CN111005229B - Carbon fiber sizing agent and preparation method thereof - Google Patents
Carbon fiber sizing agent and preparation method thereof Download PDFInfo
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- CN111005229B CN111005229B CN201911375205.7A CN201911375205A CN111005229B CN 111005229 B CN111005229 B CN 111005229B CN 201911375205 A CN201911375205 A CN 201911375205A CN 111005229 B CN111005229 B CN 111005229B
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- 238000004513 sizing Methods 0.000 title claims abstract description 69
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
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- 230000004913 activation Effects 0.000 description 4
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- 239000001257 hydrogen Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- JYGBQHPBHZTIAP-UHFFFAOYSA-N methoxymethane 2-methylprop-2-enoic acid Chemical compound C(C(=C)C)(=O)O.COC.C(C(=C)C)(=O)O JYGBQHPBHZTIAP-UHFFFAOYSA-N 0.000 description 2
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- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical group CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
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- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical group CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
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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
- 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
-
- 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
- D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
- D06M13/2246—Esters of unsaturated carboxylic acids
-
- 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
Abstract
The invention discloses a carbon fiber sizing agent which is prepared from the following raw materials: the adhesive comprises water-based bisphenol A epoxy resin, polyether alcohol, unsaturated acid and water, wherein the weight ratio of the water-based bisphenol A epoxy resin to the polyether alcohol to the unsaturated acid is 1: 0.5-5: 0.4 to 5. The polyether alcohol is selected from dimethyl trimer dimethanol; the unsaturated acid is selected from acrylic acid. The invention also discloses three preparation methods of the carbon fiber sizing agent. The invention also discloses application of the carbon fiber sizing agent in preparation of carbon fibers and carbon fiber composite materials, and the prepared carbon fibers and carbon fiber composite materials. The carbon fiber treated by the sizing agent can be soaked by polyester resin, and the carbon fiber can obtain manufacturability similar to glass fiber, so that the forming time of the carbon fiber composite material can be greatly reduced, the fixed asset investment of carbon fiber composite material forming equipment is reduced, and the low-cost and quick forming of the carbon fiber composite material is realized.
Description
Technical Field
The invention relates to a carbon fiber sizing agent and a preparation method thereof, belonging to the field of carbon fibers and carbon fiber composite materials.
Background
Resin-based composite materials are fiber-reinforced materials using an organic polymer as a matrix, and usually, fiber reinforcements such as glass fibers, carbon fibers, basalt fibers, or aramid fibers are used. The resin-based composite material has wide application in aviation, automobile and marine industries. The common resins used in the fiber reinforced resin matrix composite material are epoxy resin and unsaturated polyester resin, and the common resins are as follows: thermosetting resins, thermoplastic resins, and various modified or blended matrices. 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 70mJ per square meter, the epoxy resin is about 43mJ per square meter, and the polyester resin is about 35mJ per 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, the surface of the fiber needs to be subjected to sizing treatment by using resin so as to ensure that the resin matrix and the fiber are completely combined, for example: the resin matrix is epoxy resin, and the epoxy resin is required to be subjected to sizing treatment; the resin matrix is made of polyester resin, and the polyester resin is used for sizing. As described above, 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 good wettability only with epoxy resin, epoxy resin is generally used as a sizing agent, and thus, the carbon fiber can be wetted only with epoxy resin, and becomes a composite material after the epoxy resin is cured.
During the curing process of the resin, the viscosity of the resin is reduced along with the increase of the temperature, and when the viscosity of the resin is reduced to be less than 100mpa · s, the resin has sufficient fluidity to occupy a forming die and can completely wet fibers. For polyester resin, the viscosity can be reduced to below 100 mpa.s at 50-70 ℃ generally, and the complete curing temperature of the polyester resin is about 120 ℃ generally, so that when the polyester resin is used for composite material molding, the polyester resin can be filled at about 90 ℃ and matched with a mold, then directly heated to 120 ℃ at the speed of 10 ℃/min, and then kept at 120 ℃ for about 3 minutes to complete the molding process, and the total time of the whole molding process is about 6 minutes. For epoxy resins, the viscosity can be reduced to below 100mpa · s at a temperature of 100-110 ℃, and the complete curing temperature is generally around 130 ℃. The curing reaction of the epoxy resin is an exothermic reaction, at which the curing of the epoxy resin is started, and the exothermic reaction causes the temperature of the reaction system to rise rapidly, so that the implosion is easy to occur. In order to avoid implosion, firstly adding epoxy resin at about 80 ℃, then standing for about 30 minutes to wait for the epoxy resin to flow and fill the mold, then heating the temperature to 90 ℃ at the speed of 1 ℃/min, then standing for 30 minutes to wait for gelation, after confirming the gelation by drawing, heating the temperature to 130 ℃ at the speed of 2 ℃/min, and keeping the temperature at 130 ℃ for more than 50 minutes, thereby completing the forming process, wherein the whole forming process takes more than 120 minutes, the production efficiency is low, and the production cost is high.
