CN104629365A - Method for preparing carbon fiber-polyimide composite material - Google Patents

Method for preparing carbon fiber-polyimide composite material Download PDF

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CN104629365A
CN104629365A CN201510086537.9A CN201510086537A CN104629365A CN 104629365 A CN104629365 A CN 104629365A CN 201510086537 A CN201510086537 A CN 201510086537A CN 104629365 A CN104629365 A CN 104629365A
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dianhydride
carbon fiber
bis
polyimide
dicarboxyphenyl
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CN104629365B (en
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贺征
顾璇
李卓
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Harbin Engineering University
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Harbin Engineering University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of 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 C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • C08G73/126—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic
    • C08G73/127—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic containing oxygen in the form of ether bonds in the main chain
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/247—Heating methods
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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  • Organic Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

The invention provides a method for preparing a carbon fiber-polyimide composite material. The method comprises the following steps: (1) putting tetramine and an organic solvent into a reaction kettle, adding C=C-unsaturated-bond-containing carboxylic acid anhydride solid powder, stirring at room temperature until the solid powder is completely dissolved, continuing stirring to react, adding tetracarboxylic acid anhydride, and stirring to react at 2-5 DEG C; (2) preparing a polyamic acid solution into a solution in which the polyamic acid accounts for 35-60 wt%, wetting carbon fiber, heating to 200 DEG C, and baking to obtain the primary composite carbon fiber; (3) uniformly mixing thermosetting polyimide with the primary composite carbon fiber; and (4) carrying out compression molding, crosslinking and solidification on the polyimide-carbon fiber composite raw material obtained in the step (3), and carrying out further radiation crosslinking to obtain the polyimide-carbon fiber composite material. The carbon fiber is firstly coated with the polyamic acid and then compounded with the common thermosetting polyimide to obtain the material with excellent properties.

Description

Method for preparing carbon fiber and polyimide composite material
Technical Field
The invention relates to a method for preparing a carbon fiber-polyimide composite material.
Background
Polyimide (PI) is a high polymer material with higher heat resistance developed in the 50 th century, is high-temperature resistant and radiation resistant, has excellent mechanical property and tribological property, is known as the king of plastics, particularly has excellent antifriction and lubricating properties under severe environments of high temperature, high pressure, high speed and the like, and is widely applied to the high-tech fields of aviation, aerospace, electrical appliances, machinery, chemical engineering, microelectronics and the like. The fiber reinforced Polyimide (PI) resin-based composite material has the characteristics of high specific modulus, high specific strength, radiation resistance, excellent mechanical property at high temperature, wide use temperature range (-269 ℃ to +400 ℃) and the like, and can be selected to use the PI composite material under the condition that metal materials or other engineering plastics in aerospace aircrafts, modern weapon systems, chemical and medical industries, textile industries, automobile industries, mine industries, precision machinery industries and the like cannot meet the requirements. However, pure PI is not suitable for being used alone as a friction material due to relatively low tensile and compressive strengths, and a PI composite material with excellent mechanical properties and tribological properties can be obtained after adding a reinforcing fiber.
The carbon fiber is inorganic polymer fiber with carbon content higher than 90%. Wherein the carbon content is more than 99 percent, namely graphite fiber. The carbon fiber can be respectively prepared by carbonizing polyacrylonitrile fiber, pitch fiber, viscose or phenolic fiber; divided into filaments, staple fibers and chopped fibers according to the state; the material is divided into a general type and a high-performance type according to mechanical properties. The general-purpose carbon fiber has a strength of 1000 megapascals (MPa) and a modulus of about 100 GPa. High-performance carbon fibers are classified into high-strength carbon fibers (strength 2000MPa, modulus 250GPa) and high-model carbon fibers (modulus more than 300 GPa). The strength is more than 4000MPa and is also called ultra-high strength type; moduli greater than 450GPa are referred to as ultra-high models. The carbon fiber has the characteristics of high temperature resistance, high strength, high elastic modulus, creep resistance and the like, is the most commonly used reinforcing fiber for preparing high-performance resin matrix composite materials, and is used for modifying polyimide.
