CN112980024A - Fiber fabric reinforced polyaryletherketone resin-based prepreg, and preparation method and application thereof - Google Patents

Fiber fabric reinforced polyaryletherketone resin-based prepreg, and preparation method and application thereof Download PDF

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CN112980024A
CN112980024A CN202110200177.6A CN202110200177A CN112980024A CN 112980024 A CN112980024 A CN 112980024A CN 202110200177 A CN202110200177 A CN 202110200177A CN 112980024 A CN112980024 A CN 112980024A
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fiber
polyaryletherketone
resin
fiber fabric
solution
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CN112980024B (en
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杨砚超
施霁瑶
王贵宾
张淑玲
张梅
栾加双
王晟道
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Jilin University
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass

Abstract

The invention belongs to the technical field of resin-based composite materials, and particularly relates to a fiber fabric reinforced polyaryletherketone resin-based prepreg, a preparation method and application thereof, wherein the preparation method of the reinforced polyaryletherketone resin-based prepreg comprises the following steps: impregnating a soluble polyaryletherketone precursor polymer solution on the surface of a fiber fabric in a brushing and/or spraying manner, and then hydrolyzing, washing with deionized water, heating and drying to obtain a fiber fabric reinforced polyaryletherketone resin-based prepreg; the invention also provides the application of the fiber fabric reinforced polyaryletherketone resin-based prepreg in the preparation of the fiber fabric reinforced polyaryletherketone resin-based composite material connecting piece, and the composite material prepreg obtained by adopting a solution impregnation mode ensures the full infiltration of the resin matrix and the reinforcing fibers; the prepreg production process does not need high-temperature setting, can realize in-situ curing and forming with other resin-based composite materials, and the provided manufacturing method is simple to implement and can be used for industrial production.

Description

Fiber fabric reinforced polyaryletherketone resin-based prepreg, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of resin-based composite materials, and particularly relates to a fiber fabric reinforced polyaryletherketone resin-based prepreg, and a preparation method and application thereof.
Background
Resin-based composite materials are widely used in various fields due to their advantages such as light weight, excellent mechanical properties, designability, etc. The crystalline polyaryletherketone has excellent thermal stability, chemical stability, solvent resistance and toughness, so that the composite material taking the crystalline polyaryletherketone as the resin matrix is widely applied to various fields of aerospace, ships, military industry, nuclear industry, renewable energy sources and the like. However, the production and application of the fiber fabric reinforced crystalline polyaryletherketone resin-based composite material have the following problems:
a. problems with prepreg production: the crystalline polyaryletherketone is difficult to dissolve in an organic solvent due to excellent chemical stability and solvent resistance, and cannot be formed by solution impregnation, and the melting impregnation temperature of the crystalline polyaryletherketone is too high and is more than 350 ℃; the melt viscosity of the crystalline polyaryletherketone is too high, so that a resin matrix cannot fully infiltrate the surface of the fiber in the processes of powder impregnation and film hot-pressing impregnation, and the interface performance of the composite material is poor;
b. the crystalline polyaryletherketone has stronger chemical stability and lower surface energy, so that the composite material is difficult to form effective connection with other composite materials. Usually, the connection of the crystalline polyaryletherketone resin-based composite material is realized by bonding, the bonding connection mode has low strength, and the molded crystalline polyaryletherketone resin-based composite material needs to be subjected to surface modification, wherein the modification method is to improve the surface chemical energy by means of chemical reaction or plasma surface activation and the like. However, the above method is not only complicated in steps, but also requires the material to be placed in a sealed container (reaction kettle) and immersed in a solution or a turbid solution, and is difficult to prepare and connect large-sized parts or parts at special positions.
Therefore, how to solve the technical problems in the prepreg production process such as crystalline polyaryletherketone resin melt impregnation, powder impregnation and the like is one of the problems to be solved urgently in realizing the industrialization of the fiber reinforced crystalline polyaryletherketone resin matrix composite; how to improve the surface performance of the crystalline polyaryletherketone resin-based composite material to form stable connection with other resin-based composite materials and realize industrial production is the second difficult problem which needs to be solved urgently.
Disclosure of Invention
The invention aims to provide a forming method for dipping a soluble polyaryletherketone precursor polymer solution on the surface of a fiber fabric in a brushing and/or spraying mode and converting the fiber fabric surface into a crystalline polyaryletherketone composite prepreg through a hydrolysis process. The solution impregnation overcomes the defect of large melt viscosity of the polyaryletherketone, and solves the problem of poor interface performance of the composite material; the requirements of the painting and spraying processes on the technical level of operators are low, the hydrolysis process can be carried out in general industrial equipment, and the practicability of the invention is ensured; the method has the advantages that the non-impregnated area or the area with low resin content can be formed on the surface of the composite material by utilizing the characteristic of flexible operation in the brushing and spraying processes, the non-impregnated area is fully reserved in the hot press molding process by utilizing the characteristic of high viscosity of the crystalline polyaryletherketone resin, secondary impregnation is carried out on the area by using other resin matrixes by utilizing the characteristic of solvent resistance of the crystalline polyaryletherketone, secondary curing is realized by utilizing the characteristic of high thermal stability of the crystalline polyaryletherketone, and the composite material connecting piece can be successfully prepared. The method is easy to implement, not only solves the production problem of the fiber fabric reinforced polyaryletherketone, but also can prepare the connecting piece with strong bonding capability of special parts and other resin matrix composite materials, and widens the application field of the connecting piece.
The invention has simple operation, easy implementation and various products, and provides the fiber fabric reinforced polyether ether ketone (PEEK), polyether ether ketone (PEEKK), total biphenyl polyether ether ketone (PEDEK), total biphenyl polyether ether ketone (PEDEKK) and total biphenyl polyether ether ketone biphenyl ketone (PEDEKDK) resin-based composite material and a method for connecting the composite material with other resin-based composite materials. The invention provides a fiber fabric reinforced polyaryletherketone resin-based prepreg, and a preparation method thereof comprises the following steps:
(1) adding soluble precursor polyaryletherketone into organic solvent, and stirring to obtain the final product with density of 0.7-2.0g/cm3The polyaryletherketone solution of (1);
(2) after the polyaryletherketone solution obtained in the step (1) is used for brushing and/or spraying the surface of a fiber fabric, heating and drying, hydrolyzing with a protonic acid-water-organic solvent, washing with deionized water, heating and drying to obtain a fiber fabric reinforced polyaryletherketone resin-based prepreg, wherein the brushing is full brushing or partial brushing; the fiber volume content in the prepreg is 50% -75%, and the fiber fabric reinforced polyaryletherketone resin based prepreg is prepared by completely impregnating a fiber fabric reinforced polyaryletherketone resin based prepreg with a polyaryletherketone solution or incompletely impregnating a fiber fabric reinforced polyaryletherketone resin based prepreg with a polyaryletherketone solution; the polyaryletherketone solution incompletely impregnates the fiber fabric reinforced polyaryletherketone resin-based prepreg, which consists of a polyaryletherketone solution impregnated fiber fabric part and a polyaryletherketone solution non-impregnated fiber fabric part; the volume content of the resin of the part of the fiber fabric which is not impregnated with the polyaryletherketone solution is less than or equal to 5 percent.
Further, the soluble precursor polyaryletherketone in step (1) is one of ketimine type polyetheretherketone, hemiketal type polyetheretherketone, ketimine type all biphenyl type polyetheretherketone, hemiketal type all biphenyl type polyetheretherketone, ketimine type all biphenyl type polyetheretherketone or hemiketal type all biphenyl type polyetheretherketone, and the structural formula is as follows in sequence:
Figure BDA0002948280100000021
Figure BDA0002948280100000031
further, the organic solvent in the step (1) is any one of tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, dichloromethane, 1, 2-dichloroethane, chloroform, or N-methylpyrrolidone.