When the carbon fiber composite material is applied to automobile parts, the production efficiency of the carbon fiber composite material of the epoxy resin matrix cannot meet the requirements of automobile production, and the overhigh production cost cannot be borne by automobile manufacturers. Therefore, a carbon fiber and a production method of the carbon fiber composite material, which can improve the production efficiency of the carbon fiber composite material and reduce the production cost, are urgently needed to really realize the large-scale application of the carbon fiber composite material on automobiles.
The molding process of carbon fiber composite materials has been slow for a long time, resulting in high cost. In order to improve the molding efficiency of carbon fiber composite materials and reduce the production cost, high pressure resin transfer molding (HP-RTM) was developed by amam company of germany in combination with the company disfenbach, the company claus marfei, and the like. The method forces the epoxy resin to soak the carbon fiber by accurately controlling the flow rate of the AB component of the epoxy resin and applying high pressure to the resin (the pressure of an injection port is usually 120MPa, and the pressure of a mold locking is usually more than 1 MPa), and avoids implosion under the condition of quick reaction. By adopting the method, the forming speed of the carbon fiber composite material can be controlled to 3-20 minutes per piece according to the thickness, the product with the thickness of 1mm needs about 3 minutes, and 1 more minute is needed for each thickening of 1mm, and the specific flow is as follows: weaving carbon fibers to obtain carbon fiber fabrics, cutting the fabrics according to a designed shape, and then spreading the fabrics; performing mould pressing on the carbon fiber fabric subjected to the layering by using a performing press to obtain a carbon fiber preform; and (3) pouring resin into the carbon fiber preform in a forming die, and heating, pressurizing, curing and forming the carbon fiber preform under an HP-RTM press to obtain a carbon fiber composite material finished product.
In addition to the HP-RTM, wet molding (including static and dynamic wet molding) is a method for rapidly forming a carbon fiber composite material, and the forming rate by using the method is generally 1 minute per piece, but only thin-walled pieces with simple shapes can be formed, the thickness is not more than 3mm, and the specific flow is as follows: weaving carbon fibers to obtain carbon fiber fabrics, cutting the fabrics according to a designed shape, and then spreading the fabrics; putting the fabric subjected to layering into a wet-process mould pressing die, and uniformly spraying resin on the surface; and heating and pressurizing in wet molding equipment to cure and mold the resin to obtain the carbon fiber composite material product.
Both HP-RTM and wet molding require expensive equipment, such as a 3600-ton four-corner leveling press for Difenbach and a 1200-ton precision injection molding machine for Claus-Ma-Fei, etc., and 1200-ton press for Difenbach or CANON and a 1200-ton precision injection molding machine for Claus-Ma-Fei, etc. Equipment capital investment is very high. Meanwhile, the die also needs to be specially customized, generally customized by APEX company in Austria and CANON company in Italy, and is expensive and long in period. Although the HP-RTM can realize rapid molding of carbon fiber composite materials, the problem of low yield exists due to inherent defects of epoxy resins, and the problem of further increased production cost caused by high energy consumption and low raw material utilization rate also exists. Although the wet-process die pressing can realize the rapid forming of the carbon fiber composite material, the problems of low yield, forming of simple thin-wall parts, high energy consumption and the like exist due to the inherent defects of the epoxy resin.
