CN104945626B - Method for preparing polyimide coating adhesive with high adhesive force - Google Patents

Abstract

The invention discloses a method for preparing polyimide coating glue with high adhesion by blending two kinds of polyamic acid solutions with different relative molecular masses. Amines and aromatic organic dianhydrides are reacted to form small-molecular-weight polyamic acids, and then aromatic organic diamines and aromatic organic dianhydrides are used to react to synthesize high-molecular-weight polyamic acids, and then the two are mixed and reacted. Add 3-aminopropyltriethoxysilane end-capping, obtain the polyimide coating glue with suitable ratio of oligomer and high polymer. The imidization catalyst is added to the coating adhesive, and a high-performance polyimide film material can be obtained by heat treatment at 150-200°C. The polyimide coating glue prepared by the present invention has high adhesion, and the adhesion level with aluminum, copper, glass, ceramics and other surfaces can reach level 0, and it will not fall off after 3000 hours of boiling in water at 80°C, and can be widely used Microelectronic packaging and other fields.

Description

A kind of method for preparing high adhesion polyimide coating glue

technical field

The invention relates to a method for preparing polyimide coating glue with high adhesion by blending two kinds of polyamic acid solutions with different relative molecular masses, and belongs to the field of polymer material preparation.

Background technique

Polyimide refers to a class of polymers containing imide rings (-CO-NH-CO-) in the main chain. Because of its outstanding comprehensive performance, it is widely used in aerospace, electronic appliances, automobiles and chemical industries. application. Polyimide coating adhesive is the precursor of thermoplastic polyimide. After imidization, a polyimide film material with excellent performance can be obtained, which has excellent bonding performance to glass, metal surfaces, semiconductor devices, etc. , can be used as the passivation layer of the chip, the interlayer insulating layer film of the multilayer metal interconnection circuit, glass coating, etc.

The methods currently reported to improve the adhesion of polyimide coating adhesives mainly include: multi-component copolymerization; introducing silane chain segments on the polyimide main chain; introducing phosphine groups on the polyimide main chain; Silicon doping; substrates are treated with plasma before coating, etc.

Liao Haixing [Liao Haixing. Synthesis and characterization of high heat-resistant and high adhesion copolymerized polyimide. Journal of Central China Normal University (Natural Science Edition), 2011, 45(2): 246-248.] Using self-made diamine Monomers - bis(3-aminophenyl)-3,5-bis(trifluoromethyl)phenylphosphine oxide and 4,4'-(1,3-phenylene diether)diamine, 3,3' , 4,4'- Benzophenone tetraacid dianhydride copolymerized into polyimide. Studies have shown that the introduction of oxyphosphorus groups has improved the adhesion of polyimide on glass plates, but the adhesion level has not yet reached level 0.

Huang Jie et al [Huang Jie, Ran Chenxin, Shen Xianqiang, et al. Synthesis and application of main chain polyimide with long flexible chains. Chemical New Materials, 2012, 40(2): 72-74.] reported The effect of adding 0-10% KH-550 on the adhesion of polyimide. The study found that when the amount of KH-550 added is 6%, the adhesion of polyimide is the best, but the adhesion level can only reach level 1.

Liu Li et al [Liu Li, Li Youqing, Zhao Sanping, et al. Synthesis and properties of high temperature resistant multi-component copolyimide adhesives and their films. Proceedings of the 2004 Beijing International Adhesive Technology Symposium. 2004.] From the perspective of molecular design , using a variety of diamines and dibasic anhydrides to copolymerize polyimides with appropriate "soft" and "hard" segment ratios. The study found that the simultaneous introduction of soft segments and polar groups improved the adhesion of polyimide, but it only characterized the bond shear strength between polyimide coating adhesive and titanium sheet, and did not affect the adhesion of polyimide. The bonding performance between polyimide coating adhesive and other substrates such as glass is discussed.

