CN113308218B - Cross-linkable polyimide fiber film-shaped adhesive and preparation method and application thereof - Google Patents
Cross-linkable polyimide fiber film-shaped adhesive and preparation method and application thereof Download PDFInfo
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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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- 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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- 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
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- C09J2479/00—Presence of polyamine or polyimide
- C09J2479/08—Presence of polyamine or polyimide polyimide
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- D10B2331/14—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
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Abstract
The invention provides a crosslinkable Polyimide (PI) fiber film-shaped adhesive and a preparation method and application thereof. The PI fiber film-shaped adhesive is prepared by taking phenylethynyl terminated soluble PI resin solution as a raw material and adopting an electrostatic spinning process. The phenylethynyl terminated soluble PI resin is prepared by polymerizing an aromatic dianhydride monomer containing a flexible group and an aromatic diamine monomer containing a phenolphthalein structure. Compared with the traditional liquid or powder and glue film type PI adhesives, the PI fiber film adhesive obtained by the invention has the advantages of high bonding strength, easy storage and construction and the like. The PI fiber film-shaped adhesive can be used as a high-temperature-resistant adhesive to be applied to personal protective articles, such as masks, protective clothing and the like, and can also be used as an electronic component to be applied to the high-technology fields of aviation, aerospace, photoelectrons, microelectronics, automobiles and the like.
Description
Technical Field
The invention relates to the field of functional fiber materials, in particular to a crosslinkable polyimide fiber film-shaped adhesive and a preparation method and application thereof
Background
High temperature bonding is a scenario that is often used in modern industry. The use of high temperature resistant adhesives is one of the most effective ways to achieve high temperature bonding. Aromatic heterocyclic polymer bonding materials occupy an important position in high-temperature resistant bonding materials due to the highly conjugated structural characteristics and strong intramolecular and intermolecular forces. The aromatic heterocyclic polymer bonding material can effectively fill the gap caused by the brittleness of inorganic bonding materials and the low thermal stability of conventional polymer materials, and has attracted wide attention in the high-tech fields of aviation, aerospace, weapon manufacturing and the like. Common aromatic heterocyclic polymer materials mainly include Polyimide (PI), Polybenzimidazole (PBI), Polybenzoxazole (PBO), Polyquinoxaline (PQ), polyphenylquinoxaline (PPQ), Polybenzoxazine (PBZ), and the like. These materials have been studied in the field of high temperature resistant bonding, and the basic and application studies of PI bonding materials are the most intensive. PI refers in particular to an organic polymer material containing imide ring in a molecular structure. The rigid imide ring framework structure endows the polyimide resin with excellent comprehensive properties, including heat resistance and thermal oxidation stability, good mechanical and dielectric properties in a wide temperature range, excellent radiation resistance and environmental stability, good bonding strength with metal and other base materials and the like. These excellent properties make PI significantly superior to other polymeric materials when used as a high temperature resistant adhesive material. However, PI bonding materials also have some significant performance defects in the application process, such as a problem of high porosity inside the bonding body due to volatilization of a solvent or small water during imidization (or curing), a problem of long curing time, a problem of high curing temperature, and the like.
In addition, PI bonding materials are most commonly classified according to the application form. The application forms can be divided into liquid, paste, powder, film and the like, and all the application forms have respective advantages and disadvantages. For example, the liquid PI bonding material is most commonly applied, has a wide formula and is easy to use; high solvent content, long curing time and easy generation of air holes in an adhesive layer during curing. Powdered PI bonding materials are easy to store, solvent free, precisely metered, but have a low formulation and require mixing and heating to promote curing. The film-shaped PI bonding material has low solvent content, easy shaping, less waste and uniform thickness, but is only limited to plane bonding and the like.
Summarizing, the problems of the existing PI bonding materials mainly include the following two aspects: 1) the existing PI material has poor solubility in organic solvent, and is usually used in the form of a soluble precursor, namely polyamic acid (PAA) in practical application. The solids content of the PAA adhesive is generally less than 30 wt%. Therefore, when the PAA type adhesive is cured at high temperature, the solvent is removed; on the other hand, the high-temperature dehydration and imidization are needed, so that defects such as holes and bubbles are easily formed on the bonding layer, and the bonding strength is further influenced; 2) the solubility of the prior Soluble PI (SPI) resin in an organic solvent is usually lower than 30 wt%, so that the problem of adhesive layer defect caused by volatilization of a large amount of solvent also exists during high-temperature curing of the soluble PI adhesive. Therefore, how to realize solvent-free or less solvation of PI bonding materials has become a hot topic in the research field of high-performance PI bonding materials.
