CN108047470A - A kind of preparation method and product of continuous carbon fibre reinforced polyether ether ketone composite material - Google Patents
A kind of preparation method and product of continuous carbon fibre reinforced polyether ether ketone composite material Download PDFInfo
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- CN108047470A CN108047470A CN201711429254.5A CN201711429254A CN108047470A CN 108047470 A CN108047470 A CN 108047470A CN 201711429254 A CN201711429254 A CN 201711429254A CN 108047470 A CN108047470 A CN 108047470A
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/02—Condensation polymers of aldehydes or ketones with phenols only of ketones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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- 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
- 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
Abstract
The invention belongs to fiber-reinforced resin matrix compound material field, and disclose a kind of preparation method and product of continuous carbon fibre reinforced polyether ether ketone composite material.The preparation method includes completing the sulfonation modifying of polyether-ether-ketone by the copolyreaction of sulfonated monomer；Composite material prepreg is prepared using solution dipping method；Continuous lod polyether-ether-ketone composite material is prepared by heat pressure forming process.The invention also discloses the products obtained according to the preparation method.Pass through the present invention, solve the problems, such as that polyether-ether-ketone is practically insoluble in any solvent, propose the method that solution dipping method prepares prepreg tape, solves the problems, such as the preparation of continuous carbon fibre reinforced polyether ether ketone composite material, simultaneously, polyether-ether-ketone after sulfonation can improve the binding ability of polymeric matrix and fiber interface, so as to improve the mechanical performance of fiber reinforcement polyether-ether-ketone composite material.
Description
Technical field
The invention belongs to fiber-reinforced resin matrix compound material fields, enhance more particularly, to a kind of continuous carbon fibre
The preparation method and product of polyether-ether-ketone composite material.
Background technology
Polyether-ether-ketone is a kind of engineering plastics with excellent mechanical performance, heat resistance and chemical resistance.Due to
Its excellent comprehensive performance, polyether-ether-ketone and the continuous carbon fibre using polyether-ether-ketone as polymeric matrix have enhanced composite material
It is widely used in the fields such as aerospace, electronic information, the energy and medical treatment.The system of continuous fiber reinforced thermoplastic composite material
Polymeric matrix and fibre reinforcement are processed as prepreg tape with certain impregnation technology first during standby；Then, prepreg tape
Cure under certain process conditions and obtain the closely knit continuous fiber reinforced thermoplastic joint product of structure.At present, continuous fiber
The manufacturing method of reinforced thermoplastics composite material prepreg mainly includes melt impregnation, powder infusion and solution impregnating.
However, since the melt viscosity of polyether-ether-ketone resin is larger, prepares the polyether-ether-ketone melted during composite material and be difficult to penetrate into
In the beam of carbon fiber, final polyether-ether-ketone resin is very limited to the effect of impregnation of carbon fiber, can hardly play carbon fiber
Enhancing effect, therefore using melt impregnation and powder infusion method when preparing continuous carbon fibre reinforced polyether ether ketone composite material
It is difficult to overcome the problems, such as the high melt viscosity of polyether-ether-ketone.In addition, polyether-ether-ketone has very outstanding solvent resistance, in room temperature
Under be practically insoluble in all organic solvents, solution prepreg method manufacture continuous lod polyether-ether-ketone composite material also becomes difficult to
It realizes.Therefore, the very high melt viscosity of polyether-ether-ketone and the characteristics of be practically insoluble in any solvent so that continuous carbon fibre increases
The preparation of strong polyether-ether-ketone composite material always exists larger technical bottleneck.
Patent CN201510111874.9 discloses a kind of preparation side of carbon fibre fabric reinforced polyether ether ketone composite material
Method.Polyether-ether-ketone powder is added in the chloroform of polyarylsulfone (PAS) or N,N-dimethylformamide (DMF) solution and stirred in the patent
It mixes and uniformly obtains suspension, then suspension is poured on carbon fibre fabric and using the method that low pressure filters solvent is made to wave completely
Hair, while polyether-ether-ketone powder is promoted to be penetrated into fibre bundle.But the technological requirement polyether-ether-ketone powder must possess very little
Grain size (100 mesh~600 mesh), manufacture superfine powder can greatly improve manufacture cost；Meanwhile there is no inherently solve the technique
Certainly the high melt viscosity of polyether-ether-ketone and it is practically insoluble in the problem of any solvent.
