CN1580095A - Polyimide material, and its preparing method and use - Google Patents

Abstract

A kind of polyimide material will produce pyridine diphenol and its ramification by condensation reaction between hydroxyl hypnone and substituted benzaldehyde. The etherification reaction will occur to the products and 3-nitryl-near chlorine benzotrifluoride and will derive binitro compound. The binitro compound will be deoxidized into diamine monomer of aromatic trifluoromethyl by the ethanol solution of iron dust/HCl. This monomer will derive polyamic acid solution by adding molecular weight regulator, assistant adhesive and aromatic tetracid dual-anhydride. The polyamic acid solution will become into aromatic polyimide after being processed by chemical imine or heat imine.

Description

A kind of polyimide material and preparation method and application

technical field

The invention relates to a polyimide material.

The present invention also relates to a preparation method of the above-mentioned polyimide material.

The present invention also relates to the application of the above-mentioned polyimide material.

Background technique

Polyimide materials have excellent comprehensive properties and are increasingly widely used in aerospace, aviation, space, microelectronics, and electrical appliances. As a functional material, polyimide materials must have properties that can meet special application purposes on the basis of existing comprehensive properties; for example, as VLSI and microelectronic packaging materials, polyimide materials must not only In addition to high thermal stability, high mechanical properties, high electrical insulation, low dielectric constant, low dielectric loss, etc., it must also have the advantages of high solubility, low moisture absorption, low expansion coefficient, and low molding temperature; Therefore, in order to meet the special needs in the high-tech field, people have been continuously researching and developing new polyimide materials with various special properties in recent years. Ichino et al [T.Ichino, S.Sasaki, T.Matsuura and S.nishi.J.Polym.Sci.Polym.Chem.Ed.1990, 28, 323] reported a series of meta- The polyimide material prepared by diamine has a minimum dielectric constant of 2.6, and has low water absorption and good solubility, but its longer fluorine-containing alkane substituent group not only reduces the reactivity of the monomer , and also lowered the glass transition temperature (T _g 189°C) of the prepared polyimide. Hongham[G.Hougham and G.Tesoro.Polym.Mater.Sci.Eng.1989,61,369] etc. have reported polyimide materials prepared from perfluoroaromatic diamines; Low dielectric constant (2.75) and high glass transition temperature (T _g >330°C); but because the introduction of fluorine atoms greatly reduces the reactivity of aromatic diamines, it is difficult to obtain high molecular weight and excellent performance polyimide polymer material. [RABuchanan, RFMundhenke, and HCLin.Polym.Prepr, 1991, 32(2), 193] reported a trifluoromethyl-containing aromatic diamine monomer, 4,4'-diamino-2 , 2′-bistrifluoromethyl-diphenyl ether, this monomer has higher reactivity, can obtain high molecular weight, high-quality polyimide polymer material with 6FDA polymerization; The prepared polymer has relatively High glass transition temperature (295°C) and low dielectric constant 2.76 (1MHz), with excellent solubility properties.

Contents of the invention

The invention discloses a polyimide material, which not only has excellent comprehensive properties, such as high heat resistance stability, high mechanical and mechanical properties, high glass transition temperature, high electrical insulation performance, low dielectric Electrical constant and dielectric loss, while having excellent solubility and very low moisture absorption characteristics.

The invention also discloses a preparation method of the above-mentioned polyimide material, which is specifically prepared from fluorine-containing aromatic organic diamine and its derivatives.

The polyimide material disclosed by the present invention has the following chemical structure:

R＝—O CO C(CF ₃ ) ₂ C(CF ₃ )(C ₆ H ₅ )

The preparation method of above-mentioned material is:

a) Condensation reaction of p-hydroxyacetophenone (270-300 parts) and substituted benzaldehyde (100-360 parts) at 60-150° C. to generate pyridinediol and its derivatives;

b) Etherification of the obtained pyridine-containing diphenol and its derivatives (100 parts) with 3-nitro-o-chlorobenzotrifluoride (440-500 parts) at a temperature of 80-150 ° C to obtain a dinitro compound ;

c) Reducing the obtained dinitro compound (220 parts) with iron powder/HCl aqueous ethanol solution (180-250 parts) at 60-120° C. to obtain a trifluoromethyl-containing aromatic diamine monomer.

Its preparation route is:

The structures of the above-mentioned fluorine-containing aromatic organic diamines and derivatives thereof are shown in the following formula:

d) Under the protection of nitrogen, dissolve 8-12 parts of the fluorine-containing aromatic organic diamine and its derivatives prepared in step c in an organic solvent under stirring, and after all the solids are dissolved, add 2-10 parts to adjust the molecular weight agent and adhesion promoter; under ice bath cooling, add 8-12 parts of aromatic tetra-acid dianhydride in batches, remove the ice-water bath, stir and react at room temperature under nitrogen protection for 10-36 hours to obtain a polyamic acid solution;

e) Coat the polyamic acid solution obtained in step d on the surface of the glass or silicon wafer, and gradually heat to 250-350° C. to convert the polyamic acid into a polyimide material.