However, the surface of the carbon fiber is inert, and the bonding strength of the interface between the untreated composite material fiber and the resin is weak, thereby influencing the application of the material. Therefore, before the polyimide is reinforced with carbon fibers, the scientific and technological community generally performs a surface treatment on the carbon fibers to generate more active functional groups and form ravines. The crystal nucleus can be added into a high polymer material to be used as a crystal nucleus to induce the crystallization of a high polymer around the crystal nucleus, so that the order of macromolecules of the high polymer material can be improved, the aggregation state structure of the high polymer is changed, and the performance of the high polymer material is influenced. Most of the carbon fiber modification methods adopted at home and abroad at present have complex processes and harsh conditions, such as an air oxidation method (requiring ablation for 40 minutes at 450 ℃ in a muffle furnace), a nitric acid oxidation method (soaking carbon fibers in nitric acid for treatment for a period of time), low-temperature liquid nitrogen treatment (soaking in liquid nitrogen (-196 ℃) for 10 minutes), and the like. The method has complex conditions, the treatment time is not easy to control, and the modulus and the breaking strength of the carbon fiber are easy to reduce, thereby greatly reducing the performance of the composite material.
Therefore, there is a need for a novel carbon fiber and polyimide composite material that can be directly compounded without changing the surface structure of the carbon fiber and has more excellent properties.
Disclosure of Invention
The invention aims to provide a method for preparing a carbon fiber and polyimide composite material, which can obtain a material with good mechanical property.
The purpose of the invention is realized as follows:
(1) putting tetramine and an organic solvent into a reaction kettle, stirring and dissolving completely at room temperature, adding carbon-carbon unsaturated double bond-containing carboxylic anhydride solid powder, stirring at room temperature until the carboxylic anhydride solid powder is completely dissolved, continuing stirring and reacting, adding tetracarboxylic anhydride, and stirring and reacting at 2-5 ℃ to obtain a viscous polyamic acid solution;
(2) preparing a polyamic acid solution into a solution with the mass fraction of polyamic acid accounting for 35-60%, infiltrating carbon fiber, heating to 200 ℃, and drying to obtain primarily compounded carbon fiber;
(3) uniformly mixing thermosetting polyimide with the primarily compounded carbon fiber;
(4) and (4) carrying out compression molding, crosslinking and curing on the polyimide carbon fiber composite raw material obtained in the step (3), and then further carrying out radiation crosslinking to obtain the polyimide carbon fiber composite material.
The present invention may further comprise:
1. the structure of the polyamic acid is as follows:
wherein R is1Is a group containing a carbon-carbon unsaturated double bond; r2Is one or more of the following structures:wherein X is selected from one or more of the following divalent groups: -CO-, -O-, -S-, -SO2-、-CH2-、-C(CH3)2-、-C(CF3)2-。
2. The carboxylic anhydride containing carbon-carbon unsaturated double bond is one or more of the following structures:
3. the tetracarboxylic acid anhydride is selected from pyromellitic dianhydride, 2, 3, 6, 7-naphthalenetetracarboxylic dianhydride, 3, 3 ', 4, 4 ' -biphenyltetracarboxylic dianhydride, 1,2, 5, 6-naphthalenetetracarboxylic dianhydride, 2 ', 3, 3 ' -biphenyltetracarboxylic dianhydride, 3, 3 ', 4, 4 ' -benzophenonetetracarboxylic dianhydride, 4, 4 ' -oxydiphthalic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 3,4, 9, 10-perylenetetracarboxylic dianhydride, bis (3, 4-dicarboxyphenyl) propane dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, bis (2, 3-dicarboxyphenyl) methane dianhydride, bis (3-dicarboxyphenyl) methane dianhydride, One or more of bis (3, 4-dicarboxyphenyl) ethane dianhydride, oxydiphthalic dianhydride, bis (3, 4-dicarboxyphenyl) sulfone dianhydride, p-phenylene bis (trimellitic acid monoester anhydride), ethylene bis (trimellitic acid monoester anhydride) and bisphenol A bis (trimellitic acid monoester anhydride).
The thermosetting polyimide is synthesized from tetracarboxylic dianhydride, diamine and a capping reagent, wherein the capping reagent of the thermosetting polyimide is fluorine-containing phenylacetylene phthalic anhydride.
The polyamic acid is adopted to coat the carbon fiber, and then is compounded with the common thermosetting polyimide to obtain the material with excellent performance.
Drawings
FIG. 1 is an infrared spectrum of some embodiments.
