CN108641665B - Polyimide adhesive and preparation method thereof - Google Patents
Polyimide adhesive and preparation method thereof Download PDFInfo
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- CN108641665B CN108641665B CN201810457995.2A CN201810457995A CN108641665B CN 108641665 B CN108641665 B CN 108641665B CN 201810457995 A CN201810457995 A CN 201810457995A CN 108641665 B CN108641665 B CN 108641665B
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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
- 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
- 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
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
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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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
Abstract
The invention relates to a polyimide adhesive and a preparation method thereof, belongs to the technical field of adhesives, and solves the problems that the polyimide adhesive is unstable in heat resistance and reduced in adhesive property when the temperature is higher than 350 ℃ in the prior art. A polyimide adhesive is obtained by curing a polyimide adhesive prepolymer, wherein the polyimide adhesive prepolymer is prepared from aromatic diamine containing a biphenyl structure, aromatic diamine containing a siloxane structure, aromatic dianhydride and a capping agent. Dissolving a polyimide adhesive prepolymer in an organic solvent to obtain a homogeneous solution; and coating the homogeneous solution on the surface of the bonded object, removing the organic solvent, and curing to obtain the polyimide adhesive to finish bonding of the bonded object. The polyimide adhesive disclosed by the invention can be applied to the bonding of high-temperature-resistant parts in the fields of aviation, aerospace, precision machinery, petrochemical industry and the like.
Description
Technical Field
The invention relates to the technical field of adhesives, and particularly relates to a polyimide adhesive and a preparation method thereof.
Background
With the rapid development of aerospace technology, organic high-temperature-resistant adhesives are widely applied to the manufacturing of various aircrafts.
Polyimide adhesives are increasingly favored by people due to excellent heat resistance and high-temperature adhesive property. Generally, the polyimide adhesive is divided according to a processing and synthesis method and comprises the following steps: condensation, thermoplastic and addition. Aiming at the condensed polyimide adhesive, the curing process of the condensed polyimide adhesive, namely the dehydration and cyclization process of polyamic acid, has water in the middle to generate pores, is easy to form and is not suitable for large-area bonding. Aiming at thermoplastic polyimide adhesive, although pores can be avoided by directly hot-melting materials for bonding, the adhesive has insufficient heat resistance and glass transitionTemperature (T)g) Generally not exceeding 250 ℃. The addition type polyimide adhesive is usually used in a prepolymer form with a reactive end-capping agent, and a resin prepolymer is firstly melted and infiltrated into a bonding material in the heating forming process and then is cured to form a three-dimensional network structure, so that the polyimide adhesive has higher heat resistance and bonding performance than the former two types. The addition type polyimide adhesive terminated by phenylethynyl has a rigid main chain structure, strong molecular chain interaction and high crosslinking density, has outstanding heat resistance and is most widely applied. However, the interaction between the rigid main chain structure and the strong molecular chain increases the melt viscosity of the polyimide adhesive prepolymer, and cannot better infiltrate the surface of the bonded material, thereby reducing the bonding performance. Meanwhile, the high crosslinking density in the structure can bring obvious curing shrinkage stress, thereby affecting the bonding performance. In order to obtain the phenylethynyl terminated addition type polyimide adhesive with heat resistance stability and bonding performance, a series of research works are carried out by scientific research workers. PETI-5 was an addition type polyimide adhesive developed earlier and was a polyimide adhesive prepolymer prepared by polymerizing 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride (s-BPDA) with 15% 1, 3-bis (3-aminophenoxy) benzene (1,3,3-APB) and 85% 3,4 '-diaminodiphenyl ether (3, 4' -ODA) and end-capped with 4-phenylethynylphthalic anhydride (PEPA) and designed to have a molecular weight of 5000 g/mol. The glass transition temperature of a condensate is 270 ℃, the titanium alloy after adhesive film bonding treatment is prepared by taking E-112 fiber glass cloth as a carrier, the shear strength at room temperature is 49.0MPa, the shear strength at 177 ℃ is 29.7MPa, but the melt viscosity of the adhesive is higher, and the lowest melt viscosity is 10000 Pa.s. Researchers further increase the branching degree of the PETI-5 structure by introducing triamine monomers, and the minimum melt viscosity of the modified PETI-5 is 60 pas. The shear strength of the titanium alloy bonded by the titanium alloy is 41MPa and 36MPa respectively at normal temperature and 177 ℃. Domestic researchers have also conducted a great deal of research on the high-temperature adhesive property of polyimide adhesives, for example, the glass transition temperature of PEPA-terminated thermosetting polyimide adhesives developed by the chemical institute of Chinese academy of sciences exceeds 310 ℃, the shear strength for adhering stainless steel sheets is 13MPa at room temperature and 10MPa at 316 ℃, but the shear strength is more than 10MPaIs still a melt of relatively high viscosity (>300Pa · s), a problem of a bonding defect is likely to occur.
By combining the existing research results, the polyimide adhesive still has the problems of unstable heat resistance and reduced adhesive property when used at high temperature, and cannot meet the use requirement of the aerospace field for higher temperature-resistant adhesives.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide a polyimide adhesive and a preparation method thereof, so as to solve the problems of unstable heat resistance and reduced adhesive property of the polyimide adhesive at a temperature higher than 350 ℃.
The purpose of the invention is mainly realized by the following technical scheme:
the invention provides a polyimide adhesive which is obtained by curing a polyimide adhesive prepolymer, wherein the polyimide adhesive prepolymer is prepared from aromatic diamine containing a biphenyl structure, aromatic diamine containing a siloxane structure, aromatic dianhydride and a capping agent.