The carbon fiber is fibrous carbon material with carbon content over 90%, and is carbon chain of relatively high purity prepared through carbonizing various carbon-containing organic fiber in inert gas at high temperature. Currently, the industrial production of carbon fibers can be divided into two main categories, namely Polyacrylonitrile (PAN) -based carbon fibers and pitch-based carbon fibers according to the raw material route, wherein the Polyacrylonitrile (PAN) -based carbon fibers are the most important. The carbon fiber production is a process for continuously removing impurity elements (mainly H, N, O, K, Na), reducing defects, purifying and reforming carbon chains. The production process of Polyacrylonitrile (PAN) based carbon fiber is mainly divided into two parts of protofilament production and protofilament carbonization. The protofilament production process mainly comprises the working procedures of polymerization, defoaming, metering, spinning, traction, water washing, oiling, drying and filament winding and the like, and protofilament carbonization mainly comprises the working procedures of filament unwinding, preoxidation, low-temperature carbonization, high-temperature carbonization, surface treatment, sizing and drying, winding and filament winding and the like.
Sizing is the last process step before the carbon fiber is wound into a finished carbon fiber product after surface treatment. The sizing has the main functions of bundling the carbon fibers, enabling the carbon fibers to be gathered together like an adhesive, improving the process performance, facilitating the processing, simultaneously playing a role in protection, reducing the friction among the carbon fibers, and reducing the loss of the carbon fibers in the subsequent rolling, packaging and transportation processes. Through sizing treatment on the carbon fibers, a polymer layer formed on the surface of the carbon fibers can play a role similar to a coupling agent, so that the chemical bonding between the carbon fibers and resin is improved, the interfacial property of the composite material is improved, the polymer on the surface of the carbon fibers can also improve the wetting property of the carbon fibers, the resin impregnation is facilitated, the preparation time of the composite material is shortened, and the quality of the composite material is improved. Different sizing agents and sizing processes in the production process of the carbon fiber have important influences on the mechanical property, the processing property and the composite material mechanics of the carbon fiber.
Disclosure of Invention
Aiming at the prior art, the invention provides a carbon fiber sizing agent and a preparation method thereof, aiming at accelerating the forming speed of a carbon fiber composite material, avoiding huge fixed asset investment and use cost of an HP-RTM scheme and realizing the forming of a carbon fiber composite material product with a complex structure which cannot be realized by wet-process mould pressing. The invention obtains the high-process carbon fiber capable of being infiltrated by polyester resin by improving the preparation method of the carbon fiber, and the carbon fiber and the polyester resin can reach the production rhythm of HP-RTM (high pressure-resin transfer molding) under the low-pressure (mold locking pressure is less than 2Mpa) resin transfer molding (LP-RTM) process, thereby realizing the rapid molding of the carbon fiber composite material. The invention solves the problem of low forming efficiency of the carbon fiber composite material. The invention solves the problem of high forming cost of the carbon fiber composite material.
The invention is realized by the following technical scheme:
a carbon fiber sizing agent is prepared from the following raw materials: the adhesive comprises water-based bisphenol A epoxy resin, polyether alcohol, unsaturated acid and water, wherein the weight ratio of the water-based bisphenol A epoxy resin to the polyether alcohol to the unsaturated acid is 1: 0.5-5: 0.4 to 5, preferably 1:0.6 to 3: 0.4 to 2.
Further, in the carbon fiber sizing agent, water accounts for 65-98% of the total weight, and preferably 70-98%.
Further, the polyether alcohol is selected from the group consisting of dimethyl trimer.
Further, the unsaturated acid is selected from acrylic acid.