Patent [CN 104277458 A] discloses a polyimide with high adhesion and low linear expansion coefficient synthesized by diamine containing rigid structure and cyano group in proportion to other diamines and acid anhydride monomers, but its The imidization temperature is high, and only the adhesion between the polyimide coating glue and the copper plate is given, and other substrates are not described.

Contents of the invention

The purpose of the present invention is to propose a method for preparing high-adhesion polyimide coating glue by blending two kinds of polyamic acid solutions with different relative molecular weights, so that there is an appropriate proportion of low polyimide coating glue in the polyimide coating glue. Polymers and high polymers, improve their adhesion, and use imidization catalysts to cure them at low temperatures to form high-performance polyimide films, making them widely used in microelectronic packaging and other fields.

The technical solution that realizes the object of the present invention is: a kind of method for preparing high adhesion polyimide coating adhesive, comprises the steps:

(1) Under the protection of nitrogen at 15-40°C, dissolve the aromatic organic diamine in an organic solvent. After completely dissolving, lower the reaction system to 0-5°C, add aromatic organic dianhydride, and react for 0.3-1 hour Add 3-aminopropyltriethoxysilane and react for 0.4 to 1 hour to form an oligomer polyamic acid solution;

(2) Under the protection of nitrogen at 15-40°C, dissolve the aromatic organic diamine in an organic solvent. After completely dissolving, lower the reaction system to 0-5°C, add aromatic organic dianhydride, and react for 8-10 hours Form a high polymer polyamic acid solution;

(3) Under the protection of nitrogen at 0-5°C, add the solution obtained in step (1) to the solution obtained in step (2) and mix to continue the reaction. After 2-3 hours, add 3-aminopropyltriethoxysilane to react After 1-1.5 hours, a polyimide coating glue is obtained.

In the above step (1), the relative number average molecular mass of the oligomer polyamic acid is 2×10 ³ -8×10 ³ .

In the above step (2), the relative number average molecular mass of the high polymer polyamic acid is 1×10 ⁵ -6×10 ⁵ .

In the above step (1) and step (2),

The aromatic organic diamine is 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, p-phenylenediamine, m-phenylenediamine, 2,2-[4-(4 -aminophenoxy)phenyl]propane, 3,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane Phenyl ether, 3,3'-diaminodiphenylmethane, 1,3-bis(aminopropyl)tetramethyldisiloxane, α,ω-diaminobutylpolymethicone, aminopropyl One or more of group-terminated polydimethylsiloxanes;

The aromatic organic dianhydride is pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2 ,3,3',4-Biphenyltetracarboxylic dianhydride, 4,4'-(4,4'-isopropyldiphenoxy)diphthalic anhydride, 3,3',4,4' -One of diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-triphenyl ether tetracarboxylic dianhydride or Several;

The organic solvent is N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide or dimethylsulfoxide.

In the above step (1), the molar ratio of 3-aminopropyltriethoxysilane, aromatic organic diamine, and aromatic organic dianhydride is 1: (25-30): (25-33), and the solid content of the solution 15-25%.

In the above step (2), the molar ratio of the aromatic organic diamine to the aromatic organic dianhydride is 1: (1.0-1.1), and the solid content of the solution is 15-25%.

The molar ratio of the aromatic organic diamine in the above step (1) to the aromatic organic diamine in the step (2) is 1: (4-5).

The molar ratio of the 3-aminopropyltriethoxysilane in the above step (3) to the 3-aminopropyltriethoxysilane in the step (1) is (5-6):1.

The present invention has the following significant advantages:

(1) The synthesis process is simple, the monomers used have been commercialized, and the cost is reduced.

(2) Due to the encirclement of the large molecular weight polymer, the intermolecular force between the small molecular weight polymer and the substrate is strengthened, and the triethoxysilane group in the end-capping agent is easily hydrolyzed and can form a hydrogen bond with the substrate, so the present invention The adhesion level of the prepared polyimide coating glue to metals such as aluminum, copper, iron, titanium, and glass, silicon wafers, single crystals, and ceramics can reach level 0, and it will not fall off at all after cooking in 80°C water for 3000 hours.

