CN113563577A - Phenolphthalein modified polyaryletherketone water-based sizing agent and preparation method and application thereof - Google Patents
Phenolphthalein modified polyaryletherketone water-based sizing agent and preparation method and application thereof Download PDFInfo
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- CN113563577A CN113563577A CN202110848769.9A CN202110848769A CN113563577A CN 113563577 A CN113563577 A CN 113563577A CN 202110848769 A CN202110848769 A CN 202110848769A CN 113563577 A CN113563577 A CN 113563577A
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- China
- Prior art keywords
- sizing agent
- polyaryletherketone
- phenolphthalein
- agent
- phenolphthalein modified
- Prior art date
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- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 title claims abstract description 166
- 238000004513 sizing Methods 0.000 title claims abstract description 127
- 229920006260 polyaryletherketone Polymers 0.000 title claims abstract description 124
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 121
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
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- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 7
- 239000002216 antistatic agent Substances 0.000 claims abstract description 7
- 239000000314 lubricant Substances 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
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- 239000004917 carbon fiber Substances 0.000 claims description 102
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 76
- 239000002131 composite material Substances 0.000 claims description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 23
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- 239000004696 Poly ether ether ketone Substances 0.000 claims description 17
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
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- 238000001035 drying Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
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- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 6
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- 238000013329 compounding Methods 0.000 claims description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 6
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- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 5
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- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 claims description 4
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
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- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 2
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- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 2
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- IJCWFDPJFXGQBN-RYNSOKOISA-N [(2R)-2-[(2R,3R,4S)-4-hydroxy-3-octadecanoyloxyoxolan-2-yl]-2-octadecanoyloxyethyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCCCCCCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCCCCCCCCCCCC IJCWFDPJFXGQBN-RYNSOKOISA-N 0.000 claims description 2
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 claims description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 2
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- 238000009835 boiling Methods 0.000 claims description 2
- ULBTUVJTXULMLP-UHFFFAOYSA-N butyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCC ULBTUVJTXULMLP-UHFFFAOYSA-N 0.000 claims description 2
- 229940078456 calcium stearate Drugs 0.000 claims description 2
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 2
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- 235000013922 glutamic acid Nutrition 0.000 claims description 2
- 125000005456 glyceride group Chemical group 0.000 claims description 2
- ZFUZDIJGWTXGKG-UHFFFAOYSA-N hexadecanoic acid;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.CCCCCCCCCCCCCCCC(O)=O ZFUZDIJGWTXGKG-UHFFFAOYSA-N 0.000 claims description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
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- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 6
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Classifications
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
- C08G65/4043—(I) or (II) containing oxygen other than as phenol or carbonyl group
- C08G65/405—(I) or (II) containing oxygen other than as phenol or carbonyl group in ring structure, e.g. phenolphtalein
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
- C08G65/4043—(I) or (II) containing oxygen other than as phenol or carbonyl group
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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
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention provides a phenolphthalein modified polyaryletherketone water sizing agent, and a preparation method and application thereof. The sizing agent comprises the following components in percentage by mass: 0.5-3 parts of phenolphthalein modified polyaryletherketone resin, 0.2-5 parts of surfactant, 0.1-1 part of flatting agent, 0.1-1 part of lubricant, 0.1-1 part of defoaming agent, 0.1-2 parts of adhesive, 0.2-1 part of antistatic agent and 86-98.7 parts of deionized water; according to the principle of 'similar compatibility', the main sizing agent provided by the invention is polyaryletherketone resin containing twisted non-coplanar groups and having a carboxyl functional side group phenolphthalein structural unit, so that excellent compatibility between the sizing agent and polyaryletherketone matrix resin can be ensured, and the sizing agent also has better thermal stability. Finally, the aqueous sizing agent is prepared by an emulsion solvent volatilization method, the diffusion and physical entanglement effects between the sizing agent and the matrix resin can enhance the interface adhesion, and the carboxyl contained in the phenolphthalein can also form a hydrogen bond with the ketone group in the matrix resin, thereby further improving the interface adhesion between the two.
Description
Technical Field
The invention belongs to the technical field of sizing agents, and particularly relates to a phenolphthalein modified polyaryletherketone aqueous sizing agent, and a preparation method and application thereof.
Background
As a special engineering plastic, the Polyaryletherketone (PAEK) polymer has outstanding characteristics of high heat resistance, high strength, high rigidity, creep resistance, toughness and the like because the main chain of the Polyaryletherketone (PAEK) polymer has a special molecular structure containing rigid and heat-resistant phenylene and flexible and heat-resistant oxygen ether bonds. However, in some advanced fields, the performance of the PAEK is limited by using the PAEK alone, and the Carbon Fiber (CF) has excellent mechanical properties and good reinforcing effect, and is generally used as a reinforcing body to improve the performance of the PAEK. Carbon fiber reinforced polyaryletherketone (CF/PAEK) composite materials are widely used due to their advantages of low density, high specific strength, high thermal stability, etc. However, the CF/PAEK composite material has undesirable interface performance due to chemical inertness caused by the lack of active functional groups on the surface of the CF and the inactivity of the PAEK molecular chain structure.
