CN114456539A - Preparation method of high-solid-content polyether-ether-ketone aqueous suspension and composite fiber - Google Patents
Preparation method of high-solid-content polyether-ether-ketone aqueous suspension and composite fiber Download PDFInfo
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- 239000004696 Poly ether ether ketone Substances 0.000 title claims abstract description 91
- 229920002530 polyetherether ketone Polymers 0.000 title claims abstract description 91
- 239000007900 aqueous suspension Substances 0.000 title claims abstract description 35
- 239000000835 fiber Substances 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 45
- 239000004917 carbon fiber Substances 0.000 claims abstract description 45
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000725 suspension Substances 0.000 claims abstract description 41
- 239000000243 solution Substances 0.000 claims abstract description 40
- 239000007787 solid Substances 0.000 claims abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 33
- 229920005989 resin Polymers 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 32
- 239000004094 surface-active agent Substances 0.000 claims abstract description 29
- 238000000576 coating method Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 238000009998 heat setting Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 6
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 5
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- 238000009990 desizing Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 238000004513 sizing Methods 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 125000000129 anionic group Chemical group 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000009471 action Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 238000005470 impregnation Methods 0.000 description 10
- 238000002834 transmittance Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 229920005992 thermoplastic resin Polymers 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229920006258 high performance thermoplastic Polymers 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011208 reinforced composite material Substances 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- 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
- D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
- D06M15/41—Phenol-aldehyde or phenol-ketone resins
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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
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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
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
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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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
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Abstract
The invention discloses a preparation method of aqueous suspension and composite fiber of high solid content polyetheretherketone, the suspension comprises disperse phase polyetheretherketone resin powder, surfactant and continuous phase deionized water, the solid content is 10-40 (mass)%; the composite fiber comprises carbon fiber reinforced polyetheretherketone composite fiber, and the preparation method comprises the following steps: uniformly dispersing a surfactant in deionized water, adjusting the pH value of the solution to 2-12 by using an acid solution or an alkali solution, mixing the mixed solution with polyether-ether-ketone resin powder drop by drop to form a suspension, then coating the suspension on the surface of carbon fiber, drying, standing at a constant temperature in a heat setting device, and cooling to obtain the carbon fiber composite material. The aqueous suspension of the polyether-ether-ketone has good standing stability, easily obtained raw materials and environmental protection, and can be uniformly coated on the surface of carbon fiber to form composite fiber, improve the interface action between the fiber and resin and obtain the composite fiber with good mechanical property.
Description
Technical Field
The invention belongs to the technical field of plastic modification, and particularly relates to a preparation method of a high-solid-content polyether-ether-ketone aqueous suspension and composite fibers.
Background
The carbon fiber is prepared from precursors such as polyacrylonitrile fiber, viscose fiber, pitch and the like through the processes of oxidation, carbonization, graphitization and the like, and is the most widely applied fiber in modern industry. The carbon fiber reinforced composite material has the remarkable advantages of high specific strength, high specific modulus, high temperature resistance, corrosion resistance, high damage tolerance, strong designability and the like, and compared with a carbon fiber reinforced thermosetting material, the carbon fiber reinforced thermoplastic material has stronger impact toughness resistance and higher damage tolerance, and also has the advantages of short molding period, low recovery cost, repeatable processing and the like.
The thermoplastic resin caters to the development direction of environmental protection of the current materials due to good toughness, large damage tolerance, good recoverability, repeatable processing and the like. Wherein the polyetheretherketone is a high-performance thermoplastic resin, the main chain structure of which is composed of repeating units of a ketone bond and two ether bonds, and is a semi-crystalline polymer material, as shown in the following formula 1:
therefore, the molecular structure and the crystallization property of the polyether-ether-ketone determine that the polyether-ether-ketone has excellent comprehensive properties, including good mechanical properties, good thermal stability, corrosion resistance, excellent comprehensive electrical properties, good processing and forming properties and the like.
The continuous carbon fiber reinforced polyether-ether-ketone composite material combines the excellent performances of carbon fiber and polyether-ether-ketone resin, and has a very high potential development prospect. However, the prepreg of the composite material prepared by the common powder impregnation, melt impregnation and other pre-impregnation methods has the problems of uneven resin distribution, unsatisfactory impregnation effect and the like, and how to overcome the defects that the traditional pre-impregnation method obtains better impregnation effect and interface interaction, so that the continuous carbon fiber reinforced polyetheretherketone composite material with excellent comprehensive performance is obtained is an important problem to be researched and solved in the field of plastic modification.
