CN111574719B - Thermoplastic epoxy resin and application thereof, and surface modifier for carbon fiber - Google Patents

Thermoplastic epoxy resin and application thereof, and surface modifier for carbon fiber Download PDF

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CN111574719B
CN111574719B CN202010272364.0A CN202010272364A CN111574719B CN 111574719 B CN111574719 B CN 111574719B CN 202010272364 A CN202010272364 A CN 202010272364A CN 111574719 B CN111574719 B CN 111574719B
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epoxy resin
thermoplastic epoxy
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carbon fiber
heating
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CN111574719A (en
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晏义伍
朱敏杰
李常胜
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Shenzhen Academy of Aerospace Technology
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • 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
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    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
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    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
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    • 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
    • D06M15/59—Polyamides; Polyimides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon

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Abstract

The invention discloses a thermoplastic epoxy resin and application thereof, and a surface modifier for carbon fibers, wherein the thermoplastic epoxy resin comprises a structure of a formula (I):

Description

Thermoplastic epoxy resin and application thereof, and surface modifier for carbon fiber
Technical Field
The invention relates to the technical field of carbon fiber modification, in particular to thermoplastic epoxy resin and application thereof, and a surface modifier for carbon fibers.
Background
Carbon fiber has the characteristics of high strength, high modulus, small thermal expansion coefficient, good chemical stability and the like as a high-performance fiber, and becomes an important reinforcing material of a resin matrix composite in recent years. And with the continuous deep research on carbon fiber materials and the continuous perfection of processing technology, the carbon fiber with excellent mechanical properties can realize planned production and is widely applied to the fields of aerospace, national defense industry, automobile manufacturing, sports goods and the like. At present, the base resin has the highest use ratio of thermosetting resin, but the defects of difficult recovery, high cost, long molding cycle, poor toughness and the like are also present. Thermoplastic resins, however, are not only easy to mold, but also exhibit greater advantages in terms of heat resistance and mechanical strength.
Compared with thermosetting resin, the thermoplastic resin has high viscosity and poor fluidity, and almost has no chemical reaction with the surface of the carbon fiber, and mainly relies on physical diffusion and permeation. Thermoplastic composite systems therefore place higher demands on the surface properties of the carbon fibers. Firstly, a certain roughness is required on the surface of the carbon fiber, so that the infiltration contact area is increased; secondly, the carbon fiber surface is required to have a certain compatibility with the thermoplastic resin, i.e., the surface energy is close to or higher. The patent document CN105348768A is subjected to surface metal plating treatment and surface heat treatment to obtain the carbon fiber thermoplastic composite material with the highest tensile strength of 180 MPa. CN109826013a provides a sizing agent containing nano-materials to improve wettability between carbon fibers and thermoplastic resins. The method for carrying out surface modification on the carbon fiber by using the sizing agent can improve the interfacial compatibility of the carbon fiber and the corresponding thermoplastic resin to a certain extent, but firstly, desizing treatment is needed, so that the process is complex, the cost is increased, and the mechanical property of the carbon fiber is greatly damaged.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides the thermoplastic epoxy resin, the application thereof and the surface modifier for the carbon fiber, and the thermoplastic epoxy resin can improve the interfacial compatibility between the carbon fiber and the thermoplastic matrix resin without desizing treatment.
