CN109957969B - Carbon fiber sizing agent, preparation method thereof, reinforced carbon fiber and carbon fiber composite material - Google Patents
Carbon fiber sizing agent, preparation method thereof, reinforced carbon fiber and carbon fiber composite material Download PDFInfo
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- CN109957969B CN109957969B CN201711415332.6A CN201711415332A CN109957969B CN 109957969 B CN109957969 B CN 109957969B CN 201711415332 A CN201711415332 A CN 201711415332A CN 109957969 B CN109957969 B CN 109957969B
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
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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
- D06M15/55—Epoxy 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
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/10—Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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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
Abstract
The invention discloses a carbon fiber sizing agent, a preparation method thereof, reinforced carbon fibers and a carbon fiber composite material, wherein the carbon fiber sizing agent comprises the following components in parts by weight: modified epoxy resin, organic solvent, surfactant and water; the modified epoxy resin is obtained by modifying the epoxy resin by polyurethane and acrylic monomers; the polyurethane is obtained by reacting isocyanate with hydroxyl polymer. The carbon fiber sizing agent prepared by the invention is used for sizing carbon fibers to obtain reinforced carbon fibers, and then the reinforced carbon fibers are compounded with the resin matrix to obtain the carbon fiber composite material, wherein a sizing agent transition layer between the carbon fibers and the resin matrix of the carbon fiber composite material can bear higher impact force and destructive force, so that the bonding force between the carbon fibers and the resin matrix in the carbon fiber composite material is increased.
Description
Technical Field
The invention belongs to the technical field of carbon fibers, and particularly relates to a carbon fiber sizing agent, a preparation method thereof, reinforced carbon fibers and a carbon fiber composite material.
Background
Unsaturated resin is used as an important base material of a resin-based composite material, and has the advantages of high strength, good cohesiveness, heat resistance, chemical corrosion resistance, easiness in processing and the like, but a cured product of the unsaturated resin is poor in cohesiveness with carbon fiber and easy to crack, so that the increasingly developed engineering technical requirements are difficult to meet. On the other hand, the surface of the carbon fiber is completely composed of a graphitized carbon layer, so that the surface activity of the carbon fiber is very low, and when the carbon fiber is mixed with general resin to prepare a composite material, the infiltration and bonding property between the carbon fiber and the resin is very poor, so that the shearing strength between layers of the carbon fiber resin composite material is very low, and the characteristics of light weight and high strength of the carbon fiber cannot be exerted. In the carbon fiber resin composite material, the interface layer of carbon fiber and resin matrix plays an important role in the mechanical property of the composite material, good interface combination increases the integrity of the composite material structure, load is effectively transmitted to the carbon fiber through the resin matrix, so that the carbon fiber really plays a bearing role, in order to improve the combination capacity between the carbon fiber and the resin matrix, a proper sizing agent needs to be selected for sizing the carbon fiber, the sizing agent serves as a transition bonding layer between the carbon fiber and the resin matrix, and the combination property between the carbon fiber and the resin can be improved.
Disclosure of Invention
The invention aims to provide a carbon fiber sizing agent capable of increasing the binding force between carbon fibers and a resin matrix, a preparation method thereof, reinforced carbon fibers and a carbon fiber composite material.
One aspect of the present invention provides a carbon fiber sizing agent, comprising: modified epoxy resin, organic solvent, surfactant and water; the modified epoxy resin is obtained by modifying the epoxy resin by polyurethane and acrylic monomers; the polyurethane is obtained by reacting isocyanate with hydroxyl polymer; the hydroxyl polymer is at least one of polytetrahydrofuran, polypropylene oxide, polycaprolactone, polylactic acid and polycarbonate.
The invention also provides a preparation method of the carbon fiber sizing agent, which comprises the following steps:
s1: adding the epoxy resin, the isocyanate, the hydroxyl polymer, the acrylic acid monomer and the solvent in the carbon fiber sizing agent into a stirring kettle, and uniformly mixing and stirring to obtain a prefabricated body;
s2: adding a surfactant and water into the preform prepared in step S1, and uniformly stirring to obtain a sizing agent.
In still another aspect, the present invention provides a reinforced carbon fiber obtained by sizing a carbon fiber using the above carbon fiber sizing agent.
