'-diamino diphenyl ether, the modifying monomer and the pyromellitic anhydride in step A2 is 9:1:10.

[0012] Further, the molar ratio of the Si-H bond on the polyamic acid and the modifier in step A3 is 1:1, the amount of chloroplatinic acid is 1‰ of the mass of the modifier, and the mass ratio of the polyamic acid and N-methyl pyrrolidone is 1:6.

[0013] Further, the modifying monomer is prepared by the following steps:

[0014] Step B1: (4,4'-dinitro[1,1'-biphenyl]2,2'-di)dimethylol, acrylic acid, p-toluenesulfonic acid, hydroquinone and DMF are mixed uniformly, and then nitrogen is introduced for protection, and then the reaction is carried out at a rotation speed of 150-200r / min and a temperature of 110-120℃ for 6-8h to obtain intermediate 1, and then intermediate 1, phenyldiethoxysilane, chloroplatinic acid and dichloroethane are mixed, and then nitrogen is introduced for protection, and then the reaction is carried out at a rotation speed of 200-300r / min and a temperature of 70-80℃ for 8-10h to obtain intermediate 2;

[0015] Step B2: Intermediate 2 and dichloromethane are mixed, and then nitrogen is introduced for protection, and then stirred at a rotation speed of 150-200r / min and a temperature of 0℃, and then acetyl chloride is added, and then warmed to 20-25℃, and then the reaction is carried out for 3-5h to obtain a capping agent, and then dimethylhydrogen lithium silanol and tetrahydrofuran are mixed, and then nitrogen is introduced for protection, and then stirred at a rotation speed of 120-150r / min and a temperature of 0℃, and then trifluoropropylmethylcyclotrisiloxane is added, and then warmed to 20-25℃, and then the reaction is carried out for 18-20h, and then the capping agent is added, and then the reaction is continued for 1-1.5h to obtain a pretreated polysiloxane;

[0016] Step B3: The pretreated polysiloxane is dissolved in tetrahydrofuran, and argon is introduced for protection. Stannous chloride dihydrate and concentrated hydrochloric acid are added under stirring at a rotation speed of 60-80 r / min and a temperature of 0-5 DEG C. The reaction is carried out at a temperature of 68-70 DEG C for 12-15 h. Then, sodium hydroxide solution is added to adjust the pH value to 7.5-8.5 to obtain the modified monomer.

[0017] Further, the molar ratio of (4,4'-dinitro[1,1'-biphenyl] 2,2'-di) dimethylol to acrylic acid in step B1 is 1:2, the amount of p-toluenesulfonic acid is 5% of the mass of (4,4'-dinitro[1,1'-biphenyl] 2,2'-di) dimethylol, the amount of hydroquinone is 1% of the mass of acrylic acid, the molar ratio of intermediate 1 to phenyldiethoxysilane is 1:2, and the amount of chloroplatinic acid is 30 ppm of the mass sum of intermediate 1 and phenyldiethoxysilane.

[0018] Further, the molar ratio of intermediate 2 to acetyl chloride in step B2 is 1:5, and the molar ratio of lithium dimethylhydrogen silyl, trifluoropropylmethylcyclotrisiloxane and Si-Cl on the blocking agent is 1:2.5:1.

[0019] Further, the amount ratio of pretreated polysiloxane, stannous chloride dihydrate and concentrated hydrochloric acid in step B3 is 1 mmol:8 mmol:3.6 mL, the mass fraction of concentrated hydrochloric acid is 36%, and the mass fraction of sodium hydroxide solution is 15%.

[0020] The aging-resistant organic silicon modified polyimide film disclosed by the application is prepared by coating a coating liquid on a glass plate and high-temperature heat preservation. The coating liquid is prepared by mixing a polyamide acid and a modifier, the polyamide acid is prepared by low-temperature polycondensation of 4,4'-diamino diphenyl ether, a modified monomer and pyromellitic anhydride as raw materials, and the modifier is prepared by dehydration condensation of an amino group on o-phenylenediamine and a carboxyl group on acrylic acid under the action of concentrated hydrochloric acid, and intramolecular nucleophilic addition of the remaining amino group as a nucleophilic group to form a five-membered imidazole ring.