Further, the fiber fabric in the step (2) is any one of carbon fiber, glass fiber, basalt fiber, boron nitride fiber, carbon nanotube fiber or graphene fiber; the shape of the fiber fabric is any one of plain weave fabric, twill weave fabric, satin weave fabric and three-dimensional weaving fabric.
Further, the heating and drying temperature in the step (2) is 50-300 ℃, and the time is 3-10 h.
Further, the preparation method of the protonic acid-water-organic solvent in the step (2) comprises the following steps: according to the volume ratio of 1-10: 2-5, mixing protonic acid aqueous solution with the concentration of 1-20mol/L with an organic solvent; the protonic acid is any one of hydrochloric acid, sulfuric acid, methanesulfonic acid, benzenesulfonic acid, trifluoroacetic acid or trifluorobenzene sulfonic acid; the organic solvent is any one of tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone.
Further, the hydrolysis in the step (2) is a brushing hydrolysis method or an acid boiling hydrolysis method, wherein the brushing hydrolysis method is to brush a mixed solution of protonic acid, water and an organic solvent on the surface of the fiber fabric impregnated with the polyaryletherketone resin; the acid boiling hydrolysis method is characterized in that the fiber fabric impregnated with the polyaryletherketone resin is immersed in a mixed solution of protonic acid, water and an organic solvent and hydrolyzed at the temperature of 50-150 ℃.
Further, the hydrolysis time in the step (2) is 6-15 h.
The invention also provides an application of the fiber fabric reinforced polyaryletherketone resin-based prepreg in the preparation of a fiber fabric reinforced polyaryletherketone resin-based composite material connecting piece, which comprises the following steps:
(1) laying a reinforced polyaryletherketone resin-based prepreg which is prepared by completely impregnating a fiber fabric with a polyaryletherketone solution and/or a reinforced polyaryletherketone resin-based prepreg which is prepared by incompletely impregnating a fiber fabric into a mold, carrying out mold pressing at 550 ℃ under vacuum of 350-10 MPa for 10-25min, cooling to room temperature at 10-25 ℃/min, and demolding to obtain a reinforced polyaryletherketone resin-based composite material which is prepared by completely or incompletely impregnating a fiber fabric with a polyaryletherketone solution, wherein the fiber volume content of the composite material is 60-75%;
(2) fully soaking the part, which is not soaked in the polyaryletherketone solution, of the reinforced polyaryletherketone resin-based prepreg, of the fiber fabric, which is not completely soaked in the step (1), in a resin-tetrahydrofuran solution, and drying, curing and molding to obtain a connector of the polyaryletherketone fiber composite material and the resin-based composite material; the resin is isocyanate, epoxy resin or phenolic resin; the curing molding is hot-press molding or non-hot-press molding.
Further, the polyaryletherketone fiber composite material obtained in the step (2) and the connecting piece of the resin-based composite material are directly subjected to resin transfer molding or are matched with fibers to be connected to be subjected to resin transfer molding together.
The advantages of the invention are as follows:
1. the invention provides a preparation method of a fiber fabric reinforced PEEK, PEEKK, PEDEK, PEDEKK and PEDEKDK resin-based prepreg, a resin-based prepreg composite material and a connecting piece formed by compounding the resin-based prepreg composite material with other materials;
2. the manufacturing method provided by the invention is simple to implement and can be used for industrial production;
3. the composite material prepreg is obtained by adopting a solution impregnation mode, so that the full infiltration of the resin matrix and the reinforced fibers is ensured;
4. the prepreg production process provided by the invention does not need high-temperature shaping, so that the equipment and equipment operation cost are reduced;
5. the reinforced fiber fabric reinforced PEEK, PEEKK, PEDEK, PEDEKK and PEDEKDK composite material connector provided by the invention can realize effective connection with other resin-based composite materials without additional surface treatment, and can realize in-situ curing molding with other resin-based composite materials, so that the operation procedures are reduced, and the connection cost is reduced;
6. the reinforced fiber fabric reinforced PEEK, PEEKK, PEDEK, PEDEKK and PEDEKDK composite material connector disclosed by the invention does not need an additional adhesive layer when being connected with other resin matrix composite materials, and other components except two resin matrix materials are not introduced, so that the connection quality is ensured.
Drawings
FIG. 1 shows the chemical structure of soluble precursor polyaryletherketone;
fig. 2 is a schematic diagram of the preparation process of the fiber fabric reinforced resin-based (PEEK, PEEKK, PEDEK, PEDEKK or PEDEKDK) composite material and the composite material and other resin-based composite connectors.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention.
Example 1:
(1) dissolving ketimine type polyether ether ketone (KI-PEEK) in Tetrahydrofuran (THF) under high speed stirring to obtain a solution with a density of 0.987g/cm3The polymer solution of (4);
(2) brushing the surface of the carbon fiber plain woven fabric with the polymer solution obtained in the step (1) in a unidirectional manner by using a polypropylene brush, brushing the surface of the carbon fiber plain woven fabric from a first brushing end point by using the polymer solution dipped by using the brush until the first brushing start point is reached, and drying the carbon fiber plain woven fabric brushed with the polymer solution at 120 ℃ for 5 hours to obtain a KI-PEEK carbon fiber plain woven fabric;
(3) mixing hydrochloric acid aqueous solution with the concentration of 1mol/L and THF according to the volume ratio of 1:10 to obtain protonic acid-water-organic solvent mixed solution, spraying the mixed solution on the carbon fiber plain woven fabric obtained in the step (2), performing hydrolysis treatment for 12 hours, washing with deionized water, and drying to obtain PEEK carbon fiber plain woven fabric A type prepreg, wherein the fiber volume content in the prepreg is 55%;
(4) cutting the A-type prepreg obtained in the step (3) into a plurality of layers according to the required size, sequentially paving the layers in a mould, carrying out mould pressing at the vacuum temperature of 380 ℃ and under the pressure of 5MPa for 10min, then cooling to the room temperature at the speed of 10 ℃/min, and demoulding to obtain the PEEK carbon fiber plain woven fabric A-type composite material, wherein the fiber volume content in the composite material is 60%. The PEEK carbon fiber plain weave A-type composite material has the interlaminar shear strength of 61MPa and can be used for a long time at 270 ℃.
Example 2:
(1) 88.56g of ketimine-type polyether ether ketone (KI-PEEK) was dissolved in 208mL of THF under high-speed stirring to prepare a solution having a density of 1.187g/cm3221mL of the polymer solution (A);
(2) spraying the polymer solution obtained in step (1) along a non-overlapping path onto a fiber having a volume of 113cm3After the surface of the carbon fiber plain woven fabric is completely sprayed on the surface of the fabric, drying the fabric at 120 ℃ for 5 hours to obtain the KI-PEEK carbon fiber plain woven fabric;
(3) mixing 10mol/L trifluoroacetic acid aqueous solution and N, N-Dimethylformamide (DMF) according to the volume ratio of 2:5 to obtain protonic acid-water-organic solvent mixed solution, spraying the mixed solution on the surface of the KI-PEEK carbon fiber plain woven fabric obtained in the step (2), performing hydrolysis treatment for 12 hours, washing with deionized water, and drying to obtain PEEK carbon fiber plain woven fabric A-type prepreg, wherein the fiber volume content in the prepreg is 65%;
(4) cutting the A-type prepreg obtained in the step (3) into a plurality of layers according to the required size, sequentially paving the layers in a mould, carrying out mould pressing for 25min in a vacuum environment of 380 ℃ and 10MPa, then cooling to room temperature at 15 ℃/min, and demoulding to obtain the PEEK carbon fiber plain woven fabric A-type composite material, wherein the fiber volume content in the composite material is 70%. The PEEK carbon fiber plain weave A-type composite material has the interlaminar shear strength of 61MPa and can be used for a long time at 270 ℃.
