CN113818250A - Sizing agent for carbon fiber, preparation method thereof and composite material - Google Patents
Sizing agent for carbon fiber, preparation method thereof and composite material Download PDFInfo
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- CN113818250A CN113818250A CN202110961619.9A CN202110961619A CN113818250A CN 113818250 A CN113818250 A CN 113818250A CN 202110961619 A CN202110961619 A CN 202110961619A CN 113818250 A CN113818250 A CN 113818250A
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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
- 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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- 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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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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
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Abstract
The invention discloses a sizing agent for carbon fibers, a preparation method thereof and a composite material, wherein the sizing agent comprises a hyperbranched prepolymer, an emulsifier, a dispersant and water, and the method for preparing the hyperbranched prepolymer comprises the following steps: and mixing the bisphenol A epoxy resin with polyhydric alcohol and a catalyst for reaction to obtain the hyperbranched prepolymer. The hyperbranched prepolymer structure contained in the sizing agent contains hydroxyl, and simultaneously has a dendritic hyperbranched physical structure, so that the hydroxyl can react with carboxyl on the surface of the carbon fiber subjected to surface treatment and can be linked with a resin matrix through the physical structure, thereby effectively improving the interfacial property between the carbon fiber and the resin and preparing the composite material with excellent performance.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a sizing agent for carbon fibers, a preparation method of the sizing agent and a composite material.
Background
The carbon fiber reinforced resin composite material has excellent performance, has the defect of low interface bonding strength between carbon fibers and a resin matrix, and is used for improving the chemical bonding effect between the carbon fibers and resin by carrying out surface modification on the carbon fibers by researchers.
The sizing agent is a protective glue attached to the surface of the carbon fiber. Its very low content is an important constituent of carbon fibres and plays a different role in the different application phases of carbon fibres. In the production process of the carbon fiber, the sizing agent can play a role in protecting the fiber and reducing broken filaments and monofilament breakage. In the subsequent deep processing process, the sizing agent has the functions of reducing the generation of broken filaments, endowing the carbon fibers with yarn spreading performance and bundling performance and improving the processability of the fibers. In the carbon fiber composite material, the sizing agent is used as an interface transition layer between the matrix resin and the carbon fiber to transfer load, and the overall mechanical property of the carbon fiber composite material is influenced. However, it is difficult to improve the interfacial properties between the carbon fibers and the resin matrix with the conventional sizing agent for carbon fibers.
Disclosure of Invention
The invention aims to solve the technical problem of providing a sizing agent for carbon fibers, a preparation method thereof and a composite material, wherein the sizing agent contains a hyperbranched prepolymer structure, the hyperbranched structure contains hydroxyl and simultaneously has a dendritic hyperbranched physical structure, so that the hydroxyl can react with carboxyl on the surface of the carbon fibers subjected to surface treatment and can be linked with a resin matrix through the physical structure, thereby effectively improving the interface performance between the carbon fibers and the resin and preparing the composite material with excellent performance.
In one aspect of the present invention, a sizing agent for carbon fibers is provided. According to an embodiment of the present invention, the sizing agent includes: hyperbranched prepolymer, an emulsifier, a dispersant and water, wherein the method for preparing the hyperbranched prepolymer comprises the following steps: and mixing the bisphenol A epoxy resin with polyhydric alcohol and a catalyst for reaction to obtain the hyperbranched prepolymer.
Preferably, the sizing agent comprises: 15-30 parts by weight of hyperbranched prepolymer, 0.5-3 parts by weight of emulsifier, 0.5-2 parts by weight of dispersant and 60-80 parts by weight of water.
Preferably, the polyol comprises at least one of glycerol and a polyether polyol.
Preferably, the mass ratio of the bisphenol A epoxy resin to the polyhydric alcohol and the catalyst is (50-120): (20-100): (1-5).
Preferably, the reaction is carried out at 70-160 ℃ for 30 min-8 h.