In still another aspect, the present invention provides a carbon fiber composite material comprising a resin matrix and the above-described reinforcing carbon fiber.
The carbon fiber sizing agent is prepared from modified epoxy resin, an organic solvent, a surfactant and water, wherein the modified epoxy resin is polyurethane obtained by reacting isocyanate and a hydroxyl polymer, and the epoxy resin is modified by the polyurethane and an acrylic monomer together to obtain the modified epoxy resin. The polyurethane has good elasticity, so that the toughness of a sizing agent coated on the surface of carbon fiber can be improved by modifying epoxy resin with the polyurethane, and interface fracture is not easy to occur; the acrylic monomer is used for modifying the epoxy resin, so that double bonds can be introduced into the epoxy resin molecules, and the compatibility and the bonding force of the epoxy resin and a carbon fiber composite material resin matrix are increased. The carbon fiber sizing agent prepared by the invention is used for sizing carbon fibers to obtain reinforced carbon fibers, and then the reinforced carbon fibers are compounded with the resin matrix to prepare the carbon fiber composite material, wherein a sizing agent transition layer between the carbon fibers and the resin matrix of the carbon fiber composite material can bear higher impact force and destructive force, so that the bonding force between the carbon fibers and the resin matrix in the carbon fiber composite material is increased.
Detailed Description
The following detailed description of embodiments of the invention is provided for purposes of illustration only and is not intended to limit the scope or application of the invention.
The invention provides a carbon fiber sizing agent, which comprises: modified epoxy resin, organic solvent, surfactant and water; the modified epoxy resin is obtained by modifying the epoxy resin by polyurethane and acrylic monomers; the polyurethane is obtained by reacting isocyanate with hydroxyl polymer; the hydroxyl polymer is at least one of polytetrahydrofuran, polypropylene oxide, polycaprolactone, polylactic acid and polycarbonate. According to the invention, the isocyanate, the hydroxyl polymer and the acrylic monomer are adopted to modify the epoxy resin (firstly, the isocyanate and the hydroxyl polymer react to obtain polyurethane, and then the polyurethane and the acrylic monomer modify the epoxy resin together), so that the compatibility of the epoxy resin in the carbon fiber sizing agent and a carbon fiber composite material resin matrix can be increased, and meanwhile, the toughness of the sizing agent coated on the surface of the carbon fiber can be increased, and the carbon fiber sizing agent is not easy to generate interface fracture.
In the present invention, the hydroxyl polymer is preferably polytetrahydrofuran. Therefore, the epoxy resin is modified by adopting the isocyanate, the polytetrahydrofuran and the acrylic monomer (firstly, the polytetrahydrofuran type polyurethane is obtained by the reaction of the isocyanate and the polytetrahydrofuran, and then the polytetrahydrofuran type polyurethane and the acrylic monomer are used together for modifying the epoxy resin), so that the phenomenon that a sizing agent layer is easy to become brittle under the low-temperature condition can be improved, and the using effect of the prepared carbon fiber sizing agent under the low-temperature condition is ensured.
In the invention, the acrylic monomer is at least one of acrylic acid, methacrylic acid, phenyl-alpha-acrylic acid and acrylic acid-beta-hydroxyethyl ester. The acrylic monomer is used as a modifier of the epoxy resin, so that the modified epoxy resin contains double bonds on molecules, and the bonding capability between different types of resins (namely the epoxy resin in the sizing agent and the matrix resin in the carbon fiber composite material) can be improved.
In the present invention, the isocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and naphthalene 1, 5-diisocyanate.
In the invention, the reaction of the isocyanate and the hydroxyl polymer is carried out under the catalysis of a catalyst; the isocyanate and the hydroxyl polymer react to obtain polyurethane, and the modification of the polyurethane on the epoxy resin is also carried out under the catalytic action of a catalyst; the catalyst is at least one of dibutyltin dilaurate and dibutyltin diacetate.
In the invention, the epoxy resin is bisphenol A type epoxy resin, the epoxy equivalent of the bisphenol A type epoxy resin is 180-250, and the probability of chemical bond connection between the epoxy resin and the carbon fiber resin matrix can be increased by selecting the bisphenol A type epoxy resin with low epoxy equivalent (namely, the number of active groups in the epoxy resin is large), so that the bonding force between the epoxy resin and the carbon fiber resin matrix is improved.