[0021] The modified monomer is prepared by using (4,4'-dinitro[1,1'-biphenyl] 2,2'-di) dimethylol and acrylic acid as raw materials, esterifying the hydroxyl group on the (4,4'-dinitro[1,1'-biphenyl] 2,2'-di) dimethylol and the carboxyl group on the acrylic acid, obtaining intermediate 1, reacting the double bond on the intermediate 1 and the Si-H bond on the phenyldiethoxysilane, obtaining intermediate 2, treating the intermediate 2 with acetyl chloride to convert the ethoxyl group on the intermediate 2 into chlorine to form a Si-Cl bond, obtaining a capping agent, using lithium dimethylhydrogen silanol as an initiator, trifluoropropylmethylcyclotrisiloxane as a polymerization monomer, and then adding the capping agent to make the Si-Cl bond on the capping agent react with the silanol lithium, obtaining a pretreated siloxane, and treating the pretreated polysiloxane with stannous chloride dihydrate to convert the nitro group on the pretreated polysiloxane into an amino group, obtaining the modified monomer.

[0022] In the reaction of the polyamic acid and the modifier, the Si-H bond on the polyamic acid reacts with the double bond on the modifier, and then the benzimidazole structure is grafted on the side chain of the polyamic acid molecule. The nitrogen atom in the benzimidazole has a lone pair of electrons and can act as a free radical trapping agent to interrupt the autocatalytic oxidative chain reaction of the polyimide in a high-temperature aerobic environment. At the same time, the side chain contains a fluorosilicone segment, and the strong electronegativity and hydrophobicity of the fluorine atom can inhibit the formation of a charge transfer complex, thereby reducing the aging of the polyimide. In addition, the large atomic radius can increase the intermolecular spacing and reduce the stacking density of the molecular chain, cooperate with the polysiloxane segment, and make it more difficult for aging media such as water vapor and oxygen to penetrate and diffuse, thereby improving the aging resistance of the polyimide film. DETAILED DESCRIPTION

[0023] The technical solutions in the embodiments of the present application will be described below in a clear and complete manner. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by a person of ordinary skill in the art without creative labor fall within the scope of protection of the present application.

[0024] Embodiment 1: A kind of aging-resistant organic silicon modified polyimide film, specifically comprising the following steps:

[0025] Step A1: uniformly mix o-phenylenediamine, acrylic acid, p-hydroquinone and dimethylbenzene, under the condition of 150 r / min of rotation speed and 20 DEG C of temperature, stirring and adding concentrated hydrochloric acid, heating to 120 DEG C, and reacting for 3 h, adjusting the pH value to 9, to obtain a modifier;

[0026] Step A2: 4,4'-diamino diphenyl ether, modified monomer and N-methyl pyrrolidone were mixed uniformly, and under the condition of 200 r / min of rotation speed and 20℃ of temperature, pyromellitic anhydride was added and stirred, and the reaction was carried out for 5 h to prepare polyamic acid;

[0027] Step A3: polyamic acid, modifier, chloroplatinic acid and N-methyl pyrrolidone were mixed, and nitrogen was introduced for protection, and the reaction was carried out for 6 h under the condition of 120 r / min of rotation speed and 60℃ of temperature to prepare a coating solution;

[0028] Step A4: the coating solution was coated on a glass plate, and the temperature was kept at 80℃ for 2 h, 100℃ for 1 h, 150℃ for 1 h, 200℃ for 1 h and 250℃ for 1 h to prepare an aging-resistant silicone-modified polyimide film.

[0029] The amount ratio of o-diphenylamine, acrylic acid and concentrated hydrochloric acid in step A1 was 30 mmol:60 mmol:15 mL, the mass fraction of concentrated hydrochloric acid was 36%, and the amount of hydroquinone was 1% of the mass of acrylic acid.

[0030] The molar ratio of 4,4'-diamino diphenyl ether, modified monomer and pyromellitic anhydride in step A2 was 9:1:10.

[0031] The molar ratio of Si-H bond on polyamic acid and modifier in step A3 was 1:1, the amount of chloroplatinic acid was 1‰ of the mass of the modifier, and the mass ratio of polyamic acid and N-methyl pyrrolidone was 1:6.