(3) The polyimide coating glue prepared by the present invention can be cured at low temperature (150-200° C.), and will not cause damage to the attached substrate due to high-temperature heat treatment.

(4) The polyimide coating adhesive prepared by the present invention has a lower end group content and has excellent hydrolysis resistance and thermal stability.

detailed description

The present invention prepares high-adhesion polyimide coating glue by blending two kinds of polyamic acid solutions with different relative molecular masses, and the specific preparation process is as follows:

(1) Under the protection of nitrogen at 15-40°C, dissolve the aromatic organic diamine in an organic solvent. After completely dissolving, lower the reaction system to 0-5°C, add aromatic organic dianhydride, and react for 0.3-1 hour Add 3-aminopropyltriethoxysilane and react for 0.4 to 1 hour to form an oligomer polyamic acid solution;

(2) Under the protection of nitrogen at 15-40°C, dissolve the aromatic organic diamine in an organic solvent. After completely dissolving, lower the reaction system to 0-5°C, add aromatic organic dianhydride, and react for 8-10 hours Form a high polymer polyamic acid solution;

(3) Under the protection of nitrogen at 0-5°C, add the solution obtained in step (1) to the solution obtained in step (2) and mix to continue the reaction. After 2-3 hours, add 3-aminopropyltriethoxysilane to react After 1-1.5 hours, a polyimide coating glue is obtained.

In the above step (1), the relative number-average molecular mass of the oligomer polyamic acid is 2×10 ³ to 8×10 ³ ; in the above step (2), the relative number average molecular mass of the high polymer polyamic acid The relative number-average molecular mass is 1×10 ⁵ to 6×10 ⁵ ; in the above step (1), the molar ratio of 3-aminopropyltriethoxysilane, aromatic organic diamine, and aromatic organic dianhydride is 1 : (25 ~ 30): (25 ~ 33), the solid content of the solution is 15 ~ 25%; in the above step (2), the mol ratio of aromatic organic diamine and aromatic organic dianhydride is 1: (1.0 ~ 1.1 ), the solid content of the solution is 15 to 25%; the mol ratio of the aromatic organic diamine in the above step (1) to the aromatic organic diamine in the step (2) is 1: (4 to 5); the above step ( The molar ratio of 3-aminopropyltriethoxysilane in 3) to 3-aminopropyltriethoxysilane in step (1) is (5-6):1.

The imidization catalyst is added to the polyimide coating adhesive prepared in the present invention, and the heat treatment is carried out at 150-200 DEG C by adopting a stepwise heating method to obtain a high-performance polyimide film fixedly attached to the substrate.

Above-mentioned imidization catalyst is m-hydroxybenzoic acid, p-hydroxybenzoic acid, p-hydroxyphenylacetic acid, p-hydroxybenzenesulfonic acid, p-aminophenol, m-aminobenzoic acid, p-aminobenzoic acid, quinoline, isoquinoline, One of benzimidazole, pyridine and collidine.

The molar ratio between the imidization catalyst and the aromatic organic diamine contained in the polyimide coating glue is (1-2):1.

The above stepwise heating method refers to curing by gradually increasing the temperature at 80°C/1h, 130°C/1h, and 150-200°C/1h.

The following is a detailed description of the embodiments of the present invention, but the present invention is not limited within the scope of the embodiments.

Example 1

(1) Under nitrogen protection at 15-20°C, dissolve 4.005g (0.02mol) 4,4'-diaminodiphenyl ether in 43mL N-methylpyrrolidone, and lower the reaction system to 0-5°C after complete dissolution , add 6.825g (0.022mol) 4,4'-oxydiphthalic dianhydride, add 0.188mL (0.0008mol) 3-aminopropyltriethoxysilane after 1 hour of reaction, form low Polymer polyamic acid solution;

(2) Under the protection of nitrogen at 15-20°C, dissolve 16.019g (0.08mol) of 4,4'-diaminodiphenyl ether in 173mL of N-methylpyrrolidone, and lower the reaction system to 0-5°C after complete dissolution , add 27.299g (0.088mol) 4,4'-oxydiphthalic dianhydride, and react for 10 hours to form a high polymer polyamic acid solution;

(3) Under the protection of nitrogen at 0-5°C, add the solution obtained in step (1) to the solution obtained in step (2) and mix to continue the reaction. After 2.5 hours, add 0.936mL (0.004mol) of 3-aminopropyltriethoxy base silane, after 1.5 hours of reaction, polyimide coating glue was obtained.