In the invention, the organic solvent is at least one of xylene, ethyl acetate and butyl acetate.
In the invention, the surfactant is at least one of tween 60, tween 80 and saiban 20, and the surfactant is helpful for the sizing agent to form an emulsion state and keep stable.
In the invention, the carbon fiber sizing agent comprises the following components in parts by weight: 20-50 parts of modified epoxy resin, 10-30 parts of organic solvent, 3-10 parts of surfactant and 30-50 parts of water.
In the invention, the solid content of the carbon fiber sizing agent is 20-50%, the emulsion formed by the sizing agent can be kept in a stable state when the solid content is in the range, the solid content is too high, and the emulsion formed by the sizing agent is unstable and can generate precipitation.
The invention provides a preparation method of a carbon fiber sizing agent, which comprises the following steps:
s1: adding the epoxy resin, the isocyanate, the hydroxyl polymer, the acrylic acid monomer and the solvent in the carbon fiber sizing agent into a stirring kettle, and uniformly mixing and stirring to obtain a prefabricated body;
s2: adding a surfactant and water into the preform prepared in step S1, and uniformly stirring to obtain a sizing agent.
In the present invention, in step S1, the epoxy resin, the isocyanate, the hydroxyl polymer, the acrylic monomer, the catalyst and the solvent are preferably added into a stirring tank, and the mixture is uniformly mixed and stirred to obtain a preform.
In the invention, in the step S1, 10-30 parts by weight of epoxy resin, 2-5 parts by weight of isocyanate, 2-5 parts by weight of hydroxyl polymer, 5-10 parts by weight of acrylic monomer, 1-3 parts by weight of catalyst, 10-30 parts by weight of solvent, 3-10 parts by weight of surfactant and 30-50 parts by weight of water are added into a stirring kettle, and the mixture is uniformly mixed and stirred to obtain the preform.
In the present invention, the step S2 is to add 3 to 10 parts of surfactant and 30 to 50 parts of water to the preform prepared in the step S1, and to stir the mixture uniformly to obtain a sizing agent.
The invention provides a reinforced carbon fiber, which is prepared by sizing the carbon fiber by using the carbon fiber sizing agent. Preferably, the carbon fibers can be subjected to plasma treatment before sizing, so that active groups on the surfaces of the carbon fibers are increased, and the wettability and the bonding force between the carbon fibers and the sizing agent are improved.
The invention provides a carbon fiber composite material which comprises a resin matrix and the reinforced carbon fiber. The resin matrix is vinyl resin or unsaturated resin.
The carbon fiber sizing agent is prepared from modified epoxy resin, an organic solvent, a surfactant and water, wherein the modified epoxy resin is polyurethane obtained by reacting isocyanate and a hydroxyl polymer, and the epoxy resin is modified by the polyurethane and an acrylic monomer together to obtain the modified epoxy resin. The polyurethane has good elasticity, so that the toughness of a sizing agent coated on the surface of carbon fiber can be improved by modifying epoxy resin with the polyurethane, and interface fracture is not easy to occur; the acrylic monomer is used for modifying the epoxy resin, so that double bonds can be introduced into the epoxy resin molecules, and the compatibility and the bonding force of the epoxy resin and a carbon fiber composite material resin matrix are increased. The carbon fiber sizing agent prepared by the invention is used for sizing carbon fibers to obtain reinforced carbon fibers, and then the reinforced carbon fibers are compounded with the resin matrix to prepare the carbon fiber composite material, wherein a sizing agent transition layer between the carbon fibers and the resin matrix of the carbon fiber composite material can bear higher impact force and destructive force, so that the bonding force between the carbon fibers and the resin matrix in the carbon fiber composite material is increased.
The present invention is further illustrated by the following examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. The raw materials used in the examples and comparative examples were commercially available, and the present invention is not particularly limited.