Preferably, the emulsifier comprises at least one of castor oil polyoxyethylene ether, bisphenol a polyoxyethylene ether, sodium dodecylbenzene sulfonate, alkylphenol polyoxyethylene ether and span series emulsifiers.
Preferably, the dispersant comprises at least one of neopentyl glycol glycidyl ether, a cellulose derivative and sodium lauryl sulfate.
In a second aspect of the invention, the invention proposes a process for preparing the above sizing agent. According to an embodiment of the invention, the method comprises: (1) mixing bisphenol A epoxy resin with polyhydric alcohol and a catalyst for reaction so as to obtain a hyperbranched prepolymer; (2) mixing the hyperbranched prepolymer, an emulsifier and a dispersant; (3) adding water dropwise into the reacted liquid obtained in the step (2) to obtain a sizing agent.
Preferably, in the step (2), the hyperbranched prepolymer, the emulsifier and the dispersant are mixed and stirred for 15-50 min at 40-70 ℃ and 4000-18000 r/min.
Preferably, in the step (3), the dropping speed of the water is 1-5 ml/min, and the dropping time is 1.5-2.5 h.
In a third aspect of the invention, a composite material is presented. According to the embodiment of the invention, the composite material is compounded by the sizing agent, the carbon fibers and the resin matrix.
Preferably, the resin matrix comprises an epoxy resin.
Compared with the prior art, the hyperbranched prepolymer is prepared by mixing bisphenol A epoxy resin, polyhydric alcohol and a catalyst for reaction, and the hyperbranched prepolymer is compounded with an emulsifier, a dispersant and water to prepare the carbon fiber sizing agent, so that the obtained sizing agent contains a hyperbranched prepolymer structure which contains hydroxyl and has a dendritic hyperbranched physical structure, and the hydroxyl can react with carboxyl on the surface of the carbon fiber subjected to surface treatment and can be linked with a resin matrix through the physical structure, thereby effectively improving the interface performance between the carbon fiber and the resin and preparing the composite material with excellent performance.
Detailed Description
The present invention will be further described with reference to the following examples, which are illustrative only and not intended to be limiting, and the scope of the present invention is not limited thereby.
In one aspect of the present invention, a sizing agent for carbon fibers is provided. According to an embodiment of the invention, the sizing agent comprises a hyperbranched prepolymer, an emulsifier, a dispersant and water, wherein a method for preparing the hyperbranched prepolymer comprises the following steps: the preparation method comprises the steps of mixing bisphenol A epoxy resin with polyol and a catalyst, under the action of the catalyst, firstly, carrying out ring opening on an epoxy group of the bisphenol A epoxy resin, then, abstracting a hydrogen atom from hydroxyl in the polyol to form a new hydroxyl with an oxygen radical after ring opening, combining the polyol losing the hydrogen atom with a carbon radical of the epoxy group, reacting epoxy groups at two ends of the epoxy resin with the polyol, reacting the remaining hydroxyl with more epoxy resins to form a tree-shaped hyperbranched structure, and finally, obtaining the hyperbranched prepolymer in a subsequent ring opening reaction. The inventor finds that the bisphenol A epoxy resin, the polyol and the catalyst are mixed to react to prepare the hyperbranched prepolymer, and the hyperbranched prepolymer, the emulsifier, the dispersant and the water are compounded to prepare the carbon fiber sizing agent, in the process, the dispersant and the hyperbranched prepolymer are mixed to cooperatively reduce the system viscosity, the emulsifier is coated on the surface of the hyperbranched prepolymer, so that the prepolymer has hydrophilic property, the obtained sizing agent contains a hyperbranched prepolymer structure, the hyperbranched structure contains hydroxyl and also has a dendritic hyperbranched physical structure, and the hydroxyl can react with carboxyl on the surface of the carbon fiber subjected to surface treatment and can be linked with a resin matrix through the physical structure, so that the interfacial property between the carbon fiber and the resin is effectively improved, and the composite material with excellent performance is prepared.