Detailed Description
The method for preparing the carbon fiber-polyimide composite material comprises the following steps:
(1) putting tetramine and an organic solvent into a reaction kettle, stirring and dissolving completely at room temperature, adding carbon-carbon unsaturated double bond-containing carboxylic anhydride solid powder, stirring at room temperature until the carboxylic anhydride solid powder is completely dissolved, continuing stirring and reacting, adding tetracarboxylic anhydride, and stirring and reacting at 2-5 ℃ to obtain a viscous polyamic acid solution;
(2) preparing polyamic acid into a solution with the mass fraction of polyamic acid accounting for 35-60%, infiltrating carbon fiber, heating to 200 ℃, and drying to obtain primary composite carbon fiber;
(3) providing thermosetting polyimide and the preliminarily compounded carbon fiber, and uniformly mixing;
(4) and (3) carrying out compression molding, crosslinking and curing on the polyimide carbon fiber composite material, and then carrying out further radiation crosslinking to obtain the polyimide carbon fiber composite material.
Preferably, the mass ratio of the polyamic acid to the carbon fiber is 1/10-1/1; more preferably, the mass ratio of the polyamic acid to the carbon fiber is 2/10.
Preferably, the thermosetting polyimide accounts for 10-100% of the mass of the composite material; more preferably, the thermosetting polyimide accounts for 40% of the mass fraction of the composite material.
Wherein the structure of the polyamic acid is as follows:
the R is1Is a group containing a carbon-to-carbon unsaturated double bond, R2One or more of the following structures:
wherein,
x is selected from one or more of the following divalent groups: -CO-, -O-, -S-, -SO2-、-CH2-、-C(CH3)2-、-C(CF3)2-。
The tetracarboxylic acid anhydrides mentioned above are commercially available and are available directly from reagent companies.
The carboxylic anhydride containing carbon-carbon unsaturated double bond has one or more of the following structures:
(4- (4-methyl-3-pentene) -4-cyclohexene-1, 2-dicarboxylic anhydride),(tetrapropenylene succinic anhydride),
The carboxylic acid anhydrides containing carbon-carbon unsaturated double bonds are commercially available and can be purchased directly from reagent companies.
The method for producing a carbon fiber-polyimide composite material according to the first aspect, wherein the tetracarboxylic acid anhydride is selected from the group consisting of pyromellitic dianhydride, 2, 3, 6, 7-naphthalenetetracarboxylic dianhydride, 3, 3 ', 4, 4 ' -biphenyltetracarboxylic dianhydride, 1,2, 5, 6-naphthalenetetracarboxylic dianhydride, 2 ', 3, 3 ' -biphenyltetracarboxylic dianhydride, 3, 3 ', 4, 4 ' -benzophenonetetracarboxylic dianhydride, 4, 4 ' -oxydiphthalic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 3,4, 9, 10-perylenetetracarboxylic dianhydride, bis (3, 4-dicarboxyphenyl) propane dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, bis (2, 3-dicarboxyphenyl) methane dianhydride, bis (3, 4-dicarboxyphenyl) ethane dianhydride, oxydiphthalic dianhydride, bis (3, 4-dicarboxyphenyl) sulfone dianhydride, p-phenylene bis (trimellitic acid monoester anhydride), ethylene bis (trimellitic acid monoester anhydride), bisphenol A bis (trimellitic acid monoester anhydride).
The organic solvent to be used may be selected from N-methyl-2-pyrrolidone, N-dimethylacetamide, N-diethylacetamide, N-dimethylformamide, N-diethylformamide, N-methylcaprolactam, hexamethylphosphoramide, tetramethylene sulfone, dimethyl sulfoxide, m-cresol, phenol, p-chlorophenol, 2-chloro-4-hydroxytoluene, diglyme, triglyme, tetraglyme, dioxane, gamma-butyrolactone, dioxolane, cyclohexanone, cyclopentanone, dichlorotoluene, chloroform, 1, 2-dichloroethane, 1, 2-trichloroethane, dibromomethane, tribromomethane, 1, 2-dibromoethane, 1, 2-tribromoethane, etc., two or more kinds may be used in combination.