Example 1
Adding 10 parts by weight of bisphenol A epoxy resin, 5 parts by weight of methacrylic acid, 2.5 parts by weight of toluene diisocyanate, 2.5 parts by weight of polypropylene oxide, 2 parts by weight of dibutyltin dilaurate and 20 parts by weight of xylene into a stirring kettle, controlling the temperature at 60 ℃, and stirring at constant temperature for 5 hours to obtain a prefabricated body; adding 3 parts of Tween 60 and 30 parts of distilled water into the prepared preform, and stirring for 2 hours at room temperature to prepare a sizing agent (the solid content is 33%);
sizing the carbon fiber by using a sizing agent, wherein the sizing speed is 1 m/min, the drying temperature is 120 ℃, and the drying time is 1 min, so as to prepare the reinforced carbon fiber;
and (3) winding the reinforced carbon fibers and the resin matrix to obtain the carbon fiber composite material S1.
Example 2
Adding 20 parts by weight of bisphenol A epoxy resin, 8 parts by weight of methacrylic acid, 3.5 parts by weight of diphenylmethane diisocyanate, 3.5 parts by weight of polycarbonate, 3 parts by weight of dibutyltin dilaurate and 20 parts by weight of ethyl acetate into a stirring kettle, controlling the temperature at 60 ℃, and stirring at constant temperature for 5 hours to obtain a prefabricated body; adding 5 parts of Tween 60 and 40 parts of distilled water into the prepared preform, and stirring for 2 hours at room temperature to prepare a sizing agent (the solid content is 41%);
sizing the carbon fiber by using a sizing agent, wherein the sizing speed is 1 m/min, the drying temperature is 120 ℃, and the drying time is 1 min, so as to prepare the reinforced carbon fiber;
and (3) winding the reinforced carbon fibers and the resin matrix to obtain the carbon fiber composite material S2.
Example 3
Adding 30 parts by weight of bisphenol A epoxy resin, 8 parts by weight of acrylic acid, 4 parts by weight of hexamethylene diisocyanate, 4 parts by weight of polytetrahydrofuran, 3 parts by weight of dibutyltin dilaurate and 30 parts by weight of dimethylbenzene into a stirring kettle, controlling the temperature at 60 ℃, and stirring at constant temperature for 5 hours to obtain a preform; adding 5 parts of Tween 80 and 40 parts of distilled water into the prepared preform, and stirring for 2 hours at room temperature to prepare a sizing agent (the solid content is 43%);
sizing the carbon fiber by using a sizing agent, wherein the sizing speed is 1 m/min, the drying temperature is 120 ℃, and the drying time is 1 min, so as to prepare the reinforced carbon fiber;
and (3) winding the reinforced carbon fibers and the resin matrix to obtain the carbon fiber composite material S3.
Example 4
Adding 30 parts by weight of bisphenol A epoxy resin, 10 parts by weight of acrylic acid-beta-hydroxyethyl ester, 4.5 parts by weight of xylylene diisocyanate, 4.5 parts by weight of polytetrahydrofuran, 3 parts by weight of dibutyltin diacetate and 30 parts by weight of dimethylbenzene into a stirring kettle, controlling the temperature at 60 ℃, and stirring at constant temperature for 5 hours to prepare a preform; adding 8 parts of Tween 80 and 50 parts of distilled water into the prepared preform, and stirring for 2 hours at room temperature to prepare a sizing agent (the solid content is 42%);
sizing the carbon fiber by using a sizing agent, wherein the sizing speed is 1 m/min, the drying temperature is 120 ℃, and the drying time is 1 min, so as to prepare the reinforced carbon fiber;
and (3) winding the reinforced carbon fibers and the resin matrix to obtain the carbon fiber composite material S4.
Example 5
Adding 30 parts by weight of bisphenol A epoxy resin, 8 parts by weight of phenyl-alpha-acrylic acid, 5 parts by weight of naphthalene-1, 5-diisocyanate, 5 parts by weight of polylactic acid, 3 parts by weight of dibutyltin diacetate and 30 parts by weight of butyl acetate into a stirring kettle, controlling the temperature at 60 ℃, and stirring at constant temperature for 5 hours to prepare a prefabricated body; adding 10 parts of Saiban 20 and 50 parts of distilled water into the prepared preform, and stirring for 2 hours at room temperature to prepare a sizing agent (the solid content is 43%);
sizing the carbon fiber by using a sizing agent, wherein the sizing speed is 1 m/min, the drying temperature is 120 ℃, and the drying time is 1 min, so as to prepare the reinforced carbon fiber;
and (3) winding the reinforced carbon fibers and the resin matrix to obtain the carbon fiber composite material S5.
