CN114182533A - Carbon fiber sizing agent and preparation method thereof, and carbon fiber composite material and preparation method thereof - Google Patents
Carbon fiber sizing agent and preparation method thereof, and carbon fiber composite material and preparation method thereof Download PDFInfo
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- CN114182533A CN114182533A CN202111482905.3A CN202111482905A CN114182533A CN 114182533 A CN114182533 A CN 114182533A CN 202111482905 A CN202111482905 A CN 202111482905A CN 114182533 A CN114182533 A CN 114182533A
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- carbon fiber
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 155
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 155
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 238000004513 sizing Methods 0.000 title claims abstract description 76
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000003795 chemical substances by application Substances 0.000 title description 7
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 37
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 24
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 23
- 239000004593 Epoxy Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000003822 epoxy resin Substances 0.000 claims description 30
- 229920000647 polyepoxide Polymers 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- 125000003700 epoxy group Chemical group 0.000 claims description 12
- 150000002009 diols Chemical class 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- -1 polyoxypropylene Polymers 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- 239000012948 isocyanate Substances 0.000 claims description 7
- 150000002513 isocyanates Chemical class 0.000 claims description 7
- 229920005862 polyol Polymers 0.000 claims description 7
- 150000003077 polyols Chemical class 0.000 claims description 7
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 abstract description 16
- 239000000243 solution Substances 0.000 description 25
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- 239000000835 fiber Substances 0.000 description 8
- 238000002791 soaking Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
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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
- D06M15/53—Polyethers
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
-
- 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
-
- 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
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/144—Alcohols; Metal alcoholates
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
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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
- D06M15/55—Epoxy resins
-
- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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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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- 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
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Textile Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a carbon fiber sizing solution and a preparation method thereof, and a carbon fiber composite material and a preparation method thereof, wherein the preparation method of the carbon fiber sizing solution comprises the following steps: and adding an epoxy-containing silane coupling agent into the polyoxypropylene glycol, and mixing to obtain carbon fiber sizing liquid. The carbon fiber sizing prepared by the preparation method of the carbon fiber sizing can enable the carbon fibers to be soaked by the polyurethane resin, so that the carbon fiber composite material taking the polyurethane resin as a matrix is obtained, the toughness and the reliability of the carbon fiber composite material can be improved, the curing time is shortened, the production cost is reduced, and the application of the carbon fiber composite material is expanded.
Description
Technical Field
The invention relates to the field of carbon fibers and carbon fiber composites, in particular to carbon fiber sizing liquid and a preparation method thereof, and a carbon fiber composite and a preparation method thereof.
Background
The molding process of the fiber reinforced resin matrix composite material comprises the following steps: and (3) firstly soaking the fibers with the resin, then carrying out crosslinking reaction on the resin after soaking the fibers, and curing to obtain the composite material. In the molding process of the composite material, when the activation energy of the fiber surface is greater than that of the resin surface, the process of infiltrating the fiber with the resin can be realized. The activation energy of the carbon fiber surface is about 70 mJ/square meter, the epoxy resin is about 43 mJ/square meter, and the polyurethane resin is about 35 mJ/square meter. By contrast, the glass fibers have a surface activation energy of about 560 mJ/square meter. The glass fibers are therefore impregnated with most of the resin and become a composite after the resin is cured. And because the surface activation energy of the carbon fiber is low, the carbon fiber can only be subjected to affinity between oxygen-containing groups generated by oxidation of the surface of the carbon fiber in the plasma oxidation process and oxygen-containing functional groups in the epoxy resin, so that the carbon fiber is soaked by the epoxy resin.
