CN110669218B - Modified polyimide, adhesive composition, and preparation method and application thereof - Google Patents
Modified polyimide, adhesive composition, and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
- C09J171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C09J171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C09J171/12—Polyphenylene oxides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The embodiment of the invention provides modified polyimide, an adhesive composition, a preparation method and an application thereof, wherein the modified polyimide can provide good film forming property, adhesion and toughness for the adhesive composition, the adhesive composition is suitable for manufacturing a high-frequency covering film and a high-frequency copper-clad foil, and the high-frequency covering film and the copper-clad foil manufactured by using the adhesive composition have the dielectric constant (DK) of 2.8-3.1, the dissipation factor (Df) of 0.003-0.005, the peel strength of 1.0-1.5 kgf/cm and the soldering tin heat resistance of 300 ℃ for 10 s/3 times.
Description
Technical Field
The invention belongs to the technical field of flexible circuit boards, and particularly relates to modified polyimide, an adhesive composition, and preparation methods and applications thereof.
Background
In recent years, with the development of wireless networks and civil high-frequency communication of satellites, a large amount of rapid wireless transmission signals are required. The 5G is used as an extension of the 4G communication technology, and the technical indexes such as transmission rate, user experience rate, flow density, end-to-end time delay, network energy efficiency and the like are greatly improved. Most of the materials required for the new generation of flexible printed circuit board products are high frequency covering films and high frequency copper-clad foils with low dielectric constants and low dielectric dissipation factors.
In order to achieve flexibility and adhesion properties of flexible printed circuit boards, modified epoxy adhesives are generally used in current adhesive compositions. In the prior art, polytetrafluoroethylene, polyphenyl ether, polyimide and the like are mainly added into an epoxy adhesive to reduce the dielectric property, however, the addition of the agents reduces the dielectric property, simultaneously reduces the low peel strength and the heat resistance, and simultaneously can not reduce the loss factor to be less than 0.005.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. To this end, the present invention proposes a modified polyimide that can provide film forming properties, adhesion properties, and toughness to an adhesive composition.
The invention also provides a preparation method of the modified polyimide.
The invention also provides an adhesive composition.
The invention also provides a preparation method of the adhesive composition.
The invention also provides the application of the adhesive composition.
The modified polyimide according to the embodiment of the first aspect of the invention comprises the following preparation raw materials in parts by weight:
4, 4' -biphenyl ether dianhydride: 5 to 15 parts of (A) a water-soluble polymer,
hexafluoro dianhydride: 25 to 30 parts of a water-soluble polymer,
2, 2-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl ] propane: 25 to 35 parts by weight of a surfactant,
4, 4' -diaminodiphenyl ether: 5 to 10 parts by weight of a surfactant,
dimethyl acetamide: 5 to 10 parts by weight of a surfactant,
pyridine: 15-20 parts.
In the above raw material, the amount of hexafluorodianhydride is preferably in the range of 25 to 30 parts, because an excessively small amount results in an excessively high dissipation factor and an excessively large amount results in a poor peel strength. The dimethyl acetamide serves as a solvent, and the modified polyimide prepared from the preparation raw materials according to the proportion has the solid content of 15-20%, the molecular weight of 120000-150000, the dielectric constant of 2.5-2.7 and the loss factor of 0.002-0.004.
The modified polyimide provided by the embodiment of the invention has at least the following technical effects:
the modified polyimide can provide good film forming property, adhesion and toughness for the adhesive composition. The modified polyimide is soluble low-dielectric polyimide.
According to a second aspect of the present invention, there is provided a method for producing a modified polyimide, comprising the steps of:
s1: weighing the 4, 4' -diphenyl ether dianhydride, the hexafluoro dianhydride, the 2, 2-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl ] propane, the 4, 4' -diaminodiphenyl ether and the pyridine according to the proportion, sequentially adding the 2, 2-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl ] propane, the 4, 4' -diaminodiphenyl ether and the dimethylacetamide into a container, introducing nitrogen at low temperature, and stirring until the nitrogen is dissolved;
s2: adding 4, 4' -diphenyl ether dianhydride and hexafluoro dianhydride in batches at intervals to the product of the step S1 for reaction;
s3: and (3) adding pyridine into the product obtained in the step S2 at the temperature of 5-8 ℃, preserving heat, and then heating for reaction to obtain the modified polyimide.
