CN115160977B - Polyimide fiber membrane adhesive and preparation method and application thereof - Google Patents
Polyimide fiber membrane adhesive and preparation method and application thereof Download PDFInfo
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- CN115160977B CN115160977B CN202210992050.7A CN202210992050A CN115160977B CN 115160977 B CN115160977 B CN 115160977B CN 202210992050 A CN202210992050 A CN 202210992050A CN 115160977 B CN115160977 B CN 115160977B
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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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- 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
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/011—Layered products comprising a layer of metal all layers being exclusively metallic all layers being formed of iron alloys or steels
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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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B37/1207—Heat-activated adhesive
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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
- C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
- C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid
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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
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B37/1207—Heat-activated adhesive
- B32B2037/1215—Hot-melt adhesive
- B32B2037/1223—Hot-melt adhesive film-shaped
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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
- C08G2170/00—Compositions for adhesives
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to the technical field of functional fiber materials, in particular to a polyimide fiber membrane adhesive and a preparation method and application thereof. The invention adopts soluble polyimide resin capped by propynyl as raw material, and prepares the polyimide fiber membrane adhesive in an electrostatic spinning mode. The propynyl end capping is adopted in the polyimide fiber film adhesive, so that the curing temperature can be greatly reduced, and the bonding procedure at a lower temperature can be realized, thereby reducing the processing difficulty; the superfine fiber film is used as a bonding medium, has the characteristic of no solvent, and is convenient to process and store. The polyimide fiber membrane adhesive has excellent bonding strength particularly for metals such as stainless steel and the like, and can be used for bonding the stainless steel.
Description
Technical Field
The invention relates to the technical field of functional fiber materials, in particular to a polyimide fiber membrane adhesive and a preparation method and application thereof.
Background
The high-temperature-resistant adhesive is a special adhesive which can be applied to hundreds of degrees centigrade for a long time and can resist thousands of degrees centigrade instantaneously. Because of the better fatigue resistance and higher strength to weight ratio, the method has been widely applied to replace traditional connection methods such as riveting, welding, mechanical fastening and the like in the aerospace field.
The organic polymer adhesive material in the high temperature resistant adhesive has been widely used and studied in recent years due to its low cost, certain toughness, high adhesive strength, good processability, good mechanical properties and other advantages. The aromatic heterocyclic polymer has excellent heat resistance stability due to the highly conjugated structural characteristics and strong intermolecular interaction, and meanwhile, the flexible and changeable molecular structure designability has broad application prospects in the field of high-temperature-resistant adhesion. The common aromatic heterocyclic polymer materials mainly comprise Polybenzoxazine (PBZ), polybenzimidazole (PBI), polyquinoxaline (PQ), polyphenyl quinoxaline (PPQ), polybenzoxazole (PBO), polyimide (PI) and the like. Among common aromatic heterocyclic polymers, the PI bonding materials are particularly used as the basis and application for the most intensive research. The rigid imide ring structure in the PI main chain endows the material with good heat-resistant stability, mechanical and dielectric properties at high temperature, irradiation resistance and good adhesion property with metals. At present, the problems of the existing PI bonding materials are mainly focused on solvent problems, namely the problems of hole formation, bubble formation and the like of a bonding layer caused by solvent volatilization or polymerization dehydration in the bonding process exist in both the Soluble PI (SPI) type adhesive and the polyamide acid (PAA) type adhesive, so that the bonding strength is reduced, and the application difficulty of the particle type bonding materials with less solvents is higher. In addition, the problem of higher curing temperature of the conventional cross-linked PI bonding materials results in increased processing difficulties due to the rigid backbone and end capping groups, for example: NA anhydride (5-norbornene-2, 3-dicarboxylic anhydride) capped LARC-13 curing temperature developed by Langley research center of NASA was at 343 ℃, and ethynyl capped Thermid 600 curing temperature, commercially available from International starch and chemistry Co., ltd (National Starch and Chemical Company) after Hughes aircraft Co., USA was 340-350 ℃, and phenylethynyl capped PETI-5 curing temperature developed by Langley research center was above 370 ℃. Therefore, how to achieve solvent-free or low-solvation of PI bonding materials and to reduce the curing temperature has become a hot spot in the current research field of high-performance PI bonding materials.
In view of this, the present invention has been made.
Disclosure of Invention
The first object of the present invention is to provide a polyimide fiber membrane adhesive, which has the advantages of high adhesive strength, high temperature resistance, low curing temperature, no solvent, etc., and solves the problems of the prior art that the polyimide adhesive material has high curing temperature, which results in high processing difficulty, large solvent amount in the polyimide adhesive material, etc.
The second object of the invention is to provide a preparation method of the polyimide fiber membrane adhesive, which has simple steps.
A third object of the present invention is to provide a method for bonding stainless steel, comprising using the polyimide fiber film adhesive as described above, which has excellent bonding strength to stainless steel.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the invention provides a polyimide fiber membrane adhesive, which comprises the following components: a propynyl terminated soluble polyimide resin;
the propynyl terminated soluble polyimide resin has a structural general formula shown in the specification:
wherein R is 1 Selected from H or CF 3 ；
X is selected fromAny one of them;
n is an integer of 1 to 100.