The described step that polyamic acid is converted into polyimide material can also be:

Add 40-100 parts of the imidization accelerator solution into the polyamic acid solution obtained in step d under stirring, raise the temperature to 100-160°C for 3-8 hours, cool to room temperature, and precipitate the obtained liquid into the organic in an alcohol solvent; collect the precipitate and wash it with an organic alcohol solvent, and then dry it at 40-60 ° C to obtain a polyimide solid resin; mix the polyimide solid resin with an organic solvent, and filter it after it is completely dissolved to obtain a polyimide solid resin. Imide coating glue solution; then apply the obtained polyimide coating glue solution on the surface of glass or silicon wafer, and heat up to 200-250°C to obtain polyimide coating or film;

The aromatic tetra-acid dianhydride refers to an aromatic organic compound containing two acid anhydrides, including 3,3',4,4'-diphenylmethyl ether tetra-acid dianhydride (ODPA), 3,3',4 , 4'-Benzophenone tetra-acid dianhydride (BTDA), 3,3',4,4'-biphenyl tetra-acid dianhydride (BPDA), 3,3',4,4'-triphenylene ether Tetraacid dianhydride (HQDPA), 4,4'-(hexafluoroisopropyl)diphthalic dianhydride (6FDA), 3,3',4,4'-pyromellitic dianhydride (PMDA) and other mixtures in any proportion.

Described organic solvent comprises N-methylpyrrolidone, N, N'-dimethylacetamide, N, N'-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone and the above-mentioned solvent according to Mixed solution in any proportion.

The molecular weight regulator and adhesion promoter refer to organic compounds or organosilicon compounds and mixtures thereof that can regulate the molecular chain length of polyimide polymers and increase their adhesive properties, including γ-aminopropyl triethoxy Silane, γ-aminopropyltrimethoxysilane, bis-(γ-aminopropyl)tetramethylsiloxane, bis-(γ-aminobutyl)tetramethylsiloxane, bis-(γ-ammonia Propyl)methicone, bis-(γ-aminobutyl)methicone, bis-(γ-aminopropyl)tetraphenyldisiloxane, bis-(γ-aminopropyl) Base) phenylpolysiloxane, bis-(γ-aminobutyl) tetraphenylsiloxane, bis-(γ-aminobutyl)phenylpolysiloxane and their mixtures in any proportion wait.

Table 1 The main properties of typical polyimides Example main components Intrinsic viscosity (dL/g) T _g (°C) T ₅ (℃) T ₁₀ (℃) Water absorption (%) 6 ODPA/6FPDA 0.74 259 578 613 0.44 7 BTDA/6FPDA 0.83 271 607 640 0.78 8 BPDA/6FPDA 0.78 284 622 656 0.53 9 PMDA/6FPDA 0.95 312 583 617 0.60 10 6FDA/6FPDA 0.65 281 561 587 0.41

In the table: T _g - glass transition temperature (DSC); T ₅ - thermal decomposition temperature of 5% weight loss; T ₁₀ - thermal decomposition temperature of 10 weight loss (TGA).

The polyimide material of the present invention has excellent solubility properties, and is not only soluble in strongly polar aprotic organic solvents, including N-methylpyrrolidone, N, N'-dimethylacetamide, N, N'-dimethylformamide, dimethyl sulfoxide; also soluble in some common organic solvents with low boiling point and low polarity, including γ-butyrolactone, cyclopentanone, tetrahydrofuran, dioxane ring, chloroform, methyl acetate. Dissolve the polyimide solid resin obtained by the chemical imidization method in an appropriate organic solvent system to obtain a polyimide resin solution with a solid content of more than 20 wt%, and then use the spin coating method, dipping method, spraying method or Screen printing and other methods are coated on the substrate, and after heating to remove the solvent, a flexible polymer film can be obtained; the typical properties of the obtained polyimide film are shown in Table 1; the intrinsic viscosity of the obtained polyimide resin is 0.65 The range of -0.95, glass transition temperature between 259-312 ℃, 5% thermal weight loss temperature between 561-622 ℃; Table 2 lists the main mechanical properties and electrical properties of polyimide materials; it can be seen , the polyimide material has excellent mechanical properties and electrical insulation properties; in addition, the prepared material has excellent resistance to heat and humidity, and its water absorption is in the range of 0.41-0.78%. There is no significant change in the properties of the material for more than an hour. In addition, this type of material has excellent visible light transparency, light color, and the transmittance of 30 μm film to 450nm light is greater than 80%.

The polyimide resin of the present invention has excellent comprehensive properties and has important application value in microelectronic packaging. Typical applications include surface chip passivation layer, stress buffer inner coating, contact protection film, multilayer interconnection Interlayer dielectric insulating layer films of circuits, liquid crystal molecular orientation films in liquid crystal display technology, and high temperature resistant adhesives, etc.