In order to improve the interfacial adhesion between the fibers and the matrix and the mechanical properties of the composite, the sizing method is considered to be a low-cost, simple and effective method to solve the above problems. The surface of the carbon fiber is coated with a layer of sizing agent, so that the fluffing and breaking phenomena of the fiber can be reduced, and in addition, the coated sizing agent layer plays a role in connection similar to a bridge, so that the interface interaction between the fiber and the resin is enhanced. However, commercial epoxy sizing agents are mostly used in the market at present, and the structure of the sizing agent is similar to that of thermosetting matrix resin, such as epoxy resin, unsaturated polyester and the like, and the compatibility with PAEK resin is poor; on the other hand, it is relatively poor in thermal stability, and generally decomposes at temperatures exceeding 250 ℃ and cannot satisfy the processing temperature of PAEK (380 to 400 ℃). The problem of poor compatibility and permeability inevitably occurs after the CF surface is coated with the sizing agent, and further defects occur on the CF/PAEK composite material interface. Therefore, the development of PAEK sizing agent matched with PAEK matrix resin has important research significance. According to the report, the sizing agents which are developed by the prior experiments and are suitable for the PAEK resin are mostly solvent-based, and the practical application of the sizing agents is limited due to the high cost and the environmental pollution caused by the sizing agents. Therefore, the development of the low-cost water-based sizing agent has good application prospect.
Most of polyaryletherketone resins are insoluble in polar aprotic solvents, and in order to change the solubility of the polyaryletherketone resins, the polyaryletherketone resins can be dissolved in the polar aprotic solvents, so that the solvent is recovered to prepare the solvent-free waterborne sizing agent. The introduction of non-coplanar groups on the main chain segment of the PAEK resin causes the regularity of the PAEK resin structure to generate defects, and the PAEK resin is easy to dissolve in a polar aprotic solvent. Meanwhile, the introduced side chain group can generate chemical bond and hydrogen bond with the matrix resin, so that the interface performance of the composite material can be further improved.
In recent years, researchers have studied sizing agents suitable for thermoplastic resins. Patent CN 107022901B discloses a composite water-based carbon fiber sizing agent, a preparation method and a use method thereof, although the thermal decomposition temperature of the sizing agent can meet the processing temperature of PEEK, epoxy resin existing in the main sizing agent of the sizing agent has poor compatibility with PEEK resin matrix, and organic solvent contained in the sizing agent has adverse effects on the safety of operators and the development of environment. Patent CN 109930388A discloses a preparation method of a modified polyetheretherketone resin-based sizing agent for carbon fibers, which has good compatibility with PEEK resin and significantly improves the interfacial bonding between fibers and resin, but the main component of the sizing agent contains an organic solvent, so the application cost is correspondingly increased, and the application range may be limited. Patent CN 102926203B provides a sizing agent for emulsion carbon fiber, which has good compatibility with thermoplastic Polycarbonate (PC) resin and improves the interlaminar shear strength of the composite material by more than 20%, but the main sizing agent of the sizing agent contains epoxy resin, which is easily decomposed during high temperature processing and has relatively poor heat resistance. Patent CN 112695531 a provides a composite high temperature resistant sizing agent for carbon fibers, a preparation method and applications thereof, the sizing agent can significantly improve the interface between carbon fibers and a resin matrix and can improve the tensile strength of a composite material, but the main component of the sizing agent contains an organic solvent, which can damage operating equipment and threaten the safety of operators, and does not meet the requirements of green chemical development. Therefore, the development of the water sizing agent suitable for the carbon fiber reinforced polyaryletherketone (CF/PAEK) composite material system is significant. In addition, the carbon fiber treated by the aqueous sizing agent has good dispersibility in water, and can be used in various fields, such as: preparing carbon paper, carbon felt and carbon-carbon composite material.
Disclosure of Invention
In order to solve the technical problem, the invention provides a phenolphthalein modified polyaryletherketone water sizing agent, and the preparation method comprises the following steps:
(1) placing the phenolphthalein modified polyaryletherketone resin into an organic solvent, and fully stirring to completely dissolve the phenolphthalein modified polyaryletherketone resin to form a uniform solution;
(2) adding a surfactant into deionized water, fully stirring, adding the solution obtained in the step (1), uniformly mixing, performing ultrasonic shearing treatment, and keeping the temperature of the solution at 15-45 ℃ to obtain a mixed solution;
(3) adding a leveling agent, a lubricant, a defoaming agent, an adhesive and an antistatic agent into the mixed solution obtained in the step (2), uniformly stirring, and then recovering the organic solvent by distillation or rotary evaporation to obtain the phenolphthalein modified polyaryletherketone aqueous sizing agent;
the organic solvent in the step (1) is any one of dichloromethane or trichloromethane;
the ultrasonic shearing treatment time in the step (2) is 2-20 min, and the power is 100-1000W;
the composite material comprises the following components in percentage by mass:
0.5-3% of phenolphthalein modified polyaryletherketone resin, 0.2-5% of surfactant, 0.1-1% of flatting agent, 0.1-1% of lubricant, 0.1-1% of defoaming agent, 0.1-2% of adhesive, 0.2-1% of antistatic agent and 86-98.7% of deionized water;
the phenolphthalein modified polyaryletherketone resin in the step (1) has a structural formula shown in a formula 1:
Further, the phenolphthalein modified polyaryletherketone resin in the step (1) is prepared by the following steps:
according to the mass ratio of 5-50: 1-10: 18-25: 15-20 mixing a reactant monomer A, a monomer B, 4' -difluorobenzophenone and anhydrous potassium carbonate, adding toluene and dimethyl sulfoxide, mechanically stirring under a nitrogen atmosphere, heating to 128-155 ℃, then reacting for 2-6 hours to fully remove water generated in the reaction, evaporating toluene after water is removed, heating to 165-175 ℃ for reacting for 2-30 hours to obtain a viscous solution, pouring the viscous solution into a mixed precipitator prepared from deionized water and dilute hydrochloric acid to precipitate a large amount of white polymer solids, crushing the polymer solids into fine powder by a crusher, repeatedly boiling and washing by using the deionized water added with the dilute hydrochloric acid for 5-10 hours, and drying at 60-120 ℃ to obtain the phenolphthalein modified polyaryletherketone resin,
the reactant monomer A is
the structural formula of the reactant monomer B is as follows:
further, the surfactant in step (2) is one or any combination of cetyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, calcium stearate, benzyl chloride, lauryl oil, palm oil, glutamic acid, glycine, alpha-alkyl betaine, N-alkyl betaine, fatty glyceride, span 20, span 60, span 65, span 80, Tween 20, Tween 40, Tween 80 or OP-4, OP-7, OP-9, OP-10, OP-13, OP-15, OP-20, OP-30, OP-40 and OP-50.