Further, the number average molecular weight of the propynyl terminated soluble polyimide resin is 2500 to 30000g mol -1 。
Further, the bonding temperature of the polyimide fiber membrane adhesive is 260-350 ℃.
Preferably, the bonding temperature of the polyimide fiber membrane adhesive is 280-330 ℃.
The invention also provides a preparation method of the polyimide fiber membrane adhesive, which comprises the following steps:
the polyimide fiber membrane adhesive is obtained by electrostatic spinning of an organic solution containing a propynyl-terminated soluble polyimide resin;
the preparation method of the propynyl terminated soluble polyimide resin comprises the following steps:
carrying out high-temperature polymerization on an aromatic dianhydride monomer containing a flexible group, an aromatic diamine monomer containing a phenolphthalein group and a capping agent containing propynyl to obtain the propynyl capped soluble polyimide resin;
the aromatic dianhydride monomer containing the flexible group comprises any one of 3,3',4' -diphenyl ether tetrahydric dianhydride, 2, 3',4' -diphenyl ether tetrahydric dianhydride and 5- [3- [ (1, 3-dioxo-2-benzofuran-5-yl) oxy ] phenoxy ] -2-benzofuran-1, 3-dione;
the aromatic diamine monomer containing phenolphthalein groups comprises 3, 3-bis [4- (4-aminophenoxy) phenyl ] phthalein;
the propynyl containing capping agent comprises 4- (methylethynyl) phthalic anhydride.
Further, the preparation method of the propynyl terminated soluble polyimide resin comprises the following steps:
A. the aromatic diamine monomer containing phenolphthalein groups, the aromatic dianhydride monomer containing flexible groups and the blocking agent containing propynyl are subjected to polymerization reaction in a strong polar aprotic solvent to obtain a propynyl-blocked polyamide acid solution;
B. the propynyl-terminated polyamic acid solution, toluene and isoquinoline react to obtain a soluble polyimide solution;
C. and (3) precipitating the soluble polyimide solution in absolute ethyl alcohol to obtain the propynyl-terminated soluble polyimide resin.
Further, in the step A, the strong polar aprotic solvent includes one or more of N-methylpyrrolidone, m-cresol, dimethyl sulfoxide and γ -butyrolactone.
Preferably, the strongly polar aprotic solvent is N-methylpyrrolidone.
Further, in the step A, the blocking agent containing propynyl accounts for 1-10% of the total mass of the aromatic diamine monomer containing phenolphthalein groups, the aromatic dianhydride monomer containing flexible groups, the blocking agent containing propynyl and the strong polar aprotic solvent.
Further, parameters of the electrospinning are set as follows:
the inner diameter of the spinneret is 0.18-0.50 mm, the distance between the spinneret and the rolling receiving device is 10-25 cm, the positive high voltage is applied to be 12-20 kV, the negative high voltage is applied to be-8-0 kV, the injection speed is set to be 0.005-0.015 mL/min, and the relative humidity of the environment is 10-50%.
Preferably, the rotation speed of the rolling receiving device is controlled to be 50-2500 rpm.
The invention also provides a method for bonding stainless steel, which comprises the step of adopting the polyimide fiber membranous adhesive.
Further, the method for bonding the stainless steel comprises the following steps:
a. placing the polyimide fiber film adhesive at the lap joint position of two stainless steel plates, and fixing the lap joint position by using a clamp to obtain a stainless steel adherend;
b. and (3) carrying out bonding treatment on the stainless steel adherends.
Preferably, the pressure of the bonding treatment is 0-5 MPa; the temperature of the bonding treatment is 260-350 ℃, and the time of the bonding treatment is 1-5 min.
Preferably, the temperature of the bonding treatment is 280-330 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the polyimide fiber membrane adhesive provided by the invention depends on a flexible and designable molecular structure of polyimide, propynyl is selected for end sealing, and the adhesive material with high adhesive strength, high temperature resistance and low curing temperature is prepared, wherein the adhesive temperature is 260-350 ℃, and the problem of high processing difficulty caused by high curing temperature of the existing polyimide adhesive material is solved.
The polyimide fiber membrane adhesive takes the form of a superfine fiber membrane as an adhesive medium, has the characteristics of no solvent, high entanglement degree, high specific surface area, good flexibility and the like, and overcomes the defect of large solvent amount in polyimide adhesive materials in the prior art.
The polyimide fiber membrane adhesive can be applied to the high-tech fields of aviation, aerospace, automobiles, microelectronics, wearable equipment and the like. Particularly has excellent bonding strength to metals such as stainless steel and the like, and can be used for bonding stainless steel plates.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
Fig. 1 is an infrared spectrum of the polyimide fiber membrane adhesives prepared in example 1, example 2 and example 3 of the present invention.
Fig. 2 is a scanning electron microscope image of the polyimide fiber film adhesives prepared in example 1, example 2 and example 3 of the present invention.
FIG. 3 shows the TGA and DTG spectra of polyimide fiber film adhesives prepared in examples 1, 2 and 3 of the present invention.