The content of the invention
For the disadvantages described above or Improvement requirement of the prior art, the present invention provides a kind of continuous carbon fibres to enhance polyethers ether
The preparation method and product of ketone composite material, by using the sulfonated polyether-ether-ketone after sulfonation modifying so that polyether-ether-ketone can
It is dissolved into common organic solvents, so as to solve the high melt viscosity of polyether-ether-ketone and be practically insoluble in asking for any solvent
Topic, in addition, the polyether-ether-ketone after sulfonation can improve the binding ability of polymeric matrix and fiber interface so that fibre reinforced
The solution dip forming of polyether-ether-ketone composite material prepreg tape is possibly realized, therefore it is compound also to solve fiber reinforcement polyether-ether-ketone
The preparation problem of material prepreg tape.
To achieve the above object, one side according to the invention provides a kind of continuous carbon fibre reinforced polyether ether ketone
The preparation method of composite material, which is characterized in that the preparation method comprises the following steps：
(a) polyether-ether-ketone sulfonation modifying is obtained into sulfonated polyether-ether-ketone powder, which is dissolved in
In organic solvent, uniform polymer solution is stirred to get, carbon fibre fabric is placed in the polymer solution and is impregnated, is taken out
Fabric after immersion simultaneously dries acquisition prepreg；
(b) hot-forming after multiple prepreg overlays obtained through step (a) are stacked, hot-forming temperature is 360
DEG C~400 DEG C, pressure is 1MPa~5MPa, and the dwell time is 10min~20min, laminate is obtained after cooling, by the laminate
Required composite product is obtained after cutting polishing.
It is further preferred that in step (a), the polyether-ether-ketone sulfonation modifying process preferably according to the following steps,
(a1) 4,4'- difluoro benzophenones and mass fraction for 30% oleum are mixed, are continuously stirred and heated to
110 DEG C make its reaction, and reaction time 6h will be poured into after the solution cooling after reaction in ice water, and then adding in sodium hydroxide makes
It obtains the solution to be in neutrality, which is saltoutd, filtered and dried according to this, be derived from sulfonated monomer 3, bis- sulphurs of 3'-
Sour sodium base -4,4'- difluoro benzophenones；Then pure sulfonated monomer is recrystallized to give three times with the aqueous solution of methanol；
(a2) by non-sulfonated monomer 4,4'- difluoro benzophenones, 3,3', 5,5'- tetramethyl -4,4'- dihydroxy of bis-phenol connection
The sulfonated monomer 3 that benzene and step (a) obtain, 3'- sodium disulfonate base -4,4'- difluoro benzophenones are mixed to form solution,
Dimethyl sulfoxide (DMSO) (DMSO), Anhydrous potassium carbonate, toluene are added in the solution, and 3h is stirred to react at 140 DEG C, it is molten after reaction
Liquid is then warming up to 170 DEG C the reaction was continued that 7h obtains intermediate solution；
During intermediate solution cooling is fallen back, flocky precipitate is obtained, which is taken out and crushed
To the sulfonated polyether-ether-ketone crude product containing impurity；
Crude product with distilled water and methanol is boiled, filters to remove inorganic salts and solvent therein, is institute after drying
The sulfonated polyether-ether-ketone needed.
It is further preferred that in step (a), the mass fraction of the polymer solution is 5%~10%.
It is further preferred that in step (b), the temperature is more preferably 380 DEG C, and pressure is more preferably
3MPa。
It is further preferred that in step (a), the drying preferably uses microwave drying.
It is another aspect of this invention to provide that provide a kind of polyether-ether-ketone composite wood obtained using above-mentioned preparation method
Expect product.