Example 3:
(1) 79.70g of ketimine-type polyether ether ketone (KI-PEEK) was dissolved in THF under high-speed stirring to prepare a solution having a density of 1.187g/cm3The polymer solution of (4);
(2) 0.1m2The stainless steel plate was placed in a fiber volume of 113cm3Spraying the polymer solution obtained in the step (1) on the surface of the fiber fabric covered by the stainless steel plate along a non-overlapping path at the center of the surface of the carbon fiber plain fabric, and drying for 5 hours at 120 ℃ after the surface of the fabric is completely sprayed to obtain the KI-PEEK carbon fiber plain fabric;
(3) mixing a 15mol/L sulfuric acid aqueous solution and N, N-dimethylacetamide (DMAc) according to a volume ratio of 2:5 to obtain a protonic acid-water-organic solvent mixed solution, quickly immersing the KI-PEEK carbon fiber plain woven fabric obtained in the step (2) into the protonic acid-water-organic solvent mixed solution, heating to 100 ℃ for 8 hours, washing with deionized water, and drying to obtain a PEEK carbon fiber plain woven fabric B-type prepreg, wherein the volume content of fibers in a fully-impregnated polymer area in the prepreg is 65%, and the volume content of fibers in an uninimpregnated polymer area (a part of a stainless steel plate covering the carbon fiber plain woven fabric) is less than or equal to 5%;
(4) stacking 4B-type prepregs obtained in the step (3), placing the stacked prepregs in a mold, performing mold pressing for 10min at the vacuum temperature of 380 ℃ and under the pressure of 5MPa, cooling to room temperature at the speed of 10 ℃/min, and demolding to obtain a PEEK carbon fiber plain woven fabric connector blank, wherein the fiber volume content of a fully-impregnated polymer area is 70%;
(5) 84mL of a solution having a density of 1.187g/cm3And (3) fully soaking the area, which is not soaked with the polymer, of the PEEK carbon fiber plain woven fabric connecting piece blank obtained in the step (4) by using the epoxy resin-THF solution, and curing by using a drying and autoclave process to obtain the connecting piece of the KI-PEEK carbon fiber plain woven fabric composite material and the epoxy resin matrix composite material, wherein the epoxy resin area of the connecting piece can be used for bonding the epoxy resin matrix composite material or directly curing the epoxy resin matrix composite material with the surface of the connecting piece.
Example 4:
(1) dissolving ketimine type polyether ether ketone (KI-PEEK) in T under high-speed stirring conditionHF prepared at a density of 1.187g/cm3The polymer solution of (4);
(2) 0.1m2The stainless steel plate was placed in a fiber volume of 113cm3Coating the carbon fiber plain woven fabric outside the stainless steel plate cover in a unidirectional non-overlapping manner after dipping the polymer solution obtained in the step (1) by using a polypropylene brush, then coating the polymer solution again by using the brush from the first coating end point to the first coating starting point, and drying for 5 hours at 120 ℃ to obtain the KI-PEEK fiber fabric;
(3) mixing a methanesulfonic acid aqueous solution with the concentration of 15mol/L and N-methylpyrrolidone (NMP) according to the volume ratio of 2:5 to obtain a methanesulfonic acid-water-NMP solution, fully stirring to obtain a protonic acid-water-organic solvent mixed solution for a hydrolysis process, quickly immersing the KI-PEEK fiber fabric obtained in the step (2) into the methanesulfonic acid-water-NMP mixed solution, heating to 100 ℃ for 8 hours, washing with deionized water, and drying to obtain a B-type prepreg of carbon fiber plain fabric reinforced PEEK, wherein the fiber volume content of a fully-impregnated polymer area in the prepreg is 65%, and the fiber volume content of an unimpregnated polymer area is less than or equal to 5%;
(4) 2 pieces of the B-type prepreg obtained in the step (3) are laid on the upper surface of 2 pieces of the A-type prepreg obtained in the embodiment 2, then the four pieces of prepreg are laid in a mold, the mold pressing is carried out for 10min under the vacuum environment of 380 ℃ and 5MPa, then the temperature is reduced to the room temperature at 15 ℃/min, and the carbon fiber plain weave fabric reinforced PEEK composite material connecting piece blank is obtained after demolding, wherein the fiber volume content of a fully impregnated area is 70%;
(5) 21mL of a density of 1.187g/cm was used3And (3) fully soaking the non-soaked polymer area of the carbon fiber plain weave fabric reinforced PEEK composite material connecting piece blank obtained in the step (4) by using a phenolic resin-THF solution, and co-curing the carbon fiber plain weave fabric reinforced PEEK composite material blank with a hot pressing process after drying a solvent to obtain the connecting piece of the carbon fiber plain weave reinforced PEEK composite material and the phenolic resin matrix composite material.
Example 5:
(1) 79.70g of ketimine-type polyetheretherketone (KI-PEEK) were dissolved in 187mL of THF with high-speed stirring to prepare a densityIs 1.187g/cm3199mL of the polymer solution (2);
(2) 0.1m2The stainless steel plate was placed in a fiber volume of 113cm3The surface center of the carbon fiber plain woven fabric is prepared by spraying the polymer solution obtained in the step (1) on the surface of the fiber woven fabric covered by the stainless steel plate in a one-way non-overlapping mode, drying the fiber woven fabric at 120 ℃ for 5 hours, and removing 0.1m2After the above-mentioned completely immersed area was covered with a stainless steel plate, 1.05mL of a stainless steel plate having a density of 1.187g/cm3The polymer solution is sprayed on the polymer-unsubmerged area to form a polymer-unsubmerged area, and then dried at 120 ℃ for 5 hours to obtain a KI-PEEK fiber fabric;
(3) mixing benzene sulfonic acid aqueous solution (the concentration is 15mol/L) and DMAc according to the volume ratio of 2:5 to obtain a benzene sulfonic acid-water-DMAc mixed solution, immersing the KI-PEEK fiber fabric obtained in the step (2) into the benzene sulfonic acid-water-DMAc mixed solution, treating at 100 ℃ for 8 hours, washing with deionized water, and drying to obtain a carbon fiber plain fabric reinforced PEEK B type prepreg, wherein the fiber volume content of a fully impregnated area in the B type prepreg is 65%, and the fiber volume content of an insufficiently impregnated polymer area in the B type prepreg is 5%;
(4) sequentially laying 4B-type prepregs obtained in the step (3) in a mould, carrying out mould pressing for 10min at the vacuum temperature of 380 ℃ and under the pressure of 5MPa, then cooling to room temperature at the speed of 10 ℃/min, and demoulding to obtain a carbon fiber plain weave fabric reinforced PEEK composite material connecting piece blank, wherein the fiber volume content of a fully impregnated area is 70%;
(5) 80mL of a solution having a density of 1.187g/cm was used3And (3) fully dipping the insufficient dipping polymer area of the PEEK composite material connecting piece blank obtained in the step (4) by using an isocyanate resin-THF solution, drying the solvent, and curing by using a non-autoclave process to obtain the connecting piece of the carbon fiber plain weave fabric reinforced PEEK composite material and the isocyanate-based composite material, wherein the isocyanate area of the connecting piece can be used for bonding the isocyanate-based composite material or directly curing the isocyanate-based composite material with the surface of the connecting piece.