The polyimide adhesive disclosed by the invention has the following beneficial effects:
on one hand, the aromatic diamine with a siloxane structure is selected as a preparation raw material of the polyimide adhesive prepolymer, and the siloxane structure with flexibility is introduced into the rigid main chain structure of the polyimide, so that the melt viscosity of the prepolymer is greatly reduced, the surface of a bonded material can be better infiltrated, and the bonding performance is improved; on the other hand, the polyimide adhesive prepolymer is cured to form a three-dimensional network structure, so that the glass transition temperature of the cured adhesive is increased, and the adhesive has excellent bonding performance and heat resistance under the conditions of room temperature and high temperature.
On the basis of the scheme, the invention is further improved as follows:
further, the polyimide adhesive prepolymer has a structure of formula I:
wherein Ar is selected from any one of the following aromatic structures:
R1is a biphenyl structure, R2Is a siloxane structure, the ratio of x to y is (9:1) - (7:3), and n is 1-3.
Considering that the interaction between the rigid main chain structure and the strong molecular chain increases the melt viscosity of the polyimide adhesive prepolymer, and cannot better infiltrate the surface of the bonded material, thereby reducing the bonding performance. The polyimide adhesive prepolymer with the structure shown in the general formula I is selected, and the flexible siloxane structure is introduced into the rigid main chain structure, so that the melt viscosity of the prepolymer is greatly reduced, the surface of a material to be bonded can be better infiltrated, and the bonding performance is improved.
The number average molecular weight (M) of the polyimide adhesive prepolymer when the ratio of x to y is (9:1) - (7:3) and n is 1-3n) Between 1100 and 2900 g/mol. The proper molecular weight of the polyimide adhesive prepolymer is beneficial to the compatibility of the adhesive property and the heat resistance. The above prepolymer molecular weights ensure good melt viscosity and suitable crosslink density.
Further, the aromatic diamine having a siloxane structure is bis (4-aminophenoxy) tetramethyldisiloxane and/or bis (4- (4-aminophenoxy) benzene) tetramethyldisiloxane.
The long-chain-segment disiloxane and the aromatic structure in the structure of the two aromatic diamines containing siloxane structures endow the polyimide adhesive with excellent melt flowability and heat resistance, so the two aromatic diamines containing siloxane structures are preferably used as the raw materials for preparing the polyimide adhesive prepolymer.
R2Any one selected from the following structures:
further, the aromatic diamine of biphenyl structure is 4,4 '-diamino-2, 2' -dimethylbiphenyl and/or 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl.
In consideration of the fact that the methyl substitution and the trifluoromethyl substitution in the biphenyl structure can effectively reduce the stacking among molecular chains, so that the wettability of the adhesive and a bonded material is improved, and the bonding performance and the heat resistance are improved, the aromatic diamine with the two biphenyl structures is preferably used as a raw material for preparing the polyimide adhesive prepolymer.
R1Any one selected from the following structures:
further, the aromatic dianhydride is one or more of pyromellitic dianhydride, 3 ', 4, 4' -biphenyl tetracarboxylic dianhydride or 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride; the end-capping reagent is 4-phenylethynyl phthalic anhydride.
In experiments, dianhydride with a rigid symmetric structure can endow the polyimide adhesive with outstanding heat resistance, and pyromellitic dianhydride, 3 ', 4, 4' -biphenyl tetracarboxylic dianhydride and 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride have rigid symmetric structures, so that the aromatic dianhydride is preferably used as a raw material for preparing the adhesive prepolymer, and the prepared polyimide adhesive has good heat resistance stability and excellent adhesive property when used at the temperature of more than 350 ℃.
Notably, the phenylethynyl end-capping agent can endow the polyimide adhesive with a wider molding temperature window, and no small-molecule volatile is generated in the curing and molding process. Therefore, 4-phenylethynyl phthalic anhydride is preferred as the end-capping agent in the present invention.
The invention also provides a preparation method of the polyimide adhesive, which comprises the following steps:
step 1: dissolving a polyimide adhesive prepolymer in an organic solvent to obtain a homogeneous solution;
step 2: and coating the homogeneous solution on the surface of the bonded object, removing the organic solvent, and curing to obtain the polyimide adhesive to finish bonding of the bonded object.
In the preparation method of the polyimide adhesive, the step heating removal is used for removing the organic solvent, and the specific process is as follows: 60-80 ℃ for 1-4 hours; 120 ℃ and 150 ℃ for 0.5 to 4 hours; 180 ℃ and 200 ℃ for 0.5 to 4 hours.
The organic solvent used in the preparation method of the polyimide adhesive is one or more of N-methylpyrrolidone (NMP), N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and cyclopentanone.
The preparation method of the polyimide adhesive has the following beneficial effects:
on one hand, as a flexible siloxane structure is introduced into a polyimide rigid main chain structure, the melt viscosity of the prepolymer is greatly reduced, so that the prepolymer can better infiltrate the surface of a bonded material to improve the bonding performance; on the other hand, as siloxane has the organic-inorganic conversion characteristic of oxidative crosslinking at high temperature, the polyimide adhesive generates a silica-like inorganic structure in the curing process, so that the heat resistance of the polyimide adhesive is further improved. The polyimide adhesive prepared by the method still has excellent heat-resistant stability and outstanding adhesive property at the high temperature of more than 350 ℃. The preparation method has simple process and easy operation.