As the carbon fiber, carbon fibers of all kinds can be used according to the use, but carbon fibers having a tensile elastic modulus of at most 400GPa are preferable from the viewpoint of impact resistance. In addition, from the viewpoint of strength, since a composite material having high rigidity and mechanical strength can be obtained, carbon fibers having a tensile strength of preferably 4.4 to 6.5GPa are used. In addition, tensile elongation is also an important factor, and high-strength and high-elongation carbon fibers of 1.7 to 2.3% are preferable. Therefore, a carbon fiber having a tensile elastic modulus of at least 230GPa, a tensile strength of at least 4.4GPa, and a tensile elongation of at least 1.7% is most preferable.
Commercially available carbon fibers include Torayca T800G-24K, Torayca T800S-24K, Torayca T700G-24K, Torayca T300-3K, and Torayca T700S-12K.
The thermosetting polyimide is synthesized from tetracarboxylic dianhydride, diamine and a blocking agent, wherein the blocking agent of the thermosetting polyimide is fluorine-containing phenylacetylene phthalic anhydride. The flame retardant property of the material can be improved by substituting fluorine.
The tetracarboxylic dianhydrides used in the present invention for the preparation of polyimide include pyromellitic dianhydride, 2, 3, 6, 7-naphthalenetetracarboxylic dianhydride, 3, 3 ', 4, 4 ' -biphenyltetracarboxylic dianhydride, 1,2, 5, 6-naphthalenetetracarboxylic dianhydride, 2 ', 3, 3 ' -biphenyltetracarboxylic dianhydride, 3, 3 ', 4, 4 ' -benzophenonetetracarboxylic dianhydride, 4, 4 ' -oxydiphthalic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 3,4, 9, 10-perylenetetracarboxylic dianhydride, bis (3, 4-dicarboxyphenyl) propane dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, bis (2, 3-dicarboxyphenyl) methane dianhydride, Bis (3, 4-dicarboxyphenyl) ethane dianhydride, oxydiphthalic dianhydride, bis (3, 4-dicarboxyphenyl) sulfone dianhydride, p-phenylene bis (trimellitic acid monoester anhydride), ethylene bis (trimellitic acid monoester anhydride), bisphenol a bis (trimellitic acid monoester anhydride) and the like of these, and these may be preferably used alone or in a mixture of any proportions.
The diamine used for the preparation of the polyimide of the present invention includes, for example, 4 ' -diaminodiphenylpropane, 4 ' -diaminodiphenylmethane, benzidine, 3 ' -dichlorobenzidine, 3 ' -dimethylbenzidine, 2 ' -dimethylbenzidine, 3 ' -dimethoxybenzidine, 2 ' -dimethoxybenzidine, 4 ' -diaminodiphenyl sulfide, 3 ' -diaminodiphenyl sulfone, 4 ' -diaminodiphenyl ether, 3 ' -diaminodiphenyl ether, 3,4 ' -diaminodiphenyl ether, 1, 5-diaminonaphthalene, 4 ' -diaminodiphenyldiethylsilane, 4 ' -diaminodiphenylsilane, 4 ' -diaminodiphenylsilane, and mixtures thereof, 4, 4 ' -diaminodiphenylethylphosphine oxide, 4 ' -diaminodiphenyl-N-methylamine, 4 ' -diaminodiphenyl-N-aniline, 1, 4-diaminobenzene (p-phenylenediamine), 1, 3-diaminobenzene, 1, 2-diaminobenzene, bis {4- (4-aminophenoxy) phenyl } sulfone, bis {4- (4-aminophenoxy) phenyl } propane, bis {4- (3-aminophenoxy) phenyl } sulfone, 4 ' -bis (4-aminophenoxy) biphenyl, 4 ' -bis (3-aminophenoxy) biphenyl, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, 3 '-diaminobenzophenone, 4' -diaminobenzophenone, and the like.
As the end capping component of polyimide, dicarboxylic anhydride, monoamine, and the like can be used. Examples of the dicarboxylic anhydride include phthalic anhydride, naphthalic anhydride, biphenyldicarboxylic anhydride, 1,2, 3, 6-tetrahydrophthalic anhydride, 1, 2-cyclohexanedicarboxylic anhydride, 5-norbornene-2, 3-dicarboxylic anhydride, methyl-5-norbornene-2, 3-dicarboxylic anhydride, citraconic anhydride, maleic anhydride, 3-ethynylphthalic acid, 4-phenylethynylphthalic acid, and 3-fluoro-4-phenylethynylphthalic anhydride. Examples of the monoamine include aniline, aminonaphthalene, aminobiphenyl, 3-ethynylaniline, and 4-ethynylaniline. Preferably, the end capping agent is fluoro phenyl ethynyl phthalic anhydride, which can inhibit the candle wick effect. Of course, the end-capping agent is not limited thereto. These may be used alone or in combination of two or more.