[0032] The modified monomer was prepared by the following steps:

[0033] Step B1: (4,4'-dinitro[1,1'-biphenyl]2,2'-di)dimethylol, acrylic acid, p-toluenesulfonic acid, hydroquinone and DMF were mixed uniformly, and nitrogen was introduced for protection, and the reaction was carried out for 6 h under the condition of 150 r / min of rotation speed and 110℃ of temperature to prepare intermediate 1, and intermediate 1, phenyldiethoxysilane, chloroplatinic acid and dichloroethane were mixed, and nitrogen was introduced for protection, and the reaction was carried out for 8 h under the condition of 200 r / min of rotation speed and 70℃ of temperature to prepare intermediate 2;

[0034] Step B2: Intermediate 2 and dichloromethane were mixed, protected by nitrogen, stirred at a rotation speed of 150 r / min and a temperature of 0 ℃, and acetyl chloride was added, the temperature was raised to 20 ℃, and the reaction was carried out for 3 h to obtain a capping agent. Lithium dimethylhydrogen silanol and tetrahydrofuran were mixed, protected by nitrogen, stirred at a rotation speed of 120 r / min and a temperature of 0 ℃, and trifluoropropylmethylcyclotrisiloxane was added, the temperature was raised to 20 ℃, and the reaction was carried out for 18 h. Then, the capping agent was added, and the reaction was continued for 1 h to obtain a pretreated polysiloxane.

[0035] Step B3: The pretreated polysiloxane was dissolved in tetrahydrofuran, protected by argon, stirred at a rotation speed of 60 r / min and a temperature of 0 ℃, and stannous chloride dihydrate and concentrated hydrochloric acid were added. The temperature was raised to 68 ℃, and the reaction was carried out for 12 h. Then, sodium hydroxide solution was added until the pH value was 7.5 to obtain a modified monomer.

[0036] The molar ratio of (4,4'-dinitro[1,1'-biphenyl]-2,2'-di)dimethylol to acrylic acid in step B1 was 1:2, the amount of p-toluenesulfonic acid was 5% of the mass of (4,4'-dinitro[1,1'-biphenyl]-2,2'-di)dimethylol, the amount of hydroquinone was 1% of the mass of acrylic acid, the molar ratio of intermediate 1 to phenyldiethoxysilane was 1:2, and the amount of chloroplatinic acid was 30 ppm of the mass sum of intermediate 1 and phenyldiethoxysilane.

[0037] The molar ratio of intermediate 2 to acetyl chloride in step B2 was 1:5, and the molar ratio of lithium dimethylhydrogen silanol, trifluoropropylmethylcyclotrisiloxane, and Si-Cl on the capping agent was 1:2.5:1.

[0038] The amount ratio of pretreated polysiloxane, stannous chloride dihydrate, and concentrated hydrochloric acid in step B3 was 1 mmol:8 mmol:3.6 mL, and the mass fraction of concentrated hydrochloric acid was 36%. The mass fraction of sodium hydroxide solution was 15%.

[0039] Example 2, an anti-aging silicone-modified polyimide film, specifically includes the following steps:

[0040] Step A1: Ortho-phenylenediamine, acrylic acid, hydroquinone, and dimethylbenzene were uniformly mixed, protected by nitrogen, stirred at a rotation speed of 150 r / min and a temperature of 25 ℃, and concentrated hydrochloric acid was added. The temperature was raised to 125 ℃, and the reaction was carried out for 4 h. Then, the pH value was adjusted to 9 to obtain a modifier.

[0041] Step A2: 4,4'-diamino diphenyl ether, the modified monomer, and N-methyl pyrrolidone were uniformly mixed, protected by nitrogen, stirred at a rotation speed of 200 r / min and a temperature of 25 ℃, and pyromellitic anhydride was added. The reaction was carried out for 6 h to obtain a polyamic acid.

[0042] Step A3: mixing polyamic acid, modifier, chloroplatinic acid and N-methyl pyrrolidone, protecting by nitrogen, under the condition of 120r / min rotation speed and 65℃ temperature, reacting for 7h, to obtain coating solution;

[0043] Step A4: coating the coating solution on glass plate, respectively under the condition of 80℃ temperature, 2h holding, 100℃ temperature, 1h holding, 150℃ temperature, 1h holding, 200℃ temperature, 1h holding, 250℃ temperature, 1h holding, to obtain aging-resistant silicone-modified polyimide film.