Example 6:
(1) 79.70g of ketimine were added under high-speed stirringType polyetheretherketone (KI-PEEK) was dissolved in 187mL of THF and prepared to have a density of 1.187g/cm3199mL of the polymer solution (2);
(2) 0.1m2The stainless steel plate was placed in a fiber volume of 113cm3The surface center of the carbon fiber plain woven fabric is prepared by spraying the polymer solution obtained in the step (1) on the surface of the fiber woven fabric covered by the stainless steel plate in a one-way non-overlapping mode, drying the fiber woven fabric at 120 ℃ for 5 hours, and removing 0.1m2After the above-mentioned completely immersed area was covered with a stainless steel plate, 20mL of a stainless steel plate having a density of 1.187g/cm was placed3The polymer solution is sprayed on the area which is not dipped with the polymer, and then dried for 5 hours at the temperature of 120 ℃ to obtain the KI-PEEK fiber fabric;
(3) according to the volume ratio of 2:5, benzene sulfonic acid aqueous solution (the concentration is 15mol/L) and DMAc are mixed to obtain a benzene sulfonic acid-water-DMAc mixed solution, and the mixed solution is fully stirred to obtain a protonic acid-water-organic solvent mixed solution for a hydrolysis process; rapidly immersing the KI-PEEK fiber fabric obtained in the step (2) into a benzenesulfonic acid-water-DMAc mixed solution, processing at 100 ℃ for 8h, washing with deionized water to be neutral, and drying to obtain a B-type prepreg of carbon fiber plain fabric reinforced PEEK, wherein the fiber volume content of a fully-impregnated area in the prepreg is 65%, and the fiber volume content of an insufficiently-impregnated polymer area is 60%;
(4) sequentially paving 4B-type prepregs obtained in the step (3) in a mould, carrying out mould pressing for 10min at the temperature of 380 ℃ and the pressure of 5MPa in vacuum, cooling to room temperature at the temperature of 10 ℃/min, and demoulding to obtain a carbon fiber plain weave fabric reinforced PEEK composite material connecting piece blank, wherein the fiber volume content of a fully-impregnated polymer area is 70%;
(5) 4.2mL of a density 1.187g/cm were used3And (3) fully soaking the non-soaked polymer area of the carbon fiber plain weave fabric reinforced PEEK composite material connecting piece blank obtained in the step (4) by using a cyanate ester resin-THF solution, drying the solvent to obtain a composite material connecting piece prefabricated body with the surface of which a three-dimensional woven carbon fiber fabric reinforced cyanate ester resin matrix prepreg is laid, and co-curing by using an autoclave process to obtain the connecting piece of the carbon fiber plain weave fabric reinforced PEEK composite material and the cyanate ester resin matrix composite material.
Example 7:
(1) dissolving hemiketal type polyetheretherketone (Dio-PEEK) in DMF under high speed stirring to obtain a solution with a density of 1.045g/cm3The polymer solution of (4);
(2) coating the surface of the glass fiber twill fabric with a polymer solution obtained in the step (1) along a single direction by using a polypropylene brush, coating the surface of the glass fiber twill fabric with the polymer solution by using the brush from a first coating end point until a first coating start point is reached, repeating the processes without overlapping until all the fiber fabric is coated once, and drying the glass fiber twill fabric coated with the polymer solution at 200 ℃ for 5 hours to obtain a Dio-PEEK glass fiber twill fabric;
(3) mixing 1mol/L benzenesulfonic acid aqueous solution and THF according to the volume ratio of 1:10 to obtain protonic acid-water-organic solvent mixed solution, spraying the mixed solution on the Dio-PEEK glass fiber twill fabric obtained in the step (2), performing hydrolysis treatment for 12 hours, washing with deionized water, and drying to obtain a glass fiber twill fabric reinforced PEEK A type prepreg, wherein the fiber volume content in the prepreg is 55%;
(4) cutting the A-type prepreg obtained in the step (3) into a plurality of layers according to the required size, sequentially paving the A-type prepreg in a mould, carrying out mould pressing for 10min in a vacuum 380 ℃ and 5MPa environment, then cooling to room temperature at a speed of 10 ℃/min, and demoulding to obtain the glass fiber twill fabric reinforced PEEK composite material, wherein the fiber volume content in the composite material is 60%. The PEEK glass fiber twill fabric A-type composite material has the interlaminar shear strength of 62MPa and can be used for a long time at 270 ℃.
Example 8:
(1) dissolving ketimine type polyetheretherketon (KI-PEEKK) in DMF under high speed stirring to obtain a solution with a density of 1.245g/cm3The polymer solution of (4);
(2) coating the surface of the basalt fiber satin fabric with the polymer solution obtained in the step (1) in a unidirectional manner by using a polypropylene brush, then coating the surface of the basalt fiber satin fabric with the polymer solution dipped by using the brush from a first coating end point until a first coating starting point is reached, repeating the processes without overlapping until all the fiber fabrics are coated once, and drying the basalt fiber satin fabric coated with the polymer solution at 200 ℃ for 5 hours to obtain a KI-PEEKK basalt fiber satin fabric;
(3) mixing 1mol/L trifluorobenzene sulfonic acid water solution and THF according to the volume ratio of 1:10 to obtain protonic acid-water-organic solvent mixed solution, spraying the mixed solution on the KI-PEEKK fiber fabric obtained in the step (2), performing hydrolysis treatment for 12 hours, washing with deionized water, and drying to obtain basalt fiber satin fabric reinforced PEEKK A-type prepreg with the fiber volume content of 65% in the prepreg;
(4) cutting the A-type prepreg of the basalt fiber satin fabric reinforced PEEKK obtained in the step (3) into a plurality of layers according to the required size, sequentially paving the layers in a mould, carrying out mould pressing at the vacuum temperature of 420 ℃ and the pressure of 5MPa for 10min, then cooling to the room temperature at the speed of 10 ℃/min, and demoulding to obtain the basalt fiber satin fabric reinforced PEEKK composite material, wherein the fiber volume content in the composite material is 70%. The interlaminar shear strength of the PEEKK basalt satin fabric A composite material is 612MPa, and the composite material can be used for a long time at 270 ℃.
Example 9:
(1) dissolving hemiketal polyetheretherketone (Dio-PEEKK) in DMAc under high-speed stirring to obtain a solution with a density of 1.037g/cm3The polymer solution of (4);
(2) coating the surface of the boron nitride fiber three-dimensional woven fabric with the polymer solution obtained in the step (1) along a single direction by using a polypropylene brush, then coating the surface of the boron nitride fiber three-dimensional woven fabric with the polymer solution by using the brush from a first coating end point until a first coating starting point is reached, repeating the processes without overlapping until all the fiber fabrics are coated once, and drying the surface of the boron nitride fiber three-dimensional woven fabric coated with the polymer solution at 210 ℃ for 5 hours to obtain a KI-PEEKK basalt fiber satin fabric;
(3) mixing 1mol/L trifluorobenzene sulfonic acid water solution and THF according to the volume ratio of 1:10 to obtain protonic acid-water-organic solvent mixed solution, spraying the mixed solution on the Dio-PEEKK fiber fabric obtained in the step (2), performing hydrolysis treatment for 12 hours, washing with deionized water, and drying to obtain a class A prepreg of boron nitride fiber three-dimensional woven fabric reinforced PEEKK, wherein the fiber volume content in the prepreg is 55%;
(4) cutting the A-type prepreg of the boron nitride fiber three-dimensional woven fabric reinforced PEEKK obtained in the step (3) into a plurality of layers according to the required size, sequentially laying the layers in a mould, carrying out mould pressing at the vacuum temperature of 420 ℃ and the pressure of 5MPa for 10min, then cooling to the room temperature at the speed of 10 ℃/min, and demoulding to obtain the boron nitride fiber three-dimensional woven fabric reinforced PEEKK composite material, wherein the fiber volume content in the composite material is 60%. The interlaminar shear strength of the PEEKK boron nitride fiber three-dimensional woven fabric A composite material is 83MPa, and the PEEKK boron nitride fiber three-dimensional woven fabric A composite material can be used for a long time at 295 ℃.