One of the methods for producing the carbon fiber sizing agent (production method a) includes the steps of:
(1) adding water-based bisphenol A epoxy resin into water at the temperature of 10-40 ℃, uniformly stirring (stirring for 1-60 minutes at the speed of 10-600 r/min by using a stirrer), and standing (standing for 1-60 minutes) to obtain a suspension;
in the process of the epoxy resin meeting water, hydroxyl groups and epoxy groups in the epoxy resin have affinity with water, and ether groups are not dissolved in water or have affinity with water, so that after the epoxy resin is added into water, the hydroxyl groups and the epoxy groups are shielded, and the ether groups are exposed;
(2) adding unsaturated acid into polyether alcohol at the temperature of 10-40 ℃, uniformly stirring (stirring for 1-60 minutes at the speed of 10-600 r/min by using a stirrer), heating for 1-30 minutes at the temperature of 40-100 ℃, reacting to obtain a mixed solution of polyether alcohol unsaturated acid ester and water, and extracting the polyether alcohol unsaturated acid ester for later use;
(3) adding polyether alcohol unsaturated acid ester into the suspension obtained in the step (1), uniformly stirring (stirring for 1-30 minutes at a speed of 10-600 r/min by using a stirrer), and standing (standing for 1-60 minutes) to obtain an emulsion;
the exposed ether group of the epoxy resin in water has affinity with the ether bond in the unsaturated acid ester of polyether alcohol, so that the epoxy resin is partially dissolved in the unsaturated acid ester of polyether alcohol, and the ester group in the unsaturated acid ester of polyether alcohol is not dissolved in water, thereby forming an emulsion system of epoxy-unsaturated acid ester of polyether alcohol-water.
One of the methods for producing the carbon fiber sizing agent (production method B) includes the steps of:
(1) under the environment of 10-40 ℃, mixing the waterborne bisphenol A epoxy resin with polyether alcohol, uniformly stirring (stirring for 1-30 minutes at the speed of 10-600 r/min by using a stirrer), and standing (standing for 1-60 minutes) to obtain a solution which is uniform and transparent;
after the epoxy resin is added into the polyether alcohol, ether bonds and epoxy groups in the epoxy resin can make the epoxy resin dissolve in the polyether alcohol, and hydroxyl groups are exposed;
(2) adding unsaturated acid into the solution at the temperature of 10-40 ℃, uniformly stirring (stirring for 1-30 minutes at the speed of 10-600 r/min by using a stirrer), heating for 1-30 minutes at the temperature of 40-100 ℃, reacting the unsaturated acid with hydroxyl in the solution to generate unsaturated acid ester and water, standing for 1-60 minutes, and layering;
(3) and adding water into the layered mixture to obtain an epoxy-polyether alcohol unsaturated acid-water emulsion system.
One of the methods for producing the carbon fiber sizing agent (production method C) includes the steps of:
(1) mixing unsaturated acid and polyether alcohol at the temperature of 10-40 ℃, uniformly stirring (stirring for 1-30 minutes at the speed of 10-600 r/min by using a stirrer), heating for 1-30 minutes at the temperature of 40-100 ℃, reacting the unsaturated acid and the polyether alcohol to generate polyether alcohol unsaturated acid ester and water, and extracting the polyether alcohol unsaturated acid ester for later use;
(2) adding bisphenol A epoxy resin into polyether alcohol unsaturated acid ester at the temperature of 10-40 ℃, uniformly stirring (stirring for 1-30 minutes at the speed of 10-600 r/min by using a stirrer), and standing (standing for 1-60 minutes) to obtain a solution which is uniform and transparent;
after the epoxy resin is added into the polyether alcohol unsaturated acid ester, ether bonds and epoxy groups in the epoxy resin can make the epoxy resin dissolve in the polyether alcohol unsaturated acid ester, and the hydroxyl is exposed;
(3) adding water into the solution, dissolving hydroxyl in the water, and dispersing the solution to obtain the epoxy-polyether alcohol unsaturated acid-water emulsion system.
The three preparation methods have the same raw materials and processes, and only have different charging and process sequences.
The carbon fiber sizing agent is applied to the preparation of carbon fibers and carbon fiber composite materials.
A carbon fiber is obtained by sizing a carbon fiber using the carbon fiber sizing agent.
A carbon fiber composite material comprises a resin matrix and the carbon fiber. The resin matrix is selected from unsaturated polyester and vinyl ester resin.
Preferably, the specific method for sizing the carbon fiber may be: and placing the carbon fiber tows in a sizing tank filled with a sizing agent, so that the sizing agent submerges the carbon fiber tows, and extruding redundant sizing liquid on the fibers through continuous 1-40 groups of upper and lower squeezing rollers at a linear speed of 0.1-8 m/s under the traction of a motor. Or: the carbon fiber tows are placed above the sizing groove, the sizing agent is sprayed to the surface of the carbon fiber tows through a nozzle, the spraying flow is 0.5-1000 mL per minute, and the sizing agent is determined according to the thickness of the carbon fiber tows and the concentration of sizing agent in sizing liquid.