In general, by the above technical scheme conceived by the present invention compared with prior art, it can obtain down and show
Beneficial effect：
1st, the present invention solves polyether-ether-ketone and is practically insoluble in any solvent by using the polyether-ether-ketone after sulfonation modifying
Problem, it is proposed that the method that solution dipping method prepares prepreg tape solves continuous carbon fibre reinforced polyether ether ketone composite material
The problem of preparation, meanwhile, the polyether-ether-ketone after sulfonation can improve the binding ability of polymeric matrix and fiber interface, so as to carry
The mechanical performance of high microsteping reinforced polyether ether ketone composite material；
2nd, the carbon fiber reinforced polyetheretherketonecomposite composite material prepared by method provided by the invention, tensile strength is high, highest
Up to 640MPa, interlaminar shear strength reaches as high as 90MPa, and fiber has good wettability and adhesiveness with resin matrix；
3rd, the present invention uses hot-forming temperature dwell pressure 3MPa ensure that polyether-ether-ketone matrix and carbon for 380 DEG C
Wetting effect between fibre reinforced materials, and performance impairment and pressure caused by preventing that temperature is excessively high and causing matrix thermal degradation
Fibre deformation caused by excessive so that there is optimal mechanical performance according to the contemplated composite material of the present invention.
Description of the drawings
Fig. 1 is the system of the continuous carbon fibre reinforced polyether ether ketone composite material constructed by preferred embodiment according to the invention
Preparation Method flow chart；
Fig. 2 is the schematic diagram for preparing prepreg constructed by preferred embodiment according to the invention；
Fig. 3 is the sulfonated monomer 3,3'- sodium disulfonate base -4,4'- difluoros constructed by preferred embodiment according to the invention
The synthesis schematic diagram of benzophenone；
Fig. 4 is the synthesis schematic diagram of the sulfonated polyether-ether-ketone constructed by preferred embodiment according to the invention；
Fig. 5 is the polyether-ether-ketone composite material cross-section morphology figure constructed by preferred embodiment according to the invention.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, it is right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Conflict is not formed each other to can be combined with each other.
A kind of preparation method of continuous carbon fibre reinforced polyether ether ketone composite material, comprises the following steps：
1) solution dipping method prepares prepreg tape：Sulfonated polyether-ether-ketone powder is dissolved in organic solvent, is stirred continuously and obtains
Uniform polymer solution is obtained, then carbon fibre fabric is placed in polymer solution, certain time is impregnated under room temperature and is taken out, most
Using microwave drying technology the solvent in fabric is made to volatilize completely afterwards and obtain prepregs；
2) preparation of carbon fiber reinforced polyetheretherketonecomposite composite material：Prepregs in step 1 are spread in certain sequence
Layer is placed in hot press, is heated to 360~400 DEG C, is applied the pressure and 10~20min of pressurize of 1~5MPa, is acted in pressure
Under be cooled to room temperature to obtain laminate, finally to laminate carry out cut polishing be made composite product.
Heating temperature is 360~400 DEG C, is because with the increase of forming temperature, the viscosity of polyether-ether-ketone resin melt
Decline, wellability is improved between matrix and carbon fiber, and the effect that load passes to fiber by resin improves, thus compound
The tensile property of material increases, and when temperature continues to increase, after 380 DEG C, thermal degradation takes place in matrix, causes the property of matrix
Can be impaired, under tensile load, the matrix that these are degraded is relatively fragile, is easy to cause stress concentration, causes composite material
Tensile property declines；The pressure for applying 1~5MPa is because of under relatively low dwell pressure, and polyether-ether-ketone resin can not penetrate into carbon
Good wetting effect is formed in fibre bundle, still, dwell pressure is excessive, and resin easily causes the change of fiber while flowing
Shape makes carbon fiber tortuous, it is impossible to give full play to its advantage as reinforcement, the tensile property of composite material is also under
Drop.
Prepreg tape preparation in step 1 is as follows：
Sulfonated polyether-ether-ketone powder is dissolved in organic solvent n,N-Dimethylformamide (DMF), is stirred continuously acquisition
Carbon fibre fabric, is then placed in polymer solution, under room temperature by the polymer solution that uniform mass fraction is 5%~10%
It is taken out after impregnating 5~10min, it is finally that carbon fibre fabric is evenly laid out on the glass plate of barrier paper is placed with, it is placed in microwave
Vacuum drying chamber uses microwave drying technology that the solvent in fabric is made to volatilize completely and obtains prepregs.