Add 17.613mL (0.15mol) isoquinoline to the obtained polyimide coating glue, mix and stir evenly, then coat on the surface of aluminum, iron, copper, glass, etc., put it in an oven at 80°C/1h, 130°C /1h, 170°C/1h heat treatment to obtain a polyimide film fixedly attached to the substrate.

Adopt gel permeation chromatography to measure, the relative number-average molecular mass of the oligomer polyamic acid gained in the step (1) is 8×10 ³ ; The relative number-average molecular mass of the gained polymer polyamic acid in the step (2) The mass is 6×10 ⁵ . The tensile strength of the obtained polyimide film is 109.44MPa, the initial temperature of thermal decomposition is 538.69°C, the adhesion level with different substrates all reaches level 0, and it does not fall off at all after being boiled in 80°C water for 3000 hours. The surface shear strength of the aluminum junction is 5.78MPa.

Example 2

(1) Under nitrogen protection at 20-25°C, dissolve 2.002g (0.01mol) 4,4'-diaminodiphenyl ether in 18mL N-methylpyrrolidone, and lower the reaction system to 0-5°C after complete dissolution , add 2.482g (0.008mol) 4,4'-oxydiphthalic dianhydride and 0.436g (0.002mol) pyromellitic dianhydride, add 0.089mL (0.00038mol) 3-aminopropane after reacting for 0.5 hours Base triethoxysilane, after reacting for 0.5 hours, polyamic acid oligomer solution was formed;

(2) Under the protection of nitrogen at 20-25°C, dissolve 9.011g (0.045mol) of 4,4'-diaminodiphenyl ether in 88mL of N-methylpyrrolidone, and lower the reaction system to 0-5°C after complete dissolution , add 11.168g (0.036mol) 4,4'-oxydiphthalic dianhydride and 1.963g (0.009mol) pyromellitic dianhydride, react for 9 hours to form a high polymer polyamic acid solution;

(3) Under the protection of nitrogen at 0-5°C, add the solution obtained in step (1) to the solution obtained in step (2) and mix to continue the reaction. After 2.6 hours, add 0.491 mL (0.0021 mol) of 3-aminopropyl triethoxy base silane, after 1.3 hours of reaction, polyimide coating glue was obtained.

Add 10.902mL (0.0825mol) collidine to the obtained polyimide coating glue, mix and stir evenly, and then coat the surface of aluminum, iron, copper, glass, etc., put it in an oven at 80°C/1h, 130 °C/1h, 190°C/1h heat treatment to obtain a polyimide film fixedly attached to the substrate.

Adopt gel permeation chromatography to measure, the relative number average molecular weight of the oligomer polyamic acid gained in step (1) is 4.7 * 10 ³ ; The relative number average molecular mass of the gained high polymer polyamic acid in step (2) The mass is 4.2×10 ⁵ . The tensile strength of the obtained polyimide film is 112.68MPa, the initial temperature of thermal decomposition is 543.32°C, the adhesion level with different substrates all reaches level 0, and it does not fall off at all after being boiled in 80°C water for 3000 hours. The surface shear strength of the aluminum sheet is 5.03MPa.