After sizing is finished, as water is dried, epoxy groups and hydroxyl groups in epoxy resin in the sizing agent are released, and the epoxy groups and the hydroxyl groups can form hydrogen bonds with polar groups such as hydroxyl groups, carboxyl groups and the like on the surface of the carbon fiber after surface treatment, so that the sizing agent is firmly attached to the surface of the carbon fiber; and ester bonds in the unsaturated ester of polyether alcohol in the slurry can be compatible with ester bonds in the polyester resin to form hydrogen bonds, so that the carbon fibers can be soaked by the polyester resin, and carbon-carbon double bonds in the unsaturated ester of polyether alcohol can participate in the curing reaction of the unsaturated resin and the vinyl resin, thereby realizing the improvement of the manufacturability of the carbon fibers.
When the carbon fiber treated by the sizing agent is used for preparing the carbon fiber composite material, the carbon fiber can be soaked by polyester resin (such as unsaturated polyester and vinyl ester resin), and the carbon fiber can obtain manufacturability similar to glass fiber, so that the forming time of the carbon fiber composite material can be greatly reduced, the fixed asset investment of carbon fiber composite material forming equipment is reduced, and the low-cost and rapid forming of the carbon fiber composite material is realized.
In the invention, the carbon fiber is obtained based on a Polyacrylonitrile (PAN) base carbon fiber production process, and the invention is applicable to the invention as long as the polyacrylonitrile protofilament capable of being carbonized is produced, no matter what process parameters are adopted in the whole process in the protofilament production process. The method is applicable to the invention as long as the conversion from polyacrylonitrile protofilament to carbon fiber can be realized no matter what process parameters are adopted in the processes of filament unwinding, pre-oxidation, low-temperature carbonization, high-temperature carbonization, surface treatment, filament winding and the like in the protofilament carbonization process. In the process of protofilament carbonization, when the polyacrylonitrile protofilament is finally subjected to surface treatment through a series of processes, the carbon fiber tows which are rough in surface and have oxygen-containing polar groups (such as hydroxyl, carboxyl and the like) are obtained. The method is applicable to the invention as long as the carbon fiber tows with rough surfaces and oxygen-containing polar groups (such as hydroxyl, carboxyl and the like) are finally obtained no matter what process parameters are adopted in the previous production. After the surface is sized, the carbon fiber tows need to be dried to remove liquid components in the slurry, and dry slurry is left on the surface of the carbon fibers. The drying must be done with hot air, which can be assisted with electric drying. The drying temperature should be controlled between 40-150 deg.C during drying process to prevent the slurry from losing efficacy due to decomposition or reaction. Other process control points in the drying process are applicable to the invention no matter what process parameters are adopted, as long as the dried carbon fiber tows are finally obtained. After the carbon fibers are dried, the carbon fiber tows need to be wound and collected, and no matter what process parameters are adopted in the process, the method is applicable to the invention as long as the coiled carbon fibers are finally obtained. Namely: the invention is not described in detail in the prior art.
The various terms and phrases used herein have the ordinary meaning as is well known to those skilled in the art. To the extent that the terms and phrases are not inconsistent with known meanings, the meaning of the present invention will prevail.
Drawings
FIG. 1: the carbon fiber of the present invention and vinyl ester resin are compounded to form a cross section.
FIG. 2: the cross section formed by compounding carbon fiber and vinyl ester resin is common in the market.
Detailed Description
The present invention will be further described with reference to the following examples. However, the scope of the present invention is not limited to the following examples. It will be understood by those skilled in the art that various changes and modifications may be made to the invention without departing from the spirit and scope of the invention.
The present invention has been described generally and/or specifically with respect to materials used in testing and testing methods. Although many materials and methods of operation are known in the art for the purpose of carrying out the invention, the invention is nevertheless described herein in as detail as possible.
The instruments, reagents, materials and the like used in the following examples are conventional instruments, reagents, materials and the like in the prior art and are commercially available in a normal manner unless otherwise specified. Unless otherwise specified, the experimental methods, detection methods, and the like described in the following examples are conventional experimental methods, detection methods, and the like in the prior art.