Disclosure of Invention
In view of the above, the main object of the present invention is to provide an aqueous suspension of high solids polyetheretherketone which has good stability on standing.
The invention also aims to provide a preparation method of the composite fiber, which is obtained by coating the high-solid-content polyether-ether-ketone aqueous suspension on the surface of carbon fiber for pretreatment, can improve the interface action between the carbon fiber and the polyether-ether-ketone thermoplastic resin, and can improve the mechanical property of the carbon fiber by combining the carbon fiber and the polyether-ether-ketone thermoplastic resin.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a high-solid-content aqueous suspension of polyether-ether-ketone, wherein the solid content of the high-solid-content aqueous suspension of polyether-ether-ketone is 10-40 (mass)%, the high-solid-content aqueous suspension of polyether-ether-ketone comprises disperse-phase polyether-ether-ketone resin powder, a surfactant and continuous-phase deionized water, and the mass ratio of the surfactant to the polyether-ether-ketone resin powder is 1: 2.5-10; the preparation method comprises the steps of uniformly dispersing a surfactant in deionized water, adjusting the pH value of a mixed solution to 2-12 by using an acid solution or an alkali solution, and then dropwise adding the obtained mixed solution into polyether-ether-ketone resin powder according to a ratio for mixing.
Preferably, the high-solid content aqueous suspension of polyetheretherketone has a total content of polyetheretherketone resin powder and surfactant of 10-60 parts by weight, based on 100 parts by weight of deionized water, wherein the surfactant content is 1-17 parts by weight and the polyetheretherketone resin powder content is 7-55 parts by weight.
Preferably, the surfactant is selected from one of nonionic surfactant polyethylene glycol, polyethylene glycol monostearate and anionic surfactant sodium dodecyl sulfate and sodium dodecyl benzene sulfonate, or any one of the anionic surfactant and the nonionic surfactant is mixed according to the mass ratio of 1-9: 3 a compound surfactant.
Preferably, the acid solution is a hydrochloric acid solution, and the alkali solution is a sodium hydroxide solution, the concentration of which depends on the pH value of the mixed solution.
The second aspect of the present invention also provides a method for preparing a composite fiber, wherein the composite fiber comprises a carbon fiber reinforced polyetheretherketone composite fiber, and is obtained by coating the high solid content polyetheretherketone aqueous suspension on the surface of carbon fibers, drying the carbon fibers, standing the carbon fibers at a constant temperature in a heat setting device, and cooling the carbon fibers, and the method comprises the following steps:
s1, uniformly dispersing a surfactant in deionized water, and adjusting the pH value of the mixed solution to 2-12 by using an acid solution or an alkali solution;
s2, dropwise adding the mixed solution obtained in the step S1 into polyether-ether-ketone resin powder according to the proportion, and mixing to form high-solid-content polyether-ether-ketone aqueous suspension;
and S3, coating the high-solid-content polyether-ether-ketone water suspension on the surface of the carbon fiber, drying, standing at a constant temperature in a heat setting device, and cooling to obtain the composite fiber.
Preferably, in step S1, the surfactant is dispersed in the deionized water by using an ultrasonic oscillator until the solution is clear and transparent, which is regarded as the completion of the dispersion.
Preferably, in step S2, the mixing method is magnetic stirring, the stirring speed is 250-1000 rpm, the stirring time is 20-120 minutes, and the stirring temperature is 25 ℃.
Preferably, in step S3, the carbon fiber is a desized carbon fiber monofilament, and the desizing method is a firing method, i.e., a sizing agent on the surface of the carbon fiber is decomposed at a high temperature in a muffle furnace, wherein the firing temperature is 400 ℃ and the firing time is 1 hour.
Preferably, in step S3, the aqueous suspension of high solid content polyetheretherketone is coated on the surface of the carbon fiber by a dropper coating method, the number of coating times is 5 to 20, and the coating speed is 0.5 to 3 cm/S.
Preferably, in step S3, the coated carbon fiber is dried in an electrothermal constant temperature drying oven at 120 ℃ and 100 ℃ until the moisture is volatilized, the temperature of the heat setting device is 360 ℃ and 400 ℃, and the heat setting time is 15-60 seconds.