[0044] The amount ratio of o-phenylenediamine, acrylic acid and concentrated hydrochloric acid in step A1 is 30mmol:60mmol:15mL, the mass fraction of concentrated hydrochloric acid is 36%, and the amount of hydroquinone is 1% of the mass of acrylic acid.

[0045] The molar ratio of 4,4'-diamino diphenyl ether, modifier monomer and pyromellitic anhydride in step A2 is 9:1:10.

[0046] The molar ratio of Si-H bond on polyamic acid and modifier in step A3 is 1:1, the amount of chloroplatinic acid is 1‰ of the mass of modifier, and the mass ratio of polyamic acid and N-methyl pyrrolidone is 1:6.

[0047] The modifier monomer is prepared by the following steps:

[0048] Step B1: mixing (4,4'-dinitro[1,1'-biphenyl]2,2'-di)dimethylol, acrylic acid, p-toluenesulfonic acid, hydroquinone and DMF uniformly, protecting by nitrogen, under the condition of 200r / min rotation speed and 115℃ temperature, reacting for 7h, to obtain intermediate 1, mixing intermediate 1, phenyldiethoxysilane, chloroplatinic acid and dichloroethane, protecting by nitrogen, under the condition of 200r / min rotation speed and 75℃ temperature, reacting for 9h, to obtain intermediate 2;

[0049] Step B2: mixing intermediate 2 and dichloromethane, protecting by nitrogen, under the condition of 150r / min rotation speed and 0℃ temperature, stirring and adding acetyl chloride, warming to 25℃, reacting for 4h, to obtain end-capping agent, mixing dimethylhydrogen silyl lithium and tetrahydrofuran, protecting by nitrogen, under the condition of 120r / min rotation speed and 0℃ temperature, stirring and adding trifluoropropylmethylcyclotrisiloxane, warming to 25℃, reacting for 19h, then adding end-capping agent, continuing to react for 1.3h, to obtain pretreated polysiloxane;

[0050] Step B3: Dissolve the pretreated polysiloxane in tetrahydrofuran, purge with argon gas, stir at 60 r / min and 5°C, add stannous chloride dihydrate and concentrated hydrochloric acid, heat to 68°C and react for 13 h, then add sodium hydroxide solution to bring the pH to 8 to obtain the modified monomer.

[0051] The molar ratio of (4,4'-dinitro[1,1'-biphenyl]2,2'-di)dihydroxymethyl to acrylic acid in step B1 is 1:2, the amount of p-benzylsulfonic acid is 5% of the mass of (4,4'-dinitro[1,1'-biphenyl]2,2'-di)dihydroxymethyl, the amount of hydroquinone is 1% of the mass of acrylic acid, the molar ratio of intermediate 1 to phenyldiethoxysilane is 1:2, and the amount of chloroplatinic acid is 30 ppm of the sum of the masses of intermediate 1 and phenyldiethoxysilane.

[0052] The molar ratio of intermediate 2 and acetyl chloride in step B2 is 1:5, and the molar ratio of lithium dimethylhydrosilyl alcohol, trifluoropropylmethylcyclotrisiloxane and Si-Cl on the end-capping agent is 1:2.5:1.

[0053] The ratio of the pretreated polysiloxane, stannous chloride dihydrate, and concentrated hydrochloric acid in step B3 is 1 mmol: 8 mmol: 3.6 mL, the mass fraction of concentrated hydrochloric acid is 36%, and the mass fraction of sodium hydroxide solution is 15%.

[0054] Example 3, an aging-resistant silicone-modified polyimide film, specifically includes the following steps:

[0055] Step A1: Mix o-phenylenediamine, acrylic acid, hydroquinone and xylene evenly, stir and add concentrated hydrochloric acid at a speed of 200 r / min and a temperature of 25℃, raise the temperature to 130℃ and react for 5 h, adjust the pH value to 9 to obtain the modifier.

[0056] Step A2: Mix 4,4'-diaminodiphenyl ether, modified monomer and N-methylpyrrolidone evenly, stir and add pyromellitic anhydride at 300 r / min and 25 ℃, and react for 7 h to obtain polyamic acid;

[0057] Step A3: Mix polyamic acid, modifier, chloroplatinic acid and N-methylpyrrolidone, purge with nitrogen, and react for 8 hours at a speed of 150 r / min and a temperature of 70℃ to obtain the coating liquid.