The technical scheme adopted by the invention is as follows:
in a first aspect of the present invention, there is provided a thermoplastic epoxy resin comprising the structure of formula (I):
Figure BDA0002443542110000021
wherein X is at least one of hydroxyl, A1, A2, A3 and A4, and A1 to A4 are respectively as follows:
Figure BDA0002443542110000022
y is selected from sulfur atom, oxygen atom or carbon atom;
n1-n5 are integers, and 0< n1 is less than or equal to 600,0< n2, n3, n4, n5 is less than or equal to 30;
W 1 ～W 14 is C1-C15 alkyl. According to some embodiments of the invention, the thermoplastic epoxy resin has a number average molecular weight of 1.0X10 3 ～1.0×10 5 。
According to some embodiments of the invention, when X is at least one of A1-A4, the molecular weight of the X grafts is 10% to 50% of the total number average molecular weight of the thermoplastic epoxy resin. When X is hydroxy, the thermoplastic epoxy resin B of formula (I) is of an ungrafted A1-A4 structure, and when X is selected from at least one of A1-A4, it means that the A1-A4 graft segments react with the reactive hydroxy groups in the thermoplastic epoxy resin B to form a resin of formula (I) having the A1-A4 graft segments grafted onto the thermoplastic epoxy resin B, and the resulting material is typically a mixture, in some embodiments, the molecular weight of the A1-A4 graft segments is from 10% to 50% of the total number average molecular weight of the thermoplastic epoxy resin, since not all hydroxy groups in the thermoplastic epoxy resin B structure can be grafted with A1-A4.
In a second aspect of the invention there is provided the use of a thermoplastic epoxy resin as described above in the treatment of carbon fibres.
In a third aspect of the present invention, there is provided a surface modifier for carbon fibers comprising the thermoplastic epoxy resin described above.
Surface modifying agents for carbon fibers according to some embodiments of the present invention further include a solvent. The surface modifier for carbon fiber may be a thermoplastic epoxy resin dissolved in a solvent or dispersed in water in the form of an emulsion.
According to some embodiments of the invention, the solvent is at least one selected from toluene, hexane, propanol, acetone, methanol, ethylene glycol, butanone, and ether.
Surface modifying agents for carbon fibers according to some embodiments of the present invention further include an emulsifier.
According to some embodiments of the present invention, the surface modifier for carbon fiber is at least one selected from alkylphenol ethoxylates, phenethyl phenol ethoxylates, benzyl phenol ethoxylates, phenethyl phenol polyoxyethylene polyoxypropylene ethers.
In a fourth aspect of the present invention, there is provided a modified carbon fiber obtained by treating a carbon fiber with the surface modifier.
In a fifth aspect of the present invention, there is provided a carbon fiber thermoplastic composite material comprising a thermoplastic matrix resin and the modified carbon fiber described above.
According to some embodiments of the invention, the thermoplastic matrix resin is selected from at least one of polyurethane resin, polyamide resin, polyester resin.
The embodiment of the invention has the beneficial effects that:
the embodiment of the invention provides a principle that the thermoplastic epoxy resin can be used as a surface modifier in the surface treatment of carbon fibers, and the carbon fibers treated by the thermoplastic epoxy resin have better interface compatibility with thermoplastic matrix resin, so that the interface compatibility of the carbon fibers and the thermoplastic matrix resin is improved: (1) The thermoplastic epoxy resin can be grafted on the active site on the surface of the carbon fiber through a chemical bond, so that the surface roughness of the carbon fiber is improved, the infiltration contact area of the thermoplastic matrix resin is increased, the mechanical engagement effect between the matrix resin and the carbon fiber is enhanced, and the wettability between the matrix resin and the carbon fiber is improved; (2) The thermoplastic epoxy resin is a thermoplastic material, and ether bonds and hydroxyl groups of the thermoplastic epoxy resin can form hydrogen bonding with matrix resins such as polyurethane resin, polyamide resin, polyester resin and the like, so that the interaction between the matrix resins and carbon fibers is improved; (3) The grafting segment in the thermoplastic epoxy resin can further improve the compatibility between the thermoplastic epoxy resin and polyurethane resin, polyamide resin and polyester resin based on the similar compatibility principle. Experimental results show that in the process of preparing the thermoplastic composite material, the thermoplastic resin can fully impregnate the surface of the carbon fiber, so that the composite material has good mechanical properties and good processability. The thermoplastic epoxy resin provided by the invention has good interfacial compatibility with carbon fibers, can be suitable for the surfaces of the carbon fibers after desizing, the surfaces of the carbon fibers coated with conventional sizing agents and the surfaces of the carbon fibers coated with thermoplastic sizing agents, has a wide application range, does not need desizing treatment, has small influence on the strength loss of the carbon fibers, and can fully infiltrate the surfaces of the carbon fibers in the process of preparing the carbon fiber thermoplastic composite material by using the carbon fibers treated by using the thermoplastic epoxy resin as a surface modifier, so that the composite material is endowed with good mechanical property and good processing property.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
Example 1
The embodiment provides a modified carbon fiber, which is prepared according to the following steps:
(1) Synthesis of thermoplastic epoxy resin:
1000g of bisphenol A type epoxy resin E51 and 250g of benzylamine are mixed and stirred uniformly, and the mixture is heated to 150 ℃ and heated for 2 hours, so that thermoplastic epoxy resin B is obtained.