Example 3

(1) Under the protection of nitrogen at 35-40°C, mix 0.801g (0.004mol) 4,4'-diaminodiphenyl ether and 0.276mL (0.001mol) 1,3-di(aminopropyl)tetramethyldiphenyl ether Dissolve siloxane in 12mL N,N-dimethylformamide, after complete dissolution, lower the reaction system to 0-5°C, add 1.7725g (0.0055mol) 3,3',4,4'-benzophenone Tetraacid dianhydride, add 0.04mL (0.00017mol) 3-aminopropyltriethoxysilane after reacting for 0.3 hours, form oligomer polyamic acid solution after reacting for 1 hour;

(2) Under nitrogen protection at 35-40°C, mix 4.005g (0.02mol) 4,4'-diaminodiphenyl ether and 1.381mL (0.005mol) 1,3-di(aminopropyl)tetramethyldiphenyl ether Dissolve siloxane in 57mL N,N-dimethylformamide, after complete dissolution, lower the reaction system to 0-5°C, add 8.862g (0.028mol) 3,3',4,4'-benzophenone Tetraacid dianhydride, form high polymer polyamic acid solution after reacting for 8 hours;

(3) Under the protection of nitrogen at 0-5°C, add the solution obtained in step (1) to the solution obtained in step (2) and mix to continue the reaction. After 2 hours, add 0.24mL (0.001mol) 3-aminopropyltriethoxy base silane, polyimide coating glue was obtained after reacting for 1 hour.

Add 7.078mL (0.06mol) quinoline to the obtained polyimide coating glue, mix and stir evenly, and then coat the surface of aluminum, iron, copper, glass, etc., put it in an oven at 80°C/1h, 130°C/ 1h, 180°C/1h heat treatment to obtain a polyimide film fixedly attached to the substrate.

Adopt gel permeation chromatography to measure, the relative number-average molecular mass of the oligomer polyamic acid gained in step (1) is 2×10 ³ ; The mass is 1×10 ⁵ . The tensile strength of the obtained polyimide film is 100.37MPa, the initial temperature of thermal decomposition is 515.83°C, the adhesion level with different substrates all reaches level 0, and it does not fall off at all after being boiled in 80°C water for 3000 hours. The surface shear strength of the aluminum junction is 5.29MPa.

Example 4

(1) Under nitrogen protection at 20-25°C, mix 2.874g (0.007mol) 2,2-[4-(4-aminophenoxy)phenyl]propane and 0.588g (0.003mol) 4,4'- Dissolve diaminodiphenylmethane in 26mL of N-methylpyrrolidone, after complete dissolution, lower the reaction system to 0-5°C, add 1.933g (0.006mol) 3,3',4,4'-benzophenone tetraacid Dianhydride and 1.241g (0.004mol) 4,4'-oxydiphthalic dianhydride, reacted for 0.5 hours, added 0.089mL (0.00038mol) 3-aminopropyltriethoxysilane, reacted for 0.5 hours to form Oligomer polyamic acid solution;

(2) Under nitrogen protection at 20-25°C, mix 11.494g (0.028mol) 2,2-[4-(4-aminophenoxy)phenyl]propane and 2.352g (0.012mol) 4,4'- Dissolve diaminodiphenylmethane in 117mL of N-methylpyrrolidone, after complete dissolution, lower the reaction system to 0-5°C, add 7.733g (0.024mol) of 3,3',4,4'-benzophenone tetraacid Dianhydride and 4.963g (0.016mol) 4,4'-oxydiphthalic acid dianhydride, reacted to form high polymer polyamic acid solution after 10 hours;

(3) Under the protection of nitrogen at 0-5°C, add the solution obtained in step (1) to the solution obtained in step (2) and mix to continue the reaction. After 2.5 hours, add 0.491 mL (0.0021 mol) of 3-aminopropyl triethoxy base silane, after 1.5 hours of reaction, polyimide coating glue was obtained.

Add 6.07mL (0.05mol) isoquinoline to the obtained polyimide coating glue, mix and stir evenly, then coat on the surface of aluminum, iron, copper, glass, etc., put it in an oven at 80°C/1h, 130°C /1h, 160°C/1h heat treatment to obtain a polyimide film fixedly attached to the substrate.