FIG. 4 is a DSC chart of the polyimide fiber membrane adhesives prepared in example 1, example 2 and example 3 of the present invention.
Fig. 5 is a rheological test spectrum of the polyimide fiber membrane adhesives prepared in example 1, example 2, example 3 and comparative example 1 of the present invention.
Fig. 6 is an SEM image of the microscopic morphology of the polyimide fiber film adhesives prepared in example 1, example 2 and example 3 according to the present invention, as a function of temperature.
Fig. 7 is a schematic view showing the bonding of stainless steel plates using polyimide fiber membrane adhesives in example 1 of the present invention and the single-lap tensile shear strength of the polyimide fiber membrane adhesives prepared in example 1, example 2, example 3, comparative example 1 and comparative example 2.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and detailed description, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative of the present invention only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The polyimide fiber membrane adhesive, the preparation method and the application thereof are specifically described below.
In an embodiment of the present invention, there is provided a polyimide fiber membrane adhesive comprising: a propynyl terminated soluble polyimide resin;
the propynyl terminated soluble polyimide resin has the following structural general formula:
wherein R is 1 Selected from H or CF 3 ；
X is selected fromAny one of them;
n is an integer of 1 to 100.
According to the invention, by relying on a flexible and designable molecular structure of polyimide, propynyl is selected for end sealing, so that the adhesive material with high adhesive strength, high temperature resistance, excellent heat resistance stability and low curing temperature is prepared, and the problem of high processing difficulty caused by high curing temperature in the adhesive process is solved; the propynyl is adopted for end capping, so that the curing temperature is greatly reduced, and the bonding procedure at a lower temperature is realized, thereby reducing the processing difficulty.
The invention uses the superfine fiber film as the bonding medium, has the characteristics of no solvent, high entanglement degree, high specific surface area, good flexibility and the like, and overcomes the defect of large solvent amount in the bonding material in the prior art.
In some embodiments of the invention, X is
In some embodiments of the invention, the propynyl terminated soluble polyimide resin has a molecular weight of 2500 to 30000g mol -1 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, the propynyl terminated soluble polyimide resin has a molecular weight of 8000 to 15000g mol -1 The method comprises the steps of carrying out a first treatment on the surface of the The polyimide fiber membrane adhesive has more excellent comprehensive performance and bonding strength due to the proper molecular weight.
In some embodiments of the invention, the polyimide fibrous membrane adhesive has a bonding temperature of 260 to 350 ℃; typical, but not limiting, for example, polyimide fiber membrane adhesives have a bonding temperature of 260 ℃, 270 ℃, 280 ℃, 29 ℃, 300 ℃, 310 ℃, 320 ℃,330 ℃, 340 ℃, or 350 ℃, etc.; preferably, the bonding temperature of the polyimide fiber membrane adhesive is 280-330 ℃.
The polyimide fiber membranous adhesive is a low-temperature curing adhesive, and the bonding temperature is lower than that of the existing polyimide bonding material.
In some embodiments of the present invention, a method for preparing the polyimide fiber membrane adhesive is provided, which includes the following steps:
and (3) carrying out electrostatic spinning on an organic solution containing the propynyl-terminated soluble polyimide resin to obtain the polyimide fiber membrane adhesive.
The invention takes the soluble polyimide resin capped by propynyl as the raw material, adopts the electrostatic spinning mode to prepare the polyimide fiber film adhesive, and can form the superfine fiber film with low curing temperature and no solvent.
In some embodiments of the invention, the solvent in the organic solution containing the propynyl terminated soluble polyimide resin comprises N, N-dimethylacetamide (DMAc).
In some embodiments of the invention, the organic solution containing the propynyl terminated soluble polyimide resin has a solids content of 20wt% to 50wt% (weight percent).
In some embodiments of the invention, a method of preparing a propynyl terminated soluble polyimide resin comprises:
the aromatic dianhydride monomer containing flexible groups, the aromatic diamine monomer containing phenolphthalein groups and the blocking agent containing propynyl are subjected to high-temperature polymerization reaction to obtain the propynyl-blocked soluble polyimide resin.
In some embodiments of the present invention, the aromatic dianhydride monomer containing a flexible group includes any of 3,3',4' -diphenyl ether tetracarboxylic dianhydride (ODPA), 2, 3',4' -diphenyl ether tetracarboxylic dianhydride (aODPA) and 5- [3- [ (1, 3-dioxo-2-benzofuran-5-yl) oxy ] phenoxy ] -2-benzofuran-1, 3-dione.
In some embodiments of the invention, the aromatic diamine monomer containing a phenolphthalein group comprises 3, 3-bis [4- (4-aminophenoxy) phenyl ] phthalein (BAPPT).
In some embodiments of the invention, the propynyl-containing capping agent comprises 4- (methylethynyl) phthalic anhydride (MEPA).
In some embodiments of the present invention, a method of preparing a propynyl terminated soluble polyimide resin comprises the steps of:
A. carrying out polymerization reaction on an aromatic diamine monomer containing a phenolphthalein group, an aromatic dianhydride monomer containing a flexible group and a blocking agent containing propynyl in a strong polar aprotic solvent to obtain a propynyl blocked polyamide acid (PAA) solution;
B. the propynyl terminated polyamic acid solution, toluene and isoquinoline react to obtain Soluble Polyimide (SPI) solution;
C. the Soluble Polyimide (SPI) solution was precipitated in absolute ethanol to obtain a propynyl terminated soluble polyimide resin.