30g of caprolactam is added into a three-neck flask, after original water is removed by heating under reduced pressure, 2g of water, 5g of oxalic acid and 1g of concentrated phosphoric acid are sequentially added, the mixture is heated to 160 ℃ under the protection of nitrogen, the reaction is carried out for 1 hour, and then the temperature is raised to 250 ℃ for 2 hours, and the reaction is continued. Slowly cooling after the reaction is finished to obtain the polyamide. 150g of the thermoplastic epoxy resin B described above was heated to 160℃and then 30g of polyamide and 0.005g of stannous octoate were added for reaction for 6 hours. Adding 0.005g stannous octoate, reacting for 8 hours to obtain the polyamide grafted thermoplastic epoxy resin containing the structure of the formula (I)
Figure BDA0002443542110000041
Wherein Y is a carbon atom and X is
Figure BDA0002443542110000042
Or hydroxyl groups, representing the grafting of polyamides in thermoplastic epoxy resins, but not every structural unit of the formula (I) in which W in A2 is grafted with polyamides 4 ＝W 5 ＝W 6 Alkyl of =c5. The number average molecular weight of the whole was about 47000, and the molecular weight of the graft segment was about 17%.
(2) Preparing a surface modifier for carbon fiber: and (3) dissolving the resin obtained in the step (1) in an acetone solution containing 20g of an emulsifier, wherein the emulsifier comprises nonylphenol polyoxyethylene ether and phenethylphenol polyoxyethylene polyoxypropylene ether in a mass ratio of 1:1. Subsequently, 720mL of deionized water was added dropwise to the solution at a rate of 2mL/min under stirring at a constant temperature of 50℃and at 11000 rpm. After the deionized water is added dropwise, stirring is continued for 20min. After cooling to room temperature, acetone was removed using a rotary evaporator. Deionized water is added dropwise to reduce the solid content of the resin to 3 percent.
(3) Modification treatment: and (3) immersing the T700 carbon fiber in the emulsion, wherein the wire feeding speed is 2cm/s, then, drying in an oven at the temperature of 150 ℃ for 5min, and finally, winding to obtain the surface-treated modified carbon fiber.
Example 2
The embodiment provides a modified carbon fiber, which is prepared according to the following steps:
(1) Synthesis of thermoplastic epoxy resin:
1000g of bisphenol A type epoxy resin E51 and 250g of benzylamine are mixed and stirred uniformly, and the mixture is heated to 150 ℃ and heated for 2 hours, so that thermoplastic epoxy resin B is obtained.
30g of caprolactam is added into a three-neck flask, after original water is removed by heating under reduced pressure, 2g of water, 5g of oxalic acid and 1g of concentrated phosphoric acid are sequentially added, the mixture is heated to 160 ℃ under the protection of nitrogen, the reaction is carried out for 1 hour, and then the temperature is raised to 250 ℃ for 2 hours, and the reaction is continued. Slowly cooling after the reaction is finished to obtain the polyamide. 150g of the thermoplastic epoxy resin B described above was heated to 160℃and then 30g of polyamide and 0.005g of stannous octoate were added for reaction for 6 hours. Adding 0.005g stannous octoate, reacting for 8 hours to obtain the polyamide grafted thermoplastic epoxy resin containing the structure of the formula (I)
Figure BDA0002443542110000051
Wherein Y is a carbon atom and X is
Figure BDA0002443542110000052
Or hydroxyl groups, representing the grafting of a polyamide in a thermoplastic epoxy resin, but not every structural unit of formula (I) is grafted with a polyamide, wherein W in A2 4 ＝W 5 ＝W 6 Alkyl of =c5. The number average molecular weight of the whole was about 47000, and the molecular weight of the graft segment was about 17%.