Further, the solid content of the homogeneous solution in the above preparation method is 40 wt.% to 65 wt.%.
In experiments, the solid content of the homogeneous solution in the preparation method is too low, so that the solvent is easy to remain, and the bonding performance of the homogeneous solution is influenced; the solid content is too high to be stored easily, so the solid content of the homogeneous solution is controlled to be 40-65 wt% in the preparation process of the polyimide adhesive.
Further, the curing in step 2 of the preparation method is temperature-rise curing, and the temperature-rise curing process is as follows: the temperature is raised to 350-400 ℃ at the temperature raising rate of 2-6 ℃/min, and the curing reaction time is 1-6 hours.
The heating rate of 2-6 ℃/min is favorable for better removing the solvent, and the influence of solvent residue on the bonding performance of the adhesive is avoided.
The temperature range of 350-400 ℃ is the reaction temperature of the phenylethynyl group in the end-capping reagent for thermosetting, incomplete curing can be caused if the temperature is too low, and decomposition can be caused if the temperature is too high, which is not beneficial to the adhesive property of the adhesive. Therefore, the curing temperature is preferably 350-400 ℃ in the invention.
In the experiment, the reaction time is less than 1 hour, and the curing reaction is not completely carried out; the curing reaction is completed when the reaction time is 6 hours, so that the curing reaction time is controlled to be 1 to 6 hours in the above preparation method.
Further, the polyimide adhesive prepolymer is prepared by the following method:
dissolving aromatic diamine containing a biphenyl structure and aromatic diamine containing a siloxane structure in an organic solvent, and completely dissolving under the protection of inert gas to obtain a mixed solution; sequentially adding aromatic dianhydride and a capping agent into the mixed solution, completely dissolving under the protection of inert gas, and stirring for reaction to obtain a homogeneous solution of a prepolymer raw material; and adding a dehydrating agent into the homogeneous phase solution of the prepolymer raw material to perform azeotropic reaction, removing the dehydrating agent, cooling, and performing precipitation separation to obtain the polyimide adhesive prepolymer.
In the preparation method of the polyimide adhesive prepolymer, the used organic solvent is the same as the organic solvent used in the preparation method of the polyimide adhesive.
In the preparation method of the polyimide adhesive prepolymer, stirring reaction is carried out at room temperature, the stirring reaction time is 6-24 hours, and the solid content of the obtained prepolymer raw material homogeneous solution is 25-40 wt.%.
In consideration of the solid content range, the preparation method is favorable for obtaining the polyimide adhesive prepolymer with the expected structure and designed molecular weight, and the proper molecular weight of the polyimide adhesive prepolymer is favorable for the compatibility of the adhesive property and the heat resistance. Therefore, in the preparation method of the polyimide adhesive prepolymer, the solid content of the homogeneous solution of the prepolymer raw material is controlled to be 25-40 wt.%.
In the preparation method of the polyimide adhesive prepolymer, in order to realize complete dehydration and cyclization of the polyamic acid, the used dehydrating agent is toluene or xylene, and the mass ratio of the dehydrating agent to the organic solvent is (0.5-1.5): 10. the azeotropic reaction is carried out at the temperature of 120-190 ℃ under the protection of nitrogen, and the azeotropic reaction time is 6-18 hours. After the dehydrating agent was removed, the reaction solution was cooled to 80-120 ℃.
In the preparation method of the polyimide adhesive prepolymer, the precipitant used for precipitation separation is any one or a mixture of several of water, methanol, ethanol, propanol, isopropanol or butanol in any proportion. And (3) obtaining resin precipitate after precipitation separation, repeatedly washing, filtering and drying to obtain the polyimide adhesive prepolymer. The resin precipitate can be washed by one or more of hot water, methanol, ethanol or other low boiling point alcohol solvents.
When the polyimide adhesive is used for bonding objects, a polyimide resin prepolymer is dissolved in an organic solvent to prepare a homogeneous solution with a certain solid content; the homogeneous solution is uniformly coated on the surface of an object to be bonded, the solvent is removed through step heating, and then a firm bonding body is obtained through the heating and curing process.
The bonded material in the invention can be common metals such as stainless steel, aluminum alloy, titanium alloy and the like, and high temperature resistant resin matrix composite materials and the like.
In the invention, the technical schemes can be combined with each other to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention.
Fig. 1 is a rheological curve of the polyimide adhesive prepolymer prepared in example 1.
FIG. 2 is a DMA curve for the polyimide adhesive prepared in example 1.
FIG. 3 is a TEM image of the polyimide adhesive prepared in example 1 after a single lap shear test at a high temperature of 380 ℃.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. In the following examples, typical diamine, dianhydride, end capping agent and other monomer raw materials are selected to prepare addition type polyimide adhesives with different structures, typical stainless steel is selected as an adherend to be subjected to an adhesion performance test, the raw material monomers or the adherend in the examples are replaced by other raw material monomers or other types of adherends, and the prepared polyimide adhesives have the same effect as the polyimide adhesives prepared by the preparation method and conditions described in the disclosure of the invention.
In the present invention, the percentage content and the percentage concentration are both the mass percentage content and the mass percentage concentration unless otherwise specified. The starting materials are commercially available from published sources unless otherwise specified.
Example 1
(1) In a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen inlet/outlet, and a thermometer, 28.82 g (0.09 mol) of 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl, 3.49 g (0.01 mol) of bis (4-aminophenoxy) tetramethyldisiloxane, and 110 g of N-methylpyrrolidone were charged, and stirred under nitrogen atmosphere until they were completely dissolved. Then, 16.11 g (0.05 mol) of 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride and 24.82 g (0.10 mol) of 4-phenylethynylphthalic anhydride were added and stirred under nitrogen atmosphere until completely dissolved. Stirring at room temperature for 12 hours gave a homogeneous solution with a solids content of 40 wt.%.