In some embodiments of the invention, in step a, the strongly polar aprotic solvent comprises one or more of N-methylpyrrolidone (NMP), m-cresol, dimethyl sulfoxide (DMSO), and γ -butyrolactone; preferably, the strongly polar aprotic solvent is N-methylpyrrolidone (NMP).
In some embodiments of the present invention, the propynyl-containing capping agent comprises 1% to 10% of the total mass of the phenolphthalein group-containing aromatic diamine monomer, the flexible group-containing aromatic dianhydride monomer, the propynyl-containing capping agent and the strongly polar aprotic solvent; preferably 3% to 5%.
In some embodiments of the invention, in step a, the molar ratio of the aromatic diamine monomer containing phenolphthalein groups to the aromatic dianhydride monomer containing flexible groups is from 1.02 to 1.25:1, a step of; preferably 1.05 to 1.15:1.
in some embodiments of the invention, in step a, the ratio of the total mass of the aromatic diamine monomer containing phenolphthalein groups and the aromatic dianhydride monomer containing flexible groups to the mass of the capping agent containing propynyl groups is from 10 to 40:1, a step of; preferably 15 to 30:1.
in some embodiments of the invention, the mass ratio of the total mass of the phenolphthalein group-containing aromatic diamine monomer, the flexible group-containing aromatic dianhydride monomer, and the propynyl group-containing capping agent to the strongly polar aprotic solvent is 1:3 to 5.
In some embodiments of the invention, in step a, the temperature of the polymerization reaction is 10 to 35 ℃, preferably 20 to 25 ℃; the polymerization reaction time is 12-20 h.
In some embodiments of the invention, in step B, the mass ratio of propynyl terminated polyamic acid solution, toluene, and isoquinoline is 140 to 170:100:1.
in some embodiments of the invention, in step B, the temperature of the reaction is 140 to 170 ℃ and the time of the reaction is 8 to 16 hours.
In some embodiments of the invention, parameters for electrospinning are set as follows:
the inner diameter of the spinneret is 0.18-0.50 mm, the distance between the spinneret and the rolling receiving device is 10-25 cm, the positive high voltage is 12-20 kV, the negative high voltage is-8-0 kV, the injection speed is set to be 0.005-0.015 mL/min, and the relative humidity of the environment is 10-50%; preferably, the inner diameter of the spinneret is 0.21mm, the distance between the spinneret and the rolling receiving device is 15-20 cm, the injection speed is set to be 0.01mL/min, and the relative humidity of the environment is 15-35%.
In some embodiments of the invention, the rotational speed of the rolling receiving device is controlled to be 50-2500 rpm; preferably, the rotational speed of the rolling reception device is controlled at 200rpm.
The polyimide fiber membrane adhesive can be applied to the high-tech fields of aviation, aerospace, automobiles, microelectronics, wearable equipment and the like; particularly has excellent bonding strength to metals such as stainless steel.
In some embodiments of the invention, a method of bonding stainless steel is also provided, comprising using the polyimide fiber film adhesive described above.
In some embodiments of the invention, a method of bonding stainless steel comprises the steps of:
a. placing polyimide fiber film adhesive at the lap joint position of two stainless steel plates, and fixing the lap joint position by using a clamp to obtain a stainless steel adherend;
b. and (5) bonding the stainless steel adherends.
In some embodiments of the invention, the pressure of the bonding process is 0 to 5MPa; the temperature of the bonding treatment is 260-350 ℃, and the time of the bonding treatment is 1-5 min; preferably, the temperature of the bonding treatment is 280 to 330 ℃.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The polyimide fiber membrane adhesive provided in the embodiment designs the number average molecular weight M by calculating the proportion of raw materials n ＝20000g mol -1 N=25, designated as METI-20K fibrous membrane.
The preparation method of the polyimide fiber membrane adhesive of the embodiment comprises the following steps:
3, 3-bis [4- (4-aminophenoxy) phenyl ] phthalide (BAPPT, 19.3218g,38.6019 mmol) and N-methylpyrrolidone (NMP, 100 g) were charged into a 500mL three-necked flask equipped with a mechanical stirrer, an electric jacket, and a Dean-Stark trap at 25℃and nitrogen gas was introduced, then 3,3',4' -diphenylether tetracarboxylic dianhydride (ODPA, 11.5094g,37.1019 mmol) was added and stirred for 5 hours, and after that 4- (methylethynyl) phthalic anhydride (MEPA, 0.5585g,3 mmol) and N-methylpyrrolidone (NMP, 25 g) were added to control the solid content of the reaction system at 20wt%; the reaction was then stirred at 25 ℃ for a further 14h to give a propynyl-terminated polyamic acid (PAA) solution. Toluene (100 g) and isoquinoline (1.0 g) are then added to the solution, the reaction mixture is heated to 140-145 ℃ and maintained for reflux dehydration reaction for 16 hours, and the water by-product generated by the reaction is removed by toluene/water azeotrope; toluene was then distilled from the reaction system until the internal temperature of the reaction reached 180℃and reacted at 180℃for 1 hour to obtain a Soluble Polyimide (SPI) solution. The Soluble Polyimide (SPI) solution was then cooled to 70 ℃ and reprecipitated in an excess of aqueous ethanol (10 wt%) to give a precipitate. The precipitate was dried at 25℃for 24 hours and then at 130℃under vacuum for 24 hours to finally obtain a white short filamentous propynyl-terminated soluble polyimide resin (METI-20K resin).