Table 2 Mechanical properties and electrical properties of typical polyimide films Example Tensile strength (MPa) Tensile modulus (GPa) R _S () R _V (·cm) Dielectric constant (1MHz) Dielectric Loss (1MHz) 6 103 2.36 6.3×10 ¹⁴ 3.5×10 ¹⁵ 2.98 3.2×10 ^-3 7 97.3 2.07 2.7×10 ¹⁵ 2.5×10 ¹⁵ 3.12 4.3×10 ^-3 8 77.8 2.20 3.6×10 ¹⁵ 5.8×10 ¹⁵ 2.94 3.9×10 ^-3 9 88.0 2.20 8.2×10 ¹⁴ 1.9×10 ¹⁵ 3.21 5.2×10 ^-3 10 73.4 2.35 4.1×10 ¹⁵ 4.3×10 ¹⁵ 2.85 2.9×10 ^-3

Detailed ways

Example 1

4-phenyl-2,6 bis(4-hydroxy-phenyl)-pyridine: In the three-necked flask equipped with mechanical stirring, condenser and nitrogen inlet and outlet, add 530 parts of benzaldehyde and 250 parts of p-hydroxyacetophenone , 1000 parts of ammonium acetate, 2000ml of glacial acetic acid. The reaction mixture was refluxed for 4-6 hours with stirring to obtain a homogeneous orange-red solution, which was poured into 4000 ml of water to obtain a yellow-brown precipitate. Collect the precipitate by filtration and wash it with water 3 times to obtain the crude product; dissolve the crude product in 1000ml 2/1 tetrahydrofuran/petroleum ether mixed solvent, collect the filtrate by filtration; freeze the filtrate overnight in the refrigerator below -15°C, and filter to obtain light yellow Powdered 4-phenyl-2,6-bis(4-hydroxy-phenyl)-pyridine.

4-phenyl-2,6-bis(4-(4-nitro-2-trifluoromethyl-phenoxy)-phenyl)pyridine: 100 parts of 4-phenyl-2,6-bis(4 -Hydroxy-phenyl)-pyridine and 30 parts of potassium hydroxide, 500ml dimethyl sulfoxide, and 300ml toluene are added in the there-necked flask equipped with mechanical stirring, thermometer, reflux condenser, water separator and nitrogen inlet and outlet; The system was heated to reflux temperature, and after reflux for 14 hours, 150 parts of 2-trifluoromethyl-4-nitrochlorobenzene was added, and the reaction was continued at 110-120°C for 16 hours. After the system was cooled to room temperature, the reaction mixture was poured into 2000ml of water, and a tan powdery solid precipitated out. The precipitate was collected by filtration and washed several times with water; then recrystallized with ethanol to obtain light gray solid powder 4-phenyl-2,6-bis(4-(4-nitro-2-trifluoromethyl-phenoxy) -phenyl)pyridine.

4-phenyl-2,6-bis(4-(4-amino-2-trifluoromethyl-phenoxy)-phenyl)pyridine: 200 parts of 4-phenyl-2,6-bis(4 -(4-nitro-2-trifluoromethyl-phenoxy)-phenyl)pyridine and 190 parts of reduced iron powder, 500ml of 50% ethanol aqueous solution are added to the The funnel and the three-necked flask with nitrogen inlet and outlet. Mix 15ml of concentrated hydrochloric acid with 80ml of 50% ethanol aqueous solution and add to the dropping funnel. Start stirring and heat the reaction system to the reflux temperature, slowly add hydrochloric acid solution dropwise at the reflux temperature, and maintain the reflux temperature to continue the reaction for 3 hours after the dropwise addition is completed. Add 50ml of ammonia water and 50ml of ethanol to the reaction system, continue to reflux for 0.5 hours, filter while hot, and collect the filtrate. The filtrate was concentrated under reduced pressure and poured into water, and the precipitate was collected by filtration to obtain a crude product. The crude product was recrystallized from ethanol to obtain pink 4-phenyl-2,6-bis(4-(4-amino-2-trifluoromethyl-phenoxy)-phenyl)pyridine.

Example 2

4-(4-trifluoromethylphenyl)-2,6 bis(4-hydroxyl-phenyl)-pyridine: Add p-trifluoro 1050 parts of methyl benzaldehyde, 300 parts of p-hydroxyacetophenone, 1000 parts of ammonium acetate, 1200 ml of glacial acetic acid. The reaction mixture was refluxed for 4-5 hours with stirring to obtain a homogeneous orange-red solution, which was poured into 6000 ml of water to obtain a yellow-brown precipitate. The precipitate was collected by filtration and washed with water to obtain a crude product; recrystallized from acetone to obtain light yellow powder 4-(4-trifluoromethylphenyl)-2,6bis(4-hydroxy-phenyl)-pyridine.

4-(4-trifluoromethylphenyl)-2,6-bis(4-(4-nitro-2-trifluoromethyl-phenoxy)-phenyl)pyridine: 240 parts of 4-( 4-trifluoromethylphenyl)-2,6 bis(4-hydroxy-phenyl)-pyridine and 60 parts of potassium hydroxide, 1000ml dimethyl sulfoxide, 600ml toluene were added equipped with mechanical stirring, thermometer, reflux condensation Pipe, water separator and three-necked flask with nitrogen inlet and outlet; add the reaction system to the reflux temperature, add 300 parts of 2-trifluoromethyl-4-nitrochlorobenzene after reflux for 14 hours, and continue the reaction at 110-120 ° C 16 hours. After the system was cooled to room temperature, the reaction mixture was poured into 5000ml of water, and a tan powdery solid precipitated out. The precipitate was collected by filtration, and then recrystallized with ethylene glycol monomethyl ether to obtain light yellow solid powder 4-(p-trifluoromethylphenyl)-2,6-bis(4-(4-nitro-2- Trifluoromethyl-phenoxy)-phenyl)pyridine.