Further, the leveling agent in the step (3) is one or any combination of polyether modified polysiloxane, polydimethylsiloxane, polymethylphenylsiloxane, polyether polyester modified organosiloxane or alkyl modified organosiloxane.
Further, the lubricant in the step (3) is one or any combination of calcium stearate, stearic acid amide, N-ethylene bis-stearamide, oleic acid amide, erucic acid amide, N-butyl stearate or glycerol tristearate.
Further, the defoaming agent in the step (3) is one or any combination of polysiloxane, polyether modified silicone oil, lauric acid, trialkyl melamine palmitate, cyanuric chloride melamine or fatty amine.
Further, the adhesive in the step (3) is one or any combination of starch, dextrin, polyvinyl alcohol, carboxymethyl cellulose, acrylate or ethyl acetate.
Further, the antistatic agent in the step (3) is one or any combination of sodium dodecyl sulfate, ethoxylated amine laurate, glycerol stearate, ethoxylated alkylamine and ethoxylated amine alkanoate.
The invention also provides an application of the phenolphthalein modified polyaryletherketone aqueous sizing agent in the field of preparation of carbon fiber reinforced polyaryletherketone composite materials, and the method comprises the following steps:
soaking commercial carbon fibers subjected to size removal in a phenolphthalein modified polyaryletherketone aqueous sizing agent for running for 8-35 s at the speed of 10m/min to obtain carbon fibers subjected to sizing treatment by the phenolphthalein modified polyaryletherketone aqueous sizing agent, drying at the drying temperature of 90-110 ℃, winding on a rectangular iron frame after drying, then compounding the carbon fibers subjected to sizing treatment by the phenolphthalein modified polyaryletherketone aqueous sizing agent and a polyaryletherketone film to obtain a prepreg, cutting the prepreg into a proper size, putting the prepreg into a mold coated with a release agent, and carrying out hot press molding on the prepreg at the fiber layering direction of 0 ℃ to obtain the carbon fiber reinforced polyaryletherketone composite material.
Further, the polyaryletherketone is any one of polyetheretherketone, polyetheretherketoneketone, polyetherketoneketone, polyetherketone or polyetherketoneetherketoneketone.
The invention has the beneficial effects that:
the invention provides a phenolphthalein modified polyaryletherketone aqueous sizing agent, wherein the main sizing agent of the sizing agent is a novel PEKC-COOH resin consisting of non-coplanar phenolphthalein side groups and hydrophilic groups (carboxyl groups). The introduced groups can destroy the crystallinity of the original polyaryletherketone, and improve the solubility of the polyaryletherketone, so that the waterborne sizing agent can be prepared through further processing. In addition, the carboxyl groups located in the phenolphthalein may interact with the PAEK matrix resin. The sizing agent exhibits good kinetic stability, can be stored for 6 months or more without precipitation and firmly adheres to the CF surface by pi-pi action and van der Waals force. Meanwhile, the sizing agent has good compatibility with PAEK matrix resin and brings good interface bonding due to physical entanglement and diffusion among molecular chains, the binding force between the matrix and CF is enhanced, and the interface adhesion is improved. The interfacial adhesion may be further promoted by hydrogen bonds formed between the ketone groups of the PAEK resin and the carboxyl groups in the aqueous sizing.
The method adopted by the invention is simple, convenient and easy to operate, easy to repeatedly realize, environment-friendly, low in cost and good in industrialization prospect.
Drawings
The invention is further described below with reference to the accompanying drawings and the detailed description.
FIGS. 1a and 1b are scanning electron micrographs of unsized carbon fiber and sized carbon fiber, respectively, in example 1 of the present invention;
FIG. 2 and FIG. 3 are the thermogravimetric curve and the glass transition temperature curve of the phenolphthalein modified polyaryletherketone aqueous sizing agent in example 1 of the present invention, respectively;
FIG. 4 shows the particle size of the sizing agents obtained in examples 1 to 4 of the present invention;
FIG. 5 is a pictorial representation of a sizing agent obtained in example 2 of the present invention after 6 months of storage;
FIG. 6 shows the results of testing the interlaminar shear strength of the composites of examples 1-4 of the present invention and comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to examples. The examples are intended to illustrate the invention only and do not limit the scope of the invention. After reading the disclosure of the present invention, various changes or modifications may be made by those skilled in the art, and such equivalents are also within the scope of the present invention.