Sulfonated polyether-ether-ketone in step 1 is to react to introduce sulfonic group with oleum by sulfonated monomer, Ran Houli
With nucleophilic condensation polymerization, sulfonated polyether-ether-ketone is prepared by copolyreaction in sulfonated monomer, non-sulfonated monomer and bis-phenol, leads to
The sulfonation degree of polyether-ether-ketone can be changed by crossing the ratio of change sulfonated monomer and non-sulfonated monomer, and then obtain different dipping effects
Prepreg tape, polyether-ether-ketone sulfonation modifying is as follows：
1.1) synthesis of sulfonated monomer (3,3'- sodium disulfonate base -4,4'- difluoro benzophenones)
4,4'- difluoro benzophenones and 30% oleum are sequentially added equipped with mechanical agitation, thermometer and returned cold
In the three-necked flask of solidifying pipe, 110 DEG C of reaction 6h are continuously stirred and heated to, are slowly poured into after cooling in ice water, ice water temperature is 0
DEG C adding in sodium hydroxide to solution is in neutrality, and then adds in sodium chloride and saltouts, filters and be dried to obtain sulfonated monomer, then uses methanol
Aqueous solution be recrystallized to give the sulfonated monomer of high-purity three times；
1.2) synthesis of sulfonated polyether-ether-ketone (SPEEK)
By sulfonated monomer 3,3'- sodium disulfonate base -4,4'- difluoro benzophenones, non-sulfonated monomer 4,4'- difluorodiphenyl first
Ketone and bis-phenol 3,3', 5,5'- tetramethyl -4,4' dihydroxy diphenyl add in equipped with mechanical agitator, Dean-Stark water knockout drums and
It is catalyst, toluene by solvent (solid content is 20%~40%), Anhydrous potassium carbonate of DMSO in the three-necked flask of nitrogen port
For water entrainer, 3h is stirred to react to remove moisture at 140 DEG C, then heats to 170 DEG C of reaction 7h, it will reaction after being cooled to room temperature
Mixture is poured into water to obtain flocculent deposit, after crushing, successively boiled with distilled water and methanol, filter to remove it is therein inorganic
Salt and solvent finally, are placed in vacuum drying oven the drying at 100 DEG C and obtain sulfonated polyether-ether-ketone for 24 hours.
It further illustrates the present invention below in conjunction with specific embodiments.
The polyether-ether-ketone of different sulfonation degrees is obtained by the ratio for changing sulfonated monomer and non-sulfonated monomer and is changed over
Forming temperature, dwell pressure and dwell time during shape, so the composite material for obtaining different dipping effects obtain it is different
Embodiment.
Embodiment 1
0.5mol 4,4'- difluoro benzophenones and 30% oleums of 300mL are sequentially added equipped with mechanical agitation, temperature
In the three-necked flask of degree meter and reflux condensing tube, 110 DEG C of reaction 6h are continuously stirred and heated to, ice water is slowly poured into after cooling
In, it adds in sodium hydroxide to solution and is in neutrality, then add in sodium chloride and saltout, filter and be dried to obtain sulfonated monomer, then use first
The aqueous solution of alcohol is recrystallized to give the sulfonated monomer of high-purity three times.By 30mmol sulfonated monomer 3,3'- sodium disulfonates base-
4,4'- difluoro benzophenones, non-sulfonated monomer 70mmol 4,4'- difluoro benzophenones and 100mmol bis-phenols 3,3', 5,5'- tetra-
Methyl -4,4' dihydroxy diphenyl adds in the three-necked flask equipped with mechanical agitator, Dean-Stark water knockout drums and nitrogen port
In, using DMSO as solvent (solid content is 20%~40%), Anhydrous potassium carbonate be catalyst, toluene is water entrainer, stirred at 140 DEG C
Reaction 3h is mixed to remove moisture, 170 DEG C of reaction 7h is then heated to, is poured into water to obtain by reaction mixture after being cooled to room temperature
Flocculent deposit after crushing, is successively boiled with distilled water and methanol, filters to remove inorganic salts and solvent therein.Finally, it is placed in
It is dry at 100 DEG C in vacuum drying oven to obtain the polyether-ether-ketone that sulfonation degree is 0.6 for 24 hours.Sulfonated polyether-ether-ketone powder is dissolved in
In organic solvent DMF, the polymer solution for obtaining that uniform mass fraction is 10% is stirred continuously, then puts carbon fibre fabric
It in polymer solution, is taken out after impregnating 5~10min under room temperature, is finally being placed with barrier paper by carbon fibre fabric is evenly laid out
Glass plate on, be placed in micro-wave vacuum case makes the solvent in fabric volatilize completely to be presoaked using microwave drying technology
Material products.Finally, by prepregs, laying is placed in hot press in certain sequence, is heated to 380 DEG C, applies the pressure of 3MPa
Power and pressurize 10min are demoulded after being cooled to room temperature under pressure and are obtained the composite material that carbon fiber mass fraction is 60%,
Its tensile strength is 640MPa, and interlaminar shear strength is up to 90MPa.