Adopt gel permeation chromatography to measure, the relative number average molecular weight of the oligomer polyamic acid gained in step (1) is 6.3 * 10 ³ ; The relative number average molecular mass of the gained high polymer polyamic acid in step (2) The mass is 5.5×10 ⁵ . The tensile strength of the obtained polyimide film is 110.59 MPa, the initial temperature of thermal decomposition is 532.09 °C, the adhesion level with different substrates reaches level 0, and it does not fall off at all after being boiled in 80 °C water for 3000 hours. The surface shear strength of the aluminum junction is 5.67MPa.

Example 5

(1) Under nitrogen protection at 15-20°C, 1.811g (0.008mol) of 3,3'-dimethyl-4,4'-diaminodiphenylmethane and 1.695mL (0.002mol) of aminopropyl Dissolve polydimethylsiloxane in 22mL N,N-dimethylformamide, after complete dissolution, lower the reaction system to 0-5°C, add 2.17g (0.007mol) 2,3,3',4'- Diphenyl ether tetracarboxylic dianhydride and 0.883g (0.003mol) 2,3,3',4-biphenyl tetracarboxylic dianhydride, add 0.084mL (0.00036mol) 3-aminopropyltriethoxy after 0.4 hours of reaction Silane, after reacting for 0.4 hours, forms oligomer polyamic acid solution;

(2) Under nitrogen protection at 15-20°C, 8.15g (0.036mol) 3,3'-dimethyl-4,4'-diaminodiphenylmethane and 7.627mL (0.009mol) aminopropyl Dissolve polydimethylsiloxane in 84mL N,N-dimethylformamide, after complete dissolution, lower the reaction system to 0-5°C, add 9.765g (0.0315mol) 2,3,3',4'- Diphenyl ether tetracarboxylic dianhydride and 3.972g (0.0135mol) 2,3,3',4-biphenyl tetracarboxylic dianhydride, reacted to form a high polymer polyamic acid solution after 9 hours;

(3) Under the protection of nitrogen at 0-5°C, add the solution obtained in step (1) to the solution obtained in step (2) and mix to continue the reaction. After 3 hours, add 0.421mL (0.0018mol) of 3-aminopropyltriethoxy base silane, after 1.3 hours of reaction, polyimide coating glue was obtained.

Add 8.357g (0.0605mol) of p-hydroxybenzoic acid to the obtained polyimide coating glue, mix and stir evenly, then coat the surface of aluminum, iron, copper, glass, etc., put it in an oven at 80°C/1h, 130 °C/1h, 200°C/1h heat treatment to obtain a polyimide film fixedly attached to the substrate.

Adopt gel permeation chromatography to measure, the relative number average molecular mass of the oligomer polyamic acid gained in step (1) is 4.2 * 10 ³ ; The relative number average molecular mass of the gained high polymer polyamic acid in step (2) The mass is 4.9×10 ⁵ . The tensile strength of the obtained polyimide film is 107.11MPa, the initial temperature of thermal decomposition is 538.95°C, the adhesion level with different substrates all reaches level 0, and it does not fall off at all after being boiled in 80°C water for 3000 hours. The surface shear strength of the aluminum junction is 6.14MPa.

Example 6

(1) Under nitrogen protection at 35-40°C, add 3.079g (0.0075mol) 2,2-[4-(4-aminophenoxy)phenyl]propane, 0.401g (0.002mol) 4,4'- Dissolve diaminodiphenyl ether and 0.054g (0.0005mol) p-phenylenediamine in 26mL N,N-dimethylacetamide, after complete dissolution, lower the reaction system to 0-5°C, add 3.545g (0.011mol)3 ,3',4,4'-Benzophenone tetraacid dianhydride, add 0.094mL (0.0004mol) 3-aminopropyltriethoxysilane after 0.5 hour reaction, form oligomer polyamide after 1 hour reaction acid solution;