Dissolving the dried METI-20K resin in N, N-dimethylacetamide (DMAc) to obtain a mixed solution, controlling the solid content of the mixed solution to 33wt%, and obtaining a solution containing METI-20K resin with an absolute viscosity of 5000 mPas; after electrostatic spinning by using a solution containing METI-20K resin, the polyimide fiber membrane adhesive (METI-20K fiber membrane) is obtained after vacuum drying for 1h at 120 ℃ to remove residual solvent. Wherein, the electrostatic spinning process is as follows: uniformly injecting the solution containing the METI-20K resin into a 5mL syringe, wherein the syringe adopts a spinneret with an inner diameter of 0.21mm, and extruding the solution containing the METI-20K resin from the spinneret at a speed of 0.01mL/min by using a syringe pump; the positive voltage between the injector and the collector is 16kV, and the negative voltage is-3 kV; the distance between the spinneret and the grounded drum collector (diameter 10cm, length 30 cm) was 15cm; the relative humidity of the electrospinning was 50% + -2%, and the rotational speed of the collector was 2rpm. METI-20K fibers were densely wound and deposited on aluminum foil.
The stainless steel plate bonding method provided by the embodiment comprises the following steps:
a. stacking METI-20K fiber membranes at the lap joint positions of two stainless steel plates, and fixing the lap joint positions by using a clamp to obtain a stainless steel adherend; wherein, the corrosion resistant plate size is: 100mm (length) ×25.4mm (width) ×2mm (height), and polishing the stainless steel sample with standard sand paper for surface pretreatment before bonding; the size of the METI-20K fiber membrane is 12.5mm (length) multiplied by 25mm (width), and the overall thickness of the METI-20K fiber membrane after superposition is 0.3-0.5 mm; the overlap area was 12.5mm (length). Times.25.4 mm (width).
b. Placing the stainless steel adherends on a hot press, heating for 1min at 330 ℃ under 0.5MPa, and cooling to room temperature to finish the bonding process to obtain the bonded stainless steel plate.
Example 2
The polyimide fiber membrane adhesive provided in the embodiment designs the number average molecular weight Mn=10000 g mol by calculating the proportion of raw materials -1 N=12, designated as METI-10K fibrous membrane.
The polyimide fiber membrane adhesive of this example was prepared by referring to example 1, except that BAPPT was 19.2616g (38.4816 mmol), ODPA was 10.9975g (34.4516 mmol), MEPA was 1.1170g (6 mmol), and finally white short filiform METI-10K resin was obtained.
The dried METI-10K resin was dissolved in N, N-dimethylacetamide (DMAc) to obtain a mixed solution, and the solid content of the mixed solution was controlled to 38wt% to obtain a solution containing METI-10K resin having an absolute viscosity of 5000 mPas.
The stainless steel plate bonding method provided by the embodiment is referring to the embodiment 1, and is different in that in the step a, the METI-20K fiber film is replaced by the METI-10K fiber film; in step b, the temperature of heating was 310 ℃.
Example 3
The polyimide fiber membrane adhesive provided in the embodiment designs the number average molecular weight Mn=5000 g mol by calculating the proportion of raw materials -1 N=6, designated as METI-5K fibrous membrane.
The polyimide fiber membrane adhesive of this example was prepared by referring to example 1, except that BAPPT was 19.1412g (38.2411 mmol), ODPA was 10.0015g (32.2410 mmol), MEPA was 2.2339g (12 mmol), and finally a white short rod-like METI-5K resin was obtained.
Dissolving the dried METI-5K resin in N, N-dimethylacetamide (DMAc) to obtain a mixed solution, and controlling the solid content of the mixed solution to be 47.5wt% to obtain a solution containing METI-5K resin with an absolute viscosity of 5000 mPas.
The stainless steel plate bonding method provided by the embodiment is referring to the embodiment 1, and is different in that in the step a, the METI-20K fiber film is replaced by the METI-5K fiber film; in step b, the temperature of heating was 290 ℃.
Example 4
The polyimide fiber membrane adhesive provided in the embodiment designs the number average molecular weight Mn=10000 g mol by calculating the proportion of raw materials -1 N=6, designated METDI-10K fibrous membrane.
The polyimide fiber membrane adhesive of this example was prepared by referring to example 1, except that BAPPT was 17.3747g (34.7119 mmol) in mass, 5- [3- [ (1, 3-dioxo-2-benzofuran-5-yl) oxy ] phenoxy ] -2-benzofuran-1, 3-dione was 12.7580g (31.7119 mmol) in mass, MEPA was 1.1170g (6 mmol) in mass, and finally a white, short-filiform METII-10K resin was obtained.