Disclosure of Invention
The first purpose of the invention is to provide a cross-linking type polyimide fiber film-shaped adhesive. The electrospun fiber membrane does not contain or contains a very small amount of solvent, so that the defect of an adhesive film caused by solvent volatilization can be avoided during high-temperature bonding, and a high film remaining rate in the bonding process is ensured, so that good bonding strength can be obtained. In addition, the micro-structural and macro-structural characteristics of the superfine fiber membrane are analyzed to find that the material has the structural characteristics of high specific surface area, high entanglement, high flexibility, no solvent and the like, and the structural characteristics are required by the bonding material.
Therefore, according to the technical scheme of the invention, the bonding material with high bonding strength and high temperature resistance is prepared by combining the electrostatic spinning preparation process and relying on the structural characteristics of the polyimide fiber membrane, and the defect of large solvent amount of the PI bonding material in the prior art is overcome.
In addition, the crosslinkable polyimide fiber film-shaped adhesive provided by the invention is prepared by taking phenylethynyl terminated soluble polyimide resin solution as a raw material and then performing an electrostatic spinning process. The phenylethynyl terminated soluble polyimide resin is prepared by polymerization reaction of an aromatic dianhydride monomer containing a flexible group, an aromatic diamine monomer containing a phenolphthalein structure and a terminating agent containing phenylethynyl.
The polyimide fiber film-shaped adhesive prepared by the technical scheme of the invention can be gradually melted in the temperature rise process, the melt viscosity is obviously reduced, and further the adhesion of samples such as stainless steel and the like can be realized. When the temperature reaches the crosslinking temperature (360-370 ℃) of phenylethynyl, the polyimide adhesive undergoes thermal crosslinking reaction, and a network structure is formed inside the molecular structure, so that good bonding performance is realized.
In a preferred embodiment of the present invention, the aromatic dianhydride monomer having a flexible group is 3,3',4,4' -diphenyl ether tetracarboxylic dianhydride (ODPA) or 2,3,3',4' -diphenyl ether tetracarboxylic dianhydride (aODPA);
the aromatic diamine monomer containing the phenolphthalein structure is 3, 3-bis [4- (4-aminophenoxy) phenyl ] phthalide (BAPPT);
the end capping agent containing phenylethynyl is 4-phenylethynyl phthalic anhydride (PEPA).
In a preferred embodiment of the present invention, the polyimide is a compound represented by the following structural formula I:
in the general structural formula of the formula I, X is
In the structural general formula of the formula I, R is1is-H or-CF3；
N is an integer of 0-100 and is not 0;
in the structural general formula I, the design molecular weight of the polyimide is 2500 g/mol-20000 g/mol.
The second object of the present invention is to provide a method for preparing the polyimide fiber film-like adhesive. The method takes polyimide resin with a structure shown in formula I as a raw material, and the polyimide resin is dissolved in a polar solvent to prepare a solution with certain solid content. And preparing the fiber film-shaped adhesive by adopting an electrostatic spinning process.
The preparation method of the polyimide fiber film-shaped adhesive comprises the following steps:
1) dissolving an aromatic diamine monomer containing a phenolphthalein group in an aprotic strong polar solvent, forming a homogeneous solution under stirring, adding an aromatic dianhydride monomer containing a flexible group and a 4-phenylethynyl phthalic anhydride compound serving as a capping agent, and carrying out polymerization reaction for a period of time at a certain temperature to obtain a polyamic acid (PAA) solution;
2) adding methylbenzene and isoquinoline into the PAA solution, heating to react, and then carrying out dehydration and imidization to obtain a soluble polyimide solution;
3) precipitating the soluble polyimide solution in absolute ethyl alcohol to obtain polyimide resin;
4) and dissolving the polyimide resin in an organic solvent to obtain a polyimide solution, and preparing the polyimide fiber membrane adhesive at a certain voltage by using an electrostatic spinning technology.