Example 1
(1) Preparing a phenolphthalein modified polyaryletherketone water sizing agent:
under the nitrogen atmosphere, 29.6g of phenolphthalein (monomer A), 2.3g of phenolphthalein (monomer B), 21.8g of 4,4' -difluorobenzophenone, 16.5g of anhydrous potassium carbonate, 100mL of toluene and 150mL of dimethyl sulfoxide are mixed and stirred, the temperature is increased to 135 ℃ again to react for 4 hours, the toluene is evaporated out, the temperature is increased to 170 ℃ to react for 5 hours, the mixture is poured into a mixed solvent of deionized water and dilute hydrochloric acid to obtain a white polymer solid, the polymer solid is crushed into fine powder by a crusher, the mixed solvent of the deionized water and the dilute hydrochloric acid is repeatedly boiled and washed for 7 hours, and then the mixture is dried in a vacuum oven at 80 ℃ to obtain the phenolphthalein modified polyaryletherketone. The specific structural formula is as follows: wherein x + y is 1, y is 0.93,
(2) dissolving 18g of phenolphthalein modified polyaryletherketone obtained in the step (1) in chloroform to obtain a uniform solution;
(3) adding 8g of hexadecyl trimethyl ammonium bromide into 950mL of deionized water, fully stirring, adding the solution obtained in the step (2), uniformly mixing, performing ultrasonic shearing treatment for 8min to obtain a mixed solution, wherein the power is 400W, and keeping the temperature of the solution at 15 ℃;
(4) and (3) adding 3g of polydimethylsiloxane, 5g of calcium stearate, 3g of polysiloxane, 8g of carboxymethyl cellulose and 5g of polymethyl acrylate into the mixed solution obtained in the step (3), uniformly stirring, and recovering the organic solvent by adopting distillation and evaporation to obtain the phenolphthalein modified polyaryletherketone aqueous sizing agent.
Preparation of carbon fiber reinforced polyetheretherketone (CF/PEEK) composite:
dipping commercial carbon fibers subjected to size removal in the sizing agent prepared in the step (4) of the embodiment 1, running for 8s at a speed of 10m/min to obtain carbon fibers subjected to sizing treatment by the phenolphthalein modified polyaryletherketone aqueous sizing agent, drying at 95 ℃, winding on a rectangular iron frame, then compounding the carbon fibers subjected to sizing treatment by the phenolphthalein modified polyaryletherketone aqueous sizing agent and a polyetheretherketone film to obtain a prepreg, cutting the prepreg into a proper size, putting the prepreg into a mold coated with a release agent, and performing hot press molding on the prepreg in a fiber layering direction of 0 DEG to obtain the carbon fiber reinforced polyetheretherketone (CF/PEEK) composite material.
The particle size of the phenolphthalein modified polyaryletherketone aqueous sizing agent obtained in the step (4) of the example 1 is 75.0nm, as shown in the attached figure 4; the carbon fiber reinforced polyetheretherketone (CF/PEEK) composite material was tested to measure an interlaminar shear strength of 91.9MPa, as shown in FIG. 6.
FIG. 1a is a scanning electron microscope image comparison photograph of a commercial carbon fiber after desizing adopted in example 1 of the present invention and FIG. 1b is a carbon fiber after sizing by using a phenolphthalein modified polyaryletherketone aqueous sizing agent, and it can be seen that after the phenolphthalein modified polyaryletherketone aqueous sizing agent is coated on the surface of the carbon fiber, a layer of uniform PEKC-COOH resin film is attached to the surface of the carbon fiber, and grooves on the surface of the carbon fiber become shallow, and the surface grooves become shallow, so that surface defects of the carbon fiber caused by wet spinning in the preparation process are compensated.
Table 1 shows contact angle and surface energy data of the commercial carbon fiber after desizing obtained in example 1 of the present invention and the carbon fiber after sizing with the phenolphthalein-modified polyaryletherketone aqueous sizing agent, and can obtain: after the phenolphthalein modified polyaryletherketone aqueous sizing agent is coated on the surface of the carbon fiber, the wetting property of the carbon fiber is obviously improved; table 2 shows comparative data of the amount of the carbon fiber filaments of the commercial carbon fiber after the slurry removal and the commercial carbon fiber after the sizing with the phenolphthalein modified polyaryletherketone aqueous sizing agent, and the amount of the filaments after the sizing treatment of the present invention is significantly less than that of the commercial carbon fiber when the amount of the sizing agent is reduced compared with the amount of the commercial carbon fiber using the epoxy resin as the sizing agent.