(2) Preparing a surface modifier for carbon fiber: and (3) dissolving the resin obtained in the step (1) in an acetone solution containing 20g of an emulsifier, wherein the emulsifier comprises nonylphenol polyoxyethylene ether and phenethylphenol polyoxyethylene polyoxypropylene ether in a mass ratio of 1:1. Subsequently, 720mL of deionized water was added dropwise to the solution at a rate of 2mL/min under stirring at a constant temperature of 50℃and at 11000 rpm. After the deionized water is added dropwise, stirring is continued for 20min. After cooling to room temperature, acetone was removed using a rotary evaporator. Deionized water is added dropwise to reduce the solid content of the resin to 3 percent.
(3) Modification treatment: washing off the original sizing agent of the T700 carbon fiber by using acetone, soaking the T700 carbon fiber in the emulsion, drying in an oven at the temperature of 150 ℃ for 5min at the wire feeding speed of 2cm/s, and finally rolling to obtain the surface-treated modified carbon fiber.
Example 3
The embodiment provides a modified carbon fiber, which is prepared according to the following steps:
(1) Synthesis of thermoplastic epoxy resin:
1000g of bisphenol A type epoxy resin E51 and 250g of benzylamine are mixed and stirred uniformly, and the mixture is heated to 150 ℃ and heated for 2 hours, so that thermoplastic epoxy resin B is obtained.
10g of polyether glycol, a few drops of dibutyltin dilaurate and 10g of 2, 2-dimethylolpropionic acid dissolved in a small amount of N, N-dimethylformamide are added into a flask under the protection of nitrogen, the temperature is raised to 50 ℃ with stirring, and 10g of isophorone diisocyanate is added dropwise; after the dripping is finished, the temperature is raised to 80 ℃ and the polyurethane is obtained after 2 hours of reaction. 150g of the thermoplastic epoxy resin B is dissolved in chloroform, 3g of butyl glycidyl ether reactive diluent is added and stirred uniformly. Dropwise adding the polyurethane into a thermoplastic epoxy resin solution under the protection of nitrogen at 65 ℃, and reacting for 2 hours after the dropwise adding is finished to obtain polyurethane grafted thermoplastic epoxy resin containing a structure of a formula (I)
Figure BDA0002443542110000061
Wherein Y is a carbon atom and X is
Figure BDA0002443542110000062
Or hydroxyl groups, representing the grafting of polyurethane into the thermoplastic epoxy resin, but not every structural unit of formula (I) is grafted with polyurethane, wherein W in A3 7 ＝W 9 Alkyl of =c8, W 8 ＝W 10 Alkyl of =c10. The number average molecular weight of the whole is about 45000, and the molecular weight of the grafted segment is about 12%.
(2) Preparing a surface modifier for carbon fiber: and (3) dissolving the resin obtained in the step (1) in an acetone solution containing 20g of an emulsifier, wherein the emulsifier comprises nonylphenol polyoxyethylene ether and phenethylphenol polyoxyethylene polyoxypropylene ether in a mass ratio of 1:1. Subsequently, 720mL of deionized water was added dropwise to the solution at a rate of 2mL/min under stirring at a constant temperature of 50℃and at 11000 rpm. After the deionized water is added dropwise, stirring is continued for 20min. After cooling to room temperature, acetone was removed using a rotary evaporator. Deionized water is added dropwise to reduce the solid content of the resin to 3 percent.
(3) Modification treatment: and (3) immersing the T700 carbon fiber in the emulsion, wherein the wire feeding speed is 2cm/s, then, drying in an oven at the temperature of 150 ℃ for 5min, and finally, winding to obtain the surface-treated modified carbon fiber.