(2) Adding 16 g of toluene into the homogeneous solution, heating the reaction system to 175 ℃, reacting for 12 hours under the protection of nitrogen, then heating to 200 ℃, evaporating toluene, and stopping heating.
(3) Cooling the reaction solution to 100 ℃, pouring the reaction solution into ethanol to obtain resin precipitate, repeatedly washing the resin precipitate with ethanol and hot water, filtering, crushing and drying in an oven to obtain the polyimide adhesiveAdhesive prepolymer solid powder, yield 97% (prepolymer structure x: y ═ 9:1, n ═ 1.0, Mn＝1410g/mol)。
Adhesion experiment of polyimide adhesive and stainless steel sheet:
dissolving the polyimide adhesive solid powder in N-methyl pyrrolidone to obtain a resin solution with the solid content of 65 wt.%, uniformly coating the homogeneous solution on the surface of a stainless steel sheet, removing the solvent through a step heating process of 80 ℃/2 hours, 120 ℃/1 hour and 200 ℃/1.5 hours, then heating to 370 ℃ at the heating rate of 2 ℃/min, and curing for 2 hours to obtain the firm bonding body.
The main properties of the polyimide adhesive prepared in this example are shown in table 1.
Example 2
(1) 25.62 g (0.08 mol) of 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl, 6.97 g (0.02 mol) of bis (4-aminophenoxy) tetramethyldisiloxane and 215 g of N, N-dimethylacetamide were placed in a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen inlet/outlet and a thermometer, and stirred under nitrogen atmosphere until completely dissolved. Then, 19.33 g (0.06 mol) of 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride and 19.86 g (0.08 mol) of 4-phenylethynylphthalic anhydride were added and stirred under nitrogen atmosphere until completely dissolved. Stirring at room temperature for 12 hours gave a homogeneous solution with a solids content of 25 wt.%.
(2) Adding 11 g of dimethylbenzene into the homogeneous solution, heating the reaction system to 150 ℃, reacting for 12 hours under the protection of nitrogen, then heating to 166 ℃, distilling out dimethylbenzene, and stopping heating.
(3) Cooling the reaction solution to 80 ℃, pouring the reaction solution into methanol to obtain resin precipitate, repeatedly washing the resin precipitate with ethanol, filtering, crushing and drying the resin precipitate in an oven to obtain the polyimide adhesive prepolymer solid powder with the yield of 98% (the prepolymer structure x: y is 8:2, n is 1.5, M is Mn＝1721g/mol)。
Adhesion experiment of polyimide adhesive and stainless steel sheet:
dissolving the polyimide adhesive solid powder in N, N-dimethylacetamide to obtain a resin solution with the solid content of 50 wt.%, uniformly coating the homogeneous solution on the surface of a stainless steel sheet, removing the solvent through a step heating process of 80 ℃/2 hours, 150 ℃/2 hours and 200 ℃/1.5 hours, then heating to 350 ℃ at the heating rate of 3 ℃/min, and curing for 6 hours to obtain the firm bonding body.
The main properties of the polyimide adhesive prepared in this example are shown in table 1.
Example 3
(1) 22.42 g (0.07 mol) of 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl, 10.46 g (0.03 mol) of bis (4-aminophenoxy) tetramethyldisiloxane and 165 g of N, N-dimethylformamide were placed in a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen inlet/outlet and a thermometer, and stirred under nitrogen atmosphere until completely dissolved. 21.49 g (0.067 mol) of 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride and 16.56 g (0.067 mol) of 4-phenylethynylphthalic anhydride were then added and stirred under nitrogen atmosphere until completely dissolved. Stirring at room temperature for 8 hours gave a homogeneous solution with a solids content of 30 wt.%.
(2) Adding 8 g of toluene into the homogeneous solution, heating the reaction system to 140 ℃, reacting for 12 hours under the protection of nitrogen, then heating to 153 ℃, distilling toluene out, and stopping heating.
(3) Cooling the reaction solution to 120 ℃, pouring the reaction solution into propanol to obtain resin precipitate, repeatedly washing the resin precipitate with methanol, filtering, crushing and drying the resin precipitate in an oven to obtain the polyimide adhesive prepolymer solid powder with the yield of 96% (the prepolymer structure x: y is 7:3, n is 2.0, M isn＝2034g/mol)。
Adhesion experiment of polyimide adhesive and stainless steel sheet:
dissolving the polyimide adhesive solid powder in N, N-dimethylformamide to obtain a resin solution with the solid content of 40 wt.%, uniformly coating the homogeneous solution on the surface of a stainless steel sheet, removing the solvent through a step heating process of 60 ℃/2 hours, 120 ℃/4 hours and 200 ℃/2 hours, then heating to 400 ℃ at the heating rate of 5 ℃/min, and curing for 2 hours to obtain the firm bonding body.
The main properties of the polyimide adhesive prepared in this example are shown in table 1.
Example 4
(1) 22.42 g (0.07 mol) of 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl, 10.46 g (0.03 mol) of bis (4-aminophenoxy) tetramethyldisiloxane and 162 g of N-methylpyrrolidone were placed in a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen inlet/outlet and a thermometer, and stirred under nitrogen atmosphere until completely dissolved. Then, 24.17 g (0.075 mol) of 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride and 12.41 g (0.05 mol) of 4-phenylethynylphthalic anhydride were added and stirred under a nitrogen atmosphere until completely dissolved. Stirring at room temperature for 8 hours gave a homogeneous solution with a solids content of 30 wt.%.