Further, in the method for preparing the hyperbranched prepolymer, the polyol includes but is not limited to at least one of glycerol and polyether polyol, the catalyst includes but is not limited to ammonium salt, and the mass ratio of the bisphenol A epoxy resin to the polyol and the catalyst is (50-120): (20-100): (1-5). The inventor finds that if the addition amount of the bisphenol A epoxy resin is too high, the viscosity of the system is increased, which is not beneficial to the emulsification of the subsequent hyperbranched prepolymer, and if the addition amount of the bisphenol A epoxy resin is too low, the branching degree of the reaction product is not enough, which is not beneficial to the sizing in the later period; if the addition amount of the polyhydric alcohol is too high, the hydroxyl groups of the reaction product are too much, the branching degree is too low, and if the addition amount of the polyhydric alcohol is too low, the viscosity of the system is increased; if the catalyst addition is too high, the reaction rate is too fast, which easily results in too large molecular distribution of the reaction product, and if the catalyst addition is too low, the reaction is too slow, which is not favorable for the reaction. Meanwhile, in the method for preparing the hyperbranched prepolymer, the bisphenol A epoxy resin, the polyol and the catalyst are mixed and then react for 30min to 8h at the temperature of 70 to 160 ℃.
Further, the sizing agent comprises 15-30 parts by weight of hyperbranched prepolymer, 0.5-3 parts by weight of emulsifier, 0.5-2 parts by weight of dispersant and 60-80 parts by weight of water. The inventor finds that if the adding amount of the hyperbranched prepolymer is too high, the particle size of the sizing agent emulsion is increased, and the sizing effect is weakened; if the content of the hyperbranched prepolymer additive is too low, the main body of the sizing agent is reduced, and the sizing effect is weakened; if the addition amount of the emulsifier is too high, the water absorption capacity of the sizing agent is too strong, and the interface performance of the composite material is further influenced; if the addition amount of the emulsifier is too low, the particle size distribution of the sizing agent emulsion is not uniform, the stability is poor, and the storage period is shortened; if the addition amount of the dispersant is too high, the average molecular weight of the sizing agent is reduced, the sizing effect is poor, and if the addition amount of the dispersant is too low, the viscosity of the system is too high, which is not favorable for emulsification.
Further, the above emulsifier includes, but is not limited to, at least one of castor oil polyoxyethylene ether, bisphenol a polyoxyethylene ether, sodium dodecylbenzene sulfonate, alkylphenol polyoxyethylene ether, and span series emulsifier; the above-mentioned dispersant includes, but is not limited to, at least one of neopentyl glycol glycidyl ether, a cellulose derivative and sodium lauryl sulfate.
In a second aspect of the invention, the invention proposes a process for preparing the above sizing agent. According to an embodiment of the invention, the method comprises:
s100: mixing bisphenol A type epoxy resin with polyhydric alcohol and catalyst for reaction
In the step, bisphenol A epoxy resin is mixed with polyhydric alcohol and a catalyst, under the action of the catalyst, epoxy groups of the bisphenol A epoxy resin can firstly undergo ring opening, then hydroxyl groups in the polyhydric alcohol can be deprived of hydrogen atoms and oxygen can be gathered by radicals to form new hydroxyl groups after ring opening, the polyhydric alcohol losing the hydrogen atoms can be combined with carbon free radicals of the epoxy groups, after the epoxy groups at two ends of the epoxy resin react with the polyhydric alcohol, the remaining hydroxyl groups can react with more epoxy resins to form a tree-shaped hyperbranched structure, and finally the hyperbranched prepolymer is obtained in the subsequent ring opening reaction. Preferably, the bisphenol A epoxy resin is mixed with polyhydric alcohol and a catalyst and then reacts for 30min to 8h at the temperature of 70 to 160 ℃.