The organic solvent to be used may be selected from N-methyl-2-pyrrolidone, N-dimethylacetamide, N-diethylacetamide, N-dimethylformamide, N-diethylformamide, N-methylcaprolactam, hexamethylphosphoramide, tetramethylene sulfone, dimethyl sulfoxide, m-cresol, phenol, p-chlorophenol, 2-chloro-4-hydroxytoluene, diglyme, triglyme, tetraglyme, dioxane, gamma-butyrolactone, dioxolane, cyclohexanone, cyclopentanone, dichlorotoluene, chloroform, 1, 2-dichloroethane, 1, 2-trichloroethane, dibromomethane, tribromomethane, 1, 2-dibromoethane, 1, 2-tribromoethane, etc., two or more kinds may be used in combination.
The catalyst is preferably a tertiary amine compound, and specific examples thereof include trimethylamine, Triethylamine (TEA), tripropylamine, tributylamine, triethanolamine, N-dimethylethanolamine, N-diethylethanolamine, triethylenediamine, N-methylpyrrolidine, N-ethylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, imidazole, pyridine, quinoline, and isoquinoline. The reaction may be carried out in the presence of at least one catalyst selected from these tertiary amine compounds. When the catalyst is used, the amount of the catalyst used is preferably 0.1 to 100 mol% based on the tetracarboxylic acid component (Y), from the viewpoint of a small amount and a short reaction time as possible.
The preparation process of the composite material comprises the following steps:
adding a small amount of coupling agent (containing 1 percent of the total resin) into the thermosetting polyimide resin, uniformly mixing, mixing with the primarily compounded carbon fiber, putting into an oven at 80 ℃ for pretreatment, after 1 hour, heating to 160 ℃ for 3 hours after the solution is volatilized, and heating to 200 ℃ for 4 hours. And then putting the fiber into a vacuum oven at 250 ℃ for treatment for 5 hours to obtain a prepressing material.
Die pressing process
Starting contact, heating to 280 ℃, pressurizing, closing the mold, continuously heating to 380 ℃, keeping the temperature for 1 hour, blowing for cooling, and demolding at 150 ℃. And (4) processing the strip after demolding, drying the obtained strip by heat treatment of a box at 120 ℃, taking out, standing for 24 hours, and testing.
Test method
Unnotched impact strength test: hebei Chengde testing machine, Xa-500, 50J, GB 1043.
And (3) testing tensile strength: lloyd, Lloyd-LR-50K, GB1040, UK.
And (3) testing the bending strength: lloyd, Lloyd-LR-50K, GB9341, UK.
And (3) testing medium resistance: GBn 547.
Flame retardance: UL 94.
The invention is described in more detail below by way of example.
Example 1
Putting 0.2 mol of 2, 2-bis [4- (2, 4-diaminophenoxy) phenyl ] propane and 1000 ml of N, N-dimethylacetamide into a reaction kettle, stirring and dissolving completely at room temperature, adding 0.4 mol of 4- (4-methyl-3-pentene) -4-cyclohexene-1, 2-dicarboxylic anhydride, stirring at room temperature until the mixture is dissolved completely, continuing to stir for reaction for 0.5 hour, adding 0.2 mol of pyromellitic dianhydride, stirring and reacting at 2-5 ℃ for 2 hours, controlling the viscosity at 2-5 ℃ to be 10000 centipoises, and stopping stirring to obtain a viscous polyamide acid solution.
Preparing polyamic acid into a solution with the mass fraction of polyamic acid being 50%, infiltrating carbon fiber (Torayca T800G-24K), heating to 200 ℃, and drying (the mass ratio of polyamic acid to carbon fiber is 10:1) to obtain modified carbon fiber A1.