[0058] Step A4: Coat the glass plate with the film-forming liquid and heat it at 80℃ for 2 hours, 100℃ for 1 hour, 150℃ for 1 hour, 200℃ for 1 hour, and 250℃ for 1 hour to obtain an aging-resistant silicone-modified polyimide film.

[0059] The ratio of o-phenylenediamine, acrylic acid, and concentrated hydrochloric acid in step A1 is 30 mmol: 60 mmol: 15 mL, the mass fraction of concentrated hydrochloric acid is 36%, and the amount of hydroquinone is 1% of the mass of acrylic acid.

[0060] The molar ratio of 4,4'-diaminodiphenyl ether, modified monomer and pyromellitic anhydride mentioned in step A2 is 9:1:10.

[0061] In step A3, the molar ratio of Si-H bonds on the polyamic acid to the modifier is 1:1, the amount of chloroplatinic acid is 1‰ of the modifier mass, and the mass ratio of polyamic acid to N-methylpyrrolidone is 1:6.

[0062] The modified monomer is prepared by the following steps:

[0063] Step B1: Mix (4,4'-dinitro[1,1'-biphenyl]2,2'-di)dihydroxymethyl, acrylic acid, p-toluenesulfonic acid, hydroquinone and DMF evenly, purge with nitrogen, and react for 8 hours at 200 r / min and 120 °C to obtain intermediate 1. Mix intermediate 1, phenyldiethoxysilane, chloroplatinic acid and dichloroethane, purge with nitrogen, and react for 10 hours at 300 r / min and 80 °C to obtain intermediate 2.

[0064] Step B2: Mix intermediate 2 and dichloromethane, purge with nitrogen, stir at 200 r / min and 0°C, add acetyl chloride, heat to 25°C, and react for 5 h to obtain the end-capping agent. Mix lithium dimethylhydrosilyl alcohol and tetrahydrofuran, purge with nitrogen, stir at 150 r / min and 0°C, add trifluoropropylmethylcyclotrisiloxane, heat to 25°C, and react for 20 h. Then add the end-capping agent and continue the reaction for 1.5 h to obtain the pretreated polysiloxane.

[0065] Step B3: Dissolve the pretreated polysiloxane in tetrahydrofuran, purge with argon gas, stir at 80 r / min and 5°C, add stannous chloride dihydrate and concentrated hydrochloric acid, heat to 70°C, react for 15 h, then add sodium hydroxide solution to bring the pH to 8.5 to obtain the modified monomer.

[0066] The molar ratio of (4,4'-dinitro[1,1'-biphenyl]2,2'-di)dihydroxymethyl to acrylic acid in step B1 is 1:2, the amount of p-benzylsulfonic acid is 5% of the mass of (4,4'-dinitro[1,1'-biphenyl]2,2'-di)dihydroxymethyl, the amount of hydroquinone is 1% of the mass of acrylic acid, the molar ratio of intermediate 1 to phenyldiethoxysilane is 1:2, and the amount of chloroplatinic acid is 30 ppm of the sum of the masses of intermediate 1 and phenyldiethoxysilane.

[0067] The molar ratio of intermediate 2 and acetyl chloride in step B2 is 1:5, and the molar ratio of lithium dimethylhydrosilyl alcohol, trifluoropropylmethylcyclotrisiloxane and Si-Cl on the end-capping agent is 1:2.5:1.

[0068] The ratio of the pretreated polysiloxane, stannous chloride dihydrate, and concentrated hydrochloric acid in step B3 is 1 mmol: 8 mmol: 3.6 mL, the mass fraction of concentrated hydrochloric acid is 36%, and the mass fraction of sodium hydroxide solution is 15%.

[0069] Comparative Example 1: This comparative example did not include any modifiers compared to Example 1, but the remaining steps were the same.

[0070] Comparative Example 2: Compared with Example 1, this comparative example uses hexamethylcyclotrisiloxane instead of trifluoropropylmethylcyclotrisiloxane, and the other steps are the same.

[0071] Comparative Example 3: This comparative example uses dimethylethoxysilane instead of phenyldiethoxysilane, but the other steps are the same as in Example 1.