In a preferred embodiment of the present invention, the aprotic strongly polar solvent in step 1) is selected from at least one of N-methylpyrrolidone (NMP), m-cresol, dimethyl sulfoxide (DMSO), γ -butyrolactone, preferably NMP;
the electrostatic spinning technical parameters in the step 4) are as follows: the inner diameter of the spinneret is 0.21-0.50 mm; applying positive voltage of 12-20 kV; the negative high voltage is-5-0 kV; the push injection speed is 0.1 mL/h; the distance between the spinneret plate and the receiving device is 10-20 cm; the relative humidity was 30. + -. 10%.
The invention also aims to provide the application of the polyimide fiber or the preparation method of the polyimide fiber in personal protective articles, microelectronics, optoelectronics or wearable electronic products;
one typical application is illustrated by the bonding of stainless steel coupons; the specific application steps are as follows:
1) overlapping the polyimide fiber film-shaped adhesive to a required thickness, then placing the polyimide fiber film-shaped adhesive at the overlapping part of two stainless steel adherends, and fixing the polyimide fiber film-shaped adhesive by adopting a clamp;
2) two stainless steel adherends are placed in a high-temperature press for bonding treatment. The bonding pressure is as follows: 0-5 MPa, preferably: 0.1-0.5 Mpa, and the bonding temperature is as follows: 280-400 ℃, preferably: the temperature is 370-390 ℃, and the bonding time is as follows: 1-3 min, preferably: 0.5-2 min.
The polyimide fiber film adhesive provided by the invention is a solvent-free adhesive. The adhesive material has excellent heat resistance stability and good adhesive strength to metal adherends such as stainless steel. The polyimide fiber film adhesive can be applied to the high-technology fields of aviation, aerospace, photoelectron, microelectronics, automobiles and the like.
Drawings
FIG. 1 is an infrared (FT-IR) spectrum of a PI fiber film adhesive.
Fig. 2 is a Scanning Electron Microscope (SEM) image of the PI fiber film-shaped adhesive.
Fig. 3 is a TGA spectrum of a PI fiber film adhesive.
FIG. 4 is a DSC chart of PI fiber film adhesive.
Fig. 5 is a rheological test spectrum of the PI fiber film-shaped adhesive.
Fig. 6 is a change in the microscopic morphology of the PI fiber film adhesive with increasing heating temperature (SEM).
FIG. 7 shows the single lap tensile shear strength test results of PI fiber film adhesive bonding stainless steel sample sheets; wherein, 7a is a dimension chart of the stainless steel sample wafer, and 7b is an LSS test result.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are provided to illustrate the present invention, but are not intended to limit the scope of the present invention.
The method is a conventional method unless otherwise specified. The materials are commercially available from the open literature unless otherwise specified.
The performance evaluation method of the PI fiber film-shaped adhesive obtained in the following examples was as follows:
the microscopic morphology evaluation method of the PI fiber film-shaped adhesive comprises the following steps:
scanning Electron Microscope (SEM): the prepared PI is tested on a JSM-IT300 series scanning electron microscope of JEOL company in Japan, and the accelerating voltage is as follows: 5-20 KV.
Method for evaluating thermal decomposition temperature of PI fiber film adhesive:
thermogravimetric analysis (TGA): the prepared PI was tested on a thermogravimetric analyzer STA8000 of PerkinElmer company, usa, and the rate of temperature rise: 20 ℃/min and nitrogen atmosphere. This test can yield a 5% weight loss temperature (T) for PI5％) And (4) data.
Calorimetric differential scanning analysis (DSC): the prepared PI is tested on a U.S. TA Q100 type calorimetric differential scanner, and the temperature rise speed is as follows: 10 ℃/min, nitrogen atmosphere. This test results in the glass transition temperature (T) of the PIg) And (4) data.
And (3) rheological analysis: the measurement was carried out on an AR2000 rheometer from TA in the USA. A sample plate (diameter: 25 mm; thickness: 1.5. + -. 0.2mm) was first prepared by press-molding a PI resin. During the measurement, the PI discs were loaded into the parallel plates. The top parallel plate oscillates at a fixed angular frequency of 0.5Hz and a fixed strain of 1.0%. Data were collected over the range of 100 ℃ and 400 ℃ with a heating rate of 4 ℃/min. This test allows the melt viscosity data of the PI to be obtained.