Example 4
The embodiment provides a modified carbon fiber, which is prepared according to the following steps:
(1) Synthesis of thermoplastic epoxy resin:
1000g of bisphenol A type epoxy resin E51 and 250g of benzylamine are mixed and stirred uniformly, and the mixture is heated to 150 ℃ and heated for 2 hours, so that thermoplastic epoxy resin B is obtained.
20g of tetradecanedioic acid and 13g of 1, 6-hexanediol are heated to 230 ℃ under the protection of nitrogen, 0.04g of tetraisopropyl titanate is added, and the polyester is obtained after 4 hours of reaction. 150g of the thermoplastic epoxy resin B described above was warmed to 160℃and then 30g of polyester and 0.005g of stannous octoate were added to react for 6 hours. Adding 0.005g stannous octoate, reacting for 8 hours to obtain the polyester grafted thermoplastic epoxy resin containing the structure of formula (I)
Figure BDA0002443542110000071
Wherein Y is a carbon atom and X is
Figure BDA0002443542110000072
Or hydroxyl groups, representing the grafting of polyesters in the thermoplastic epoxy resin, but not every structural unit of formula (I) is grafted with polyesters, wherein W in A4 12 ＝W 14 Alkyl of =c12, W 11 ＝W 13 Alkyl of =c6. The number average molecular weight of the whole is about 51000, and the molecular weight of the grafted segment accounts for about 22 percent.
(2) Preparing a surface modifier for carbon fiber: and (3) dissolving the resin obtained in the step (1) in an acetone solution containing 20g of an emulsifier, wherein the emulsifier comprises nonylphenol polyoxyethylene ether and phenethylphenol polyoxyethylene polyoxypropylene ether in a mass ratio of 1:1. Subsequently, 720mL of deionized water was added dropwise to the solution at a rate of 2mL/min under stirring at a constant temperature of 50℃and at 11000 rpm. After the deionized water is added dropwise, stirring is continued for 20min. After cooling to room temperature, acetone was removed using a rotary evaporator. Deionized water is added dropwise to reduce the solid content of the resin to 3 percent.
(3) Modification treatment: and (3) immersing the T700 carbon fiber in the emulsion, wherein the wire feeding speed is 2cm/s, then, drying in an oven at the temperature of 150 ℃ for 5min, and finally, winding to obtain the surface-treated carbon fiber.
Example 5
The embodiment provides a modified carbon fiber, which is prepared according to the following steps:
(1) Synthesis of thermoplastic epoxy resin:
200g of bisphenol S-type epoxy resin and 50g of benzylamine were mixed and stirred uniformly, and heated to 150℃for 2 hours to obtain a thermoplastic bisphenol S-type epoxy resin (i.e., thermoplastic epoxy resin B which was not grafted).
30g of caprolactam is added into a three-neck flask, after original water is removed by heating under reduced pressure, 2g of water, 5g of oxalic acid and 1g of concentrated phosphoric acid are sequentially added, the mixture is heated to 160 ℃ under the protection of nitrogen, the reaction is carried out for 1 hour, and then the temperature is raised to 250 ℃ for 2 hours, and the reaction is continued. Slowly cooling after the reaction is finished to obtain the polyamide. 150g of the thermoplastic bisphenol S-type epoxy resin was heated to 160℃and then 30g of polyamide and 0.005g of stannous octoate were added to react for 6 hours. 0.005g stannous octoate was added and reacted for 8 hours to give a polyamide grafted thermoplastic epoxy.
Figure BDA0002443542110000081
Wherein Y is a sulfur atom and X is
Figure BDA0002443542110000082
Or hydroxyl groups, representing the grafting of polyamides in thermoplastic epoxy resins, but not every structural unit of the formula (I) in which W in A2 is grafted with polyamides 4 ＝W 5 ＝W 6 Alkyl of =c5. The number average molecular weight of the whole was about 47000, and the molecular weight of the graft segment was about 17%.