When the fiber is applied to composite material molding, resin is used for sizing the surface of the fiber, so that the resin matrix and the fiber can be completely combined. For example, the resin matrix is made of epoxy resin, and the epoxy resin is used for sizing; the resin matrix is made of polyurethane resin, and the polyurethane resin is used for sizing. The glass fiber can be impregnated with various resins after sizing treatment using various resins as a sizing agent, and becomes a composite material after the resins are cured. Since the carbon fiber has a surface that is only wettable with epoxy resin, epoxy resin is generally used as a sizing agent and is only wettable with epoxy resin, and the epoxy resin becomes a composite material after curing. The existing carbon fiber composite materials adopting thermosetting resin as a matrix almost all use epoxy resin as the resin matrix. The carbon fiber composite material using the epoxy resin as the matrix has the problem of poor toughness due to the low toughness of the epoxy resin, so that the reliability of the carbon fiber composite material is low, and the application of the carbon fiber composite material is limited. Meanwhile, the epoxy resin has high curing viscosity and long curing time, so that the production cost of the carbon fiber composite material is high.
Disclosure of Invention
The invention aims to provide carbon fiber sizing liquid and a preparation method thereof, a carbon fiber composite material and a preparation method thereof, and aims to solve the technical problems of poor toughness and high production cost of the conventional carbon fiber composite material.
In order to solve the above problems, in a first aspect, the present application provides a method for preparing a carbon fiber sizing solution, comprising: and adding an epoxy-containing silane coupling agent into the polyoxypropylene glycol, and mixing to obtain carbon fiber sizing liquid.
In one embodiment, after mixing the polyoxypropylene glycol and the epoxy-containing silane coupling agent, ethanol is added to obtain the carbon fiber sizing solution.
In one embodiment, the mass ratio of the polyoxypropylene diol, the silane coupling agent and the ethanol is 1:1: 2.
In one embodiment, the polyoxypropylene diol is PPG-204 having an average molecular weight of 400.
In one embodiment, the silane coupling agent is gamma-glycidoxypropyltrimethoxysilane KH-560.
In a second aspect, the present application provides a carbon fiber sizing prepared by the method of preparing a carbon fiber sizing as described in any one of the embodiments of the first aspect.
In a third aspect, the present application provides a method of making a carbon fiber composite material, the method comprising:
carrying out primary sizing on the carbon fiber by adopting epoxy resin sizing liquid to obtain primary sized carbon fiber;
performing secondary sizing on the primary sized carbon fiber by using the carbon fiber sizing solution of the third aspect to obtain a carbon fiber preform;
drying the carbon fiber preform;
preparing polyurethane resin;
and soaking the dried carbon fiber preform by using the polyurethane resin, carrying out crosslinking reaction on the polyurethane resin, curing, and obtaining the carbon fiber composite material after curing.
In one embodiment, the drying temperature for drying the carbon fiber preform is 40 to 150 ℃.
In one embodiment, the preparing the polyurethane resin includes mixing a mixture of trifunctional polyether polyol and glycerol with difunctional isocyanate in a mass ratio of 1: 1.
In a fourth aspect, the present application provides a carbon fiber composite material prepared by the method of preparing a carbon fiber composite material as described in any of the embodiments of the third aspect.
The invention has the beneficial effects that: the carbon fiber sizing agent enables carbon fibers to be soaked by polyurethane resin, so that the carbon fiber composite material taking the polyurethane resin as a matrix is obtained, the toughness and the reliability of the carbon fiber composite material are effectively improved, the curing time is shortened, the production cost is reduced, and the application of the carbon fiber composite material is expanded.
Detailed Description
The following detailed description of specific embodiments of the invention is provided, but it should be understood that the scope of the invention is not limited to the specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
In the prior art, the carbon fiber composite material using the epoxy resin as the matrix has the problem of poor toughness due to the low toughness of the epoxy resin, so that the reliability of the carbon fiber composite material is low, and the application of the carbon fiber composite material is limited. The toughness of the polyurethane resin is high, and if the polyurethane resin is used for replacing epoxy resin to soak carbon fibers, the toughness of the carbon fiber composite material can be effectively improved, but the carbon fibers cannot be directly soaked by the polyurethane resin.