The evaluation method of the PI fiber film adhesive bonding stainless steel sample sheet comprises the following steps:
the adhesion of PI fiber film adhesives to stainless steel coupons was evaluated using a single Lap Shear Strength (LSS) test conducted at a 2mm/min pull rate on an Instron 5567 universal mechanical property tester, usa. This test allows LSS data to be obtained for PI bonded stainless steel coupons at 25 deg.C and 200 deg.C.
Example 1 preparation of PI fiber film adhesive from ODPA and BAPPT (design molecular weight M)n＝10000g/mol，n＝6)
A500 mL three-necked flask equipped with a mechanical stirrer, an electric hot bath, a Dean-Stark trap device and a nitrogen port was charged with BAPPT (31.7013g, 63.3mmol) and NMP (190.0g) at room temperature. Stirring under nitrogen gave a homogeneous solution, and ODPA (18.0964g, 58.3mmol) was added to the solution. After stirring under a nitrogen stream for 5 hours PEPA (2.4823g, 10.0mmol) was added, along with additional NMP (19.0g), to control the solids content of the reaction mixture to 20 wt%. The reaction was stirred at room temperature for 14h to yield a polyamic acid (PAA) solution. Toluene (100.0g) and isoquinoline (1.0g) were added thereto. The reaction mixture was heated to 140 ℃ and 145 ℃ and the water by-product of the reaction was removed via a toluene/water azeotrope, maintaining the reflux dehydration reaction for 16 h. Then, the temperature was further raised to 180 ℃ and the residual toluene was distilled out of the reaction system until the internal temperature reached 180 ℃. The reaction was maintained at 180 ℃ for 1h and then cooled to 70 ℃. The resulting viscous solution was precipitated into an excess of aqueous ethanol (10 wt%). The precipitated PI resin was dried at room temperature for 24 hours and then further dried in vacuo at 130 ℃ for 24 hours. PI resin was obtained as light brown short filaments.
The fully dried PI resin was dissolved in freshly distilled N, N-dimethylacetamide (DMAc) at a solids content of 46.5 wt%. Standing to obtain a PI solution with the viscosity of 8000mPa s. Then, the obtained PI solution was added to a 10mL syringe equipped with a needle spinneret having an inner diameter of 0.21 mm. A positive voltage of 16kV and a negative voltage of-3 kV was applied between the syringe and the collector. The PI solution was sprayed through the spinneret using a syringe pump at a speed of 0.1 mm/min. A grounded rotating drum collector (diameter: 10 cm; length: 30cm) was placed at a 15cm distance from the spinneret. The humidity in the electrospinning apparatus was controlled to 50. + -. 2% relative humidity. The rotational speed of the collector was set at 2 rpm. The PI fibers were deposited on aluminum foil attached to the receiver surface. The obtained PI fiber membrane was dried in vacuum at 120 ℃ for 1h to obtain the final pale yellow fiber membrane-shaped adhesive.
The infrared spectrum test is shown in figure 1;
the scanning electron microscope test is shown in the attached figure 2;
TGA spectrum is shown in figure 3;
the DSC spectrum is shown in figure 4;
the rheological spectrum is shown in figure 5;
the SEM image of the microstructure of the fiber membrane with the change of temperature is shown in the attached FIG. 6.
The polyimide fiber film adhesive is applied to the adhesion test of a stainless steel sample sheet. The stainless steel sample piece had dimensions of 100mm (length) x 25.4mm (width) x 2mm (thickness). The PI fiber film-shaped adhesive is cut into sample pieces with the size of 12.5mm (length) multiplied by 25.4mm (width), and then the sample pieces are overlapped until the thickness reaches 0.3-0.5 mm. The laminated PI fiber film was then placed on the bonding site of two stainless steel sample sheets with an overlap dimension of 12.5mm (length) by 25.4mm (width). Then the stainless steel sample piece is placed in a high-temperature press for bonding treatment. The bonding pressure is as follows: 0.5 MPa. The bonding temperature is as follows: the bonding time is as follows at 370 ℃: for 1 min. After cooling to room temperature, the single lap tensile shear strength (LSS) was tested.