[0072] The polyimide films prepared in Examples 1-3 and Comparative Examples 1-3 were stretched at a speed of 50 mm / min according to GB / T1040.3-2006. After testing the tensile strength, they were irradiated for 3000 h according to ISO 4892-2. The tensile strength retention rate after photoaging was then tested. The films were then treated for 500 h at a temperature of 85°C and a humidity of 85%. The tensile strength retention rate after damp heat aging was then tested. The test results are shown in Table 1 below.

[0073] Table 1

[0074]

[0075] As shown in Table 1, this application has excellent aging resistance.

[0076] 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. An age resistant silicone-modified polyimide film characterized by: Specifically comprising the following steps: Step A1: mixing and stirring o-phenylenediamine, acrylic acid, hydroquinone and dimethylbenzene, and adding concentrated hydrochloric acid to react, adjusting the pH to alkaline to prepare a modifier; Step A2: mixing and stirring 4,4'-diamino diphenyl ether, modified monomer and N-methyl pyrrolidone, and adding pyromellitic anhydride to react to prepare polyamic acid; Step A3: mixing polyamic acid, modifier, chloroplatinic acid and N-methyl pyrrolidone, passing nitrogen protection, and reacting to prepare a coating solution; Step A4: coating the coating solution on a glass plate, respectively at a temperature of 80℃, keeping for 2h, at a temperature of 100℃, keeping for 1h, at a temperature of 150℃, keeping for 1h, at a temperature of 200℃, keeping for 1h, and at a temperature of 250℃, keeping for 1h to prepare an aging-resistant silicone-modified polyimide film.

2. The aged-resistant silicone-modified polyimide film according to claim 1, characterized in that: The amount ratio of o-phenylenediamine, acrylic acid and concentrated hydrochloric acid in step A1 is 30mmol:60mmol:15mL.

3. The aged-resistant silicone-modified polyimide film according to claim 1, characterized in that: The molar ratio of 4,4'-diamino diphenyl ether, modified monomer and pyromellitic anhydride in step A2 is 9:1:

10.

4. The aged-resistant silicone-modified polyimide film according to claim 1, characterized in that: The molar ratio of Si-H bond on polyamic acid and the modifier in step A3 is 1:1, and the mass ratio of polyamic acid and N-methyl pyrrolidone is 1:

6.

5. The aged-resistant silicone-modified polyimide film according to claim 1, characterized in that: The modified monomer is prepared by the following steps: Step B1: mixing (4,4'-dinitro[1,1'-biphenyl]2,2'-di)dimethylol, acrylic acid, p-toluenesulfonic acid, hydroquinone and DMF uniformly, passing nitrogen protection, and reacting to prepare intermediate 1, mixing intermediate 1, phenyldiethoxysilane, chloroplatinic acid and dichloroethane, passing nitrogen protection, and reacting to prepare intermediate 2; Step B2: mixing intermediate 2 and dichloromethane, passing nitrogen protection, stirring and adding acetyl chloride to react to prepare an end-capping agent, mixing dimethylhydrogen silanol lithium and tetrahydrofuran, passing nitrogen protection, stirring and adding trifluoropropylmethylcyclotrisiloxane to react, then adding the end-capping agent and continuing to react to prepare a pretreated polysiloxane; Step B3: dissolving the pretreated polysiloxane in tetrahydrofuran, passing argon protection, stirring and adding stannous chloride dihydrate and concentrated hydrochloric acid to react, then adding sodium hydroxide solution to adjust the pH to alkaline to prepare the modified monomer.

6. The aged-resistant silicone-modified polyimide film according to claim 5, characterized in that: The molar ratio of (4,4'-dinitro[1,1'-biphenyl]2,2'-di)dimethylol and acrylic acid in step B1 is 1:2, and the molar ratio of intermediate 1 and phenyldiethoxysilane is 1:

2.

7. The aged-resistant silicone-modified polyimide film according to claim 5, characterized in that: The molar ratio of intermediate 2 and acetyl chloride in step B2 is 1:5, and the molar ratio of dimethylhydrogen silanol lithium, trifluoropropylmethylcyclotrisiloxane and Si-Cl on the end-capping agent is 1:2.5:

1.

8. The aged-resistant silicone-modified polyimide film according to claim 5, characterized in that: The amount ratio of the pretreated polysiloxane, stannous chloride dihydrate and concentrated hydrochloric acid in step B3 is 1mmol:8mmol:3.6mL.

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