Example 10:
(1) dissolving ketimine type total biphenyl polyether ether ketone (KI-PEDEK) in DMAc under high-speed stirring condition to prepare the solution with the density of 1.237g/cm3The polymer solution of (4);
(2) coating the surface of the plain weave fabric of the carbon nanotube fibers along a single direction by using a polypropylene brush, then coating the surface of the plain weave fabric of the carbon nanotube fibers from a first coating end point by using the brush to dip the polymer solution, finishing one-round coating until a starting point is coated for the first time, repeating the processes without overlapping until all the fabrics are coated once, and drying the surface of the plain weave fabric of the carbon nanotube fibers coated with the polymer solution at 210 ℃ for 5 hours to obtain the KI-PEDEK plain weave fabric of the carbon nanotube fibers;
(3) mixing 1mol/L trifluorobenzene sulfonic acid water solution and THF according to the volume ratio of 1:10 to obtain protonic acid-water-organic solvent mixed solution, spraying the mixed solution on the KI-PEDEK fiber fabric obtained in the step (2), performing hydrolysis treatment for 12 hours, washing with deionized water, and drying to obtain A-type prepreg of the carbon nanotube fiber plain weave fabric reinforced PEDEK, wherein the fiber volume content in the prepreg is 65%;
(4) cutting the A-type prepreg of the carbon nanotube fiber plain weave fabric reinforced PEDEK obtained in the step (3) into a plurality of layers according to the required size, sequentially paving the layers in a mould, carrying out mould pressing at the vacuum temperature of 450 ℃ and the pressure of 5MPa for 10min, then cooling to the room temperature at the speed of 10 ℃/min, and demoulding to obtain the carbon nanotube fiber plain weave fabric reinforced PEDEK composite material, wherein the fiber volume content in the composite material is 70%. The interlayer shear strength of the PEDEK carbon nanotube fiber plain weave A composite material is 65MPa, and the PEDEK carbon nanotube fiber plain weave A composite material can be used for a long time at 340 ℃.
Example 11:
(1) dissolving hemiketal type holo-biphenyl polyetheretherketone (Dio-PEDEK) in Dichloromethane (DCM) under high-speed stirring to obtain a solution with a density of 1.425g/cm3The polymer solution of (4);
(2) coating the surface of the graphene fiber plain woven fabric with the polymer solution obtained in the step (1) along a single direction by using a polypropylene brush, then coating the surface of the graphene fiber plain woven fabric with the polymer solution by using the brush from a first coating end point until a first coating starting point is reached, repeating the processes without overlapping until all the fiber fabrics are coated once, and drying the surface of the graphene fiber plain woven fabric coated with the polymer solution at 90 ℃ for 5 hours to obtain a Dio-PEDEK graphene fiber plain woven fabric;
(3) mixing 1mol/L trifluorobenzene sulfonic acid water solution and THF according to the volume ratio of 1:10 to obtain protonic acid-water-organic solvent mixed solution, spraying the mixed solution on the Dio-PEDEK graphene fiber plain woven fabric obtained in the step (2), performing hydrolysis treatment for 12 hours, washing with deionized water, and drying to obtain A-type prepreg of graphene fiber plain woven fabric reinforced PEDEK, wherein the fiber volume content in the prepreg is 55%;
(4) cutting the A-type prepreg of the graphene fiber plain weave fabric reinforced PEDEK obtained in the step (3) into a plurality of layers according to the required size, sequentially paving the layers in a mould, carrying out mould pressing at the vacuum temperature of 450 ℃ and the pressure of 5MPa for 10min, then cooling to the room temperature at the speed of 10 ℃/min, and demoulding to obtain the carbon nanotube fiber plain weave fabric reinforced PEDEK composite material, wherein the fiber volume content in the composite material is 60%. The interlayer shear strength of the PEDEK graphene fiber plain woven fabric A composite material is 65MPa, and the PEDEK graphene fiber plain woven fabric A composite material can be used at 340 ℃ for a long time.
Example 12:
(1) dissolving ketimine type full biphenyl type polyetheretherketone (KI-PEDEKK) in DCM under high speed stirring to obtain a solution with a density of 1.625g/cm3The polymer solution of (4);
(2) coating the surface of the plain woven fabric of the carbon nanofibers along a single direction by using a polypropylene brush to dip the polymer solution obtained in the step (1), then coating the surface of the plain woven fabric of the carbon nanofibers from a first coating end point by using the brush to dip the polymer solution until a first coating start point is reached, repeating the processes without overlapping until all the fabrics are coated once, and drying the surface of the plain woven fabric of the carbon nanofibers coated with the polymer solution at 90 ℃ for 5 hours to obtain the KI-PEDEKK plain woven fabric of the carbon nanofibers;
(3) mixing 1mol/L trifluorobenzene sulfonic acid water solution and THF according to the volume ratio of 1:10 to obtain protonic acid-water-organic solvent mixed solution, spraying the mixed solution on the KI-PEDEKK nano carbon fiber plain woven fabric obtained in the step (2), performing hydrolysis treatment for 12 hours, washing with deionized water, and drying to obtain a type A prepreg of the nano carbon fiber plain woven fabric reinforced PEDEKK, wherein the fiber volume content in the prepreg is 65%;
(4) cutting the A-type prepreg of the nano carbon fiber plain woven fabric reinforced PEDEKK obtained in the step (3) into a plurality of layers according to the required size, sequentially paving the layers in a mould, carrying out mould pressing at the vacuum of 470 ℃ and the pressure of 5MPa for 10min, then cooling to the room temperature at the speed of 10 ℃/min, and demoulding to obtain the nano carbon fiber plain woven fabric reinforced PEDEKK composite material, wherein the fiber volume content in the composite material is 70%. The interlayer shear strength of the PEDEKK carbon nanotube fiber plain woven fabric A composite material is 66MPa, and the PEDEKK carbon nanotube fiber plain woven fabric A composite material can be used at 355 ℃ for a long time.
Example 13:
(1) dissolving hemiketal type total biphenyl polyetheretherketone (Dio-PEDEKK) in 1, 2-Dichloroethane (DCT) under high-speed stirring to obtain a solution with a density of 1.335g/cm3The polymer solution of (4);
(2) coating the surface of the plain woven fabric of the carbon nanofibers along a single direction by using a polypropylene brush to dip the polymer solution obtained in the step (1), then coating the surface of the plain woven fabric of the carbon nanofibers from a first coating end point by using the brush to dip the polymer solution until a first coating start point is reached, repeating the processes without overlapping until all the fabrics are coated once, and drying the surface of the fabrics coated with the polymer solution at 130 ℃ for 5 hours to obtain the Dio-PEDEKK plain woven fabric of the carbon fibers;
(3) mixing 1mol/L trifluorobenzene sulfonic acid water solution and THF according to the volume ratio of 1:10 to obtain protonic acid-water-organic solvent mixed solution, spraying the mixed solution on the surface of the Dio-PEDEKK fiber fabric obtained in the step (2), performing hydrolysis treatment for 12 hours, washing with deionized water, and drying to obtain a type A prepreg of the nano carbon fiber plain weave fabric reinforced PEDEKK, wherein the fiber volume content in the prepreg is 55%;
(4) cutting the A-type prepreg of the nano carbon fiber plain woven fabric reinforced PEDEKK obtained in the step (3) into a plurality of layers according to the required size, sequentially paving the layers in a mould, carrying out mould pressing at the vacuum of 470 ℃ and the pressure of 5MPa for 10min, then cooling to the room temperature at the speed of 10 ℃/min, and demoulding to obtain the nano carbon fiber plain woven fabric reinforced PEDEKK composite material, wherein the fiber volume content in the composite material is 60%. The interlayer shear strength of the PEDEKK carbon nanotube fiber plain woven fabric A composite material is 65MPa, and the PEDEKK carbon nanotube fiber plain woven fabric A composite material can be used at 355 ℃ for a long time.