The dried METII-10K resin was dissolved in N, N-dimethylacetamide (DMAc) to obtain a mixed solution, and the solid content of the mixed solution was controlled to 35wt% to obtain a solution containing METII-10K resin having an absolute viscosity of 5000 mPas.
The present example provides a stainless steel plate bonding method referring to example 1, except that the METI-20K fiber film is replaced with a METII-10K fiber film.
Comparative example 1
The polyimide fiber membrane adhesive provided in the comparative example designs the number average molecular weight M by calculating the proportion of raw materials n ＝10000g mol -1 N=12, designated PI-ref1 fiber membrane.
Preparation method of polyimide fiber membrane adhesive of this comparative example referring to example 1, except that 3, 3-bis [4- (4-aminophenoxy) phenyl ] phthalide (BAPPT, 31.7013g,63.3 mmol) and N-methylpyrrolidone (NMP, 190 g) were charged into a 500mL three-necked flask equipped with a mechanical stirrer, an electric jacket, a Dean-Stark trap and nitrogen gas was introduced, then 3,3',4' -diphenyl ether tetracarboxylic dianhydride (ODPA, 18.0964g,58.3 mmol) was added and stirred for 5 hours, and then 4-phenylethynyl phthalic anhydride (PEPA, 2.23 g,10.0 mmol) and N-methylpyrrolidone (NMP, 19 g) were added to control the solid content of the reaction system at 20wt%; the reaction was then stirred at 25 ℃ for a further 14h to give a phenylethynyl-terminated polyamic acid (PAA) solution. Finally, the PI-ref1 resin with light brown short filiform color is obtained.
The dried PI-ref1 resin was dissolved in N, N-dimethylacetamide (DMAc) to obtain a mixed solution, and the solid content of the mixed solution was controlled to 46.5wt% to obtain a solution containing the PI-ref1 resin having an absolute viscosity of 8000 mPas.
The comparative example provides a stainless steel plate bonding method referring to example 1, except that in step a, the METI-20K fiber film is replaced with a PI-ref1 fiber film. In step b, the temperature of heating was 370 ℃.
Comparative example 2
The polyimide fiber membrane adhesive provided in this comparative example was named PI-ref2 fiber membrane.
The preparation method of the polyimide fiber membrane adhesive of the comparative example comprises the following steps:
3, 3-bis [4- (4-aminophenoxy) phenyl ] phthalide (BAPPT, 15.8506g,31.65 mmol) and N-methylpyrrolidone (NMP, 102.5 g) were charged into a 500mL three-necked flask equipped with a mechanical stirrer, an electric jacket, a Dean-Stark trap and introduced with nitrogen gas, then 3,3',4' -diphenylether tetracarboxylic dianhydride (ODPA, 9.81 g,31.65 mmol) was added and stirred for 15 hours, toluene (100 g) and isoquinoline (1.0 g) were added, and the reaction mixture was heated to 140-145℃for 16 hours with reflux dehydration, and the water by-product of the reaction was removed by toluene/water azeotrope; and then distilling toluene from the reaction system until the internal temperature of the reaction reaches 180 ℃, and reacting for 1h at 180 ℃ to obtain a reaction liquid. The reaction solution was then cooled to 70℃and reprecipitated in an aqueous solution (10 wt%) of ethanol in excess to obtain a precipitate. The precipitate was dried at 25℃for 24 hours and then at 130℃under vacuum for 24 hours to finally give a light brown short filamentous PI-ref2 resin.
Dissolving the dried PI-ref2 resin in N, N-dimethylacetamide (DMAc) to obtain a mixed solution, controlling the solid content of the mixed solution to 21.5wt% to obtain a solution containing the PI-ref2 resin with an absolute viscosity of 8000 mPas; after electrostatic spinning with a solution containing PI-ref2 resin, the polyimide fiber film adhesive (PI-ref 2 fiber film) was obtained by vacuum drying at 120 ℃ for 1h to remove the residual solvent. Wherein the process of electrospinning is referred to in example 1.
The comparative example provides a stainless steel plate bonding method referring to comparative example 1, except that the PI-ref1 fiber film was replaced with PI-ref2 fiber film.
Test example 1
The polyimide fiber membrane adhesives prepared in examples 1 to 3 were subjected to infrared spectroscopic testing, and the results are shown in fig. 1.
As can be seen from FIG. 1 a, 4000-500 cm -1 Polyimide characteristic absorption peaks are located; as can be seen from FIG. 1 b, 2000-3000 cm -1 Enhanced alkynyl absorbance peak.
The polyimide fiber membrane adhesives prepared in examples 1 to 3 were subjected to scanning electron microscopy, and the results are shown in fig. 2. Fig. 2 (a) is example 1, fig. 2 (b) is example 2, and fig. 2 (c) is example 3; the inset in the figure shows the diameter profile of the fibers of the polyimide fibrous membrane adhesive. Among them, a field emission scanning electron microscope (FE-SEM) was used for scanning electron microscope test, and imaging was performed using a JSM-6700F type scanning electron microscope of JEOL corporation, japan, with an acceleration voltage of 15kV, and Pt/Pd was sputtered on each thin film before measurement.