TABLE 1 contact angle and surface energy data of carbon fiber after commercial desizing and carbon fiber after sizing with phenolphthalein-modified polyaryletherketone aqueous sizing agent
TABLE 2 comparative data of the amount of fuzz in carbon fibers after commercial desizing and carbon fibers after sizing with phenolphthalein-modified polyaryletherketone aqueous sizing agent
Fig. 2 and fig. 3 are a thermal weight loss curve diagram and a glass transition temperature diagram of the phenolphthalein modified polyaryletherketone aqueous sizing agent obtained in example 1 of the present invention, respectively, and it can be seen that the temperature at which the mass loss of the phenolphthalein modified polyaryletherketone aqueous sizing agent is 5% is 432.3 ℃ and the glass transition temperature is 239.0 ℃, which proves that the phenolphthalein modified polyaryletherketone aqueous sizing agent prepared by the present invention has good heat resistance.
Example 2
(1) Preparing a phenolphthalein modified polyaryletherketone water sizing agent:
under the nitrogen atmosphere, 7.9g of hydroquinone (monomer A), 9.0g of phenolphthalein (monomer B), 21.8g of 4,4' -difluorobenzophenone, 16.5g of anhydrous potassium carbonate, 100mL of toluene and 150mL of dimethyl sulfoxide are mixed and stirred, the temperature is increased to 135 ℃ for reaction for 4 hours, the toluene is evaporated, the temperature is increased to 170 ℃ for reaction for 5 hours, the mixture is poured into a mixed solvent of deionized water and dilute hydrochloric acid to obtain a white polymer solid, the polymer solid is crushed into fine powder by a crusher, the mixed solvent of the deionized water and the dilute hydrochloric acid is repeatedly boiled and washed for 7 hours, and then the mixture is dried in a vacuum oven at 80 ℃ to obtain the phenolphthalein modified polyaryletherketone. The specific structural formula is as follows: wherein x + y is 1, y is 0.72,
(2) dissolving 15g of phenolphthalein modified polyaryletherketone obtained in the step (1) in chloroform to obtain a uniform solution;
(3) adding 10g of sodium dodecyl benzene sulfonate into 954mL of deionized water, fully stirring, adding the solution obtained in the step (2), uniformly mixing, performing ultrasonic shearing treatment for 5min to obtain a mixed solution, wherein the power is 600W, and keeping the temperature of the solution at 25 ℃;
(4) and (3) adding 2g of polyether modified polysiloxane, 6g of stearic acid amide, 3g of polyether modified silicone oil, 5g of polyvinyl alcohol and 5g of sodium dodecyl sulfate into the mixed solution obtained in the step (3), uniformly stirring, and then recovering the organic solvent by distillation and evaporation to obtain the phenolphthalein modified polyaryletherketone aqueous sizing agent.
Preparing a carbon fiber reinforced polyaryletherketone (CF/PAEK) composite material:
dipping commercial carbon fibers subjected to size removal in the sizing agent prepared in the step (4) of the embodiment 2 for running for 18s at the speed of 10m/min to obtain carbon fibers subjected to sizing treatment by the phenolphthalein modified polyaryletherketone aqueous sizing agent, drying at 90 ℃, winding on a rectangular iron frame, then compounding the carbon fibers subjected to sizing treatment by the phenolphthalein modified polyaryletherketone aqueous sizing agent and a polyetherketoneketone film to obtain a prepreg, cutting the prepreg into a proper size, putting the prepreg into a mold coated with a release agent, and performing hot press molding on the prepreg in the fiber layering direction of 0 DEG to obtain the carbon fiber reinforced polyetherketoneketone (CF/PEKK) composite material.
The particle size of the phenolphthalein modified polyaryletherketone aqueous sizing agent obtained in the step (4) of the example 2 is 78.3nm, as shown in the attached figure 4; the obtained carbon fiber reinforced polyether ketone (CF/PEKK) composite material is tested, and the interlaminar shear strength of the carbon fiber reinforced polyether ketone (CF/PEKK) composite material is 88.5MPa, as shown in figure 6.
FIG. 5 is a diagram of the phenolphthalein-modified polyaryletherketone aqueous sizing agent obtained in example 2 of the present invention after 6 months of storage, and no macroscopic precipitate can be observed, indicating that the sizing agent has good storage stability.
Example 3
(1) Preparing a phenolphthalein modified polyaryletherketone water sizing agent:
under the nitrogen atmosphere, 5.6g of resorcinol (monomer A), 15.7g of phenolphthalein (monomer B), 21.8g of 4,4' -difluorobenzophenone, 16.5g of anhydrous potassium carbonate, 100mL of toluene and 150mL of dimethyl sulfoxide are mixed and stirred, the temperature is increased to 135 ℃ for reaction for 4 hours, the toluene is evaporated, the temperature is increased to 170 ℃ for reaction for 5 hours, the mixture is poured into a mixed solvent of deionized water and diluted hydrochloric acid to obtain white polymer solid, the polymer solid is crushed into fine powder by a crusher, the mixed solvent of the deionized water and the diluted hydrochloric acid is repeatedly boiled and washed for 7 hours, and then the mixture is dried in a vacuum oven at 80 ℃ to obtain the phenolphthalein modified polyaryletherketone. The specific structural formula is as follows: wherein x + y is 1, y is 0.51,
(2) dissolving 20g of phenolphthalein modified polyaryletherketone obtained in the step (1) in dichloromethane to obtain a uniform solution;
(3) adding 10g of stearic acid into 946mL of deionized water, fully stirring, adding the solution obtained in the step (2), uniformly mixing, performing ultrasonic shearing treatment for 8min to obtain a mixed solution, wherein the power is 400W, and keeping the temperature of the solution at 35 ℃;
(4) and (3) adding 3g of alkyl modified organic siloxane, 6g of oleamide, 3g of lauric acid, 7g of dextrin and 5g of ethoxy laurylamine into the mixed solution obtained in the step (3), uniformly stirring, and then recovering the organic solvent by adopting rotary evaporation to obtain the phenolphthalein modified polyaryletherketone aqueous sizing agent.