4-(4-trifluoromethylphenyl)-2,6-bis(4-(4-amino-2-trifluoromethyl-phenoxy)-phenyl)pyridine: 220 parts of 4-(4 -trifluoromethylphenyl)-2,6-bis(4-(4-nitro-2-trifluoromethyl-phenoxy)-phenyl)pyridine and 190 parts of reduced iron powder, 500ml 50% Add the ethanol aqueous solution into a three-necked flask equipped with mechanical stirring, reflux condenser, constant pressure dropping funnel and nitrogen inlet and outlet. Mix 15ml of concentrated hydrochloric acid with 80ml of 50% ethanol aqueous solution and add to the dropping funnel. Start stirring and heat the reaction system to the reflux temperature, slowly add hydrochloric acid solution dropwise at the reflux temperature, and maintain the reflux temperature to continue the reaction for 3 hours after the dropwise addition is completed. Add 50ml of ammonia water and 50ml of ethanol to the reaction system, continue to reflux for 0.5 hours, filter while hot, and collect the filtrate. The filtrate was concentrated under reduced pressure and poured into water, and the precipitate was collected by filtration to obtain a crude product. The crude product was recrystallized from acetone/water mixed solution to obtain gray 4-(4-trifluoromethylphenyl)-2,6-bis(4-(4-amino-2-trifluoromethyl-phenoxy) -phenyl)pyridine.

Example 3

4-(3', 5'-bistrifluoromethylphenyl)-2,6 bis(4-hydroxyl-phenyl)-pyridine: in a three-neck flask equipped with mechanical stirring, condenser and nitrogen inlet and outlet, Add 1200 parts of 3',5'-bistrifluoromethylbenzaldehyde, 250 parts of p-hydroxyacetophenone, 1000 parts of ammonium acetate and 2000 ml of glacial acetic acid. The reaction mixture was refluxed for 4-6 hours under stirring to obtain an orange-red homogeneous clear solution, which was poured into 5200 ml of water to obtain a yellow-brown precipitate. The precipitate was collected by filtration and washed 3 times with water to obtain a crude product; the crude product was recrystallized from a mixed solvent of diethyl ether/petroleum ether to obtain light yellow powder 4-(3',5'-bistrifluoromethylphenyl)-2 , 6 bis(4-hydroxy-phenyl)-pyridine.

4-(3', 5'-bistrifluoromethylphenyl)-2,6-bis(4-(4-nitro-2-trifluoromethyl-phenoxy)-phenyl)pyridine: the 230 parts of 4-phenyl-2,6 bis(4-hydroxy-phenyl)-pyridine, 40 parts of potassium hydroxide, 600ml dimethyl sulfoxide, and 350ml of toluene were added. In a three-necked flask with a nitrogen inlet and outlet; add the reaction system to the reflux temperature, add 160 parts of 2-trifluoromethyl-4-nitrochlorobenzene after reflux for 10 hours, and continue to react at 110-140°C for 14 hours. After the system was cooled to room temperature, the reaction mixture was poured into 2500ml of water, and a light yellow powdery solid precipitate was precipitated. The precipitate was collected by filtration and washed several times with water; then recrystallized from ethyl acetate to obtain 4-(3',5'-bistrifluoromethylphenyl)-2,6-bis(4-(4- Nitro-2-trifluoromethyl-phenoxy)-phenyl)pyridine.

4-(3',5'-ditrifluoromethylphenyl)-2,6-bis(4-(4-amino-2-trifluoromethyl-phenoxy)-phenyl)pyridine: 242 Parts of 4-(3', 5'-bistrifluoromethylphenyl)-2,6-bis(4-(4-nitro-2-trifluoromethyl-phenoxy)-phenyl)pyridine and Add 190 parts of reduced iron powder and 500ml of 50% ethanol aqueous solution into a three-neck flask equipped with mechanical stirring, reflux condenser, constant pressure dropping funnel and nitrogen inlet and outlet. Mix 15ml of concentrated hydrochloric acid with 80ml of 50% ethanol aqueous solution and add to the dropping funnel. Start stirring and heat the reaction system to the reflux temperature, slowly add hydrochloric acid solution dropwise at the reflux temperature, and maintain the reflux temperature to continue the reaction for 3 hours after the dropwise addition is completed. Add 50ml of 20% NaOH solution to the reaction system for neutralization, continue to reflux for 0.5 hours, filter while hot, and collect the filtrate. The filtrate was concentrated under reduced pressure and poured into water, and the precipitate was collected by filtration to obtain a crude product. The crude product was recrystallized from a mixed solution of ethanol and water to obtain light yellow 4-phenyl-2,6-bis(4-(4-amino-2-trifluoromethyl-phenoxy)-phenyl)pyridine.