The dimensions of the stainless steel coupons are shown in figure 7a.
The LSS test results are shown in fig. 7b.
The properties of the PI fiber film adhesives are listed in table 1.
Example 2 preparation of PI fiber film adhesive from ODPA and BAPPT (design molecular weight M)n＝20000g/mol，n＝25)
The preparation method of the PI fiber film adhesive is the same as that in example 1, except that the dosage of ODPA, BAPPT and PEPA are respectively as follows: ODPA (19.0584g, 61.4mmol), BAPPT (32.0022g, 63.9mmol) and PEPA (0.6206g, 2.5 mmol). NMP was used in an amount of 200 g.
The infrared spectrum test is shown in figure 1;
the scanning electron microscope test is shown in figure 2;
TGA spectrum is shown in figure 3;
the DSC spectrum is shown in figure 4;
the rheological spectrum is shown in figure 5;
the SEM image of the microscopic morphology of the fiber membrane along with the temperature change is shown in the attached figure 6;
the dimensions of the stainless steel coupons are shown in figure 7a.
The LSS test results are shown in fig. 7b.
The properties of the PI fiber film adhesives are listed in table 1.
Comparative example 1 preparation of PI fiber film adhesive from ODPA and BAPPT (molecular weight not controlled)
A500 mL three-necked flask equipped with a mechanical stirrer, an electric hot bath, a Dean-Stark trap device and a nitrogen inlet and outlet was charged with BAPPT (31.7013g, 63.3mmol) and NMP (205.0g) at room temperature. Stirring under nitrogen gave a homogeneous solution, and ODPA (19.6369g, 63.3mmol) was added to the solution. After stirring under a nitrogen stream for 15 hours, a polyamic acid (PAA) solution was produced. Toluene (100.0g) and isoquinoline (1.0g) were added thereto. The reaction mixture was heated to 140 ℃ and 145 ℃ and the water by-product of the reaction was removed via a toluene/water azeotrope, maintaining the reflux dehydration reaction for 16 h. Then, the temperature was further raised to 180 ℃ and the residual toluene was distilled out of the reaction system until the internal temperature reached 180 ℃. The reaction was maintained at 180 ℃ for 1h and then cooled to 70 ℃. The resulting viscous solution was precipitated into an excess of aqueous ethanol (10 wt%). The precipitated PI resin was dried at room temperature for 24 hours and then further dried in vacuo at 130 ℃ for 24 hours. PI resin was obtained as light brown short filaments.
The fully dried PI resin was dissolved in freshly distilled N, N-dimethylacetamide (DMAc) at a solids content of 21.5 wt%. Standing to obtain a PI solution with the viscosity of 8000mPa s. Then, the obtained PI solution was added to a 10mL syringe equipped with a needle spinneret having an inner diameter of 0.21 mm. A positive voltage of 16kV and a negative voltage of-3 kV was applied between the syringe and the collector. The PI solution was sprayed through the spinneret using a syringe pump at a speed of 0.1 mm/min. A grounded rotating drum collector (diameter: 10 cm; length: 30cm) was placed at a 15cm distance from the spinneret. The humidity in the electrospinning apparatus was controlled to 50. + -. 2% relative humidity. The rotation speed of the collector was set at 2 rpm. The PI fibers were deposited on aluminum foil attached to the receiver surface. The obtained PI fiber membrane is dried for 1h in vacuum at 120 ℃ to obtain the final fiber membrane-shaped adhesive.
The polyimide fiber film adhesive is applied to the adhesion test of a stainless steel sample sheet. The stainless steel sample piece had dimensions of 100mm (length) x 25.4mm (width) x 2mm (thickness). The PI fiber film-shaped adhesive is cut into sample pieces with the size of 12.5mm (length) multiplied by 25.4mm (width), and then the sample pieces are overlapped until the thickness reaches 0.3-0.5 mm. The laminated PI fiber film was then placed on the bonding site of two stainless steel sample sheets with an overlap dimension of 12.5mm (length) by 25.4mm (width). Then the stainless steel sample piece is placed in a high-temperature press for bonding treatment. The bonding pressure is as follows: 0.5 MPa. The bonding temperature is as follows: the bonding time is as follows at 370 ℃: for 1 min. After cooling to room temperature, the single lap tensile shear strength (LSS) was tested.