The preparation method of the modified polyimide provided by the embodiment of the invention has at least the following technical effects:
the preparation method has the advantages of short process flow, mild preparation conditions and easily obtained raw materials, and is suitable for industrial production.
According to some embodiments of the invention, the low temperature of the step S1 is in a range of 5-10 ℃.
In step S1, 2-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl ] propane, 4' -diaminodiphenyl ether and dimethylacetamide were added while stirring at a speed of 200rpm until the above substances were completely dissolved.
According to some embodiments of the invention, the interval of the step S2 is 0.5-1 h.
In the step S2, the 4, 4 '-diphenyl ether dianhydride and the hexafluoro dianhydride are added in batches at intervals, namely the 4, 4' -diphenyl ether dianhydride and the hexafluoro dianhydride are added into a container for 3-5 times, stirring is carried out at the speed of 200rpm while adding, and the time for carrying out reaction is 2-4 hours after adding.
According to some embodiments of the invention, the temperature of the temperature raising reaction in the step S3 is 80-100 ℃.
In step S3, the heat preservation time is 1h, and the temperature is increased to 80-100 ℃.
According to some embodiments of the invention, the temperature-raising reaction of the step S3 is performed for 3-5 hours.
The adhesive composition according to the embodiment of the third aspect of the present invention comprises the following raw materials in parts by weight:
the modified polyimide described above: 3 to 6 parts of (A) a water-soluble polymer,
polyphenylene ether: 5 to 25 parts of a solvent, and a solvent,
epoxy resin: 2-15 parts.
In the preparation raw materials, polyphenyl ether and epoxy resin are curing agents of modified polyimide, epoxy groups of the epoxy resin and carboxyl groups of the polyimide are subjected to cross-linking reaction to form a three-dimensional grid structure, good heat resistance and adhesion are provided, the epoxy resin is dicyclopentadiene epoxy resin with low water absorption, the water absorption can be reduced by introducing the epoxy resin, the dielectric property is stable, the using amount of the epoxy resin is 3-8% of the mass of the modified polyimide, if the using amount is too low, the heat resistance is poor, the peel strength is low, and if the using amount is too high, the loss factor is large.
The polyphenyl ether is low molecular weight polyphenyl ether containing hydroxyl, the dielectric constant is 2.4-2.5, and the loss factor is 0.0004-0.0007. Can react with epoxy resin and modified polyimide to improve the crosslinking density of the adhesive. Reduce water absorption and dielectric property. The highest proportion of the usage amount is 15 percent of the mass of the modified polyimide, and if the usage amount is too high, the peel strength is lower. If necessary, components such as an inorganic filler, a silane coupling agent, and an antioxidant may be added to form the modified polyimide adhesive composition.
The adhesive composition according to the embodiment of the invention has at least the following technical effects:
the adhesive composition is suitable for manufacturing a high-frequency covering film and a high-frequency copper-clad foil, and the high-frequency covering film and the copper-clad foil manufactured by using the adhesive composition have a dielectric constant (DK) of 2.8-3.1, a dissipation factor (Df) of 0.003-0.005, a peel strength of 1.0-1.5 kgf/cm, and solder heat resistance of 300 ℃ for 10s 3 times.
According to some embodiments of the invention, the epoxy resin has a water absorption of less than 1.0%.
The epoxy resin is dicyclopentadiene epoxy resin with low water absorption, the introduction of the epoxy resin can reduce the water absorption, the dielectric property is stable, the use amount is 3-8% of the mass of the modified polyimide, the heat resistance is poor when the use amount is too low, the peel strength is low, and the loss factor is large when the use amount is too high.
A method of preparing an adhesive composition according to an embodiment of the fourth aspect of the invention, the method comprising: and weighing the modified polyimide, the polyphenyl ether and the epoxy resin according to the proportion, and uniformly mixing to obtain the bonding composition.
The adhesive composition is applied to a high-frequency covering film or a high-frequency copper-clad foil.
According to some embodiments of the present invention, when the adhesive composition is applied to a high-frequency coverlay film, the structure of the high-frequency coverlay film is a modified polyimide film layer, an adhesive composition layer, and a release paper layer in this order.