Example 14:
(1) dissolving ketimine type full biphenyl polyether ether ketone biphenyl ketone (KI-PEDEKDK) in DCT under high-speed stirring condition to prepare the solution with the density of 1.535g/cm3The polymer solution of (4);
(2) coating the surface of the carbon fiber plain woven fabric with the polymer solution obtained in the step (1) in a unidirectional manner by using a polypropylene brush, coating the surface of the carbon fiber plain woven fabric with the polymer solution by using the brush from a first coating end point until a first coating starting point is reached, repeating the processes without overlapping until all the fiber fabric is coated once, and drying the surface of the fiber fabric coated with the polymer solution at 130 ℃ for 5 hours to obtain a KI-PEDEKDK carbon fiber plain woven fabric;
(3) mixing 1mol/L trifluorobenzene sulfonic acid water solution and THF according to the volume ratio of 1:10 to obtain protonic acid-water-organic solvent mixed solution, spraying the mixed solution on the surface of the KI-PEDEKDK fiber fabric obtained in the step (2), performing hydrolysis treatment for 12 hours, washing with deionized water, and drying to obtain a type A prepreg of the carbon fiber plain weave fabric reinforced PEDEKDK, wherein the fiber volume content in the prepreg is 65%;
(4) cutting the A-type prepreg of the carbon fiber plain woven fabric reinforced PEDEKDK obtained in the step (3) into a plurality of layers according to the required size, sequentially paving the layers in a mould, carrying out mould pressing at the vacuum temperature of 500 ℃ and the pressure of 5MPa for 10min, then cooling to the room temperature at the speed of 10 ℃/min, and demoulding to obtain the nano carbon fiber plain woven fabric reinforced PEDEKDK composite material, wherein the fiber volume content in the composite material is 70%. The PEDEKDK carbon fiber plain woven fabric A composite material has the interlaminar shear strength of 62MPa and can be used at 360 ℃ for a long time.
Example 15:
(1) dissolving hemiketal type total diphenyl polyether ether ketone diphenyl ketone (Dio-PEDEKDK) in chloroform under high-speed stirring to obtain a solution with a density of 1.580g/cm3The polymer solution of (4);
(2) coating the surface of the carbon fiber plain woven fabric with the polymer solution obtained in the step (1) in a unidirectional manner by using a polypropylene brush, coating the surface of the carbon fiber plain woven fabric with the polymer solution by using the brush from a first coating end point until a first coating start point is completed, repeating the processes without overlapping until all the fiber fabric is coated once, and drying the surface of the fiber fabric coated with the polymer solution at 110 ℃ for 5 hours to obtain a Dio-PEDEKDK carbon fiber plain woven fabric;
(3) mixing 1mol/L trifluorobenzene sulfonic acid water solution and THF according to the volume ratio of 1:10 to obtain protonic acid-water-organic solvent mixed solution, spraying the mixed solution on the surface of the Dio-PEDEKDK fiber fabric obtained in the step (2), performing hydrolysis treatment for 12 hours, washing with deionized water, and drying to obtain the A-type prepreg of the carbon fiber plain weave fabric reinforced PEDEKDK, wherein the fiber volume content in the prepreg is 55%;
(4) cutting the A-type prepreg of the carbon fiber plain woven fabric reinforced PEDEKDK obtained in the step (3) into a plurality of layers according to the required size, sequentially paving the layers in a mould, carrying out mould pressing at the vacuum temperature of 500 ℃ and the pressure of 5MPa for 10min, then cooling to the room temperature at the speed of 10 ℃/min, and demoulding to obtain the nano carbon fiber plain woven fabric reinforced PEDEKDK composite material, wherein the fiber volume content in the composite material is 60%.
Example 16:
(1) under the condition of high-speed stirring, dissolving hemiketal type total diphenyl polyether ether ketone diphenyl ketone (Dio-PEDEKDK) in chloroform to prepare the solution with the density of 1.780g/cm3The polymer solution of (4);
(2) coating the surface of the carbon fiber plain woven fabric with the polymer solution obtained in the step (1) in a unidirectional manner by using a polypropylene brush, coating the surface of the carbon fiber plain woven fabric with the polymer solution by using the brush from a first coating end point until a first coating start point is completed, repeating the processes without overlapping until all the fiber fabric is coated once, and drying the surface of the fiber fabric coated with the polymer solution at 110 ℃ for 5 hours to obtain a Dio-PEDEKDK carbon fiber plain woven fabric;
(3) mixing 1mol/L trifluorobenzene sulfonic acid water solution and THF according to the volume ratio of 1:10 to obtain protonic acid-water-organic solvent mixed solution, spraying the mixed solution on the surface of the Dio-PEDEKDK fiber fabric obtained in the step (2), performing hydrolysis treatment for 12 hours, washing with deionized water, and drying to obtain a type A prepreg of the carbon fiber plain weave fabric reinforced PEDEKDK, wherein the fiber volume content in the prepreg is 65%;
(4) cutting the A-type prepreg of the carbon fiber plain weave fabric reinforced PEDEKDK obtained in the step (3) into a plurality of layers according to the required size, sequentially paving the layers in a mould, carrying out mould pressing at the vacuum temperature of 500 ℃ and the pressure of 5MPa for 10min, then cooling to the room temperature at the speed of 10 ℃/min, and demoulding to obtain the carbon fiber plain weave fabric reinforced PEDEKDK composite material, wherein the fiber volume content in the composite material is 70%. The PEDEKDK carbon fiber plain woven fabric A composite material has the interlaminar shear strength of 62MPa and can be used at 360 ℃ for a long time.
Example 17:
(1) dissolving hemiketal type total diphenyl polyether ether ketone diphenyl ketone (Dio-PEDEKDK) in NMP under high-speed stirring condition to prepare the solution with the density of 1.128g/cm3The polymer solution of (4);
(2) coating the surface of the carbon fiber plain woven fabric with the polymer solution obtained in the step (1) in a unidirectional manner by using a polypropylene brush, coating the surface of the carbon fiber plain woven fabric with the polymer solution by using the brush from a first coating end point until a first coating start point is completed, repeating the processes without overlapping until all the fiber fabric is coated once, and drying the surface of the fiber fabric coated with the polymer solution at 250 ℃ for 5 hours to obtain a Dio-PEDEKDK carbon fiber plain woven fabric;
(3) mixing 1mol/L trifluorobenzene sulfonic acid water solution and THF according to the volume ratio of 1:10 to obtain protonic acid-water-organic solvent mixed solution, spraying the mixed solution on the surface of the Dio-PEDEKDK fiber fabric obtained in the step (2), performing hydrolysis treatment for 12 hours, washing with deionized water, and drying to obtain the A-type prepreg of the carbon fiber plain weave fabric reinforced PEDEKDK, wherein the fiber volume content in the prepreg is 55%;
(4) cutting the A-type prepreg of the carbon fiber plain weave fabric reinforced PEDEKDK obtained in the step (3) into a plurality of layers according to the required size, sequentially paving the layers in a mould, carrying out mould pressing at the vacuum temperature of 500 ℃ and the pressure of 5MPa for 10min, then cooling to the room temperature at the speed of 10 ℃/min, and demoulding to obtain the carbon fiber plain weave fabric reinforced PEDEKDK composite material, wherein the fiber volume content in the composite material is 60%. The PEDEKDK carbon fiber plain woven fabric A composite material has the interlaminar shear strength of 62MPa and can be used at 360 ℃ for a long time.
Example 18:
(1) dissolving hemiketal type total diphenyl polyether ether ketone diphenyl ketone (Dio-PEDEKDK) in NMP under high-speed stirring condition to prepare the solution with the density of 1.328g/cm3The polymer solution of (4);
(2) coating the surface of the carbon fiber plain woven fabric with the polymer solution obtained in the step (1) in a unidirectional manner by using a polypropylene brush, coating the surface of the carbon fiber plain woven fabric with the polymer solution by using the brush from a first coating end point until a first coating start point is completed, repeating the processes without overlapping until all the fiber fabric is coated once, and drying the surface of the fiber fabric coated with the polymer solution at 250 ℃ for 5 hours to obtain a Dio-PEDEKDK carbon fiber plain woven fabric;
(3) mixing 1mol/L trifluorobenzene sulfonic acid water solution and THF according to the volume ratio of 1:10 to obtain protonic acid-water-organic solvent mixed solution, spraying the mixed solution on the surface of the Dio-PEDEKDK fiber fabric obtained in the step (2), performing hydrolysis treatment for 12 hours, washing with deionized water, and drying to obtain a type A prepreg of the carbon fiber plain weave fabric reinforced PEDEKDK, wherein the fiber volume content in the prepreg is 65%;
(4) cutting the A-type prepreg of the carbon fiber plain weave fabric reinforced PEDEKDK obtained in the step (3) into a plurality of layers according to the required size, sequentially paving the layers in a mould, carrying out mould pressing at the vacuum temperature of 500 ℃ and the pressure of 5MPa for 10min, then cooling to the room temperature at the speed of 10 ℃/min, and demoulding to obtain the carbon fiber plain weave fabric reinforced PEDEKDK composite material, wherein the fiber volume content in the composite material is 70%. The PEDEKDK carbon fiber plain woven fabric A composite material has the interlaminar shear strength of 62MPa and can be used at 360 ℃ for a long time.