The dimensions of the stainless steel coupons are shown in figure 7a.
The LSS test results are shown in fig. 7b.
The properties of the PI fiber film adhesives are listed in table 1.
Comparative example 2 preparation of Polyamic acid (PAA) adhesive (without control of molecular weight) from ODPA and BAPPT
A500 mL three-necked flask equipped with a mechanical stirrer, an electric hot bath, a Dean-Stark trap device and a nitrogen inlet and outlet was charged with BAPPT (31.7013g, 63.3mmol) and NMP (205.0g) at room temperature. Stirring under nitrogen gave a homogeneous solution, and ODPA (19.6369g, 63.3mmol) was added to the solution. After stirring for 15 hours under a nitrogen stream, a polyamic acid (PAA) solution was formed with a test appendage content of 20 wt%.
The PAA adhesive is applied to the bonding test of stainless steel sample pieces. The stainless steel sample piece had dimensions of 100mm (length) x 25.4mm (width) x 2mm (thickness). The PAA adhesive was uniformly applied to the bonding portions of two stainless steel sample pieces, and the overlapping dimension was 12.5mm (length) × 25.4mm (width). And then placing the stainless steel sample piece in a high-temperature press for bonding treatment. The bonding pressure is as follows: 0.5 MPa. The bonding temperature is as follows: the bonding time is 370 ℃ as follows: for 1 min. After cooling to room temperature, the single lap tensile shear strength (LSS) was tested.
The properties of the PAA adhesive are listed in Table 1.
TABLE 1 index Properties of polyimide fiber film-like adhesive
Summarizing the data in Table 1, one can seeThe PI fiber film adhesives prepared in examples 1 and 2 have excellent overall properties including a high 5% weight loss temperature and TgValue and excellent bond strength to stainless steel, whether tested at room temperature or at high temperatures of 200 ℃. In contrast, the PI fiber film-shaped adhesive prepared in example 2 has a relatively low alkynyl content in the molecular structure, so the crosslinking density is lower than that of example 1, and the adhesion to stainless steel is slightly lower than that of example 1. The PI fiber film-shaped adhesive prepared in the comparative example 1 does not adopt phenylethynyl for end capping, so a cross-linked network cannot be formed at high temperature, and the bonding strength to stainless steel is obviously lower than that of the PI fiber film-shaped adhesive prepared in the examples 1 and 2. Comparative example 2 employs PAA having a high solvent content as an adhesive, and a large amount of solvent is volatilized during curing, causing a defect that a bonding area has many defects, and thus the bonding strength to stainless steel is low.
In addition, the fiber film-shaped adhesives prepared in examples 1 and 2 can be stored at 25 ℃ for more than 36 months without change in properties. However, the PAA adhesive prepared in comparative example 2 has a storage life of only 3 months at 25 ℃, and the PAA viscosity is significantly reduced beyond the storage life, so that the PAA adhesive cannot be applied to subsequent bonding operation.
Therefore, the comprehensive performance of the fiber film-shaped adhesive prepared by the soluble PI containing the phenylethynyl end group is the best, and the fiber film-shaped adhesive is superior to the polyimide adhesive in the prior art, and the embodiment has good industrial prospect.
Finally, the method of the present invention is only a preferred embodiment, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A polyimide fiber film-shaped adhesive is characterized in that a soluble polyimide resin solution terminated with phenylethynyl is used as a raw material and is prepared by an electrostatic spinning process;
the phenylethynyl-terminated soluble PI resin is prepared by polymerization reaction of an aromatic dianhydride monomer containing a flexible group, an aromatic diamine monomer containing a phenolphthalein structure and a phenylethynyl-containing terminating agent;
wherein the aromatic dianhydride monomer containing the flexible group is 3,3',4,4' -diphenyl ether tetracarboxylic dianhydride (ODPA) or 2,3,3',4' -diphenyl ether tetracarboxylic dianhydride (aODPA);
the aromatic diamine monomer containing the phenolphthalein structure is 3, 3-bis [4- (4-aminophenoxy) phenyl ] phthalide (BAPPT);
the end capping agent containing phenylethynyl is 4-phenylethynyl phthalic anhydride (4-PEPA);
the polyimide is a compound shown as the structural general formula of the following formula I:
formula I
In the general structural formula of the formula I, X is
Or
；
In the structural general formula of the formula I, R is1is-H or-CF3；
N is an integer of 0 to 100, andnis not 0;
in the structural general formula I, the design molecular weight of polyimide is 2500-20000 g/mol.