(2) Under nitrogen protection at 35-40°C, add 12.931g (0.0315mol) 2,2-[4-(4-aminophenoxy)phenyl]propane, 1.682g (0.0084mol) 4,4'- Diaminodiphenyl ether and 0.227g (0.0021mol) of p-phenylenediamine were dissolved in 122mL of N,N-dimethylacetamide. After complete dissolution, the reaction system was lowered to 0-5°C, and 14.887g (0.0462mol)3 , 3',4,4'-benzophenone tetraacid dianhydride, reacting for 9 hours to form a high polymer polyamic acid solution;

(3) Under the protection of nitrogen at 0-5°C, add the solution obtained in step (1) to the solution obtained in step (2) and mix to continue the reaction. After 2.5 hours, add 0.562mL (0.0024mol) of 3-aminopropyltriethoxy base silane, after 1.5 hours of reaction, polyimide coating glue was obtained.

Add 9.818g (0.0832mol) benzimidazole to the obtained polyimide coating glue, mix and stir evenly, then coat on the surface of aluminum, iron, copper, glass, etc., put it in an oven at 80°C/1h, 130°C /1h, 180°C/1h heat treatment to obtain a polyimide film fixedly attached to the substrate.

Adopt gel permeation chromatography to measure, the relative number-average molecular mass of the oligomer polyamic acid gained in step (1) is 7.1×10 ³ ; The mass is 5.1×10 ⁶ . The tensile strength of the obtained polyimide film is 103.45MPa, the initial temperature of thermal decomposition is 528.64°C, the adhesion level with different substrates all reaches level 0, and it does not fall off at all after being boiled in 80°C water for 3000 hours. The surface shear strength of the aluminum junction is 6.69MPa.

Example 7

(1) Under nitrogen protection at 25-30°C, add 3.284g (0.008mol) 2,2-[4-(4-aminophenoxy)phenyl]propane, 0.414mL (0.0015mol) 1,3-bis (Aminopropyl)tetramethyldisiloxane and 0.054g (0.0005mol) m-phenylenediamine were dissolved in 27mL of dimethyl sulfoxide, and after complete dissolution, the reaction system was lowered to 0-5°C, and 2.9g ( 0.009mol) 3,3',4,4'-benzophenone tetracarboxylic dianhydride and 0.218g (0.001mol) pyromellitic dianhydride, add 0.084mL (0.00036mol) 3-aminopropane after reacting for 0.35 hours Base triethoxysilane, after reacting for 0.4 hours, form oligomer polyamic acid solution;

(2) Under nitrogen protection at 25-30°C, add 13.136g (0.032mol) 2,2-[4-(4-aminophenoxy)phenyl]propane, 1.657mL (0.006mol) 1,3-bis (Aminopropyl)tetramethyldisiloxane and 0.216g (0.002mol) m-phenylenediamine were dissolved in 111mL of dimethyl sulfoxide, and after complete dissolution, the reaction system was lowered to 0-5°C, and 11.6g ( 0.036mol) 3,3',4,4'-benzophenone tetracarboxylic dianhydride and 0.872g (0.004mol) pyromellitic dianhydride, reacted to form a high polymer polyamic acid solution after 8.5 hours;

(3) Under the protection of nitrogen at 0-5°C, add the solution obtained in step (1) to the solution obtained in step (2) and mix to continue the reaction. After 2 hours, add 0.505mL (0.00216mol) of 3-aminopropyltriethoxy base silane, polyimide coating glue was obtained after reacting for 1 hour.

Add 7.524mL (0.06mol) isoquinoline to the obtained polyimide coating glue, mix and stir evenly, then coat on the surface of aluminum, iron, copper, glass, etc., put it in an oven at 80°C/1h, 130°C /1h, 170°C/1h heat treatment to obtain a polyimide film fixedly attached to the substrate.

Adopt gel permeation chromatography to measure, the relative number-average molecular weight of the oligomer polyamic acid gained in step (1) is 3.3×10 ³ ; The mass is 3.7×10 ⁵ . The tensile strength of the obtained polyimide film is 109.35MPa, the initial temperature of thermal decomposition is 534.17°C, the adhesion level with different substrates all reaches level 0, and it does not fall off at all after being boiled in 80°C water for 3000 hours. The surface shear strength of the aluminum sheet is 6.53MPa.