Preparing a carbon fiber reinforced polyaryletherketone (CF/PAEK) composite material:
dipping commercial carbon fibers subjected to size removal in the sizing agent prepared in the step (4) of the embodiment 3 for 24s at a speed of 10m/min to obtain carbon fibers subjected to sizing treatment by the phenolphthalein modified polyaryletherketone aqueous sizing agent, drying at 100 ℃, winding on a rectangular iron frame, then compounding the carbon fibers subjected to sizing treatment by the phenolphthalein modified polyaryletherketone aqueous sizing agent and a polyetheretherketone film to obtain a prepreg, cutting the prepreg into a proper size, putting the prepreg into a mold coated with a release agent, and performing hot press molding on the prepreg in a fiber layering direction of 0 DEG to obtain the carbon fiber reinforced polyetheretherketone (CF/PEEKK) composite material.
The particle size of the phenolphthalein modified polyaryletherketone aqueous sizing agent obtained in the step (4) of the example 3 is 77.2nm, as shown in the attached figure 4; the obtained carbon fiber reinforced polyetheretherketone (CF/PEEKK) composite material was tested, and the interlaminar shear strength of the carbon fiber reinforced polyetheretherketone (CF/PEEKK) composite material was 90.0MPa, as shown in FIG. 6.
Example 4
(1) Preparing a phenolphthalein modified polyaryletherketone water sizing agent:
under the nitrogen atmosphere, 8.0g of bisphenol A (monomer A), 20.8g of phenolphthalein (monomer B), 21.8g of 4,4' -difluorobenzophenone, 16.5g of anhydrous potassium carbonate, 100mL of toluene and 150mL of dimethyl sulfoxide are mixed and stirred, the temperature is increased to 135 ℃ for reaction for 4 hours, the toluene is evaporated, the temperature is increased to 170 ℃ for reaction for 5 hours, the mixture is poured into a mixed solvent of deionized water and dilute hydrochloric acid to obtain a white polymer solid, the polymer solid is crushed into fine powder by a crusher, the mixed solvent of the deionized water and the dilute hydrochloric acid is repeatedly boiled and washed for 7 hours, and then the mixture is dried in a vacuum oven at 80 ℃ to obtain the phenolphthalein modified polyaryletherketone. The specific structural formula is as follows: wherein x + y is 1, y is 0.35,
(2) dissolving 18g of phenolphthalein modified polyaryletherketone obtained in the step (1) in dichloromethane to obtain a uniform solution;
(3) adding 8g of sodium dodecyl sulfate into 949mL of deionized water, fully stirring, adding the solution obtained in the step (2), uniformly mixing, performing ultrasonic shearing treatment for 10min to obtain a mixed solution, wherein the power is 400W, and keeping the temperature of the solution at 45 ℃;
(4) and (3) adding 3g of polymethylphenylsiloxane, 7g of erucamide, 4g of palmitic acid trialkyl melamine, 5g of acrylic ester and 6g of glycerol-stearate into the mixed solution obtained in the step (3), uniformly stirring, and then recovering the organic solvent by adopting rotary evaporation to obtain the phenolphthalein modified polyaryletherketone aqueous sizing agent.
Preparing a carbon fiber reinforced polyaryletherketone (CF/PAEK) composite material:
dipping commercial carbon fibers subjected to size removal in the sizing agent prepared in the step (4) of the embodiment 4 for 35s at a speed of 10m/min to obtain carbon fibers subjected to sizing treatment by the phenolphthalein modified polyaryletherketone aqueous sizing agent, drying at 110 ℃, winding on a rectangular iron frame, then compounding the carbon fibers subjected to sizing treatment by the phenolphthalein modified polyetherketone aqueous sizing agent and a polyetherketone film to obtain a prepreg, cutting the prepreg into a proper size, putting the prepreg into a mold coated with a release agent, and carrying out hot press molding on the carbon fibers at a layering direction of 0 ℃ to obtain the carbon fiber reinforced polyetherketone (CF/PEK) composite material.
The particle size of the phenolphthalein modified polyaryletherketone aqueous sizing agent obtained in the step (4) of the example 1 is 76.6nm, as shown in the attached figure 4; the obtained carbon fiber reinforced polyether ketone (CF/PEK) composite material is tested, and the interlaminar shear strength of the carbon fiber reinforced polyether ketone (CF/PEK) composite material is 87.5MPa, as shown in figure 6.
Comparative example 1
The carbon fiber reinforced polyether ketone (CF/PEK) composite material is prepared by winding commercial carbon fibers containing epoxy resin type sizing agents on a rectangular iron frame, mixing the commercial carbon fibers containing epoxy resin type sizing agents with a polyether ketone film to prepare a prepreg, cutting the prepreg into a proper size, putting the prepreg into a mold coated with a release agent, and performing hot press molding on the fibers at the laying direction of 0 degrees.