S200: mixing the hyperbranched prepolymer, the emulsifier and the dispersant
In the step, the obtained hyperbranched prepolymer, the emulsifier and the dispersant are mixed, so that the dispersant and the hyperbranched prepolymer are uniformly mixed, the system viscosity is reduced, the emulsifier can be coated on the surface of the mixture of the prepolymer and the dispersant, the prepolymer can have hydrophilic property, and the obtained sizing agent contains a hyperbranched prepolymer structure, wherein the hyperbranched structure contains hydroxyl and also has a dendritic hyperbranched physical structure, so that the hydroxyl can react with carboxyl on the surface of carbon fiber subjected to surface treatment and can be linked with a resin matrix through the physical structure, and the interface performance between the carbon fiber and the resin is effectively improved. Preferably, the hyperbranched prepolymer, the emulsifier and the dispersant are mixed and stirred for 15-50 min at 40-70 ℃ and 4000-18000 r/min.
S300: adding water dropwise to the reacted solution obtained in step S200
In the step, water is added into the reacted liquid obtained in the step S200, and the reacted liquid is converted from a water-in-oil system to an oil-in-water system, so that the sizing agent is obtained. Preferably, the dropping speed of the water is 1-5 ml/min, and the dropping time is 1.5-2.5 h. The inventors found that if the water is added too quickly, the emulsion is not complete in phase inversion, resulting in an emulsion having an excessively large particle size, and if the water is added too slowly, a large amount of heat is generated by stirring during the reaction, resulting in an increase in the temperature of the system, and the HLB value of the emulsifier is decreased, which is disadvantageous for emulsification.
According to the method for preparing the sizing agent, disclosed by the embodiment of the invention, the bisphenol A type epoxy resin is mixed with the polyhydric alcohol and the catalyst to react to prepare the hyperbranched prepolymer, and the hyperbranched prepolymer is compounded with the emulsifier, the dispersant and the water to prepare the carbon fiber sizing agent, so that the obtained sizing agent contains a hyperbranched prepolymer structure, the hyperbranched structure contains hydroxyl and has a dendritic hyperbranched physical structure, and the hydroxyl can react with carboxyl on the surface of the carbon fiber subjected to surface treatment and can be linked with a resin matrix through the physical structure, so that the interface performance between the carbon fiber and the resin is effectively improved, and the composite material with excellent performance is prepared.
It should be noted that the features and advantages described above for the carbon fiber sizing agent are also applicable to the method for preparing the carbon fiber sizing agent, and are not described herein again.
In a third aspect of the invention, a composite material is presented. According to the embodiment of the invention, the composite material is compounded by the sizing agent or the sizing agent obtained by the method, the carbon fibers and the resin matrix. Therefore, the hyperbranched prepolymer structure contained in the sizing agent contains hydroxyl, and simultaneously has a dendritic hyperbranched physical structure, so that the hydroxyl can react with carboxyl on the surface of the carbon fiber subjected to surface treatment and can be linked with a resin matrix through the physical structure, thereby effectively improving the interface performance between the carbon fiber and the resin and preparing the composite material with excellent performance. Preferably, the resin matrix comprises an epoxy resin.
It should be noted that the features and advantages described above for the sizing agent for carbon fibers and the preparation method thereof are also applicable to the composite material, and are not described herein again.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
The method for preparing the sizing agent for the carbon fiber comprises the following steps:
(1)100g of bisphenol A epoxy resin is put at the temperature of 80 ℃ and heated for 20min, then 1.2g of tetrabutylammonium bromide and 20g of glycerol are added, and the reaction is carried out for 2h at the temperature of 140 ℃ to obtain hyperbranched prepolymer;
(2) putting 50g of hyperbranched prepolymer, 7.5g of compound emulsifier (sodium dodecyl benzene sulfonate, alkylphenol polyoxyethylene and span series emulsifier are compounded according to the mass ratio of 1: 2: 3) and 3g of neopentyl glycol glycidyl ether into a 500ml beaker, and then stirring for 30min at 70 ℃ at 5000r/min to obtain a reacted liquid;
(3) and (3) dropwise adding deionized water into the reacted solution at the speed of 3ml/min, and stirring for 20min after dropwise adding is finished to obtain the sizing agent.