The preparation process of the composite material comprises the following steps:
adding a small amount of coupling agent KH570 (containing 1 percent of the total resin) into thermosetting polyimide resin pmr-15, uniformly mixing, mixing with modified carbon fiber A1 (53 percent of the total resin), putting into an oven at 80 ℃ for pretreatment, after 1 hour, heating to 160 ℃ for 3 hours after the solution is volatilized, and heating to 200 ℃ for 4 hours. And then putting the fiber into a vacuum oven at 250 ℃ for treatment for 5 hours to obtain a prepressing material.
Die pressing process
Starting contact, heating to 280 ℃, pressurizing, closing the mold, continuously heating to 380 ℃, keeping the temperature for 1 hour, blowing for cooling, and demolding at 150 ℃. And (4) processing the strip after the mould is removed, drying the obtained strip by heat treatment in a box at 120 ℃, taking out the strip, standing for 24 hours, and performing radiation crosslinking (a cobalt-60 isotope radiation source, the dose of which is 8000Gy) to obtain a strip B1 test.
Example 2
Carboxylic anhydride containing carbon-carbon unsaturated double bond:
tetracarboxylic acid anhydride: 2, 3, 6, 7-naphthalenetetracarboxylic dianhydride
Controlling the viscosity: 10000
Mass fraction of polyamic acid: 60 percent of
Thermosetting polyimide resin: 3,4, 5-Trifluorophenylacetylene phthalic anhydride-terminated polyimide resin (same as PMR-15 monomer)
Preparation method is the same as example, and sample B2 is obtained
Example 3
Carboxylic anhydride containing carbon-carbon unsaturated double bond:
tetracarboxylic acid anhydride: 2, 3, 6, 7-naphthalenetetracarboxylic dianhydride
Controlling the viscosity: 9000
Mass fraction of polyamic acid: 35 percent of
Preparation method is the same as example, and sample B3 is obtained
Example 4
Carboxylic anhydride containing carbon-carbon unsaturated double bond:
tetracarboxylic acid anhydride: 2, 3, 6, 7-naphthalenetetracarboxylic dianhydride
Controlling the viscosity: 20000
Mass fraction of polyamic acid: 35 percent of
Preparation method is the same as example, and sample B4 is obtained
Example 5
Carboxylic anhydride containing carbon-carbon unsaturated double bond:
tetracarboxylic acid anhydride: 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride
Controlling the viscosity: 18000
Mass fraction of polyamic acid: 35 percent of
Preparation method is the same as example, and sample B5 is obtained
Example 6
Carboxylic anhydride containing carbon-carbon unsaturated double bond: norbornene dicarboxylic anhydride. Otherwise, as in example 1, a sample B6 was obtained.
Example 7
Carboxylic anhydride containing carbon-carbon unsaturated double bond: maleic anhydride. Otherwise, as in example 1, a sample B7 was obtained.
Comparative example 1
Same as example 1, but without the radiation crosslinking step. Sample bar D1 is obtained
Comparative example 2
The viscosity was controlled to 30000, and the procedure was repeated in the same manner as in example 1 to obtain a sample D2.
The test results are shown in table 1:
TABLE 1
The results in table 1 show that the polyimide carbon fiber composite materials all have very excellent mechanical properties (the tensile strength is greater than 490MPa), and the mechanical properties of the composite materials can be further improved through radiation crosslinking. In addition, the experimental result also shows that the polyimide carbon fiber composite material has very excellent flame retardant property (meeting the UL-0 or UL-1 standard). In view of the excellent mechanical and flame retardant properties of the polyimide carbon fiber composite material, the polyimide carbon fiber composite material can be widely applied to the high-tech fields of aviation, aerospace, electrical appliances, machinery, chemical engineering, microelectronics and the like.

Claims (9)

1. A method for preparing a carbon fiber and polyimide composite material is characterized by comprising the following steps:
(1) putting tetramine and an organic solvent into a reaction kettle, stirring and dissolving completely at room temperature, adding carbon-carbon unsaturated double bond-containing carboxylic anhydride solid powder, stirring at room temperature until the carboxylic anhydride solid powder is completely dissolved, continuing stirring and reacting, adding tetracarboxylic anhydride, and stirring and reacting at 2-5 ℃ to obtain a viscous polyamic acid solution;
(2) preparing a polyamic acid solution into a solution with the mass fraction of polyamic acid accounting for 35-60%, infiltrating carbon fiber, heating to 200 ℃, and drying to obtain primarily compounded carbon fiber;
(3) uniformly mixing thermosetting polyimide with the primarily compounded carbon fiber;
(4) and (4) carrying out compression molding, crosslinking and curing on the polyimide carbon fiber composite raw material obtained in the step (3), and then further carrying out radiation crosslinking to obtain the polyimide carbon fiber composite material.