(2) Adding 16 g of toluene into the homogeneous solution, heating the reaction system to 180 ℃, reacting for 12 hours under the protection of nitrogen, heating to 200 ℃, evaporating toluene, and stopping heating.
(3) Cooling the reaction solution to 120 ℃, pouring the reaction solution into propanol to obtain resin precipitate, repeatedly washing the resin precipitate with ethanol and hot water, filtering, crushing and drying the resin precipitate in an oven to obtain the polyimide adhesive prepolymer solid powder with the yield of 96% (the prepolymer structure x: y is 7:3, n is 3.0, M isn＝2649g/mol)。
Adhesion experiment of polyimide adhesive and stainless steel sheet:
dissolving the polyimide adhesive solid powder in N, N-dimethylformamide to obtain a resin solution with the solid content of 40 wt.%, uniformly coating the homogeneous solution on the surface of a stainless steel sheet, removing the solvent through a step heating process of 60 ℃/4 hours, 120 ℃/3 hours and 200 ℃/1 hour, then heating to 400 ℃ at the heating rate of 6 ℃/min, and curing for 2 hours to obtain the firm bonding body.
The main properties of the polyimide adhesive prepared in this example are shown in table 1.
Example 5
(1) 22.42 g (0.07 mol) of 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl, 16.70 g (0.03 mol) of bis (4- (4-aminobenzoate) benzene) tetramethyldisiloxane and 176 g of dimethyl sulfoxide were put into a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen inlet/outlet and a thermometer, and stirred under nitrogen atmosphere until completely dissolved. Then, 24.17 g (0.075 mol) of 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride and 12.41 g (0.05 mol) of 4-phenylethynylphthalic anhydride were added and stirred under a nitrogen atmosphere until completely dissolved. Stirring at room temperature for 6 hours gave a homogeneous solution with a solids content of 30 wt.%.
(2) Adding 18 g of toluene into the homogeneous solution, heating the reaction system to 160 ℃, reacting for 18 hours under the protection of nitrogen, then heating to 177 ℃, distilling out toluene, and stopping heating.
(3) Cooling the reaction solution to 80 ℃, pouring the reaction solution into ethanol to obtain resin precipitate, repeatedly washing the resin precipitate with ethanol and hot water, filtering, crushing and drying the resin precipitate in an oven to obtain the polyimide adhesive prepolymer solid powder with the yield of 97% (the prepolymer structure x: y is 7:3, n is 3.0, M isn＝2867g/mol)。
Adhesion experiment of polyimide adhesive and stainless steel sheet:
dissolving the polyimide adhesive solid powder in dimethyl sulfoxide to obtain a resin solution with the solid content of 50 wt.%, uniformly coating the homogeneous solution on the surface of a stainless steel sheet, removing the solvent through a step heating process of 80 ℃/4 hours, 150 ℃/2 hours and 200 ℃/4 hours, then heating to 400 ℃ at the heating rate of 2 ℃/min, and curing for 1 hour to obtain the firm bonding body.
The main properties of the polyimide adhesive prepared in this example are shown in Table 1
Example 6
(1) 28.82 g (0.09 mol) of 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl, 5.5676 g (0.01 mol) of bis (4- (4-aminobenzoate) benzene) tetramethyldisiloxane and 172 g of N-methylpyrrolidone were placed in a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen inlet/outlet and a thermometer, and stirred under nitrogen atmosphere until completely dissolved. Then, 14.71 g (0.05 mol) of 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride and 24.82 g (0.10 mol) of 4-phenylethynylphthalic anhydride were added thereto, and the mixture was stirred under a nitrogen atmosphere until completely dissolved. Stirring was carried out at room temperature for 12 hours to obtain a homogeneous solution having a solid content of 30 wt.%.
(2) 9 g of toluene is added into the homogeneous solution, the reaction system is heated to 190 ℃, the reaction is carried out for 6 hours under the protection of nitrogen, and then the temperature is raised to 200 ℃ to evaporate toluene and stop heating.
(3) Cooling the reaction solution to 100 ℃, pouring into isopropanol to obtain resin precipitate, repeatedly washing with methanol and hot water, filtering, crushing and drying in an oven to obtain the polyimide adhesive prepolymer solid powder with the yield of 98% (prepolymer structure x: y ═ 9:1, n ═ 1.0, M ═ 9:1, M ═ 1.0)n＝1400g/mol)。
Adhesion experiment of polyimide adhesive and stainless steel sheet:
dissolving the polyimide adhesive solid powder in N, N-dimethylacetamide to obtain a resin solution with the solid content of 50 wt.%, uniformly coating the homogeneous solution on the surface of a stainless steel sheet, removing the solvent through a step heating process of 80 ℃/1 hour, 150 ℃/4 hours and 200 ℃/1 hour, then heating to 350 ℃ at the heating rate of 2 ℃/min, and curing for 3 hours to obtain the firm bonding body.