Claims (5)

1. a kind of method for preparing high adhesion force polyimide coating glue, it is characterised in that comprise the steps：

（1）Under 15 ~ 40 DEG C of nitrogen protections, aromatic series organic diamine is dissolved in organic solvent, by reactant after being completely dissolved System is down to 0 ~ 5 DEG C, adds the organic dianhydride of aromatic series, reaction that 3- aminopropyl triethoxysilanes, reaction are added after 0.3 ~ 1 hour Oligomer polyamic acid solution is formed after 0.4 ~ 1 hour；

（2）Under 15 ~ 40 DEG C of nitrogen protections, aromatic series organic diamine is dissolved in organic solvent, by reactant after being completely dissolved System is down to 0 ~ 5 DEG C, adds the organic dianhydride of aromatic series, reaction to form high polymer polyamic acid solution after 8 ~ 10 hours；

（3）Under 0 ~ 5 DEG C of nitrogen protection, by step（1）Resulting solution is added to step（2）Mixing in resulting solution continues anti- Should, add 3- aminopropyl triethoxysilanes, reaction to obtain polyimide coating glue after 1 ~ 1.5 hour after 2 ~ 3 hours；

Wherein, the number average mol weight of described oligomer polyamic acid is 2 × 10³~8×10³；

The number average mol weight of described high polymer polyamic acid is 1 × 10⁵~6×10⁵；

Step（1）In aromatic series organic diamine and step（2）In aromatic series organic diamine mol ratio be 1：（4~5）.

2. the method for preparing high adhesion force polyimide coating glue as claimed in claim 1, it is characterised in that step（1）With Step（2）In,

Described aromatic series organic diamine is 4,4'- diaminodiphenyl ethers, 4,4'- MDAs, p-phenylenediamine, isophthalic Diamidogen, 2,2- [4- (4- amino-benzene oxygens) phenyl] propane, 3,4'- MDAs, 3,3'- dimethyl -4,4'- diaminos Base diphenyl-methane, 3,4'- diaminodiphenyl ethers, 3,3'- MDAs, the silica of 1,3- bis- (aminopropyl) tetramethyl two One or more in alkane, aminopropyl end-blocking polydimethylsiloxane；

The organic dianhydride of described aromatic series is pyromellitic acid anhydride, 3,3', and 4,4'- benzophenone tetracarboxylic dianhydrides, 4,4'- oxygen are double O-phthalic acid dianhydride, 2,3,3', 4- bibenzene tetracarboxylic dianhydrides, 4,4'- (4,4'- isopropyl diphenoxies) double phthalic acids Acid anhydride, 3,3', 4,4 '-diphenyl ether tetraformic dianhydride, 2,3,3', 4'- diphenyl ether tetraformic dianhydrides, 3,3', 4,4'- triphens diether four One or more in formic acid dianhydride；

Described organic solvent is N-Methyl pyrrolidone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or dimethyl Sulfoxide.

3. the method for preparing high adhesion force polyimide coating glue as claimed in claim 1, it is characterised in that step（1）In, 3- aminopropyl triethoxysilanes, aromatic series organic diamine, the mol ratio of the organic dianhydride of aromatic series are 1：（25~30）：（25~ 33）, solution solid content is 15 ~ 25%.

4. the method for preparing high adhesion force polyimide coating glue as claimed in claim 1, it is characterised in that step（2）In, Aromatic series organic diamine is 1 with the mol ratio of the organic dianhydride of aromatic series：（1.0~1.1）, solution solid content is 15 ~ 25%.

5. the method for preparing high adhesion force polyimide coating glue as claimed in claim 1, it is characterised in that step（3）In 3- aminopropyl triethoxysilanes and step（1）In the mol ratio of 3- aminopropyl triethoxysilanes be（5~6）：1.