The polyimide fiber membrane adhesives prepared in examples 1 to 3 and comparative examples 1 to 2 were tested for performance, and the results are shown in table 1. The TGA and DTG spectra of examples 1 to 3 are shown in fig. 3, the DSC spectra of examples 1 to 3 are shown in fig. 4, the first temperature rise process is shown in fig. 4 (a), and the second temperature rise process is shown in fig. 4 (b).
Thermogravimetric analysis (TGA): the test is carried out by a TA-Q50 thermal analyzer of Perkin-Elmer company in the United states, the test temperature range is 30-760 ℃, the temperature rising rate is 20 ℃/min, the test environment is nitrogen, and the gas flow is 20mL/min. This test can obtain a polyimide fibrous membrane adhesive with a 5% weight loss temperature (T 5％ ) Data.
Differential Scanning Calorimetry (DSC): the test is carried out by adopting a DSC 214 type calorimetric differential scanner of German resistant company, the test temperature range is 30-400 ℃, the heating rate is 10 ℃/min, the test environment is nitrogen, and the gas flow is 20mL/min. The test can obtain the crosslinking temperature (T c ) Glass transition temperature (T) g ) Data.
TABLE 1
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | |
| Design molecular weight (g/mol) | 20000 | 10000 | 5000 | 10000 | — |
| Solids content (%) | 100 | 100 | 100 | 100 | 100 |
| Curing temperature (. Degree. C.) | 323.6 | 301.9 | 276.1 | 361.0 | — |
| Processing temperature (. Degree. C.) | 330 | 310 | 290 | 370 | 370 |
| T 5％ (℃) | 534.8 | 520.2 | 522.5 | 531.7 | 514.1 |
| Post cure T g (℃) | 276.7 | 276.5 | 274.5 | 270.6 | 288.7 |
The polyimide fiber film adhesives prepared in examples 1 to 3 and comparative example 1 were subjected to rheological tests, and the results are shown in fig. 5.
Rheological analysis: the powder of the polyimide fiber film adhesive was subjected to compression molding to obtain a sample disk (diameter: 25mm, thickness: 1.5.+ -. 0.2 mm) by using an AR2000 type rheometer of TA instruments Co. In the United states. During the measurement, the sample plate was loaded into a parallel plate, the top plate oscillated at a fixed angular frequency of 0.5Hz and a fixed strain of 1.0%, the data acquisition range was 100-440℃and the heating rate was 4℃min -1 . This test can obtain melt viscosity data for polyimide fiber film adhesives.
The microscopic morphologies of the polyimide fiber film adhesives prepared in examples 1 to 3 according to the change in temperature were measured, and the results are shown in fig. 6. Fig. 6 (a) shows example 1, fig. 6 (b) shows example 2, and fig. 6 (c) shows example 3.
The bonded stainless steel sheets of examples 1 to 3 and comparative examples 1 to 2 were tested for single lap tensile shear strength (LSS), and the results are shown in table 2. A schematic view of the bonding of the stainless steel plate using the polyimide fiber film-like adhesive in example 1 is shown in fig. 7 (a); the single lap tensile shear strength of the bonded stainless steel sheets of examples 1 to 3 and comparative examples 1 to 2 is shown in fig. 7 (b).
The adhesion effect of the polyimide fiber film adhesive to the stainless steel plate was evaluated using single Lap Shear Strength (LSS), and the test was performed on an Instron 5567 type tensile machine at a tensile speed of 2mm/min. The test yielded LSS data for polyimide fiber film adhesive bonded stainless steel plates at 25℃and 200 ℃.
LSS value at room temperature (25 ℃) is measured according to GB/T7124-2008 method for measuring tensile shear Strength of adhesive (rigid Material to rigid Material). High temperature (200 ℃ C.) LSS testing was performed according to GJB444-1988 "adhesive high temperature tensile shear Strength test method (Metal-to-Metal)". In the LSS test, 5 shear specimens were tested at room temperature and 200℃respectively, and the average data was recorded.
TABLE 2
As can be seen from tables 1 and 2, examples 1 to 3 show good overall properties including a higher 5% weight loss temperature, a higher glass transition temperature after curing, and a higher adhesive strength to stainless steel plates at both room temperature (25 ℃) and high temperature (200 ℃). With the decrease of the designed molecular weight, the content of the end capping groups gradually increases, the curing temperature and the processing temperature gradually decrease, but the glass transition temperature and the heat resistance stability after curing also decrease. Example 2, among other things, shows the best combination of properties and bond strength at the appropriate molecular weight design.
The most critical point is that the curing temperature of propynyl terminated example 2, which is also set to a molecular weight of 10000g/mol, is reduced by nearly 60℃compared to phenylethynyl terminated comparative example 1, while other properties remain at similar levels. Also, compared with the processing temperature of comparative example 2 which is not subjected to molecular weight control and is not blocked, the processing temperature of the composition is greatly reduced, and the introduction of alkynyl crosslinking groups also greatly improves the bonding performance of the composition on stainless steel plates.