Example 4

4-(4-fluorophenyl)-2,6 bis(4-hydroxy-phenyl)-pyridine: Add 620 parts of 4-fluorobenzaldehyde to a three-necked flask equipped with mechanical stirring, condenser tube and nitrogen inlet and outlet , 250 parts of p-hydroxyacetophenone, 1000 parts of ammonium acetate, 2000 ml of glacial acetic acid. The reaction mixture was refluxed for 4-6 hours with stirring to obtain a homogeneous orange-red solution, which was poured into 4000 ml of water to obtain a yellow-brown precipitate. The precipitate was collected by filtration and washed 3 times with water to obtain a crude product, which was recrystallized from tetrahydrofuran/toluene to obtain light yellow powder 4-(4-fluorophenyl)-2,6 bis(4-hydroxy-phenyl)-pyridine .

4-(4-fluorophenyl)-2,6-bis(4-(4-nitro-2-trifluoromethyl-phenoxy)-phenyl)pyridine: 105 parts of 4-(4-fluoro Phenyl)-2,6 bis(4-hydroxy-phenyl)-pyridine and 30 parts of potassium hydroxide, 500ml dimethyl sulfoxide, and 300ml toluene are added with mechanical stirring, thermometer, reflux condenser, water separator and nitrogen In the three-necked flask of import and export; add the reaction system to the reflux temperature, add 150 parts of 2-trifluoromethyl-4-nitrochlorobenzene after reflux for 10 hours, and continue to react at 110-120°C for 16 hours. After the system was cooled to room temperature, the reaction mixture was poured into 2000ml of water, and a tan powdery solid precipitated out. The precipitate was collected by filtration and recrystallized 3 times with ethanol to obtain 4-(4-fluorophenyl)-2,6-bis(4-(4-nitro-2-trifluoromethyl-phenoxy) in the form of light gray solid powder )-phenyl)pyridine.

4-(4-fluorophenyl)-2,6-bis(4-(4-amino-2-trifluoromethyl-phenoxy)-phenyl)pyridine: 103 parts of 4-(4-fluorobenzene base)-2,6-bis(4-(4-nitro-2-trifluoromethyl-phenoxy group)-phenyl)pyridine and 95 parts of reduced iron powder, 250ml 50% ethanol aqueous solution are added to the machine Stirring, reflux condenser, constant pressure dropping funnel and three-neck flask with nitrogen inlet and outlet. Mix 8ml of concentrated hydrochloric acid with 40ml of 50% ethanol aqueous solution and add to the dropping funnel. Start stirring and heat the reaction system to the reflux temperature, slowly add hydrochloric acid solution dropwise at the reflux temperature, and maintain the reflux temperature to continue the reaction for 3 hours after the dropwise addition is completed. Add 20ml of ammonia water and 25ml of ethanol to the reaction system, continue to reflux for 0.5 hours, filter while hot, and collect the filtrate. The filtrate was concentrated under reduced pressure and poured into water, and the precipitate was collected by filtration to obtain a crude product. Recrystallize the crude product from methanol alcohol to give light pink 4-(4-fluorophenyl)-2,6-bis(4-(4-amino-2-trifluoromethyl-phenoxy)-phenyl)pyridine .

Example 5

4-(m-trifluoromethylphenyl)-2,6 bis(4-hydroxyl-phenyl)-pyridine: Add m-trifluoro 1050 parts of methyl benzaldehyde, 300 parts of p-hydroxyacetophenone, 1200 parts of ammonium acetate, 2400 ml of glacial acetic acid. The reaction mixture was refluxed for 4-6 hours under stirring to obtain an orange-red homogeneous clear solution, which was poured into 6000ml of water to obtain a yellow-brown precipitate, which was collected by filtration and recrystallized from a tetrahydrofuran/n-hexane mixed solvent to obtain a light yellow Powdered 4-(m-trifluoromethylphenyl)-2,6-bis(4-hydroxy-phenyl)-pyridine.

4-(m-trifluoromethylphenyl)-2,6-bis(4-(4-nitro-2-trifluoromethyl-phenoxy)-phenyl)pyridine: 240 parts of 4-( m-trifluoromethylphenyl)-2,6 bis(4-hydroxy-phenyl)-pyridine and 60 parts of potassium hydroxide, 1000ml dimethyl sulfoxide, 600ml toluene were added equipped with mechanical stirring, thermometer, reflux condensation Pipe, water separator and three-necked flask with nitrogen inlet and outlet; add the reaction system to the reflux temperature, add 300 parts of 2-trifluoromethyl-4-nitrochlorobenzene after reflux for 14 hours, and continue the reaction at 110-120 ° C 16 hours. After the system was cooled to room temperature, the reaction mixture was poured into 2000ml of water, and a tan powdery solid precipitated out. The precipitate was collected by filtration and washed several times with water; then recrystallized with ethanol to obtain light gray solid powder 4-(m-trifluoromethylphenyl)-2,6-bis(4-(4-nitro-2-tri Fluoromethyl-phenoxy)-phenyl)pyridine.