Embodiment 2
By 20mmol sulfonated monomer 3,3'- sodium disulfonate base -4,4'- difluoro benzophenones, non-sulfonated monomer 80mmol 4,
4'- difluoro benzophenones and 100mmol bis-phenols 3,3', 5,5'- tetramethyl -4,4' dihydroxy diphenyl are added in equipped with mechanical agitation
In the three-necked flask of device, Dean-Stark water knockout drums and nitrogen port, using DMSO as solvent (solid content is 20%~40%), nothing
Aqueous carbonate potassium is catalyst, toluene is water entrainer, and 3h is stirred to react to remove moisture at 140 DEG C, then heats to 170 DEG C of reactions
Reaction mixture is poured into water to obtain flocculent deposit after being cooled to room temperature, after crushing, successively be boiled with distilled water and methanol by 7h
Boiling is filtered to remove inorganic salts and solvent therein, finally, is placed in vacuum drying oven the drying at 100 DEG C and is obtained sulfonation degree for 24 hours
For 0.4 polyether-ether-ketone, sulfonated polyether-ether-ketone powder is dissolved in organic solvent DMF, is stirred continuously and obtains uniform quality
Fraction is 10% polymer solution, and then carbon fibre fabric is placed in polymer solution, after impregnating 5~10min under room temperature
It takes out, it is finally that carbon fibre fabric is evenly laid out on the glass plate of barrier paper is placed with, it is placed in the use of micro-wave vacuum case
Microwave drying technology make the solvent in fabric volatilize completely obtain prepregs.Finally, by prepregs in certain sequence
Laying is placed in hot press, is heated to 380 DEG C, is applied the pressure and pressurize 10min of 3MPa, is cooled to room under pressure
The demoulding obtains the composite material that carbon fiber mass fraction is 60% after temperature, and tensile strength 598MPa, interlaminar shear strength can
Up to 85MPa.
Embodiment 3
By 10mmol sulfonated monomer 3,3'- sodium disulfonate base -4,4'- difluoro benzophenones, non-sulfonated monomer 90mmol 4,
4'- difluoro benzophenones and 100mmol bis-phenols 3,3', 5,5'- tetramethyl -4,4' dihydroxy diphenyl are added in equipped with mechanical agitation
In the three-necked flask of device, Dean-Stark water knockout drums and nitrogen port, using DMSO as solvent (solid content is 20%~40%), nothing
Aqueous carbonate potassium is catalyst, toluene is water entrainer, and 3h is stirred to react to remove moisture at 140 DEG C, then heats to 170 DEG C of reactions
Reaction mixture is poured into water to obtain flocculent deposit after being cooled to room temperature, after crushing, successively be boiled with distilled water and methanol by 7h
Boiling is filtered to remove inorganic salts and solvent therein, finally, is placed in vacuum drying oven the drying at 100 DEG C and is obtained sulfonation degree for 24 hours
For 0.2 polyether-ether-ketone, sulfonated polyether-ether-ketone powder is dissolved in organic solvent DMF, is stirred continuously and obtains uniform quality
Fraction is 10% polymer solution, and then carbon fibre fabric is placed in polymer solution, after impregnating 5~10min under room temperature
It takes out, it is finally that carbon fibre fabric is evenly laid out on the glass plate of barrier paper is placed with, it is placed in the use of micro-wave vacuum case
Microwave drying technology make the solvent in fabric volatilize completely obtain prepregs.Finally, by prepregs in certain sequence
Laying is placed in hot press, is heated to 380 DEG C, is applied the pressure and pressurize 10min of 3MPa, is cooled to room under pressure
The demoulding obtains the composite material that carbon fiber mass fraction is 60% after temperature, and tensile strength 535MPa, interlaminar shear strength can
Up to 78MPa.