2. The method for preparing the polyimide fiber film-like adhesive according to claim 1, comprising the steps of:
1) dissolving an aromatic diamine monomer containing a phenolphthalein group in an aprotic strong polar solvent, forming a homogeneous solution under stirring, adding an aromatic dianhydride monomer containing a flexible group and a 4-phenylethynyl phthalic anhydride compound, and performing polymerization reaction to obtain a phenylethynyl terminated polyamide acid (PAA) solution;
2) adding methylbenzene and isoquinoline into the PAA solution, heating to react, and then carrying out dehydration and imidization to obtain a soluble polyimide solution;
3) precipitating the soluble polyimide solution in absolute ethyl alcohol to obtain polyimide resin;
4) and dissolving the polyimide resin in an organic solvent to obtain a polyimide solution, and preparing the polyimide fiber film adhesive at a certain voltage by an electrostatic spinning technology.
3. The method of claim 2, wherein the aprotic highly polar solvent in step 1) is at least one selected from the group consisting of N-methylpyrrolidone (NMP), m-cresol, dimethyl sulfoxide (DMSO), and γ -butyrolactone.
4. The method according to claim 3, wherein the aprotic highly polar solvent in step 1) is N-methylpyrrolidone (NMP).
5. The method for preparing according to any one of claims 2 to 4, wherein the technical parameters of electrostatic spinning in step 4) are as follows: the inner diameter of the spinneret is 0.21-0.50 mm; applying positive voltage of 12-20 kV; the negative high voltage is-5-0 kV; the push injection speed is 0.1 mL/h; the distance between the spinneret plate and the receiving device is 10-20 cm; the relative humidity was 30. + -. 10%.
6. Use of the polyimide fiber film adhesive of claim 1 in aerospace, personal protective, microelectronics, optoelectronics, or wearable electronics.
7. The application of the polyimide fiber film-shaped adhesive in the bonding of stainless steel sample sheets according to claim 1 comprises the following specific application steps:
1) overlapping the polyimide fiber film-shaped adhesive to a required thickness, then placing the polyimide fiber film-shaped adhesive at the overlapping part of two stainless steel adherends, and fixing the polyimide fiber film-shaped adhesive by adopting a clamp;
2) placing two stainless steel adherends in a high-temperature press for bonding treatment, wherein the bonding pressure is as follows: 0-5 MPa; the bonding temperature is as follows: 280-400 ℃; the bonding time is as follows: 1-3 min.
8. The use of the polyimide fiber film adhesive of claim 7 for bonding stainless steel sample sheets, wherein in the step 2), the bonding pressure is as follows: 0.1-0.5 Mpa; the bonding temperature is as follows: 370-390 ℃; the bonding time is as follows: 1-2 min.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999062989A1 (en) * | 1998-05-29 | 1999-12-09 | The Government Of The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration (Nasa) | Films, preimpregnated tapes and composites made from polyimide 'salt-like' solutions |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO1999062989A1 (en) * | 1998-05-29 | 1999-12-09 | The Government Of The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration (Nasa) | Films, preimpregnated tapes and composites made from polyimide 'salt-like' solutions |
Non-Patent Citations (3)
| Title |
|---|
| 含酚酞基团的聚酰亚胺膜材料的合成与性能;鲁云华等;《高分子学报》;20160630;第832页第2、3部分，第834页第6部分，第835页第8部分 * |
| 苯乙炔基封端聚酰亚胺材料研究进展;陈建升等;《高分子通报》;20061031;第36页引言部分，第39页第2段，第41页第3段，第42页第6段 * |
| 静电纺丝法制备聚酰亚胺新型材料;龚光明等;《化学进展》;20110430;第751页 * |
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