Example 2
The method for preparing the sizing agent for the carbon fiber comprises the following steps:
(1) heating 100g of bisphenol A epoxy resin at 100 ℃ for 1h, adding 1.3g of tetrabutylammonium bromide and 30g of glycerol, and reacting at 120 ℃ for 3h to obtain a hyperbranched prepolymer;
(2) putting 50g of hyperbranched prepolymer, 10g of compound emulsifier (sodium dodecyl benzene sulfonate, castor oil polyoxyethylene ether and span series emulsifier are compounded according to the mass ratio of 1: 2: 3) and 5g of neopentyl glycol glycidyl ether into a 500ml beaker, and stirring for 30min at 70 ℃ and 5000r/min to obtain reacted liquid;
(3) and (3) dropwise adding deionized water into the reacted solution at the speed of 3ml/min, and stirring for 20min after dropwise adding is finished to obtain the sizing agent.
Example 3
The method for preparing the sizing agent for the carbon fiber comprises the following steps:
(1) heating 100g of bisphenol A epoxy resin at 90 ℃ for 1h, adding 2g of tetrabutylammonium bromide and 35.5g of glycerol, and reacting at 140 ℃ for 4h to obtain a hyperbranched prepolymer;
(2) putting 50g of hyperbranched prepolymer, 15g of compound emulsifier (sodium dodecyl benzene sulfonate, bisphenol A polyoxyethylene ether and span series emulsifier are compounded according to the mass ratio of 1: 2: 3) and 8g of neopentyl glycol glycidyl ether into a 500ml beaker, and then stirring for 30min at 70 ℃ and 5000r/min to obtain a reacted liquid;
(3) and (3) dropwise adding deionized water into the reacted solution at the speed of 3ml/min, and stirring for 20min after dropwise adding is finished to obtain the sizing agent.
Example 4
The method for preparing the sizing agent for the carbon fiber comprises the following steps:
(1) heating 100g of bisphenol A epoxy resin at 100 ℃ for 1h, adding 3g of tetrabutylammonium bromide and 50g of glycerol, and reacting at 140 ℃ for 4.5h to obtain a hyperbranched prepolymer;
(2) putting 50g of hyperbranched prepolymer, 7.5g of compound emulsifier (sodium dodecyl benzene sulfonate, alkylphenol polyoxyethylene and bisphenol A polyoxyethylene ether emulsifier are compounded according to the mass ratio of 1: 1: 3) and 3g of sodium carboxymethylcellulose into a 500ml beaker, and then stirring for 30min at 70 ℃ at 5000r/min to obtain a reacted liquid;
(3) and (3) dropwise adding deionized water into the reacted solution at the speed of 3ml/min, and stirring for 20min after dropwise adding is finished to obtain the sizing agent.
Example 5
The method for preparing the sizing agent for the carbon fiber comprises the following steps:
(1) heating 100g of bisphenol A epoxy resin at 100 ℃ for 20min, adding 2.3g of tetrabutylammonium bromide and 40g of polyether polyol, and reacting at 160 ℃ for 6h to obtain a hyperbranched prepolymer;
(2) putting 50g of hyperbranched prepolymer, 10g of compound emulsifier (sodium dodecyl benzene sulfonate, alkylphenol polyoxyethylene and span series emulsifier are compounded according to the mass ratio of 1: 1: 3) and 5g of neopentyl glycol glycidyl ether into a 500ml beaker, and then stirring for 30min at 70 ℃ and 5000r/min to obtain a reacted liquid;
(3) and (3) dropwise adding deionized water into the reacted solution at the speed of 3ml/min, and stirring for 20min after dropwise adding is finished to obtain the sizing agent.