The main properties of the polyimide adhesive prepared in this example are shown in Table 1
Example 7
(1) In a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen inlet/outlet, and a thermometer, 25.62 g (0.08 mol) of 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl, 6.97 g (0.02 mol) of bis (4-aminophenoxy) tetramethyldisiloxane, and 130 g of N, N-dimethylacetamide were charged, and stirred under nitrogen protection until completely dissolved. Then, 17.65 g (0.06 mol) of 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride and 19.86 g (0.08 mol) of 4-phenylethynylphthalic anhydride were added thereto, and the mixture was stirred under a nitrogen atmosphere until completely dissolved. Stirring at room temperature for 10 hours gave a homogeneous solution with a solids content of 35 wt.%.
(2) Adding 7 g of dimethylbenzene into the homogeneous solution, heating the reaction system to 150 ℃, reacting for 10 hours under the protection of nitrogen, then heating to 166 ℃, distilling out methylbenzene, and stopping heating.
(3) Cooling the reaction solution to 80 ℃, pouring the reaction solution into butanol to obtain resin precipitate, repeatedly washing the resin precipitate with hot water, filtering, crushing and drying the resin precipitate in an oven to obtain polyimide adhesive prepolymer solid powder with the yield of 96 percent (prepolymer structure x: y)＝8:2，n＝1.5，Mn＝1665g/mol)。
Adhesion experiment of polyimide adhesive and stainless steel sheet:
dissolving the polyimide adhesive solid powder in N, N-dimethylacetamide to obtain a resin solution with the solid content of 50 wt.%, uniformly coating the homogeneous solution on the surface of a stainless steel sheet, removing the solvent through a step heating process of 80 ℃/4 hours, 150 ℃/2 hours and 200 ℃/2 hours, then heating to 370 ℃ at the heating rate of 3 ℃/min, and curing for 2 hours to obtain a firm bonding body.
The main properties of the polyimide adhesive prepared in this example are shown in Table 1
Example 8
(1) 22.42 g (0.07 mol) of 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl, 16.70 g (0.03 mol) of bis (4- (4-aminobenzoate) benzene) tetramethyldisiloxane and 112 g of N-methylpyrrolidone were placed in a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen inlet/outlet and a thermometer, and stirred under nitrogen atmosphere until they were completely dissolved. Then, 19.62 g (0.067 mol) of 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride and 16.56 g (0.067 mol) of 4-phenylethynylphthalic anhydride were added thereto, and the mixture was stirred under a nitrogen atmosphere until the mixture was completely dissolved. Stirring at room temperature for 10 hours gave a homogeneous solution with a solids content of 40 wt.%.
(2) Adding 17 g of toluene into the homogeneous solution, heating the reaction system to 175 ℃, reacting for 8 hours under the protection of nitrogen, then heating to 200 ℃, evaporating toluene, and stopping heating.
(3) Cooling the reaction solution to 100 ℃, pouring the reaction solution into hot water to obtain resin precipitate, repeatedly washing the resin precipitate with ethanol and hot water, filtering, crushing and drying the resin precipitate in an oven to obtain the polyimide adhesive prepolymer solid powder with the yield of 97% (the prepolymer structure x: y is 7:3, n is 2.0, M isn＝2120g/mol)。
Adhesion experiment of polyimide adhesive and stainless steel sheet:
dissolving the polyimide adhesive solid powder in N, N-dimethylacetamide to obtain a resin solution with the solid content of 50 wt.%, uniformly coating the homogeneous solution on the surface of a stainless steel sheet, removing the solvent through a step heating process of 80 ℃/4 hours, 150 ℃/0.5 hours and 200 ℃/2 hours, then heating to 390 ℃ at the heating rate of 3 ℃/min, and curing for 4 hours to obtain the firm bonding body.
The main properties of the polyimide adhesive prepared in this example are shown in table 1.
Example 9
(1) 19.11 g (0.09 mol) of 4,4 '-diamino-2, 2' -dimethylbiphenyl, 3.49 g (0.01 mol) of bis (4-aminophenoxy) tetramethyldisiloxane and 136 g of cyclopentanone were placed in a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen inlet/outlet and a thermometer, and stirred under nitrogen atmosphere until completely dissolved. Then, 10.91 g (0.05 mol) of pyromellitic dianhydride and 24.82 g (0.10 mol) of 4-phenylethynyl phthalic anhydride were added and stirred under a nitrogen atmosphere until completely dissolved. Stirring at room temperature for 24 hours gave a homogeneous solution with a solids content of 30 wt.%.
(2) 6.8 g of toluene is added into the homogeneous solution, the reaction system is heated to 120 ℃, the reaction is carried out for 6 hours under the protection of nitrogen, and then the temperature is raised to 130 ℃, toluene is evaporated, and the heating is stopped.
(3) Cooling the reaction solution to 100 ℃, pouring the reaction solution into ethanol to obtain resin precipitate, repeatedly washing the resin precipitate with ethanol and hot water, filtering, crushing and drying the resin precipitate in an oven to obtain the polyimide adhesive prepolymer solid powder with the yield of 95% (the prepolymer structure x: y is 9:1, n is 1.0, M is 95%) (the prepolymer structure x: y is 9:1, and the yield is 1.0n＝1116g/mol)。
Adhesion experiment of polyimide adhesive and stainless steel sheet:
dissolving the polyimide adhesive solid powder in cyclopentanone to obtain a resin solution with the solid content of 40 wt.%, uniformly coating the homogeneous solution on the surface of a stainless steel sheet, removing the solvent through a step heating process of 60 ℃/4 hours, 150 ℃/4 hours and 200 ℃/0.5 hours, then heating to 400 ℃ at the heating rate of 6 ℃/min, and curing for 2 hours to obtain the firm bonding body.
The main properties of the polyimide adhesive prepared in this example are shown in table 1.