The carbon fiber reinforced polyether ketone (CF/PEK) composite material obtained in the comparative example 1 is tested, and the interlaminar shear strength of the carbon fiber reinforced polyether ketone (CF/PEK) composite material is 61.0MPa, as shown in the attached figure 6.
It should be understood that the application of the present invention is not limited to the above examples, the design concept of the present invention is not limited thereto, and any insubstantial modifications of the present invention using the design concept shall fall within the scope of the present invention. However, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. The phenolphthalein modified polyaryletherketone water sizing agent is characterized in that the preparation method comprises the following steps:
(1) placing the phenolphthalein modified polyaryletherketone resin into an organic solvent, and fully stirring to completely dissolve the phenolphthalein modified polyaryletherketone resin to form a uniform solution;
(2) adding a surfactant into deionized water, fully stirring, adding the solution obtained in the step (1), uniformly mixing, performing ultrasonic shearing treatment, and keeping the temperature of the solution at 15-45 ℃ to obtain a mixed solution;
(3) adding a leveling agent, a lubricant, a defoaming agent, an adhesive and an antistatic agent into the mixed solution obtained in the step (2), uniformly stirring, and then recovering the organic solvent by distillation or rotary evaporation to obtain the phenolphthalein modified polyaryletherketone aqueous sizing agent;
the organic solvent in the step (1) is any one of dichloromethane or trichloromethane;
the ultrasonic shearing treatment time in the step (2) is 2-20 min, and the power is 100-1000W;
the composite material comprises the following components in percentage by mass:
0.5-3% of phenolphthalein modified polyaryletherketone resin, 0.2-5% of surfactant, 0.1-1% of flatting agent, 0.1-1% of lubricant, 0.1-1% of defoaming agent, 0.1-2% of adhesive, 0.2-1% of antistatic agent and 86-98.7% of deionized water;
the phenolphthalein modified polyaryletherketone resin in the step (1) has a structural formula shown in a formula 1:
formula 1, x + y is 1, 0< y < 0.95; r is
2. The phenolphthalein modified polyaryletherketone aqueous sizing agent according to claim 1, wherein the phenolphthalein modified polyaryletherketone resin in step (1) is prepared by the following steps:
according to the mass ratio of 5-50: 1-10: 18-25: 15-20 mixing a reactant monomer A, a monomer B, 4' -difluorobenzophenone and anhydrous potassium carbonate, adding toluene and dimethyl sulfoxide, mechanically stirring under a nitrogen atmosphere, heating to 128-155 ℃, then reacting for 2-6 hours to fully remove water generated in the reaction, evaporating toluene after water is removed, heating to 165-175 ℃ for reacting for 2-30 hours to obtain a viscous solution, pouring the viscous solution into a mixed precipitator prepared from deionized water and dilute hydrochloric acid to precipitate a large amount of white polymer solids, crushing the polymer solids into fine powder by a crusher, repeatedly boiling and washing by using the deionized water added with the dilute hydrochloric acid for 5-10 hours, and drying at 60-120 ℃ to obtain the phenolphthalein modified polyaryletherketone resin,
the reactant monomer A is
the structural formula of the reactant monomer B is as follows:
3. the phenolphthalein modified polyaryletherketone aqueous sizing agent as claimed in claim 1, wherein the surfactant in step (2) is one or any combination of cetyl trimethylammonium bromide, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, calcium stearate, benzyl chloride, laurel oil, palm oil, glutamic acid, glycine, alpha-alkylbetaine, N-alkylbetaine, fatty glyceride, span 20, span 60, span 65, span 80, tween 20, tween 40, tween 80 or OP-4, OP-7, OP-9, OP-10, OP-13, OP-15, OP-20, OP-30, OP-40, and OP-50.
4. The phenolphthalein modified polyaryletherketone aqueous sizing agent according to claim 1, wherein the leveling agent in step (3) is one or any combination of polyether modified polysiloxane, polydimethylsiloxane, polymethylphenylsiloxane, polyether polyester modified organosiloxane or alkyl modified organosiloxane.
5. The phenolphthalein modified polyaryletherketone aqueous sizing agent as claimed in claim 1, wherein the lubricant in step (3) is one or any combination of calcium stearate, stearic acid amide, N-ethylene bis-stearamide, oleic acid amide, erucic acid amide, N-butyl stearate or glycerol tristearate.
6. The phenolphthalein modified polyaryletherketone aqueous sizing agent as claimed in claim 1, wherein the defoaming agent in step (3) is one or any combination of polysiloxane, polyether modified silicone oil, lauric acid, trialkyl melamine palmitate, cyanuric chloride melamine or fatty amine.
7. The phenolphthalein modified polyaryletherketone aqueous sizing agent as claimed in claim 1, wherein the binder in step (3) is one or any combination of starch, dextrin, polyvinyl alcohol, carboxymethyl cellulose, acrylate or ethyl acetate.
8. The phenolphthalein modified polyaryletherketone aqueous sizing agent as claimed in claim 1, wherein the antistatic agent in step (3) is one or any combination of sodium dodecyl sulfate, ethoxylated lauric acid amine, glycerol stearate, ethoxylated alkylamine and ethoxylated alkylamine.