Example 19:
(1) dissolving hemiketal type total diphenyl polyether ether ketone diphenyl ketone (Dio-PEDEKDK) in NMP under high-speed stirring condition to prepare the solution with the density of 1.078g/cm3The polymer solution of (4);
(2) coating the surface of the carbon fiber plain woven fabric with the polymer solution obtained in the step (1) in a unidirectional manner by using a polypropylene brush, coating the surface of the carbon fiber plain woven fabric with the polymer solution by using the brush from a first coating end point until a first coating start point is completed, repeating the processes without overlapping until all the fiber fabric is coated once, and drying the surface of the fiber fabric coated with the polymer solution at 250 ℃ for 5 hours to obtain a Dio-PEDEKDK carbon fiber plain woven fabric;
(3) mixing 1mol/L trifluorobenzene sulfonic acid water solution and THF according to the volume ratio of 1:10 to obtain protonic acid-water-organic solvent mixed solution, spraying the mixed solution on the surface of the Dio-PEDEKDK fiber fabric obtained in the step (2), performing hydrolysis treatment for 12 hours, washing with deionized water, and drying to obtain the carbon fiber plain woven fabric reinforced Dio-PEDEKDK prepreg;
(4) repeating the carbon fiber plain fabric reinforced Dio-PEDEKDK prepreg obtained in the step (3) for 5 times according to the operation of the step (2) and the step (3) to obtain a carbon fiber plain fabric reinforced PEDEKDK A-type prepreg, wherein the fiber volume content in the prepreg is 65%;
(5) cutting the A-type prepreg of the carbon fiber plain weave fabric reinforced PEDEKDK obtained in the step (4) into a plurality of layers according to the required size, sequentially paving the layers in a mould, carrying out mould pressing at the vacuum temperature of 500 ℃ and the pressure of 5MPa for 10min, then cooling to the room temperature at the speed of 10 ℃/min, and demoulding to obtain the carbon fiber plain weave fabric reinforced PEDEKDK composite material, wherein the fiber volume content in the composite material is 70%. The PEDEKDK carbon fiber plain woven fabric A composite material has the interlaminar shear strength of 62MPa and can be used at 360 ℃ for a long time.
Example 20:
(1) dissolving hemiketal type total diphenyl polyether ether ketone diphenyl ketone (Dio-PEDEKDK) in NMP under high-speed stirring condition to prepare the solution with the density of 1.278g/cm3The polymer solution of (4);
(2) coating the surface of the carbon fiber plain woven fabric with the polymer solution obtained in the step (1) in a unidirectional manner by using a polypropylene brush, coating the surface of the carbon fiber plain woven fabric with the polymer solution by using the brush from a first coating end point until a first coating start point is completed, repeating the processes without overlapping until all the fiber fabric is coated once, and drying the surface of the fiber fabric coated with the polymer solution at 250 ℃ for 5 hours to obtain a Dio-PEDEKDK carbon fiber plain woven fabric;
(3) mixing 1mol/L trifluorobenzene sulfonic acid water solution and THF according to the volume ratio of 1:10 to obtain protonic acid-water-organic solvent mixed solution, spraying the mixed solution on the surface of the Dio-PEDEKDK fiber fabric obtained in the step (2), performing hydrolysis treatment for 12 hours, washing with deionized water, and drying to obtain the carbon fiber plain woven fabric reinforced Dio-PEDEKDK prepreg;
(4) repeating the carbon fiber plain fabric reinforced Dio-PEDEKDK prepreg obtained in the step (3) for 5 times according to the operation of the step (2) and the step (3) to obtain a carbon fiber plain fabric reinforced PEDEKDK A-type prepreg, wherein the fiber volume content in the prepreg is 55%;
(5) cutting the A-type prepreg of the carbon fiber plain weave fabric reinforced PEDEKDK obtained in the step (4) into a plurality of layers according to the required size, sequentially paving the layers in a mould, carrying out mould pressing at the vacuum temperature of 500 ℃ and the pressure of 5MPa for 10min, then cooling to the room temperature at the speed of 10 ℃/min, and demoulding to obtain the carbon fiber plain weave fabric reinforced PEDEKDK composite material, wherein the fiber volume content in the composite material is 60%. The PEDEKDK carbon fiber plain woven fabric A composite material has the interlaminar shear strength of 62MPa and can be used at 360 ℃ for a long time.
Example 21:
(1) 79.70g of ketimine-type polyether ether ketone (KI-PEEK) was dissolved in 187mL of THF under high-speed stirring, and the solution was prepared so that the density thereof was 1.187g/cm3199mL of the polymer solution (2);
(2) 0.1m2The stainless steel plate was placed in a fiber volume of 113cm3Spraying the polymer solution obtained in the step (1) on the surface of the fiber fabric covered by a stainless steel plate in a unidirectional non-overlapping mode, and drying at 120 ℃ for 5 hours to obtain the KI-PEEK carbon fiber fabric;
(3) mixing a 15mol/L sulfuric acid aqueous solution and DMAc according to the volume ratio of 2:5 to obtain a sulfuric acid-water-DMAc mixed solution, and fully stirring to obtain a protonic acid-water-organic solvent mixed solution for a hydrolysis process; rapidly immersing the KI-PEEK carbon fiber fabric obtained in the step (2) into a sulfuric acid-water-DMAc mixed solution, processing at 100 ℃ for 8h, washing with deionized water to be neutral, and drying to obtain a B-type prepreg of carbon fiber plain fabric reinforced PEEK, wherein the fiber volume content of a fully-impregnated area in the prepreg is 65%, and the fiber volume content of an insufficiently-impregnated polymer area is less than or equal to 5%;
(4) sequentially paving 4B-type prepregs obtained in the step (3) in a mould, carrying out mould pressing for 10min at the temperature of 380 ℃ and the pressure of 5MPa in vacuum, cooling to room temperature at the temperature of 10 ℃/min, and demoulding to obtain a carbon fiber plain weave fabric reinforced PEEK composite material connecting piece blank, wherein the fiber volume content of a fully-impregnated polymer area is 70%;
(5) and (3) assembling the non-impregnated polymer area and the carbon fiber fabric in a Resin Transfer Molding (RTM) forming device, and curing and forming the carbon fiber plain woven fabric reinforced PEEK composite material and unsaturated polyester-based composite material by using unsaturated polyester through an RTM process.
The interlayer shear strength of the fiber fabric reinforced polyether ether ketone (PEEK), polyether ether ketone (PEEKK), total biphenyl polyether ether ketone (PEDEK), total biphenyl polyether ether ketone (PEDEKK) and total biphenyl polyether ether ketone biphenyl ketone (PEDEKDK) resin matrix composite material obtained in the above embodiment is more than 60 MPa; under the condition of not being compounded with other resins, the fiber fabric reinforced polyether-ether-ketone resin matrix composite material can be used for a long time at 270 ℃; the fiber fabric reinforced polyether-ether-ketone resin-based composite material can be used for a long time at 295 ℃; the fiber fabric reinforced full-biphenyl polyether-ether-ketone resin matrix composite material can be used for a long time at 340 ℃; the fiber fabric reinforced full-biphenyl polyether ether ketone resin matrix composite material can be used for a long time at 355 ℃; the fiber fabric reinforced full-biphenyl polyether-ether-ketone biphenyl ketone resin-based composite material can be used at 360 ℃ for a long time.