Example 6
The method for preparing the sizing agent for the carbon fiber comprises the following steps:
(1) heating 100g of bisphenol A epoxy resin at 100 ℃ for 20min, adding 3.4g of tetrabutylammonium bromide and 50g of polyether polyol, and reacting at 150 ℃ for 5.5h to obtain a hyperbranched prepolymer;
(2) putting 50g of hyperbranched prepolymer, 15g of compound emulsifier (sodium dodecyl benzene sulfonate and alkylphenol polyoxyethylene ether emulsifier are compounded according to the mass ratio of 1: 1) and 8g of neopentyl glycol glycidyl ether into a 500ml beaker, and then stirring for 30min at 70 ℃ at 5000r/min to obtain a reacted liquid;
(3) and (3) dropwise adding deionized water into the reacted solution at the speed of 3ml/min, and stirring for 20min after dropwise adding is finished to obtain the sizing agent.
Example 7
The method for preparing the sizing agent for the carbon fiber comprises the following steps:
(1) heating 100g of bisphenol A epoxy resin at 50-100 ℃ for 10min-1h, adding 4g of tetrabutylammonium bromide and 70g of polyether polyol, and reacting at 155 ℃ for 5.5h to obtain a hyperbranched prepolymer;
(2) putting 50g of hyperbranched prepolymer, 20g of compound emulsifier (sodium dodecyl benzene sulfonate, alkylphenol polyoxyethylene and span series emulsifier are compounded according to the mass ratio of 1: 1: 3) and 10g of neopentyl glycol glycidyl ether into a 500ml beaker, and then stirring for 30min at 70 ℃ and 5000r/min to obtain a reacted liquid;
(3) and (3) dropwise adding deionized water into the reacted solution at the speed of 3ml/min, and stirring for 20min after dropwise adding is finished to obtain the sizing agent.
Example 8
The method for preparing the sizing agent for the carbon fiber comprises the following steps:
(1) heating 100g of bisphenol A epoxy resin at 80 ℃ for 20min, adding 1.2g of tetrabutylammonium bromide and 20g of glycerol, and reacting at 140 ℃ for 2h to obtain a hyperbranched prepolymer;
(2) putting 50g of hyperbranched prepolymer, 7.5g of compound emulsifier (sodium dodecyl benzene sulfonate and alkylphenol polyoxyethylene ether are compounded according to the mass ratio of 1: 1) and 3g of neopentyl glycol glycidyl ether into a 500ml beaker, and then stirring for 30min at 70 ℃ at 5000r/min to obtain a reacted liquid;
(3) and (3) dropwise adding deionized water into the reacted solution at the speed of 3ml/min, and stirring for 20min after dropwise adding is finished to obtain the sizing agent.
Example 9
The method for preparing the sizing agent for the carbon fiber comprises the following steps:
(1) heating 100g of bisphenol A epoxy resin at 100 ℃ for 1h, adding 1.3g of tetrabutylammonium bromide and 30g of glycerol, and reacting at 120 ℃ for 3h to obtain a hyperbranched prepolymer;
(2) putting 50g of hyperbranched prepolymer, 7.5g of compound emulsifier (sodium dodecyl benzene sulfonate and span series emulsifier are compounded according to the mass ratio of 1: 1) and 3g of neopentyl glycol glycidyl ether into a 500ml beaker, and stirring for 30min at 70 ℃ at 5000r/min to obtain reacted liquid;
(3) and (3) dropwise adding deionized water into the reacted solution at the speed of 3ml/min, and stirring for 20min after dropwise adding is finished to obtain the sizing agent.
Performance testing
1. The particle size distribution of the sizing agents obtained in examples 1 to 9 was measured using a laser particle size disperser;
2. the sizing agents prepared in the embodiments 1 to 9 are used for sizing the carbon fibers respectively, then the carbon fibers are thermally cured, and the microscopic appearances of the surfaces of the carbon fibers before and after sizing are observed by using an electron microscope;
3. and measuring the interlaminar shear strength of the carbon fiber after sizing by adopting a GB/T30969 polymer matrix composite material short beam shear strength experimental method.
The test results are shown in table 1.
TABLE 1
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the technical principle of the present invention, and these modifications and decorations should not be regarded as the protection scope of the invention.