In a first aspect, the present application provides a method for preparing a carbon fiber sizing solution, and carbon fibers obtained by secondary sizing of carbon fibers that have been subjected to epoxy resin sizing solution by using the carbon fiber sizing solution prepared by the method can be infiltrated by polyurethane resin, so that a high-toughness carbon fiber composite material using the polyurethane resin as a matrix can be obtained. The method comprises the following steps: and adding an epoxy-containing silane coupling agent into the polyoxypropylene glycol to obtain carbon fiber sizing liquid.
In the above-mentioned process for preparing the carbon fiber sizing agent, the epoxy group-containing silane coupling agent is added to the polyoxypropylene diol to mix, and the siloxane groups in the silane coupling agent and the hydroxyl groups in the polyoxypropylene diol combine to protect the hydroxyl groups in the polyoxypropylene diol from reacting in advance.
The carbon fiber sizing solution obtained by the preparation method is adopted to carry out secondary sizing on the carbon fiber which is sized by the epoxy resin sizing solution, and the epoxy group in the silane coupling agent in the carbon fiber sizing solution and the epoxy group in the original epoxy sizing solution on the surface of the carbon fiber are coupled, so that the polyoxypropylene glycol covers the surface of the carbon fiber to replace the epoxy group and the hydroxyl group of the epoxy sizing solution on the surface of the carbon fiber, and further the carbon fiber which is sized for the second time can be soaked by the polyurethane resin, so that the carbon fiber composite material taking the polyurethane resin as the matrix is obtained, the toughness and the reliability of the carbon fiber composite material are effectively improved, and the application of the carbon fiber composite material is further expanded. Meanwhile, the polyurethane resin has low curing viscosity and short curing time, and can reduce the production cost of the carbon fiber composite material.
It should be understood that polyurethane resins are a class of polymers containing repeating structural units of the urethane type in the macromolecular chain, all known as polyamino acid esters, all known in english as polyurethanes, abbreviated as PU or PUR. PU is a product reflected by a polyisocyanate and a polyether or polyester polyol in a certain ratio.
In some embodiments, the preparation of the slurry on the carbon fibers is performed in an environment of 10-40 ℃.
In the above examples, the preparation environment temperature of the carbon fiber sizing liquid was controlled to 10 to 40 ℃, so that the epoxy group-containing silane coupling agent could be sufficiently dissolved in the polyoxypropylene glycol.
In some embodiments, after mixing of the polyoxypropylene glycol and the epoxy-containing silane coupling agent, ethanol is added to obtain a carbon fiber sizing solution.
In the above examples, the mixed solution obtained by mixing the polyoxypropylene glycol and the silane coupling agent was diluted and dissolved by adding ethanol to the mixed solution, so that the resulting carbon fiber slurry could be more easily dispersed and attached to the surface of the carbon fiber. After the carbon fiber subjected to primary sizing is subjected to secondary sizing by using the carbon fiber sizing solution obtained after adding ethanol, the carbon fiber needs to be dried, the ethanol is completely evaporated, and then the carbon fiber is soaked by polyurethane resin to form the carbon fiber composite material.
In some embodiments, the polyoxypropylene diol is present in an amount of 10-40 parts by mass, the epoxy-containing silane coupling agent is present in an amount of 10-40 parts by mass, and the ethanol is present in an amount of 60-80 parts by mass.
The above-mentioned parts by mass mean a mass ratio of, for example, 20 parts by mass of the epoxy group-containing silane coupling agent to 20 parts by mass of the polyoxypropylene glycol is 1: 1.
In some embodiments, the mass ratio of polyoxypropylene glycol, silane coupling agent and ethanol is 1:1: 2.
In the above examples, the mass of polyoxypropylene diol employed: mass of silane coupling agent: the mass ratio of the ethanol is equal to 1:1:2, and the carbon fiber sizing solution is prepared, so that the strength and toughness of the carbon fiber composite material can be improved. As shown in table 1, table 1 is a table comparing strength and toughness of carbon fiber composites obtained after sizing carbon fiber sizing solutions of different mass ratios.