Example preparation of carbon fiber sizing agent and carbon fiber composite
The carbon fiber sizing agent is prepared by using the raw materials as shown in the table 1, wherein the formula ratio X: X: X: X is listed in the table, and the weight percentages of the raw materials from left to right are water-based bisphenol A epoxy resin (Vast EPI-KQTE 3510-W-60), dimethyl trimerization ether dimethanol, acrylic acid and purified water. The material preparation temperature is 26 ℃, and the drying temperature during sizing is 80 ℃.
The procedure for method A, as listed in the table, was as follows:
(1) adding the water-based bisphenol A epoxy resin into water at the temperature of 26 ℃, uniformly stirring (stirring for 30 minutes at the speed of 300r/min by using a stirrer), and standing (standing for 30 minutes) to obtain a suspension;
(2) adding acrylic acid into dimethyl trimer dimethanol at 26 ℃, uniformly stirring (stirring for 30 minutes at the speed of 300r/min by using a stirrer), heating for 30 minutes at 80 ℃, reacting acrylic acid with dimethyl trimer dimethanol to generate dimethyl trimer dimethacrylate and water, and extracting to obtain dimethyl trimer dimethacrylates, wherein the structural formula of the dimethyl trimer dimethacrylates is shown as follows:
(3) adding the trimeric methyl ether dimethacrylate into the suspension, uniformly stirring (stirring for 30 minutes at the speed of 300r/min by using a stirrer), and standing (standing for 30 minutes) to obtain a sizing agent emulsion.
The procedure for method B, as listed in the table, was as follows:
(1) mixing the water-based bisphenol A epoxy resin with the dimethyl trimer at 26 ℃, uniformly stirring (stirring for 30 minutes at the speed of 300r/min by using a stirrer), standing (standing for 30 minutes) to obtain a solution, and uniformly and brightly standing;
(2) adding acrylic acid into the solution at 26 ℃, uniformly stirring (stirring for 30 minutes at the speed of 300r/min by using a stirrer), heating for 30 minutes at 80 ℃, reacting acrylic acid with hydroxyl in the solution to generate acrylic ester and water, standing for 30 minutes, and layering;
(3) and adding water into the layered mixture to obtain the sizing agent emulsion.
The procedure for method C, as listed in the table, was as follows:
(1) mixing acrylic acid and dimethyl trimer dimethanol at 26 ℃, uniformly stirring (stirring for 30 minutes at the speed of 300r/min by using a stirrer), heating for 30 minutes at 80 ℃, reacting acrylic acid and dimethyl trimer dimethanol to generate dimethyl trimer dimethacrylates and water, and extracting the dimethyl trimer dimethacrylates for later use;
(2) adding bisphenol A epoxy resin into the trimeric methyl ether dimethacrylate at the temperature of 26 ℃, uniformly stirring (stirring for 30 minutes at the speed of 300r/min by using a stirrer), standing (standing for 30 minutes) to obtain a solution which is uniform and transparent;
(3) adding water into the solution, dissolving hydroxyl in water, and dispersing the solution to obtain sizing agent emulsion.
After obtaining the sizing agent, sizing the carbon fiber (unsized at the T300 level, provided by lanzhou blue star fiber limited), the sizing amount of which is shown in table 1, and the specific method is as follows: and (3) placing the carbon fiber tows in a sizing tank containing a sizing agent, so that the sizing agent submerges the carbon fiber tows, and simultaneously extruding redundant sizing liquid on the fibers through continuous 30 groups of upper and lower squeezing rollers at a linear speed of 4m/s under the traction of a motor. Then drying with hot air and electricity assistance, wherein the drying temperature is 120 ℃.
TABLE 1
After the carbon fiber is obtained, compounding the carbon fiber with unsaturated polyester and vinyl resin to obtain the carbon fiber composite material. The formula of the used vinyl resin and unsaturated polyester is as follows: resin: curing agent: the accelerator is 100:3:0.5, and the mass ratio is, wherein the unsaturated polyester is Jining HuaKai resin hk-8300, the vinyl resin is Jining HuaKai resin 901, the curing agent is methyl ethyl ketone peroxide, and the accelerator is cobalt naphthenate. The interlaminar shear strength of the composite material is shown in table 1, and a higher interlaminar shear strength indicates better bonding between the resin matrix and the carbon fibers.