Embodiment 4
0.5mol 4,4'- difluoro benzophenones and 30% oleums of 300mL are sequentially added equipped with mechanical agitation, temperature
In the three-necked flask of degree meter and reflux condensing tube, 110 DEG C of reaction 6h are continuously stirred and heated to, ice water is slowly poured into after cooling
In, it adds in sodium hydroxide to solution and is in neutrality, then add in sodium chloride and saltout, filter and be dried to obtain sulfonated monomer, then use first
The aqueous solution of alcohol is recrystallized to give the sulfonated monomer of high-purity three times.By 30mmol sulfonated monomer 3,3'- sodium disulfonates base-
4,4'- difluoro benzophenones, non-sulfonated monomer 70mmol 4,4'- difluoro benzophenones and 100mmol bis-phenols 3,3', 5,5'- tetra-
Methyl -4,4' dihydroxy diphenyl adds in the three-necked flask equipped with mechanical agitator, Dean-Stark water knockout drums and nitrogen port
In, using DMSO as solvent (solid content is 20%~40%), Anhydrous potassium carbonate be catalyst, toluene is water entrainer, stirred at 140 DEG C
Reaction 3h is mixed to remove moisture, 170 DEG C of reaction 7h is then heated to, is poured into water to obtain by reaction mixture after being cooled to room temperature
Flocculent deposit after crushing, is successively boiled with distilled water and methanol, filters to remove inorganic salts and solvent therein.Finally, it is placed in
It is dry at 100 DEG C in vacuum drying oven to obtain the polyether-ether-ketone that sulfonation degree is 0.6 for 24 hours.Sulfonated polyether-ether-ketone powder is dissolved in
In organic solvent DMF, the polymer solution for obtaining that uniform mass fraction is 10% is stirred continuously, then puts carbon fibre fabric
It in polymer solution, is taken out after impregnating 5~10min under room temperature, is finally being placed with barrier paper by carbon fibre fabric is evenly laid out
Glass plate on, be placed in micro-wave vacuum case makes the solvent in fabric volatilize completely to be presoaked using microwave drying technology
Material products.Finally, by prepregs, laying is placed in hot press in certain sequence, is heated to 360 DEG C, applies the pressure of 5MPa
Power and pressurize 20min are demoulded after being cooled to room temperature under pressure and are obtained the composite material that carbon fiber mass fraction is 64%,
Its tensile strength is 570MPa, and interlaminar shear strength is up to 73MPa.
Embodiment 5
0.5mol 4,4'- difluoro benzophenones and 30% oleums of 300mL are sequentially added equipped with mechanical agitation, temperature
In the three-necked flask of degree meter and reflux condensing tube, 110 DEG C of reaction 6h are continuously stirred and heated to, ice water is slowly poured into after cooling
In, it adds in sodium hydroxide to solution and is in neutrality, then add in sodium chloride and saltout, filter and be dried to obtain sulfonated monomer, then use first
The aqueous solution of alcohol is recrystallized to give the sulfonated monomer of high-purity three times.By 30mmol sulfonated monomer 3,3'- sodium disulfonates base-
4,4'- difluoro benzophenones, non-sulfonated monomer 70mmol 4,4'- difluoro benzophenones and 100mmol bis-phenols 3,3', 5,5'- tetra-
Methyl -4,4' dihydroxy diphenyl adds in the three-necked flask equipped with mechanical agitator, Dean-Stark water knockout drums and nitrogen port
In, using DMSO as solvent (solid content is 20%~40%), Anhydrous potassium carbonate be catalyst, toluene is water entrainer, stirred at 140 DEG C
Reaction 3h is mixed to remove moisture, 170 DEG C of reaction 7h is then heated to, is poured into water to obtain by reaction mixture after being cooled to room temperature
Flocculent deposit after crushing, is successively boiled with distilled water and methanol, filters to remove inorganic salts and solvent therein.Finally, it is placed in
It is dry at 100 DEG C in vacuum drying oven to obtain the polyether-ether-ketone that sulfonation degree is 0.6 for 24 hours.Sulfonated polyether-ether-ketone powder is dissolved in
In organic solvent DMF, the polymer solution for obtaining that uniform mass fraction is 10% is stirred continuously, then puts carbon fibre fabric
It in polymer solution, is taken out after impregnating 5~10min under room temperature, is finally being placed with barrier paper by carbon fibre fabric is evenly laid out
Glass plate on, be placed in micro-wave vacuum case makes the solvent in fabric volatilize completely to be presoaked using microwave drying technology
Material products.Finally, by prepregs, laying is placed in hot press in certain sequence, is heated to 400 DEG C, applies the pressure of 1MPa
Power and pressurize 20min are demoulded after being cooled to room temperature under pressure and are obtained the composite material that carbon fiber mass fraction is 57%,
Its tensile strength is 610MPa, and interlaminar shear strength is up to 83MPa.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, all any modification, equivalent and improvement made within the spirit and principles of the invention etc., should all include
Within protection scope of the present invention.