Compared with the prior art, the invention has the beneficial effects that:
the polyether-ether-ketone aqueous suspension has high solid content and good standing stability, wherein polyether-ether-ketone resin powder can be uniformly dispersed in water, meanwhile, the hydrophilicity of the surface of the resin is improved by adding a surfactant, the potential absolute value of the surface of the resin is increased, the steric effect among resin powder particles is enhanced, the resin powder particles are uniformly dispersed in the water to form the suspension, the standing stability of the suspension is improved, and the effect of adding a compounded surfactant is often better than that of a single surfactant. The preparation method not only abandons the use of organic solvent to form a green suspension, but also has the standing stability far superior to that of the suspension formed by dispersing the polyether-ether-ketone resin powder in organic solvent such as ethanol, isopropanol and the like, and can be applied to the preparation processes of wet powder impregnation prepreg tapes, biocompatible polyether-ether-ketone materials, carbon fiber reinforced polyether-ether-ketone composite fibers and the like.
The invention prepares the composite fiber by coating and pretreating the surface of the carbon fiber by the high-solid-content polyetheretherketone aqueous suspension, compared with the traditional powder impregnation or melt impregnation, the invention can greatly improve the interface action and the impregnation effect between the carbon fiber and the polyetheretherketone thermoplastic resin, and the combination of the carbon fiber and the polyetheretherketone thermoplastic resin can improve the mechanical property of the carbon fiber, thereby having great application potential.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the present invention will be further described with reference to the accompanying drawings:
FIG. 1 is a graph of the zeta potential of aqueous suspensions of high solids polyetheretherketone at various pH values in example 1.
FIG. 2 is a graph of the light transmittance of aqueous high solids polyetheretherketone suspensions of example 1 at various alkaline pH values.
FIG. 3 is a graph of the light transmittance of aqueous high solids polyetheretherketone suspensions of example 1 at various acidic pH values.
FIG. 4 is a graph of the zeta potential of aqueous high solids polyetheretherketone suspensions at various surfactant formulation ratios in example 2.
FIG. 5 is a graph of the light transmittance of aqueous high solids polyetheretherketone suspensions at different surfactant formulation ratios in example 2.
FIG. 6 is a graph of the light transmittance of different continuous phases of the aqueous high solids aqueous suspension of polyetheretherketone of comparative example 1.
Detailed Description
The invention will now be described more fully hereinafter with reference to the accompanying drawings, in which a process for the preparation of an aqueous suspension of high solids polyetheretherketone and composite fibres in accordance with the present invention is shown and described in more detail. The advantages and features of the present invention will become more fully apparent from the following examples and from the appended claims. It is to be noted that the drawings are in simplified form and are not to be construed as precise, so as to facilitate the clear and concise description of embodiments of the invention.
Example 1
The preparation method is adopted to prepare the aqueous suspension of the polyetheretherketone with high solid content, and tests the standing stability of the suspension under different preparation conditions, wherein the main influencing factor is the influence of the pH value of the suspension on the standing stability of the suspension, and the raw materials are as follows:
polyetheretherketone resin powder (330 UPF, 950 mesh, powder particle size 18 μm in Jilin).
The preparation method of the aqueous suspension of the high-solid-content polyether-ether-ketone comprises the following steps:
uniformly dispersing 1g of sodium dodecyl sulfate in 19g of acid solution hydrochloric acid solution or alkali solution sodium hydroxide solution by using an ultrasonic oscillator respectively, and adjusting the pH values of the solutions to be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12 respectively until the solutions are transparent and clear; weighing 5g of polyether-ether-ketone resin powder in a beaker, dropwise adding the solution into the beaker, and controlling the rotating speed of a magnetic stirrer to be 500rpm in the dropwise adding process; after all the solution is added, stirring is continued for 60 minutes, and the stirring temperature is controlled at 25 ℃. The solid content of the suspension prepared by the method is 20% by mass, and the mass ratio of the surfactant to the polyether-ether-ketone resin powder is 1: 5.
The aqueous suspensions of high solids polyetheretherketone prepared in this example were characterized for their stability at rest and the zeta potential of the suspensions was determined. Dissolving 0.05g of potassium chloride powder in water to prepare a potassium chloride solution with the mass fraction of 0.1%, dropwise adding two drops of suspension samples into the potassium chloride solution, uniformly mixing, putting a certain amount of the suspension samples into a sample cell, putting the sample cell into a nanometer particle size and zeta potential analyzer for testing, wherein the testing temperature is 25 ℃, the balance time is 30 seconds, and the testing result is shown in figure 1.