TABLE 1
In table 1, "no treatment" means: and (3) after the carbon fibers are subjected to primary sizing by using epoxy resin, directly soaking by using polyurethane resin, and obtaining the carbon fiber composite material after 300 s. Therefore, as can be seen from table 1, the carbon fiber composite material obtained by directly impregnating the carbon fiber with the epoxy resin sizing agent with the polyurethane resin had very low interlaminar shear strength and notched impact toughness. The interlaminar shear strength and the notch impact toughness of the carbon fiber composite material obtained by adopting the polyurethane resin to soak after the carbon fiber sizing liquid is subjected to secondary sizing treatment are obviously improved.
The curing time of the carbon fiber composite material taking the epoxy resin as the matrix is 14400s, the interlaminar shear strength of the carbon fiber composite material is 53.5MP, and the notch impact toughness is 22.8 KJ/square meter. As can be seen from table 1, the interlaminar strength obtained by treating the carbon fiber sizing solution with the mass ratio of 10:10:20 is substantially the same as the interlaminar shear strength of the carbon fiber composite material with the epoxy resin as the matrix, but the notched impact toughness of the carbon fiber composite material with the polyurethane resin as the matrix is 5.44 times that of the carbon fiber composite material with the epoxy resin as the matrix. Meanwhile, the curing time of the epoxy resin is 48 times that of the polyurethane resin. In conclusion, the polyurethane resin is adopted to replace epoxy resin to be compounded with carbon fibers, so that the toughness of the carbon fiber composite material can be effectively improved, the curing time is shortened, and the production cost is reduced.
Alternatively, the form of the carbon fiber may be a fabric or a tow, which is not limited in the embodiments of the present application.
Alternatively, after the epoxy group-containing silane coupling agent is added to the polyoxypropylene glycol, stirring is carried out at a speed of 10-600r/min by using a stirrer, and the mixture is left for 1-60min after being uniformly stirred, so that a clear solution can be obtained.
Optionally, after adding ethanol, stirring at a speed of 10-600r/min by using a stirrer, accelerating dilution and dissolution, and standing for 1-30min after uniformly stirring to obtain clear carbon fiber sizing solution.
In some embodiments, the polyoxypropylene diol described above is PPG-204, which has an average molecular weight of 400.
In some embodiments, the silane coupling agent is gamma-glycidoxypropyltrimethoxysilane KH-560.
In the above examples, PPG-204 and gamma-glycidoxypropyltrimethoxysilane KH-560, which have an average molecular weight of 400, are inexpensive and readily available.
In a second aspect, the present application provides a carbon fiber sizing solution, which is prepared by the carbon fiber sizing solution preparation method according to any one of the embodiments of the first aspect, so that the carbon fiber sizing solution can enable carbon fibers to be soaked by polyurethane resin, improve the toughness of a carbon fiber composite material, and reduce the production cost of the carbon fiber composite material.
In a third aspect, the present application provides a method of making a carbon fiber composite material, the method comprising:
s100: and carrying out primary sizing on the carbon fiber by adopting epoxy resin sizing liquid to obtain the primary sized carbon fiber.
S200: and performing secondary sizing on the primary sized carbon fiber by using the carbon fiber sizing solution in any embodiment of the third aspect to obtain a carbon fiber preform.
S300: and drying the carbon fiber preform.
Optionally, the drying temperature for drying the carbon fiber preform is controlled to be 40-150 ℃, so that the epoxy resin sizing solution on the carbon fiber preform and the carbon fiber sizing solution on the carbon fiber preform can be prevented from being failed due to decomposition or reaction.
Epoxy groups and hydroxyl groups are attached to the surfaces of the carbon fibers by adopting primary epoxy resin sizing, and after the carbon fiber sizing is subjected to secondary sizing, the epoxy groups in the silane coupling agent in the carbon fiber sizing and the epoxy groups in the original epoxy sizing on the surfaces of the carbon fibers are coupled, so that the surfaces of the carbon fibers are covered with the polyoxypropylene glycol, the epoxy groups and the hydroxyl groups in the epoxy sizing on the surfaces of the carbon fibers are replaced, and the carbon fiber preform can be effectively soaked by the polyurethane resin.