Claims (6)
1. a kind of preparation method of continuous carbon fibre reinforced polyether ether ketone composite material, which is characterized in that the preparation method includes
The following steps：
(a) polyether-ether-ketone sulfonation modifying is obtained into sulfonated polyether-ether-ketone powder, which is dissolved in organic
In solvent, uniform polymer solution is stirred to get, carbon fibre fabric is placed in the polymer solution and is impregnated, takes out and impregnates
Rear fabric simultaneously dries acquisition prepreg；
(b) it is hot-forming after multiple prepreg overlays obtained through step (a) are stacked, hot-forming temperature for 360 DEG C~
400 DEG C, pressure is 1MPa~5MPa, and the dwell time is 10min~20min, obtains laminate after cooling, which is cut
Required composite product is obtained after polishing.
2. a kind of preparation method of continuous carbon fibre reinforced polyether ether ketone composite material as described in claim 1, feature exist
In, in step (a), the polyether-ether-ketone sulfonation modifying process preferably according to the following steps,
(a1) 4,4'- difluoro benzophenones and mass fraction for 30% oleum are mixed, is continuously stirred and heated to 110 DEG C
Make its reaction, reaction time 6h will be poured into ice water after the solution cooling after reaction, then be added in sodium hydroxide and so that this is molten
Liquid is in neutrality, which is saltoutd, filtered and dried according to this, is derived from sulfonated monomer 3, and 3'- sodium disulfonates base-
4,4'- difluoro benzophenones；Then pure sulfonated monomer is recrystallized to give three times with the aqueous solution of methanol；
(a2) by non-sulfonated monomer 4,4'- difluoro benzophenones, 3,3', 5,5'- tetramethyl -4,4'- dihydroxybiphenyl of bis-phenol, with
And the sulfonated monomer 3 that step (a) obtains, 3'- sodium disulfonate base -4,4'- difluoro benzophenones are mixed to form solution, in the solution
Middle addition dimethyl sulfoxide (DMSO) (DMSO), Anhydrous potassium carbonate, toluene, and 3h is stirred to react at 140 DEG C, the solution after reaction is then
It is warming up to 170 DEG C the reaction was continued that 7h obtains intermediate solution；
Intermediate solution cooling is fallen back, obtains flocky precipitate, which is taken out and crushed is contained
There is the sulfonated polyether-ether-ketone crude product of impurity；
Crude product with distilled water and methanol is boiled, filters to remove inorganic salts and solvent therein, is required after drying
Sulfonated polyether-ether-ketone.
3. a kind of preparation method of continuous carbon fibre reinforced polyether ether ketone composite material as claimed in claim 1 or 2, feature
It is, in step (a), the mass fraction of the polymer solution is 5%~10%.
4. a kind of such as preparation method of continuous carbon fibre reinforced polyether ether ketone composite material of claim 1-3 any one of them,
It is characterized in that, in step (b), the temperature is more preferably 380 DEG C, and pressure is more preferably 3MPa.
5. a kind of such as preparation method of continuous carbon fibre reinforced polyether ether ketone composite material of claim 1-4 any one of them,
It is characterized in that, in step (a), the drying preferably uses microwave drying.
6. a kind of polyether-ether-ketone composite material product obtained using claim 1-5 any one of them preparation methods.
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