Example 10
(1) 16.98 g (0.08 mol) of 4,4 '-diamino-2, 2' -dimethylbiphenyl, 6.97 g (0.02 mol) of bis (4-aminophenoxy) tetramethyldisiloxane and 128 g of N, N-dimethylacetamide were placed in a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen inlet/outlet and a thermometer, and stirred under nitrogen atmosphere until completely dissolved. Then, 14.55 g (0.067 mol) of pyromellitic dianhydride and 16.56 g (0.067 mol) of 4-phenylethynylphthalic anhydride were added thereto, and the mixture was stirred under a nitrogen atmosphere until the mixture was completely dissolved. Stirring at room temperature for 10 hours gave a homogeneous solution with a solids content of 30 wt.%.
(2) Adding 13 g of toluene into the homogeneous solution, heating the reaction system to 145 ℃, reacting for 8 hours under the protection of nitrogen, then heating to 166 ℃, distilling out toluene, and stopping heating.
(3) Cooling the reaction solution to 120 ℃, pouring the reaction solution into hot water to obtain resin precipitate, repeatedly washing the resin precipitate with ethanol and hot water, filtering, crushing and drying the resin precipitate in an oven to obtain the polyimide adhesive prepolymer solid powder with the yield of 97% (prepolymer structure x: y ═ 8:2, n ═ 2.0, M ═ 2.0n＝1550g/mol)。
Adhesion experiment of polyimide adhesive and stainless steel sheet:
dissolving the polyimide adhesive solid powder in N-methyl pyrrolidone to obtain a resin solution with the solid content of 60 wt.%, uniformly coating the homogeneous solution on the surface of a stainless steel sheet, removing the solvent through a step heating process of 60 ℃/4 hours, 150 ℃/2 hours and 180 ℃/4 hours, then heating to 400 ℃ at the heating rate of 2 ℃/min, and curing for 2 hours to obtain the firm bonding body.
The main properties of the polyimide adhesive prepared in this example are shown in table 1.
Example 11
(1) 16.98 g (0.08 mol) of 4,4 '-diamino-2, 2' -dimethylbiphenyl, 11.14 g (0.02 mol) of bis (4- (4-aminobenzoate) benzene) tetramethyldisiloxane and 138 g of N, N-dimethylacetamide were placed in a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen inlet/outlet and a thermometer, and stirred under nitrogen atmosphere until they were completely dissolved. Then, 14.55 g (0.067 mol) of pyromellitic dianhydride and 16.56 g (0.067 mol) of 4-phenylethynylphthalic anhydride were added thereto, and the mixture was stirred under a nitrogen atmosphere until the mixture was completely dissolved. Stirring at room temperature for 12 hours gave a homogeneous solution with a solids content of 30 wt.%.
(2) 14 g of toluene is added into the homogeneous solution, the reaction system is heated to 145 ℃, the reaction is carried out for 10 hours under the protection of nitrogen, and then the temperature is raised to 166 ℃, toluene is evaporated, and the heating is stopped.
(3) Cooling the reaction solution to 100 ℃, pouring the reaction solution into hot water to obtain resin precipitate, repeatedly washing the resin precipitate with ethanol and hot water, filtering, crushing and drying the resin precipitate in an oven to obtain the polyimide adhesive prepolymer solid powder with the yield of 97% (the prepolymer structure x: y is 8:2, n is 2.0, M isn＝1655g/mol)。
Adhesion experiment of polyimide adhesive and stainless steel sheet:
dissolving the polyimide adhesive solid powder in N-methyl pyrrolidone to obtain a resin solution with the solid content of 65 wt.%, uniformly coating the homogeneous solution on the surface of a stainless steel sheet, removing the solvent through a step heating process of 60 ℃/4 hours, 150 ℃/2 hours and 200 ℃/4 hours, then heating to 370 ℃ at the heating rate of 4 ℃/min, and curing for 3 hours to obtain the firm bonding body.
The main properties of the polyimide adhesive prepared in this example are shown in table 1.
Comparative example 1
(1) 12.81 g (0.04 mol) of 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl and 64 g of N-methylpyrrolidone were added to a three-necked flask equipped with a mechanical stirrer, a water separator, a nitrogen inlet and outlet, and a thermometer, and stirred under nitrogen protection until completely dissolved. Then, 9.67 g (0.03 mol) of 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride and 4.96 g (0.02 mol) of 4-phenylethynylphthalic anhydride were added and stirred under a nitrogen atmosphere until completely dissolved. Stirring at room temperature for 12 hours gave a homogeneous solution with a solids content of 30 wt.%.
(2) 6 g of toluene is added into the homogeneous solution, the reaction system is heated to 180 ℃, the reaction is carried out for 12 hours under the protection of nitrogen, and then the temperature is raised to 200 ℃ to evaporate toluene and stop heating.
(3) Cooling the reaction solution to 100 deg.C, adding ethanol to obtain resin precipitate, and adding ethanolRepeatedly washing with alcohol and hot water, filtering, crushing and drying in an oven to obtain the polyimide adhesive prepolymer solid powder with the yield of 97% (the prepolymer structure x: y is 10:0, n is 3.0, M isn＝2619g/mol)。
Adhesion experiment of polyimide adhesive and stainless steel sheet:
dissolving the polyimide adhesive solid powder in N-methyl pyrrolidone to obtain a resin solution with the solid content of 65 wt.%, uniformly coating the homogeneous solution on the surface of a stainless steel sheet, removing the solvent through a step heating process of 80 ℃/2 hours, 120 ℃/1 hour and 200 ℃/1.5 hours, then heating to 370 ℃ at the heating rate of 2 ℃/min, and curing for 2 hours to obtain the firm bonding body.