Therefore, the soluble polyimide fiber membrane adhesive prepared by adopting the propynyl end capping can effectively reduce the curing temperature, so that the processing at low temperature is realized, and the application difficulty is greatly reduced. The scheme is superior to the existing polyimide adhesive, and has good industrial application prospect.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (12)
1. A polyimide fibrous membrane adhesive, comprising: a propynyl terminated soluble polyimide resin;
the propynyl terminated soluble polyimide resin has a structural general formula shown as follows:
wherein R is 1 Selected from H or CF 3 ；
X is selected from、/>And->Any one of them;
n is an integer between 1 and 100;
the bonding temperature of the polyimide fiber membrane adhesive is 260-350 ℃;
the molecular weight of the propynyl terminated soluble polyimide resin is 2500-20000 g mol -1 ；
The preparation method of the polyimide fiber membrane adhesive comprises the following steps:
the polyimide fiber membrane adhesive is obtained by electrostatic spinning of an organic solution containing a propynyl-terminated soluble polyimide resin;
the preparation method of the propynyl terminated soluble polyimide resin comprises the following steps:
carrying out high-temperature polymerization on an aromatic dianhydride monomer containing a flexible group, an aromatic diamine monomer containing a phenolphthalein group and a capping agent containing propynyl to obtain the propynyl capped soluble polyimide resin;
the aromatic dianhydride monomer containing the flexible group comprises any one of 3,3',4' -diphenyl ether tetrahydric dianhydride, 2, 3',4' -diphenyl ether tetrahydric dianhydride and 5- [3- [ (1, 3-dioxo-2-benzofuran-5-yl) oxy ] phenoxy ] -2-benzofuran-1, 3-dione;
the aromatic diamine monomer containing phenolphthalein groups comprises 3, 3-bis [4- (4-aminophenoxy) phenyl ] phthalein;
the propynyl containing capping agent comprises 4- (methylethynyl) phthalic anhydride.
2. The polyimide fiber membrane adhesive according to claim 1, wherein the bonding temperature of the polyimide fiber membrane adhesive is 280-330 ℃.
3. The polyimide fiber membrane adhesive according to claim 1, wherein the preparation method of the propynyl terminated soluble polyimide resin comprises the following steps:
A. the aromatic diamine monomer containing phenolphthalein groups, the aromatic dianhydride monomer containing flexible groups and the blocking agent containing propynyl are subjected to polymerization reaction in a strong polar aprotic solvent to obtain a propynyl-blocked polyamide acid solution;
B. the propynyl-terminated polyamic acid solution, toluene and isoquinoline react to obtain a soluble polyimide solution;
C. and (3) precipitating the soluble polyimide solution in absolute ethyl alcohol to obtain the propynyl-terminated soluble polyimide resin.
4. The polyimide fiber membrane adhesive of claim 3 wherein in step a, the strongly polar aprotic solvent comprises one or more of N-methylpyrrolidone, m-cresol, dimethyl sulfoxide, and γ -butyrolactone.
5. The polyimide fiber membrane adhesive of claim 4, the strongly polar aprotic solvent being N-methyl pyrrolidone.
6. The polyimide fiber membrane adhesive according to claim 3, wherein in the step a, the blocking agent containing propynyl accounts for 1% -10% of the total mass of the aromatic diamine monomer containing phenolphthalein groups, the aromatic dianhydride monomer containing flexible groups, the blocking agent containing propynyl groups and the strongly polar aprotic solvent.
7. The method for preparing the polyimide fiber membrane adhesive according to claim 1, wherein the parameters of the electrospinning are set as follows:
the inner diameter of the spinneret is 0.18-0.50 mm, the distance between the spinneret and the rolling receiving device is 10-25 cm, positive high voltage is applied to be 12-20 kV, negative high voltage is applied to be-8-0 kV, the injection speed is set to be 0.005-0.015 mL/min, and the relative humidity of the environment is 10% -50%.
8. The method for preparing a polyimide fiber membrane adhesive according to claim 7, wherein the rotation speed of the rolling receiving device is controlled to be 50-2500 rpm.
9. A method of bonding stainless steel, comprising using the polyimide fiber film adhesive of any one of claims 1 to 8.
10. The method of bonding stainless steel according to claim 9, comprising the steps of:
a. placing the polyimide fiber film adhesive at the lap joint position of two stainless steel plates, and fixing the lap joint position by using a clamp to obtain a stainless steel adherend;
b. and (3) carrying out bonding treatment on the stainless steel adherends.
11. The method for bonding stainless steel according to claim 10, wherein the bonding treatment pressure is 0-5 mpa; the temperature of the bonding treatment is 260-350 ℃, and the time of the bonding treatment is 1-5 min.
12. The method for bonding stainless steel according to claim 11, wherein the bonding treatment temperature is 280-330 ℃.
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| JP2003192894A (en) * | 2001-12-28 | 2003-07-09 | Sumitomo Bakelite Co Ltd | Solution of polyimide resin composition and filmy adhesive |
| JP2009185204A (en) * | 2008-02-07 | 2009-08-20 | Daiwa Can Co Ltd | Polyimide oligomer and polyimide resin formed by heating/curing the same |
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