Example 6
Adding 30 parts by weight of bisphenol A epoxy resin, 8 parts by weight of acrylic acid, 4 parts by weight of toluene diisocyanate, 4 parts by weight of polycaprolactone, 3 parts by weight of dibutyltin dilaurate and 30 parts by weight of xylene into a stirring kettle, controlling the temperature at 60 ℃, and stirring at constant temperature for 5 hours to obtain a prefabricated body; adding 5 parts of Tween 80 and 40 parts of distilled water into the prepared preform, and stirring for 2 hours at room temperature to prepare a sizing agent (the solid content is 43%);
sizing the carbon fiber by using a sizing agent, wherein the sizing speed is 1 m/min, the drying temperature is 120 ℃, and the drying time is 1 min, so as to prepare the reinforced carbon fiber;
and (3) winding the reinforced carbon fibers and the resin matrix to obtain the carbon fiber composite material S6.
Comparative example 1
Adding 20 parts by weight of bisphenol A epoxy resin and 20 parts by weight of dimethylbenzene into a stirring kettle, controlling the temperature at 60 ℃, and stirring at constant temperature for 5 hours to obtain a preform; adding 3 parts of Tween 60 and 30 parts of distilled water into the prepared preform, and stirring for 2 hours at room temperature to prepare a sizing agent (the solid content is 31%);
sizing the carbon fiber by using a sizing agent, wherein the sizing speed is 1 m/min, the drying temperature is 120 ℃, and the drying time is 1 min, so as to prepare the reinforced carbon fiber;
and (3) winding the reinforced carbon fibers and the resin matrix to obtain the carbon fiber composite material D1.
Comparative example 2
Adding 20 parts by weight of bisphenol A epoxy resin, 3.5 parts by weight of diphenylmethane diisocyanate, 3.5 parts by weight of polytetrahydrofuran, 3 parts by weight of dibutyltin diacetate and 20 parts by weight of dimethylbenzene into a stirring kettle, controlling the temperature at 60 ℃, and stirring at constant temperature for 5 hours to prepare a preform; adding 5 parts of Tween 60 and 40 parts of distilled water into the prepared preform, and stirring for 2 hours at room temperature to prepare a sizing agent (the solid content is 36%);
sizing the carbon fiber by using a sizing agent, wherein the sizing speed is 1 m/min, the drying temperature is 120 ℃, and the drying time is 1 min, so as to prepare the reinforced carbon fiber;
and (3) winding the reinforced carbon fibers and the resin matrix to obtain the carbon fiber composite material D2.
Comparative example 3
Adding 20 parts by weight of bisphenol A epoxy resin, 8 parts by weight of acrylic acid, 3 parts by weight of dibutyltin diacetate and 20 parts by weight of dimethylbenzene into a stirring kettle, controlling the temperature at 60 ℃, and stirring at constant temperature for 5 hours to prepare a prefabricated body; adding 5 parts of Tween 80 and 40 parts of distilled water into the prepared preform, and stirring for 2 hours at room temperature to obtain a sizing agent (the solid content is 37%);
sizing the carbon fiber by using a sizing agent, wherein the sizing speed is 1 m/min, the drying temperature is 120 ℃, and the drying time is 1 min, so as to prepare the reinforced carbon fiber;
and (3) winding the reinforced carbon fibers and the resin matrix to obtain the carbon fiber composite material D3.
Performance testing
1. Fiber appearance test: observing whether broken filaments exist on the surface of the carbon fiber or not and breaking the filaments by adopting a visual method;
2. and (3) interlaminar shear testing: the binding capacity between the fibres and the resin was tested using GB/T1450.1-2005.
The test results are shown in table 1.