The aqueous suspensions of high solids polyetheretherketone prepared in this example were characterized for their stability at rest and the light transmittance was measured. And taking a certain amount of the suspension liquid in a cuvette, and placing the cuvette in an ultraviolet-visible spectrophotometer for testing. The visible wavelength is in the range of 400-800 nm, and the transmittance of the suspension is the average value of the transmittance data in the wavelength range. The light transmittance of the suspension was measured at 0, 60, 120, 240, and 480 minutes of standing, and the results of the measurements are shown in fig. 2 and 3.
From FIGS. 1 to 3, it can be seen that the standing stability of the suspension increased first and then decreased as the pH increased, and that the standing stability of the suspension was optimal at a pH of 10.
Example 2
The preparation method of the invention is adopted to prepare the aqueous suspension of the polyetheretherketone with high solid content, and the standing stability of the suspension under different preparation conditions is tested, and the influence of the proportion of the compounded surfactant on the standing stability of the suspension is mainly tested, and the raw materials are the same as those in the example 1.
Uniformly dispersing 1g of surfactant in total in 19g of deionized water by using an ultrasonic oscillator until the solution is transparent and clear, wherein the mass ratio of sodium dodecyl sulfate to polyethylene glycol monostearate in the surfactant is 1:3, 1:2, 1:1, 2:1 and 3:1 respectively; weighing 5g of polyether-ether-ketone resin powder in a beaker, dropwise adding the solution into the beaker, and controlling the rotating speed of a magnetic stirrer to be 500rpm in the dropwise adding process; after all the solution is added, stirring is continued for 60 minutes, and the stirring temperature is controlled at 25 ℃. The solid content of the suspension prepared by the method is 20% by mass, and the mass ratio of the surfactant to the polyether-ether-ketone resin powder is 1: 5.
The high solids content aqueous suspensions of polyetheretherketone prepared in this example were characterized for their stability in standing and the zeta potential values of the suspensions were determined. The test method was the same as in example 1, and the test results are shown in FIG. 4.
The high solids aqueous suspensions of polyetheretherketone prepared in this example were characterized for their stability in standing and the light transmittance was measured. The test method was the same as in example 1, and the test results are shown in FIG. 5.
From fig. 4 and 5, it can be seen that when the compounding ratio of the polyethylene glycol monostearate to the sodium lauryl sulfate is 1:2 by mass, the standing stability of the suspension is optimal.
Comparative example 1
The preparation method of the invention is adopted to prepare the polyetheretherketone suspension, ethanol and isopropanol are respectively selected for the continuous phase to replace water, the standing stability of the polyetheretherketone suspension is verified to be far superior to that of the polyetheretherketone ethanol suspension and the polyetheretherketone isopropanol suspension, and the raw materials are the same as those in example 1.
Weighing 5g of polyether-ether-ketone resin powder in a beaker, dropwise adding 20g of absolute ethyl alcohol into the beaker, and controlling the rotating speed of a magnetic stirrer to be 500rpm in the dropwise adding process; after all the solution is added, stirring is continued for 60 minutes, and the stirring temperature is controlled at 25 ℃. The method prepares the polyetheretherketone ethanol suspension with the solid content of 20 percent by mass.
Weighing 5g of polyether-ether-ketone resin powder in a beaker, dropwise adding 20g of isopropanol into the beaker, and controlling the rotating speed of a magnetic stirrer to be 500rpm in the dropwise adding process; after all the solution is added, stirring is continued for 60 minutes, and the stirring temperature is controlled at 25 ℃. The method prepares the polyetheretherketone isopropanol suspension with the solid content of 20 percent by mass.
The high solids polyetheretherketone suspensions of the different continuous phases prepared in this example were characterized for their stability on standing and the light transmittance of the suspensions was determined. The test method was the same as in example 1, and the test results are shown in FIG. 6. As can be seen from fig. 6, the stability of the aqueous suspension of polyetheretherketone on standing is optimal.
Example 3
The carbon fiber reinforced polyether-ether-ketone composite fiber is prepared by the preparation method, and the mechanical properties of the composite fiber under different preparation conditions are measured. The raw materials used were as follows:
polyetheretherketone resin powder (330 UPF, 950 mesh, powder particle size 18 μm in Jilin).