Claims (10)
1. A sizing agent for carbon fibers, characterized by comprising: hyperbranched prepolymer, emulsifier, dispersant and water,
the method for preparing the hyperbranched prepolymer comprises the following steps: and mixing the bisphenol A epoxy resin with polyhydric alcohol and a catalyst for reaction to obtain the hyperbranched prepolymer.
2. The sizing agent according to claim 1, comprising:
15-30 parts by weight of a hyperbranched prepolymer;
0.5-3 parts by weight of an emulsifier;
0.5-2 parts by weight of a dispersant;
60-80 parts by weight of water.
3. The sizing agent according to claim 1 or 2, wherein said polyol comprises at least one of glycerol and a polyether polyol.
4. The sizing agent according to claim 1 or 2, wherein the mass ratio of the bisphenol A epoxy resin to the polyol and the catalyst is (50-120): (20-100): (1-5).
5. The sizing agent according to claim 1 or 2, wherein the reaction is carried out at 70-160 ℃ for 30 min-8 h.
6. The sizing agent according to claim 1 or 2, wherein the emulsifier comprises at least one of castor oil polyoxyethylene ether, bisphenol a polyoxyethylene ether, sodium dodecylbenzene sulfonate, alkylphenol polyoxyethylene ether and span series emulsifier;
optionally, the dispersant comprises at least one of neopentyl glycol glycidyl ether, a cellulose derivative, and sodium lauryl sulfate.
7. A method for preparing the sizing agent of any one of claims 1 to 6, comprising:
(1) mixing bisphenol A epoxy resin with polyhydric alcohol and a catalyst for reaction so as to obtain a hyperbranched prepolymer;
(2) mixing the hyperbranched prepolymer, an emulsifier and a dispersant;
(3) adding water dropwise into the reacted liquid obtained in the step (2) to obtain a sizing agent.
8. The method according to claim 7, wherein in the step (2), the hyperbranched prepolymer, the emulsifier and the dispersant are mixed and stirred at 40-70 ℃ and 4000-18000 r/min for 15-50 min;
optionally, in the step (3), the dropping speed of the water is 1-5 ml/min, and the dropping time is 1.5-2.5 h.
9. A composite material, wherein the composite material is compounded by the sizing agent of any one of claims 1 to 6 or the sizing agent obtained by the method of claim 7 or 8, carbon fibers and a resin matrix.
10. The composite of claim 9, wherein the resin matrix comprises an epoxy resin.
Priority Applications (1)
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| US20130224470A1 (en) * | 2012-02-28 | 2013-08-29 | Ut-Battelle, Llc | Method of improving adhesion of carbon fibers with a polymeric matrix |
| CN104562692A (en) * | 2013-10-11 | 2015-04-29 | 中国石油化工股份有限公司 | A carbon fiber composite emulsion sizing agent having low viscosity and high particle size stability and a preparing method thereof |
| CN106084240A (en) * | 2016-07-12 | 2016-11-09 | 天津工业大学 | A kind of preparation method of nonionic carbon fiber sizing agent |
| CN109868654A (en) * | 2019-02-19 | 2019-06-11 | 北京化工大学 | A kind of water-base epoxy sizing agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130224470A1 (en) * | 2012-02-28 | 2013-08-29 | Ut-Battelle, Llc | Method of improving adhesion of carbon fibers with a polymeric matrix |
| CN104562692A (en) * | 2013-10-11 | 2015-04-29 | 中国石油化工股份有限公司 | A carbon fiber composite emulsion sizing agent having low viscosity and high particle size stability and a preparing method thereof |
| CN106084240A (en) * | 2016-07-12 | 2016-11-09 | 天津工业大学 | A kind of preparation method of nonionic carbon fiber sizing agent |
| CN109868654A (en) * | 2019-02-19 | 2019-06-11 | 北京化工大学 | A kind of water-base epoxy sizing agent and preparation method thereof |
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Application publication date: 20211221 |