According to some embodiments of the present invention, when the adhesive composition is applied to a high frequency copper-clad foil, the high frequency copper-clad foil has a structure of a modified polyimide film layer, an adhesive composition layer, and a copper foil layer in this order.
Drawings
FIG. 1 is a schematic view of the structure of a high-frequency cover film using the adhesive composition of the present invention.
FIG. 2 is a schematic view of the structure of a high-frequency copper-clad foil using the adhesive composition of the present invention.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention will be further described with reference to the examples, but the present invention is not limited to the examples.
Example 1
The embodiment provides modified polyimide, which comprises the following preparation raw materials in parts by weight:
4, 4' -biphenyl ether dianhydride: 5 to 15 parts of (A) a water-soluble polymer,
hexafluoro dianhydride: 25 to 30 parts of a water-soluble polymer,
2, 2-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl ] propane: 25 to 35 parts by weight of a surfactant,
4, 4' -diaminodiphenyl ether: 5 to 10 parts by weight of a surfactant,
dimethyl acetamide: 5 to 10 parts by weight of a surfactant,
pyridine: 15-20 parts.
Example 2
The embodiment provides a preparation method of modified polyimide, which comprises the following steps:
s1: weighing the 4, 4' -diphenyl ether dianhydride, the hexafluoro dianhydride, the 2, 2-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl ] propane, the 4, 4' -diaminodiphenyl ether and the pyridine according to the proportion, sequentially adding the 2, 2-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl ] propane, the 4, 4' -diaminodiphenyl ether and the dimethylacetamide into a container, introducing nitrogen at low temperature, and stirring until the nitrogen is dissolved;
s2: adding 4, 4' -diphenyl ether dianhydride and hexafluoro dianhydride in batches at intervals to the product of the step S1 for reaction;
s3: and (3) adding pyridine into the product obtained in the step S2 at the temperature of 5-8 ℃, preserving heat, and then heating for reaction to obtain the modified polyimide.
The low temperature range of step S1 is 5-10 ℃. In step S1, 2-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl ] propane, 4' -diaminodiphenyl ether and dimethylacetamide were added while stirring at a speed of 200rpm until the above substances were completely dissolved.
The time interval in the step S2 is 0.5-1 h. In the step S2, the 4, 4 '-diphenyl ether dianhydride and the hexafluoro dianhydride are added in batches at intervals, namely the 4, 4' -diphenyl ether dianhydride and the hexafluoro dianhydride are added into a container for 3-5 times, stirring is carried out at the speed of 200rpm while adding, and the time for carrying out reaction is 2-4 hours after adding.
The temperature of the temperature rise reaction in the step S3 is 80-100 ℃. In step S3, the heat preservation time is 1h, and the temperature is increased to 80-100 ℃.
And the time of the temperature rise reaction in the step S3 is 3-5 h.
Example 3
The example provides an adhesive composition, which comprises the following preparation raw materials in parts by weight:
modified polyimide of example 1: 3 to 6 parts of (A) a water-soluble polymer,
polyphenylene ether: 5 to 25 parts of a solvent, and a solvent,
epoxy resin: 2-15 parts.
In the preparation raw materials, polyphenyl ether and epoxy resin are curing agents of modified polyimide, epoxy groups of the epoxy resin and carboxyl groups of the polyimide are subjected to cross-linking reaction to form a three-dimensional grid structure, good heat resistance and adhesion are provided, the epoxy resin is dicyclopentadiene epoxy resin with low water absorption, the water absorption can be reduced by introducing the epoxy resin, the dielectric property is stable, the using amount of the epoxy resin is 3-8% of the mass of the modified polyimide, if the using amount is too low, the heat resistance is poor, the peel strength is low, and if the using amount is too high, the loss factor is large.
The polyphenyl ether is low molecular weight polyphenyl ether containing hydroxyl, the dielectric constant is 2.4-2.5, and the loss factor is 0.0004-0.0007. Can react with epoxy resin and modified polyimide to improve the crosslinking density of the adhesive. Reduce water absorption and dielectric property. The highest proportion of the usage amount is 15 percent of the mass of the modified polyimide, and if the usage amount is too high, the peel strength is lower. If necessary, components such as an inorganic filler, a silane coupling agent, and an antioxidant may be added to form the modified polyimide adhesive composition.
The water absorption of the epoxy resin is less than 1.0%.