The main properties of the polyimide adhesive prepared in this example are shown in table 1.
TABLE 1 Main Properties of polyimide Adhesives prepared in examples 1-11 and comparative example 1
Table 1 lists the melt flowability, heat resistance, and adhesive properties of the polyimide adhesives prepared in examples 1 to 11 and comparative example 1, and specifically includes: the number average molecular weight and melt fluidity of the polyimide adhesive prepolymer and the heat resistance and the adhesive property of the polyimide adhesive cured product. As shown in Table 1, the number average molecular weight of the polyimide adhesive prepolymer prepared by the method provided by the invention is 1100-g) Not less than 360 ℃. The shear strength of the adhesive for stainless steel bonding is 18-25MPa at room temperature, and 15-18MPa and 7-10MPa at 350 ℃ and 380 ℃ respectively. Compared with the comparative example 1 without adding the diamine containing the siloxane structure, the melt viscosity of the polyimide adhesives prepared in the examples 1 to 11 is greatly reduced, and the shear strength after the polyimide adhesives are bonded with stainless steel is greatly improved. The excellent high-temperature bonding performance of the adhesive is closely related to the organic-inorganic conversion characteristic of oxidation crosslinking of silicon oxide at high temperature, and the structure of the adhesive at high temperatureThe presence of the medium inorganic phase increases its heat resistance stability. The data show that the polyimide adhesive prepared by the method provided by the invention has excellent melt flowability, heat resistance and high-temperature bonding performance, and can be applied to bonding of high-temperature resistant parts in the fields of aviation, aerospace, precision machinery, petrochemical industry and the like.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (7)
1. The polyimide adhesive is characterized by being obtained by curing a polyimide adhesive prepolymer, wherein the polyimide adhesive prepolymer is prepared from raw materials including aromatic diamine containing a biphenyl structure, aromatic diamine containing a siloxane structure, aromatic dianhydride and a capping agent;
the polyimide adhesive is used in the field of aerospace;
the polyimide adhesive prepolymer has a structure of general formula I:
wherein Ar is selected from any one or more of the following aromatic structures:
R1is a biphenyl structure, R2Is a siloxane structure, the ratio of x to y is (9:1) - (7:3), n is 1-3;
the aromatic diamine containing the siloxane structure is bis (4-aminophenoxy) tetramethyldisiloxane and/or bis (4- (4-aminobenzoate) benzene) tetramethyldisiloxane;
R2any one or more of the following structures:
the end-capping reagent is 4-phenylethynyl phthalic anhydride.
2. The polyimide adhesive according to claim 1, wherein the aromatic diamine of biphenyl structure is 4,4 '-diamino-2, 2' -dimethylbiphenyl and/or 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl;
R1any one or more of the following structures:
3. a method for preparing the polyimide adhesive according to claim 1 or 2, wherein the method comprises the following steps:
step 1: dissolving a polyimide adhesive prepolymer in an organic solvent to obtain a homogeneous solution;
step 2: and coating the homogeneous solution on the surface of the bonded object, removing the organic solvent, and curing to obtain the polyimide adhesive to finish bonding of the bonded object.
4. The method for preparing the polyimide adhesive according to claim 3, wherein the solid content of the homogeneous solution is 40-65 wt.%.
5. The method for preparing the polyimide adhesive according to claim 3, wherein the curing in the step 2 is temperature-rising curing, and the temperature-rising curing process is as follows: the temperature is raised to 350-400 ℃ at the temperature raising rate of 2-6 ℃/min, and the curing reaction time is 1-6 hours.
6. The preparation method of the polyimide adhesive according to claim 3, wherein the polyimide adhesive prepolymer is prepared by the following steps:
dissolving aromatic diamine containing a biphenyl structure and aromatic diamine containing a siloxane structure in an organic solvent, and completely dissolving under the protection of inert gas to obtain a mixed solution; sequentially adding aromatic dianhydride and a capping agent into the mixed solution, completely dissolving under the protection of inert gas, and stirring for reaction to obtain a homogeneous solution of a prepolymer raw material; and adding a dehydrating agent into the homogeneous phase solution of the prepolymer raw material to perform azeotropic reaction, removing the dehydrating agent, cooling, and performing precipitation separation to obtain the polyimide adhesive prepolymer.
7. The method for preparing the polyimide adhesive according to claim 6, wherein the solid content of the prepolymer raw material homogeneous solution is 25 wt.% to 40 wt.%.
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| CN111500247B (en) * | 2019-01-30 | 2022-04-19 | 宁波祢若电子科技有限公司 | Adhesive and application thereof in electrochromic field |
| CN110804409A (en) * | 2019-12-03 | 2020-02-18 | 山东大学 | Benzoxazine adhesive for polyimide and preparation and use methods thereof |
| CN111320752B (en) * | 2020-04-09 | 2022-11-04 | 株洲时代新材料科技股份有限公司 | Polyamide acid resin for chip packaging, and preparation method and application thereof |
| CN111440590B (en) * | 2020-04-09 | 2022-04-22 | 株洲时代新材料科技股份有限公司 | Polyamide acid adhesive composition for chip packaging, and preparation method and application thereof |
| CN111704719B (en) * | 2020-06-24 | 2021-07-20 | 中国科学院化学研究所 | Thermosetting polyimide resin, prepolymer, preparation method and application |
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