Carbon fiber (Japanese Dongli T700SC, 12K continuous carbon fiber, monofilament diameter 6.8 μm)
Uniformly dispersing 1g of polyethylene glycol monostearate in 19g of deionized water by using an ultrasonic oscillator until the solution is transparent and clear; weighing 5g of polyether-ether-ketone resin powder in a beaker, dropwise adding the solution into the beaker, and controlling the rotating speed of a magnetic stirrer to be 500rpm in the dropwise adding process; after all the solution is added, stirring is continued for 60 minutes, and the stirring temperature is controlled at 25 ℃. Placing the carbon fiber in a muffle furnace, and burning for 1 hour at a constant temperature of 400 ℃ to remove the slurry. And coating the prepared suspension on the surface of the desized carbon fiber at the coating speed of 0.5, 1, 2 and 3cm/s respectively and at the coating times of 5, 10, 15 and 20 respectively. And (3) placing the coated carbon fiber in an electric heating constant-temperature drying box, drying for 3 hours at the constant temperature of 105 ℃, heat-setting for 15 seconds at the temperature of 380 ℃, and cooling to obtain the composite fiber.
Measuring the diameter of the composite fiber prepared in the embodiment, measuring 50 groups of diameter data of each composite fiber in total under a fluorescence microscope, and calculating an average value; the mechanical properties of the composite fiber prepared in this example were characterized, and the tensile strength and elongation at break of the monofilament of the composite fiber were measured according to the standard ASTM C1557-2014, and the test results are shown in table 1, wherein the number 0 is the mechanical property data of the desized carbon fiber.
TABLE 1
| Serial number | Number of coats/number | Coating speed/(cm/s) | Diameter/. mu.m | Tensile strength/GPa | Elongation at break/% |
| 0 | / | / | 6.82 | 4.82 | 2.06 |
| 1 | 5 | 2 | 7.25 | 4.88 | 2.10 |
| 2 | 10 | 2 | 7.64 | 4.91 | 2.21 |
| 3 | 15 | 2 | 7.93 | 4.92 | 2.29 |
| 4 | 20 | 2 | 8.25 | 4.90 | 2.19 |
| 5 | 10 | 0.5 | 7.86 | 4.94 | 2.37 |
| 6 | 10 | 1 | 7.73 | 4.94 | 2.34 |
| 7 | 10 | 3 | 7.55 | 4.90 | 2.13 |
As can be seen from Table 1, the tensile strength and the elongation at break of the composite fiber are both obviously superior to those of the carbon fiber, and as the coating times are increased, the coating speed is reduced, and the diameter of the composite fiber is increased; the tensile strength and the elongation at break of the composite fiber show a tendency of increasing and then decreasing with the increase of the fiber diameter.
The above description explains the preparation method of the aqueous suspension of high solid content polyetheretherketone and the composite fiber provided by the present invention in detail, and illustrates the principle and the specific implementation of the present invention by using three examples and a comparative example, which are only used to help understand the method and the core idea of the present invention. It should be noted that, for those skilled in the art, it is possible to make several improvements and modifications to the present application without departing from the principle of the present application, and such improvements and modifications also fall within the scope of the claims of the present application.
Claims (10)
1. An aqueous suspension of high solid content polyetheretherketone having a solid content of 10 to 40 mass% and comprising a dispersed phase polyetheretherketone resin powder, a surfactant and a continuous phase deionized water, wherein the mass ratio of the surfactant to the polyetheretherketone resin powder is 1:2.5 to 10; the preparation method comprises the steps of uniformly dispersing a surfactant in deionized water, adjusting the pH value of a mixed solution to 2-12 by using an acid solution or an alkali solution, and then dropwise adding the obtained mixed solution into polyether-ether-ketone resin powder according to a ratio for mixing.
2. The aqueous high solids polyetheretherketone suspension of claim 1, wherein the aqueous high solids polyetheretherketone suspension comprises 10 to 60 parts by weight of the total amount of the polyetheretherketone resin powder and the surfactant per 100 parts by weight of deionized water.
3. The aqueous suspension of high solids polyetheretherketone according to claim 1 wherein the surfactant is selected from the group consisting of one of the nonionic surfactants polyethylene glycol, polyethylene glycol monostearate and the anionic surfactants sodium lauryl sulfate, sodium dodecylbenzene sulfonate, or any of the above anionic and nonionic surfactants in a mass ratio of 1 to 9: 3 a compound surfactant.