2. The method for preparing a carbon fiber and polyimide composite material according to claim 1, wherein the polyamic acid has the following structure:
wherein R is1Is a group containing a carbon-carbon unsaturated double bond; r2 isOne or more of the following structures:wherein X is selected from one or more of the following divalent groups: -CO-, -O-, -S-, -SO2-、-CH2-、-C(CH3)2-、-C(CF3)2-。
3. The method for preparing the carbon fiber and polyimide composite material as claimed in claim 1 or 2, wherein the carboxylic anhydride containing carbon-carbon unsaturated double bond is one or more of the following structures:
4. the method for preparing a carbon fiber and polyimide composite according to claim 1 or 2, characterized in that the tetracarboxylic acid anhydride is selected from the group consisting of pyromellitic dianhydride, 2, 3, 6, 7-naphthalenetetracarboxylic dianhydride, 3, 3 ', 4, 4 ' -biphenyltetracarboxylic dianhydride, 1,2, 5, 6-naphthalenetetracarboxylic dianhydride, 2 ', 3, 3 ' -biphenyltetracarboxylic dianhydride, 3, 3 ', 4, 4 ' -benzophenonetetracarboxylic dianhydride, 4, 4 ' -oxydiphthalic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 3,4, 9, 10-perylenetetracarboxylic dianhydride, bis (3, 4-dicarboxyphenyl) propane dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, bis (2, 3-dicarboxyphenyl) methane dianhydride, bis (3, 4-dicarboxyphenyl) ethane dianhydride, oxydiphthalic dianhydride, bis (3, 4-dicarboxyphenyl) sulfone dianhydride, p-phenylene bis (trimellitic acid monoester anhydride), ethylene bis (trimellitic acid monoester anhydride), bisphenol A bis (trimellitic acid monoester anhydride).
5. The method for preparing a carbon fiber and polyimide composite according to claim 3, wherein the tetracarboxylic acid anhydride is selected from the group consisting of pyromellitic dianhydride, 2, 3, 6, 7-naphthalenetetracarboxylic dianhydride, 3, 3 ', 4, 4 ' -biphenyltetracarboxylic dianhydride, 1,2, 5, 6-naphthalenetetracarboxylic dianhydride, 2 ', 3, 3 ' -biphenyltetracarboxylic dianhydride, 3, 3 ', 4, 4 ' -benzophenonetetracarboxylic dianhydride, 4, 4 ' -oxydiphthalic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 3,4, 9, 10-perylenetetracarboxylic dianhydride, bis (3, 4-dicarboxyphenyl) propane dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, bis (2, 3-dicarboxyphenyl) methane dianhydride, bis (3, 4-dicarboxyphenyl) ethane dianhydride, oxydiphthalic dianhydride, bis (3, 4-dicarboxyphenyl) sulfone dianhydride, p-phenylene bis (trimellitic acid monoester anhydride), ethylene bis (trimellitic acid monoester anhydride), bisphenol A bis (trimellitic acid monoester anhydride).
6. The method for preparing a carbon fiber and polyimide composite material according to claim 1 or 2, wherein: the mass ratio of the polyamic acid to the carbon fiber is 1/10-1/1; the thermosetting polyimide accounts for 10-100% of the composite material by mass.
7. The method of preparing a carbon fiber and polyimide composite as claimed in claim 3, wherein: the mass ratio of the polyamic acid to the carbon fiber is 1/10-1/1; the thermosetting polyimide accounts for 10-100% of the composite material by mass.
8. The method of preparing a carbon fiber and polyimide composite as claimed in claim 4, wherein: the mass ratio of the polyamic acid to the carbon fiber is 1/10-1/1; the thermosetting polyimide accounts for 10-100% of the composite material by mass.
9. The method of preparing a carbon fiber and polyimide composite as claimed in claim 5, wherein: the mass ratio of the polyamic acid to the carbon fiber is 1/10-1/1; the thermosetting polyimide accounts for 10-100% of the composite material by mass.
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