The attached figure 1 of the specification is a chemical structural formula of a precursor polymer, wherein: a1 is ketimine type polyetheretherketone (KI-PEEK); a2 is hemiketal type polyetheretherketone (Dio-PEEK); b1 is ketimine type polyetheretherketone (KI-PEEKK); b2 is hemiketal polyetheretherketone (Dio-PEEKK); c1 is ketimine type total biphenyl type polyether ether ketone (KI-PEDEK); c2 is hemiketal type total biphenyl polyether ether ketone (Dio-PEDEK); d1 is ketimine type full biphenyl type polyetheretherketone ketone (KI-PEDEKK); d2 is hemiketal type total biphenyl type polyetheretherketone ketone (Dio-PEDEKK); e1 is ketimine type full biphenyl type polyetheretherketone biphenyl ketone (KI-PEDEKDK); e2 is hemiketal type holobiphenyl polyetheretherketone biphenyl ketone (Dio-PEDEKDK);
FIG. 2 is a schematic diagram of the preparation process of the fiber fabric reinforced resin-based (PEEK, PEEKK, PEDEK, PEDEKK or PEDEKDK) composite material and the composite material and other resin-based composite connectors, wherein: 1 in the (1, 2) is a brushing or spraying dipping process, and 2 is a hydrolysis reaction process carried out after the brushing or spraying dipping process; (3) laying up prepreg and carrying out hot pressing treatment; (4) the method is a matching and layering process of A-type prepreg and B-type prepreg and a hot pressing process; (5) the process of preparing the composite material connecting piece prefabricated body by dipping the composite material connecting piece blank into other resin matrixes; (6) curing the composite material connecting piece prefabricated body into a composite material connecting piece; firstly, the composite material is a fiber fabric reinforced PEEK, PEEKK, PEDEK, PEDEKK or PEDEKDK resin matrix composite material; secondly, and thirdly, forming a blank of the composite material connecting piece; fourthly, a prefabricated body of the composite material connecting piece is obtained; the fifth step is a composite material connecting piece.

Claims (10)

1. A fiber fabric reinforced polyaryletherketone resin based prepreg is characterized in that: the preparation method comprises the following steps:
(1) adding soluble precursor polyaryletherketone into organic solvent, and stirring to obtain the final product with density of 0.7-2.0g/cm3The polyaryletherketone solution of (1);
(2) after the polyaryletherketone solution obtained in the step (1) is used for brushing and/or spraying the surface of a fiber fabric, heating and drying, hydrolyzing with a protonic acid-water-organic solvent, washing with deionized water, heating and drying to obtain a fiber fabric reinforced polyaryletherketone resin-based prepreg, wherein the brushing is full brushing or partial brushing; the fiber volume content in the prepreg is 50% -75%, and the fiber fabric reinforced polyaryletherketone resin based prepreg is prepared by completely impregnating a fiber fabric reinforced polyaryletherketone resin based prepreg with a polyaryletherketone solution or incompletely impregnating a fiber fabric reinforced polyaryletherketone resin based prepreg with a polyaryletherketone solution; the polyaryletherketone solution incompletely impregnates the fiber fabric reinforced polyaryletherketone resin-based prepreg, which consists of a polyaryletherketone solution impregnated fiber fabric part and a polyaryletherketone solution non-impregnated fiber fabric part; the volume content of the resin of the part of the fiber fabric which is not impregnated with the polyaryletherketone solution is less than or equal to 5 percent.
2. The fiber fabric reinforced polyaryletherketone resin based prepreg according to claim 1, which is characterized in that: the soluble precursor polyaryletherketone in the step (1) is one of ketimine type polyetheretherketone, hemiketal type polyetheretherketone, ketimine type all biphenyl type polyetheretherketone, hemiketal type all biphenyl type polyetheretherketone, ketimine type all biphenyl type polyetheretherketone biphenyl or hemiketal type all biphenyl type polyetheretherketone biphenyl, and the structural formula is as follows in sequence:
Figure FDA0002948280090000011
Figure FDA0002948280090000021
3. the fiber fabric reinforced polyaryletherketone resin based prepreg according to claim 1, which is characterized in that: the organic solvent in the step (1) is any one of tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, dichloromethane, 1, 2-dichloroethane, chloroform or N-methylpyrrolidone.
4. The fiber fabric reinforced polyaryletherketone resin based prepreg according to claim 1, which is characterized in that: the fiber fabric in the step (2) is any one of carbon fiber, glass fiber, basalt fiber, boron nitride fiber, carbon nanotube fiber or graphene fiber; the shape of the fiber fabric is any one of plain weave fabric, twill weave fabric, satin weave fabric and three-dimensional weaving fabric.
5. The fiber fabric reinforced polyaryletherketone resin based prepreg according to claim 1, which is characterized in that: the heating and drying temperature in the step (2) is 50-300 ℃, and the time is 3-10 h.
6. The fiber fabric reinforced polyaryletherketone resin based prepreg according to claim 1, which is characterized in that: the preparation method of the protonic acid-water-organic solvent in the step (2) comprises the following steps: according to the volume ratio of 1-10: 2-5, mixing protonic acid aqueous solution with the concentration of 1-20mol/L with an organic solvent; the protonic acid is any one of hydrochloric acid, sulfuric acid, methanesulfonic acid, benzenesulfonic acid, trifluoroacetic acid or trifluorobenzene sulfonic acid; the organic solvent is any one of tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone.
7. The fiber fabric reinforced polyaryletherketone resin based prepreg according to claim 1, which is characterized in that: the hydrolysis in the step (2) is a brushing hydrolysis method or an acid boiling hydrolysis method, wherein the brushing hydrolysis method is to brush a protonic acid-water-organic solvent mixed solution on the surface of the fiber fabric impregnated with the polyaryletherketone resin; the acid boiling hydrolysis method is characterized in that the fiber fabric impregnated with the polyaryletherketone resin is immersed in a mixed solution of protonic acid, water and an organic solvent and hydrolyzed at the temperature of 50-150 ℃.
8. The fiber fabric reinforced polyaryletherketone resin based prepreg according to claim 1, which is characterized in that: the hydrolysis time in the step (2) is 6-15 h.
9. The use of a fabric-reinforced polyaryletherketone resin-based prepreg according to any one of claims 1 to 8 in the preparation of a fabric-reinforced polyaryletherketone resin-based composite connector, wherein: it comprises the following steps:
(1) laying a reinforced polyaryletherketone resin-based prepreg which is prepared by completely impregnating a fiber fabric with a polyaryletherketone solution and/or a reinforced polyaryletherketone resin-based prepreg which is prepared by incompletely impregnating a fiber fabric into a mold, carrying out mold pressing at 550 ℃ under vacuum of 350-10 MPa for 10-25min, cooling to room temperature at 10-25 ℃/min, and demolding to obtain a reinforced polyaryletherketone resin-based composite material which is prepared by completely and/or incompletely impregnating a fiber fabric with a polyaryletherketone solution, wherein the fiber volume content of the composite material is 60-75%;
(2) fully soaking the part, which is not soaked in the polyaryletherketone solution, of the reinforced polyaryletherketone resin-based prepreg, of the fiber fabric, which is not completely soaked in the step (1), in a resin-tetrahydrofuran solution, and drying, curing and molding to obtain a connector of the polyaryletherketone fiber composite material and the resin-based composite material; the resin is isocyanate, epoxy resin or phenolic resin; the curing molding is hot-press molding or non-hot-press molding.
10. The use of the fiber fabric reinforced polyaryletherketone resin based prepreg according to claim 9 in the preparation of a fiber fabric reinforced polyaryletherketone resin based composite connector: the method is characterized in that: and (3) directly carrying out resin transfer molding on the polyaryletherketone fiber composite material obtained in the step (2) and a connector of the resin-based composite material or carrying out resin transfer molding together with fibers to be connected.
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