TABLE 1
| Sample (I) | Appearance of the product | Interlaminar shear strength |
| S1 | Good and has no phenomenon of broken hair and hair | 65 MPa |
| S2 | Good and has no phenomenon of broken hair and hair | 63 MPa |
| S3 | Good and has no phenomenon of broken hair and hair | 68 MPa |
| S4 | Good and has no phenomenon of broken hair and hair | 67 MPa |
| S5 | Good and has no phenomenon of broken hair and hair | 63 MPa |
| S6 | Good and has no phenomenon of broken hair and hair | 64 MPa |
| D1 | Good and has no phenomenon of broken hair and hair | 42 MPa |
| D2 | Good and has no phenomenon of broken hair and hair | 55 MPa |
| D3 | Good and has no phenomenon of broken hair and hair | 48 MPa |
As can be seen from the test results of table 1: the carbon fiber sizing agent disclosed by the invention is adopted to size carbon fibers to prepare reinforced carbon fibers, the reinforced carbon fibers and a resin matrix are wound and molded to prepare a carbon fiber composite material S1-S6, the prepared carbon fiber composite material sample S1-S6 is good in appearance, the phenomenon of broken filaments and hair is avoided, and the interlayer peeling strength of the carbon fiber composite material S1-S6 is more than 60 MPa. Comparative examples 1, 2 and 3 were not used with the carbon fiber sizing agent of the present invention (comparative example 1 was not modified with epoxy resin, comparative example 2 was modified with polyurethane, and comparative example 3 was modified with epoxy resin with acrylic monomer), and it can be seen from the test results that the interlayer peel strength of carbon fiber composite D1 prepared with the sizing agent not modified with epoxy resin was 42 MPa at the lowest, and the interlayer peel strength of carbon fiber composites D2 and D3 prepared with the sizing agent modified with either only polyurethane or only acrylic monomer was also lower, specifically 55 MPa and 48 MPa. That is, the carbon fiber sizing agent of the invention can obviously increase the bonding force between the carbon fiber and the resin matrix in the carbon fiber composite material.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (9)
1. A carbon fiber sizing agent, comprising: modified epoxy resin, organic solvent, surfactant and water; the modified epoxy resin is obtained by modifying the epoxy resin by polyurethane and acrylic monomers; the polyurethane is obtained by reacting isocyanate with hydroxyl polymer; the hydroxyl polymer is at least one of polytetrahydrofuran, polypropylene oxide, polycaprolactone, polylactic acid and polycarbonate;
the epoxy resin is bisphenol A type epoxy resin; the epoxy equivalent of the bisphenol A type epoxy resin is 180-250;
the carbon fiber sizing agent comprises the following components in parts by weight: 20-50 parts of modified epoxy resin, 10-30 parts of organic solvent, 3-10 parts of surfactant and 30-50 parts of water;
the solid content of the carbon fiber sizing agent is 20-50%.
2. The carbon fiber sizing agent according to claim 1, wherein the acrylic monomer is at least one of acrylic acid, methacrylic acid, phenyl-a-acrylic acid, and- β -hydroxyethyl acrylate.
3. The carbon fiber sizing agent according to claim 1, wherein the isocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and naphthalene 1, 5-diisocyanate.
4. The carbon fiber sizing agent according to claim 1, wherein the organic solvent is at least one of xylene, ethyl acetate and butyl acetate; the surfactant is at least one of tween 60, tween 80 and saiban 20.
5. A preparation method of a carbon fiber sizing agent is characterized by comprising the following steps:
s1: adding the epoxy resin, the isocyanate, the hydroxyl polymer, the acrylic monomer and the solvent in the carbon fiber sizing agent of any one of claims 1 to 4 into a stirring kettle, and uniformly mixing and stirring to obtain a preform;
s2: adding a surfactant and water into the preform prepared in step S1, and uniformly stirring to obtain a sizing agent.
6. A reinforced carbon fiber, characterized in that the reinforced carbon fiber is obtained by sizing a carbon fiber using the carbon fiber sizing agent according to any one of claims 1 to 4.
7. A carbon fiber composite material characterized by comprising a resin matrix and the reinforcing carbon fiber of claim 6.
8. The carbon fiber composite material as claimed in claim 7, wherein the resin matrix is an unsaturated resin.
9. The carbon fiber composite material according to claim 8, wherein the unsaturated resin is a vinyl resin.
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| CN114182533A (en) * | 2021-12-07 | 2022-03-15 | 陈宗良 | Carbon fiber sizing agent and preparation method thereof, and carbon fiber composite material and preparation method thereof |
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