S400: and (3) preparing polyurethane resin.
Alternatively, the polyurethane resin is formed by mixing a mixture of a trifunctional polyether polyol and glycerol with a difunctional isocyanate. Preferably, the mass ratio of the mixture of trifunctional polyether polyol and glycerol to difunctional isocyanate is 1: 1.
S500: and soaking the dried carbon fiber preform by using polyurethane resin to obtain the carbon fiber composite material.
In the above preparation method, the preparation of the polyurethane resin and the preparation of the carbon fiber preform are not sequentially performed, or may be performed simultaneously, which is not limited in the present application.
Optionally, the carbon fiber sizing solution is used for soaking the sized carbon fibers once by means of soaking or spraying.
Specifically, after the secondary sizing, the preparation process of the carbon fiber composite material comprises the following steps: the mixture of trifunctional polyether polyol and glycerol and difunctional isocyanate are respectively filled into two charging barrels, and then the two charging barrels are vacuumized. Stirring the mixture of trifunctional polyether polyol and glycerol and difunctional isocyanate respectively for 1-30min at 10-600r/min with a stirrer under vacuum. After stirring, stopping vacuumizing, and after the air pressure in the two charging barrels is recovered to one atmospheric pressure, respectively heating the mixture of the trifunctional polyether polyol and the glycerol and the bifunctional isocyanate at the temperature of 40-100 ℃. After heating to the specified temperature, the two materials were simultaneously added to a static mixer at a ratio of 1:1 by a metering pump, the length of the static mixer being 200 and 800mm, respectively. After mixing by a static mixer, the mixed material is poured into a closed die in which a carbon fiber preform is placed in advance, and the heating temperature of the die is 60-150 ℃. The higher the mold temperature is, the faster the solidification speed of the mixed AB material is, and the mold temperature needs to be determined according to the actual size of the product and the injection flow rate of the AB material.
In a fourth aspect, the present application provides a carbon fiber composite material prepared by the method of any one of the embodiments of the third aspect.
In the description of the present invention, reference to the description of the terms "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
While embodiments of the invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
Claims (10)
1. A method of preparing a slurry on carbon fibers, comprising:
and adding an epoxy-containing silane coupling agent into the polyoxypropylene glycol, and mixing to obtain carbon fiber sizing liquid.
2. The method of claim 1, further comprising: after mixing the polyoxypropylene glycol and the epoxy group-containing silane coupling agent, ethanol was added to obtain the carbon fiber sizing solution.
3. The method according to claim 2, wherein the mass ratio of the polyoxypropylene diol to the silane coupling agent to the ethanol is 1:1: 2.
4. The method of claim 1, wherein the polyoxypropylene diol is PPG-204 having an average molecular weight of 400.
5. The method according to claim 1, wherein the epoxy-containing silane coupling agent is gamma-glycidoxypropyltrimethoxysilane KH-560.
6. A carbon fiber sizing composition characterized by being produced by the method for producing a carbon fiber sizing composition according to claims 1 to 4.
7. A method for preparing a carbon fiber composite material is characterized by comprising the following steps:
carrying out primary sizing on the carbon fiber by adopting epoxy resin sizing liquid to obtain primary sized carbon fiber;
performing secondary sizing on the primary sized carbon fiber by using the carbon fiber sizing solution of claim 6 to obtain a carbon fiber preform;
drying the carbon fiber preform;
preparing polyurethane resin;
and infiltrating the dried carbon fiber preform by using the polyurethane resin to obtain the carbon fiber composite material.
8. The method according to claim 7, wherein the drying temperature for drying the carbon fiber preform is 40 to 150 ℃.
9. The method of claim 7, wherein the preparing a polyurethane resin comprises: and mixing a mixture of trifunctional polyether polyol and glycerol with difunctional isocyanate in a mass ratio of 1:1 to obtain the polyurethane resin.
10. A carbon fiber composite material characterized by being produced by the production method for a carbon fiber composite material according to claims 7 to 9.
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