4-(m-trifluoromethylphenyl)-2,6-bis(4-(4-amino-2-trifluoromethyl-phenoxy)-phenyl)pyridine: 110 parts of 4-(m -trifluoromethylphenyl)-2,6-bis(4-(4-nitro-2-trifluoromethyl-phenoxy)-phenyl)pyridine and 85 parts of reduced iron powder, 300ml 50% Add the ethanol aqueous solution into a three-necked flask equipped with mechanical stirring, reflux condenser, constant pressure dropping funnel and nitrogen inlet and outlet. Mix 8ml of concentrated hydrochloric acid with 41ml of 50% ethanol aqueous solution and add them into the dropping funnel. Start stirring and heat the reaction system to the reflux temperature, slowly add hydrochloric acid solution dropwise at the reflux temperature, and maintain the reflux temperature to continue the reaction for 3 hours after the dropwise addition is completed. Add 20ml of ammonia water and 25ml of ethanol to the reaction system, continue to reflux for 0.5 hours, filter while hot, and collect the filtrate. The filtrate was concentrated under reduced pressure and poured into water, and the precipitate was collected by filtration to obtain a crude product. The crude product was recrystallized from ethanol to give pink 4-(m-trifluoromethylphenyl)-2,6-bis(4-(4-amino-2-trifluoromethyl-phenoxy)-phenyl) pyridine.

Example 6

Add 61 parts of 4-phenyl-2,6-bis(4-(4-amino-2-trifluoromethyl-phenoxy)-phenyl)pyridine to 800 parts of N-methylpyrrolidone under stirring; After all the solids have dissolved, add 2 parts of bis-(γ-aminopropyl)tetraphenylsiloxane. Add 31 parts of 3,3',4,4'-diphenylmethyl ether tetra-acid dianhydride in batches at 0-4°C. The reaction was carried out at 20-25°C for 20 hours, resulting in a homogeneous viscous liquid. Add 50 parts of p-hydroxyphenylacetic acid into the above solution, raise the temperature to 140-160° C. under stirring, and react for 2-3 hours. After cooling to room temperature, the solution was dispersed into 3000 parts of ethanol, and the precipitated solid was collected, washed with methanol three times, and dried under vacuum at 40-60°C. Weigh 100 parts of dried solid resin and add 900 parts of N, N'-dimethylacetamide. After all the solids are dissolved, filter to obtain a polyimide solution. Coat the polyimide solution on the surface of a glass plate and heat it through the following procedure: heat at 80°C for 1 hour, keep at 120°C for 1 hour, keep at 200°C for 1 hour, and keep at 250°C for 0.5 hour; after the heat treatment is completed, The glass plate was immersed in water, and the polyimide film was obtained by peeling off.

Example 7

Add 100 parts of 4-phenyl-2,6-bis(4-(4-amino-2-trifluoromethyl-phenoxy)-phenyl)pyridine to 1500 parts of N-methylpyrrolidone under stirring; Add 49 parts of 3,3',4,4'-benzophenone tetraacid dianhydride in batches at 0-4°C. The reaction was carried out at 20-25° C. for 24 hours to obtain a homogeneous polyamic acid solution. Coat the polyamic acid solution on the glass surface, heat it at 100°C for 1 hour, keep it at 200°C for 1 hour, keep it at 250°C for 1 hour, and keep it at 275-300°C for 1 hour; immerse the glass plate in water and peel it off to get the polyamic acid solution. imide film.

Example 8

Add 66 parts of 4-phenyl-2,6-bis(4-(4-amino-2-trifluoromethyl-phenoxy)-phenyl)pyridine into 800 parts of N-methylpyrrolidone under stirring; Add 20 parts of 3,3',4,4'-biphenyltetraacid dianhydride in batches at 0-4°C. The reaction was carried out at 20-25°C for 24 hours to obtain a homogeneous viscous liquid. Add 53 parts of m-hydroxybenzoic acid into the above solution, raise the temperature to 140-160°C under stirring, and react for 2-3 hours. After cooling to room temperature, the solution was dispersed into 3000 parts of ethanol, and the precipitated solid was collected, washed three times with methanol, and dried under vacuum at 40-60°C. Weigh 5 parts of the dried solid resin, and add 95 parts of N-methylpyrrolidone. After all the solids are dissolved, filter to obtain a polyimide resin solution. Coat the polyimide solution on the surface of the glass plate and heat it through the following procedure: heat at 80°C for 1 hour, keep at 120°C for 1 hour, keep at 200°C for 1 hour, and keep at 250°C for 1 hour; after the heat treatment is completed, The glass plate was immersed in water, and the polyimide film was obtained by peeling off.

Example 9

100 parts of 4-phenyl-2,6-bis(4-(4-amino-2-trifluoromethyl-phenoxy)-phenyl)pyridine were added to 1500 parts of N-methylpyrrolidone under stirring. Add 33 parts of 3,3',4,4'-pyromellitic dianhydride in batches at 0-4°C. The reaction was carried out at 20-25° C. for 24 hours to obtain a homogeneous polyamic acid solution. Coat the polymer solution on a glass plate, then heat at 80°C for 1 hour, 100°C for 1 hour, 150°C for 1 hour, 200°C for 1 hour, 250°C for 1 hour, and 300°C for 0.5 hour; After cooling to room temperature, the polymer was peeled off from the glass plate to obtain a uniform and transparent polyimide film.