9. The application of the phenolphthalein modified polyaryletherketone aqueous sizing agent disclosed by any one of claims 1 to 8 in the field of preparation of carbon fiber reinforced polyaryletherketone composite materials is characterized by comprising the following steps:
soaking commercial carbon fibers subjected to size removal in a phenolphthalein modified polyaryletherketone aqueous sizing agent for running for 8-35 s at the speed of 10m/min to obtain carbon fibers subjected to sizing treatment by the phenolphthalein modified polyaryletherketone aqueous sizing agent, drying at the drying temperature of 90-110 ℃, winding on a rectangular iron frame after drying, then compounding the carbon fibers subjected to sizing treatment by the phenolphthalein modified polyaryletherketone aqueous sizing agent and a polyaryletherketone film to obtain a prepreg, cutting the prepreg into a proper size, putting the prepreg into a mold coated with a release agent, and carrying out hot press molding on the prepreg at the fiber layering direction of 0 ℃ to obtain the carbon fiber reinforced polyaryletherketone composite material.
10. The application of the phenolphthalein modified polyaryletherketone aqueous sizing agent in the field of preparing carbon fiber reinforced polyaryletherketone composite materials according to claim 9, wherein the polyaryletherketone is any one of polyetheretherketone, polyetheretherketon, polyetherketoneketone, polyetherketone or polyetherketoneetherketoneketone.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114262433A (en) * | 2021-11-15 | 2022-04-01 | 吉林省中研高分子材料股份有限公司 | Coupling agent and polyaryletherketone composite material prepared from same |
| CN114687213A (en) * | 2022-04-26 | 2022-07-01 | 浙江大学衢州研究院 | Crosslinkable polyarylether nitrile aqueous sizing agent and preparation method and application thereof |
| CN114960206A (en) * | 2022-06-22 | 2022-08-30 | 中国科学院宁波材料技术与工程研究所 | High-temperature-resistant water-soluble thermoplastic sizing agent for carbon fibers and preparation method and application thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107299531A (en) * | 2017-07-31 | 2017-10-27 | 中国科学院长春应用化学研究所 | A kind of carbon fiber heat-resistance type emulsion pasting agent and preparation method thereof |
| CN110714332A (en) * | 2019-11-20 | 2020-01-21 | 长春工业大学 | Water-based polyether sulfone sizing agent for carbon fibers and preparation method thereof |
| CN111472172A (en) * | 2020-06-05 | 2020-07-31 | 长春工业大学 | Aqueous amino modified polyaryletherketone sizing agent and preparation method thereof |
| CN112876672A (en) * | 2021-01-22 | 2021-06-01 | 电子科技大学 | Preparation method and application of water-soluble polyarylether sizing agent |
-
2021
- 2021-07-26 CN CN202110848769.9A patent/CN113563577A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107299531A (en) * | 2017-07-31 | 2017-10-27 | 中国科学院长春应用化学研究所 | A kind of carbon fiber heat-resistance type emulsion pasting agent and preparation method thereof |
| CN110714332A (en) * | 2019-11-20 | 2020-01-21 | 长春工业大学 | Water-based polyether sulfone sizing agent for carbon fibers and preparation method thereof |
| CN111472172A (en) * | 2020-06-05 | 2020-07-31 | 长春工业大学 | Aqueous amino modified polyaryletherketone sizing agent and preparation method thereof |
| CN112876672A (en) * | 2021-01-22 | 2021-06-01 | 电子科技大学 | Preparation method and application of water-soluble polyarylether sizing agent |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114262433A (en) * | 2021-11-15 | 2022-04-01 | 吉林省中研高分子材料股份有限公司 | Coupling agent and polyaryletherketone composite material prepared from same |
| CN114262433B (en) * | 2021-11-15 | 2024-04-26 | 吉林省中研高分子材料股份有限公司 | Coupling agent and polyaryletherketone composite material prepared from coupling agent |
| CN115418859A (en) * | 2022-04-08 | 2022-12-02 | 上海寅汀高科技材料有限公司 | High-temperature-resistant water-dispersible polyaryletherketone sizing agent for fibers and method for preparing carbon fiber composite material by sizing |
| CN114687213A (en) * | 2022-04-26 | 2022-07-01 | 浙江大学衢州研究院 | Crosslinkable polyarylether nitrile aqueous sizing agent and preparation method and application thereof |
| CN114687213B (en) * | 2022-04-26 | 2024-05-10 | 浙江大学衢州研究院 | Cross-linkable poly (arylene ether nitrile) aqueous sizing agent and preparation method and application thereof |
| CN114960206A (en) * | 2022-06-22 | 2022-08-30 | 中国科学院宁波材料技术与工程研究所 | High-temperature-resistant water-soluble thermoplastic sizing agent for carbon fibers and preparation method and application thereof |
| CN114960206B (en) * | 2022-06-22 | 2024-04-05 | 中国科学院宁波材料技术与工程研究所 | High-temperature-resistant water-soluble thermoplastic sizing agent for carbon fibers and preparation method and application thereof |
| CN115353713A (en) * | 2022-09-07 | 2022-11-18 | 吉林省中研高分子材料股份有限公司 | Composite material for electronic cigarette and preparation method thereof |
| CN115353713B (en) * | 2022-09-07 | 2024-01-19 | 吉林省中研高分子材料股份有限公司 | Composite material for electronic cigarette and preparation method thereof |
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