FIG. 1 is a cross-section of a carbon fiber produced by the present invention and unsaturated polyester after compositing, corresponding to recipe No. 1 in Process A. FIG. 2 is a cross-section of a composite of T300 carbon fiber commercially available from Lanzhou Lanxing fiber Co., Ltd and unsaturated polyester. As can be seen from the figure, the interface layer is formed between the carbon fibers produced by the present invention and the unsaturated polyester, and the interface layer is torn during the composite material failure. And the surface of the common carbon fiber sold in the market is not combined with the unsaturated polyester, and the surface is smooth after being damaged. Therefore, the carbon fiber produced by the invention can be soaked by unsaturated polyester, while the common carbon fiber sold in the market can not be soaked by unsaturated polyester.
The above examples are provided to those of ordinary skill in the art to fully disclose and describe how to make and use the claimed embodiments, and are not intended to limit the scope of the disclosure herein. Modifications apparent to those skilled in the art are intended to be within the scope of the appended claims.
Claims (5)
1. A carbon fiber sizing agent is characterized in that: is prepared from the following raw materials: the adhesive comprises water-based bisphenol A epoxy resin, polyether alcohol, unsaturated acid and water, wherein the weight ratio of the water-based bisphenol A epoxy resin to the polyether alcohol to the unsaturated acid is 1: 0.6-3: 0.4 to 2;
in the carbon fiber sizing agent, water accounts for 65-98% of the total weight;
the polyether alcohol is selected from dimethyl trimer dimethanol;
the unsaturated acid is selected from acrylic acid;
is prepared by one of the following methods:
the preparation method A comprises the following steps: the method comprises the following steps:
(1) adding water-based bisphenol A epoxy resin into water at the temperature of 10-40 ℃, uniformly stirring, and standing to obtain a suspension;
(2) adding unsaturated acid into polyether alcohol at the temperature of 10-40 ℃, uniformly stirring, heating at the temperature of 40-100 ℃ for 1-30 minutes, reacting to obtain a mixed solution of polyether alcohol unsaturated acid ester and water, and extracting the polyether alcohol unsaturated acid ester for later use;
(3) adding polyether alcohol unsaturated acid ester into the suspension obtained in the step (1), uniformly stirring, and standing to obtain emulsion, namely the carbon fiber sizing agent;
the preparation method C comprises the following steps: (1) mixing unsaturated acid and polyether alcohol at the temperature of 10-40 ℃, uniformly stirring, heating at the temperature of 40-100 ℃ for 1-30 minutes, reacting the unsaturated acid and the polyether alcohol to generate polyether alcohol unsaturated acid ester and water, and extracting the polyether alcohol unsaturated acid ester for later use;
(2) adding aqueous bisphenol A epoxy resin into polyether alcohol unsaturated acid ester at the temperature of 10-40 ℃, uniformly stirring, and standing to obtain a solution;
(3) and adding water into the solution, dissolving hydroxyl in the water, and dispersing the solution to obtain an epoxy-polyether alcohol unsaturated acid-water emulsion system, namely the carbon fiber sizing agent.
2. Use of the carbon fiber sizing agent of claim 1 in the preparation of carbon fibers, carbon fiber composites.
3. A carbon fiber obtained by sizing a carbon fiber with the carbon fiber sizing agent according to claim 1.
4. The carbon fiber according to claim 3, characterized in that: the specific method for sizing the carbon fiber comprises the following steps: placing the carbon fiber tows in a sizing tank containing a sizing agent, so that the sizing agent submerges the carbon fiber tows, and meanwhile, extruding redundant sizing liquid on the fibers through 1-40 groups of continuous upper and lower extrusion rollers at a linear speed of 0.1-8 m/s under the traction of a motor; or: and placing the carbon fiber tows above the sizing groove, and spraying a sizing agent to the surface of the carbon fiber tows by using a nozzle, wherein the spraying flow is 0.5-1000 mL per minute.
5. A carbon fiber composite material comprising a resin matrix and the carbon fiber of claim 3 or 4; the resin matrix is selected from unsaturated polyester and vinyl ester resin.
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| CN103797183A (en) * | 2011-09-22 | 2014-05-14 | 三洋化成工业株式会社 | Fiber sizing agent composition |
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