Example 10

Add 130 parts of 4-phenyl-2,6-bis(4-(4-amino-2-trifluoromethyl-phenoxy)-phenyl)pyridine to 1700 parts of N,N'-dimethyl in acetamide. After all the solids had dissolved, 4 parts of bis-(γ-aminopropyl)tetramethylsiloxane were added. Add 88 parts of 4,4'-(hexafluoroisopropyl)diphthalic dianhydride in batches at 0-4°C. The reaction was carried out at 20-25°C for 24 hours to give a homogeneous viscous liquid. Add 90 parts of acetic anhydride/pyridine (1:1) mixture into the above solution under stirring, raise the temperature to 40-60°C, and react for 3-4 hours. After cooling to room temperature, the solution was dispersed into 5000 parts of ethanol, and the precipitated solid was collected, washed three times with methanol, and dried under vacuum at 40-60°C. Weigh 120 parts of dried solid resin and add 900 parts of N, N'-dimethylacetamide. After all the solids are dissolved, filter to obtain a polyimide resin solution. Apply the polymer solution on the surface of the semiconductor chip, heat it at 100°C for 1 hour, keep it at 200°C for 1 hour, and keep it at 250°C for 0.5 hour. stress etc.

Example 11

Add 64 parts of 4-(4-fluorophenyl)-2,6-bis(4-(4-amino-2-trifluoromethyl-phenoxy)-phenyl)pyridine to 800 parts of N-methyl In the base pyrrolidone; after the solid is completely dissolved, add 2 parts of bis-(γ-aminopropyl)tetraphenylsiloxane. Add 31 parts of 3,3',4,4'-diphenylmethyl ether tetra-acid dianhydride in batches at 0-4°C. The reaction was carried out at 20-25°C for 20 hours, resulting in a homogeneous viscous liquid. Add 50 parts of p-hydroxyphenylacetic acid into the above solution, raise the temperature to 140-160° C. under stirring, and react for 2-3 hours. After cooling to room temperature, the solution was dispersed into 3000 parts of ethanol, and the precipitated solid was collected, washed with methanol three times, and dried under vacuum at 40-60°C. Weigh 100 parts of dried solid resin and add 900 parts of N, N'-dimethylacetamide. After all the solids are dissolved, filter to obtain a polyimide solution. Coat the polyimide solution on the surface of the glass plate and heat it through the following procedure: heat at 80°C for 1 hour, keep at 120°C for 1 hour, keep at 200°C for 1 hour, and keep at 250°C for 1 hour; after the heat treatment is completed, The glass plate was immersed in water, and the polyimide film was obtained by peeling off.

Example 12

Add 110 parts of 4-(4-trifluoromethylphenyl)-2,6-bis(4-(4-amino-2-trifluoromethyl-phenoxy)-phenyl)pyridine under stirring at 1400 Parts of N-methylpyrrolidone; 49 parts of 3,3',4,4'-benzophenone tetraacid dianhydride were added in batches at 0-4°C. The reaction was carried out at 20-25° C. for 24 hours to obtain a homogeneous polyacid solution. Coat the polyamic acid solution on the surface of the glass, and process it by temperature programming: heat at 100°C for 1 hour, keep at 200°C for 1 hour, keep at 250°C for 1 hour, and keep at 275-300°C for 1 hour; then immerse the glass plate in water , peeled off to obtain a polyimide film.

Example 13

Add 98 parts of 4-(m-trifluoromethylphenyl)-2,6-bis(4-(4-amino-2-trifluoromethyl-phenoxy)-phenyl)pyridine under stirring at 1400 Parts of N-methylpyrrolidone; After all the solids are dissolved, add 2 parts of bis-(γ-aminopropyl)tetraphenylsiloxane. Add 46 parts of 3,3',4,4'-biphenyltetraacid dianhydride in batches at 0-4°C. The reaction was carried out at 20-25°C for 20 hours, resulting in a homogeneous viscous liquid. Add 50 parts of p-hydroxyphenylacetic acid into the above solution, raise the temperature to 140-160° C. under stirring, and react for 2-3 hours. After cooling to room temperature, the solution was dispersed into 3000 parts of ethanol, and the precipitated solid was collected, washed with methanol three times, and dried under vacuum at 40-60°C. Weigh 100 parts of dried solid resin and add 900 parts of N, N'-dimethylacetamide. After all the solids are dissolved, filter to obtain a polyimide solution. Coat the polyimide solution on the surface of the glass plate and heat it through the following procedure: heat at 80°C for 1 hour, keep at 120°C for 1 hour, keep at 200°C for 1 hour, and keep at 250°C for 1 hour; after the heat treatment is completed, The glass plate was immersed in water, and the polyimide film was obtained by peeling off.