The epoxy resin is dicyclopentadiene epoxy resin with low water absorption, the introduction of the epoxy resin can reduce the water absorption, the dielectric property is stable, the use amount is 3-8% of the mass of the modified polyimide, the heat resistance is poor when the use amount is too low, the peel strength is low, and the loss factor is large when the use amount is too high.
Example 4
This example provides a method of preparing an adhesive composition comprising: and weighing the modified polyimide, the polyphenyl ether and the epoxy resin according to the proportion, and uniformly mixing to obtain the bonding composition.
Example 5
This example provides the application of the adhesive composition to a high-frequency coverlay, and when the adhesive composition is applied to a high-frequency coverlay, the structure of the high-frequency coverlay is, as shown in fig. 1, a modified polyimide film layer 1, an adhesive composition layer 2, and a release paper layer 3 in this order.
Example 6
This example provides the application of the adhesive composition to a high-frequency copper-clad foil, and when the adhesive composition is applied to a high-frequency copper-clad foil, the structure of the high-frequency copper-clad foil is, as shown in fig. 2, a modified polyimide film layer 1, an adhesive composition layer 2, and a copper foil layer 4 in this order.
Example of detection
Five adhesive composition samples a-E and five adhesive composition comparative samples a 'to E' were prepared according to the formulations of example 1 and example 3 using the methods of example 2 and example 4, as shown in table 1.
TABLE 1
The sample A-E and the comparative sample A '-E' are used for preparing a 25um modified polyimide film, and a high-frequency covering film with the glue thickness of 20um is used for detecting the characteristics of the film. The characteristics of the prepared 25um modified polyimide film, the adhesive thickness of 20um and the copper foil 12um high-frequency copper clad foil are tested, and the results are shown in table 2.
TABLE 2
Claims (10)
1. The modified polyimide is characterized by being prepared from the following raw materials in parts by weight:
4, 4' -biphenyl ether dianhydride: 5 to 15 parts of (A) a water-soluble polymer,
hexafluoro dianhydride: 25 to 30 parts of a water-soluble polymer,
2, 2-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl ] propane: 25 to 35 parts by weight of a surfactant,
4, 4' -diaminodiphenyl ether: 5 to 10 parts by weight of a surfactant,
dimethyl acetamide: 5 to 10 parts by weight of a surfactant,
pyridine: 15-20 parts.
2. The method for preparing a modified polyimide according to claim 1, comprising the steps of:
s1: weighing the 4, 4' -diphenyl ether dianhydride, the hexafluoro dianhydride, the 2, 2-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl ] propane, the 4, 4' -diaminodiphenyl ether and the pyridine according to the proportion, sequentially adding the 2, 2-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl ] propane, the 4, 4' -diaminodiphenyl ether and the dimethylacetamide into a container, introducing nitrogen at low temperature, and stirring until the nitrogen is dissolved;
s2: adding 4, 4' -diphenyl ether dianhydride and hexafluoro dianhydride in batches at intervals to the product of the step S1 for reaction;
s3: and (3) adding pyridine into the product obtained in the step S2 at the temperature of 5-8 ℃, preserving heat, and then heating for reaction to obtain the modified polyimide.
3. The method of claim 2, wherein the low temperature range of step S1 is 5-10 ℃.
4. The method of claim 2, wherein the time interval of step S2 is 0.5-1 h.
5. The method of claim 2, wherein the temperature of the temperature-raising reaction in step S3 is 80 to 100 ℃.
6. The method of claim 2, wherein the temperature-raising reaction time in step S3 is 3 to 5 hours.
7. The adhesive composition is characterized by comprising the following preparation raw materials in parts by weight:
the modified polyimide according to claim 1: 3 to 6 parts of (A) a water-soluble polymer,
polyphenylene ether: 5 to 25 parts of a solvent, and a solvent,
epoxy resin: 2-15 parts.
8. The adhesive composition of claim 7 wherein the epoxy resin has a water absorption of less than 1.0%.
9. The method for preparing an adhesive composition according to claim 7, wherein the method comprises: and weighing the modified polyimide, the polyphenyl ether and the epoxy resin according to the proportion, and uniformly mixing to obtain the bonding composition.
10. Use of the adhesive composition according to claim 7 in a high-frequency coverlay film or a high-frequency copper-clad foil.
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