4. The aqueous high solids polyetheretherketone suspension of claim 1 wherein the acid solution is a hydrochloric acid solution and the base solution is a sodium hydroxide solution, the concentrations being determined by the pH of the mixed solution.
5. Use of an aqueous high solids polyetheretherketone suspension according to any one of claims 1 to 4 in the manufacture of a wet powder impregnated prepreg tape, a biocompatible polyetheretherketone material or a carbon fibre reinforced polyetheretherketone composite fibre.
6. A method for preparing a composite fiber, which is obtained by coating the surface of carbon fiber with the aqueous suspension of high-solid content polyetheretherketone according to any one of claims 1 to 4, drying and allowing to stand at a constant temperature in a heat setting device, and then cooling, the method comprising the steps of:
s1, uniformly dispersing a surfactant in deionized water, and adjusting the pH value of the mixed solution to 2-12 by using an acid solution or an alkali solution;
s2, dropwise adding the mixed solution obtained in the step S1 into polyether-ether-ketone resin powder according to the proportion, and mixing to form high-solid-content polyether-ether-ketone aqueous suspension;
s3, coating the high-solid-content polyetheretherketone aqueous suspension obtained in the step S2 on the surface of the carbon fiber, drying, standing at a constant temperature in a heat setting device, and cooling to obtain the composite fiber.
7. The method of claim 6, wherein in step S1, the surfactant is dispersed in deionized water by using an ultrasonic oscillator until the solution is clear and transparent, which is regarded as the completion of the dispersion; and/or the mixing mode adopted in the step S2 is magnetic stirring, the stirring speed is 250-1000 rpm, the stirring time is 20-120 minutes, and the stirring temperature is 25 ℃.
8. The method of claim 6, wherein the carbon fiber is a carbon fiber monofilament subjected to desizing, and in step S3, the desizing is performed by firing, i.e., a sizing agent on the surface of the carbon fiber is decomposed at a high temperature in a muffle furnace, the firing temperature is 400 ℃, and the firing time is 1 hour.
9. The method of claim 6, wherein in step S3, the high solid content polyetheretherketone aqueous suspension is coated on the surface of the carbon fiber by a dip tube coating method at a coating rate of 0.5 to 3cm/S and a coating frequency of 5 to 20 times.
10. The method as claimed in claim 6, wherein in step S3, the coated carbon fiber is dried in an electrothermal constant temperature drying oven at 120 ℃ and 100 ℃ until the moisture is volatilized, the temperature of the heat setting device is 400 ℃ and 360 ℃ and the heat setting time is 15-60 seconds.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4897286A (en) * | 1986-12-20 | 1990-01-30 | Toho Rayon Co., Ltd. | Method for producing carbon fiber reinforced thermoplastic resin product |
| CN108004779A (en) * | 2016-10-28 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of carbon fiber ketone-grouped resin base suspension sizing agent and preparation method thereof |
| CN108359216A (en) * | 2018-03-21 | 2018-08-03 | 吉林省中研高分子材料股份有限公司 | A kind of continuous lod polyether-ether-ketone resin and its forming method |
| CN109722902A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of polyphenylene sulfide base carbon fibre suspension sizing agent and preparation method thereof |
| CN111057346A (en) * | 2020-01-09 | 2020-04-24 | 江苏韩塑新材料有限公司 | Carbon fiber reinforced PEEK unidirectional tape and preparation method thereof |
-
2022
- 2022-01-24 CN CN202210080258.1A patent/CN114456539A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4897286A (en) * | 1986-12-20 | 1990-01-30 | Toho Rayon Co., Ltd. | Method for producing carbon fiber reinforced thermoplastic resin product |
| CN108004779A (en) * | 2016-10-28 | 2018-05-08 | 中国石油化工股份有限公司 | A kind of carbon fiber ketone-grouped resin base suspension sizing agent and preparation method thereof |
| CN109722902A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of polyphenylene sulfide base carbon fibre suspension sizing agent and preparation method thereof |
| CN108359216A (en) * | 2018-03-21 | 2018-08-03 | 吉林省中研高分子材料股份有限公司 | A kind of continuous lod polyether-ether-ketone resin and its forming method |
| CN111057346A (en) * | 2020-01-09 | 2020-04-24 | 江苏韩塑新材料有限公司 | Carbon fiber reinforced PEEK unidirectional tape and preparation method thereof |
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