Example 14

157 parts of 4-(3,5'-ditrifluoromethylphenyl)-2,6-bis(4-(4-amino-2-trifluoromethyl-phenoxy)-phenyl)pyridine in Add 2100 parts of N,N'-dimethylacetamide under stirring. After all the solids had dissolved, 4 parts of bis-(γ-aminopropyl)tetramethylsiloxane were added. Add 88 parts of 4,4'-(hexafluoroisopropyl)diphthalic dianhydride in batches at 0-4°C. The reaction was carried out at 20-25°C for 24 hours to give a homogeneous viscous liquid. Add 80 parts of p-hydroxyphenylacetic acid into the above solution under stirring, raise the temperature to 140-160°C, and react for 3-4 hours. After cooling to room temperature, the solution was dispersed into 6000 parts of ethanol, and the precipitated solid was collected, washed three times with methanol, and dried under vacuum at 40-60°C. Weigh 120 parts of dried solid resin and add 800 parts of N, N'-dimethylacetamide. After all the solids are dissolved, filter to obtain a polyimide resin solution. Apply the polymer solution on the surface of the semiconductor chip, heat it at 100°C for 1 hour, keep it at 200°C for 1 hour, and keep it at 250°C for 0.5 hour. stress etc.

Claims (7)

1. A polyimide material prepared from fluorine-containing aromatic organic diamine and its derivatives, its chemical structure is as follows:

R＝- O CO C(CF ₃ ) ₂ C(CF ₃ )(C ₆ H ₅ ) 2. A method for preparing the material according to claim 1, which is prepared as follows: a) Condensing 270-300 parts of p-hydroxyacetophenone and 100-360 parts of substituted benzaldehyde at 60-150°C to generate pyridinediol and its derivatives; b) Etherifying 100 parts of the obtained pyridinediol and its derivatives with 440-500 parts of 3-nitro-o-chlorobenzotrifluoride at a temperature of 80-150° C. to obtain a dinitro compound; c) Reducing 220 parts of the obtained dinitro compound with 180-250 parts of iron powder/HCl ethanol aqueous solution at 60-120° C. to obtain a trifluoromethyl-containing aromatic diamine monomer; The structures of the above-mentioned fluorine-containing aromatic organic diamines and derivatives thereof are shown in the following formula: Its preparation route is:

d) Under the protection of nitrogen, dissolve 8-12 parts of the fluorine-containing aromatic organic diamine and its derivatives prepared in step c in an organic solvent under stirring, and after all the solids are dissolved, add 2-10 parts to adjust the molecular weight agent and adhesion promoter; under ice bath cooling, add 8-12 parts of aromatic tetra-acid dianhydride in batches, remove the ice-water bath, stir and react at room temperature under nitrogen protection for 10-36 hours to obtain a polyamic acid solution; e) Coat the polyamic acid solution obtained in step d on the surface of the glass or silicon wafer, and gradually heat to 250-350° C. to convert the polyamic acid into a polyimide material. 3. The preparation method according to claim 2, characterized in that the organic aromatic tetra-acid dianhydride is 3,3',4,4'-diphenylmethyl ether tetra-acid dianhydride, 3,3', 4,4'-benzophenone tetra-acid dianhydride, 3,3',4,4'-biphenyl tetra-acid dianhydride, 3,3',4,4'-triphenylene ether tetra-acid dianhydride, One of 4,4'-(hexafluoroisopropyl)diphthalic dianhydride and 3,3',4,4'-pyromellitic dianhydride or a mixture of two or more in any proportion. 4. The preparation method according to claim 2, wherein the organic solvent is N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, γ-butyl One of lactone and dimethyl sulfoxide or a mixed solvent of two or more in any proportion. 5. The preparation method according to claim 2, characterized in that the molecular weight regulator and auxiliary agent are organic compounds or organosilicon compounds that regulate the molecular chain length of the polyimide polymer and increase its adhesion and coating performance Mixtures, specifically: γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, bis-(γ-aminopropyl)tetramethylsiloxane, bis-(γ-aminobutyric base) tetramethylpolysiloxane, bis-(γ-aminopropyl) tetramethylpolysiloxane, bis-(γ-aminopropyl) tetramethylpolysiloxane, bis-(γ-aminopropyl) base) tetraphenylsiloxane, bis-(γ-aminopropyl)tetraphenylpolysiloxane, bis-(γ-aminobutyl)tetraphenylsiloxane and bis-(γ-aminobutyl ) one or a mixture of two or more of tetraphenylpolysiloxanes in any proportion. 6. The preparation method according to claim 2, characterized in that, the step of converting polyamic acid into polyimide material is: Add 40-100 parts of the imidization accelerator solution into the polyamic acid solution obtained in step d under stirring, raise the temperature to 100-160°C for 3-8 hours, cool to room temperature, and precipitate the obtained liquid into the organic in an alcohol solvent; collect the precipitate and wash it with an organic alcohol solvent, and then dry it at 40-60 ° C to obtain a polyimide solid resin; mix the polyimide solid resin with an organic solvent, and filter it after it is completely dissolved to obtain a polyimide solid resin. Imide coating glue solution; Then apply the obtained polyimide coating glue solution on the surface of glass or silicon wafer, and heat up to 200-250°C to obtain polyimide coating or film; 7. According to the polyimide material described in any one of the above claims, the surface chip passivation layer, the stress buffer inner coating, the contact protection film, and the interlayer dielectric insulation of the multilayer interconnection circuit in the preparation of the microelectronic package Application of layer film, solder ball array package, chip scale package, liquid crystal molecular alignment film and adhesive in liquid crystal display technology.