(2) Preparing a surface modifier for carbon fiber: and (3) dissolving the resin obtained in the step (1) in an acetone solution containing 20g of an emulsifier, wherein the emulsifier comprises nonylphenol polyoxyethylene ether and phenethylphenol polyoxyethylene polyoxypropylene ether in a mass ratio of 1:1. Subsequently, 720mL of deionized water was added dropwise to the solution at a rate of 2mL/min under stirring at a constant temperature of 50℃and at 11000 rpm. After the deionized water is added dropwise, stirring is continued for 20min. After cooling to room temperature, acetone was removed using a rotary evaporator. Deionized water is added dropwise to reduce the solid content of the resin to 3 percent.
(3) Modification treatment: and (3) immersing the T700 carbon fiber in the emulsion, wherein the wire feeding speed is 2cm/s, then, drying in an oven at the temperature of 150 ℃ for 5min, and finally, winding to obtain the surface-treated modified carbon fiber.
Effect example 1
Comparative example 1: comparative example 1 provides an ungrafted modified carbon fiber, prepared in the same manner as in example 1, except that the thermoplastic epoxy resin B was directly subjected to steps (2) and (3) without performing the grafting step.
The ungrafted modified carbon fiber obtained in comparative example 1 and the modified carbon fibers obtained in examples 1 to 5 were tested for interfacial shear strength (IFSS) with polyamide resin by a micro-debonding method, and the results are shown in table 1. The results show that the thermoplastic epoxy resin provided by the embodiment of the invention can keep better interface compatibility with the thermoplastic matrix resin without desizing treatment, and experiments show that the thermoplastic epoxy resin provided by the embodiment of the invention can be suitable for the surface of the desized carbon fiber, the surface of the carbon fiber coated with a conventional sizing agent and the surface of the carbon fiber coated with the thermoplastic sizing agent, has wide application range, does not need desizing treatment, has little influence on the strength loss of the carbon fiber, and can improve the interface shear strength between the carbon fiber and the thermoplastic matrix resin by treating the carbon fiber with the thermoplastic epoxy resin prepared by the embodiment of the invention, thereby improving the compatibility between the carbon fiber and the thermoplastic matrix resin.
TABLE 1 interfacial shear strength of untreated carbon fibers and modified carbon fibers of examples 1-5 with polyamide resins
Example 1 Example 2 Example 3 Example 4 Example 5 Comparative example 1
IFSS/MPa 26.41 23.50 28.99 25.76 26.11 21.65

Claims (10)

1. A grafted thermoplastic epoxy resin, characterized in that the grafted thermoplastic epoxy resin comprises a polyamide grafted thermoplastic epoxy resin, and the preparation method of the polyamide grafted thermoplastic epoxy resin comprises the following steps:
step S11, mixing 1000g of bisphenol A epoxy resin E51 with 250g of benzylamine, uniformly stirring, and heating to 150 ℃ for 2 hours to obtain thermoplastic epoxy resin B;
step S12, adding 30g of caprolactam into a three-neck flask, heating under reduced pressure to remove original water, sequentially adding 2g of water, 5g of oxalic acid and 1g of concentrated phosphoric acid, heating to 160 ℃ under the protection of nitrogen, reacting for 1 hour, then heating to 250 ℃ to continue reacting for 2 hours, and slowly cooling after the reaction is finished to obtain polyamide;
step S13, heating 150g of the thermoplastic epoxy resin B to 160 ℃, then adding 30g of the polyamide and 0.005g of stannous octoate for reaction for 6 hours, and then adding 0.005g of stannous octoate for reaction for 8 hours to obtain the polyamide grafted thermoplastic epoxy resin;
or, the preparation method of the polyamide grafted thermoplastic epoxy resin comprises the following steps:
step S21, mixing 200g of bisphenol S-type epoxy resin with 50g of benzylamine, uniformly stirring, and heating to 150 ℃ for 2 hours to obtain thermoplastic bisphenol S-type epoxy resin;
step S22, adding 30g of caprolactam into a three-neck flask, heating under reduced pressure to remove original water, sequentially adding 2g of water, 5g of oxalic acid and 1g of concentrated phosphoric acid, heating to 160 ℃ under the protection of nitrogen, reacting for 1 hour, then heating to 250 ℃ to continue reacting for 2 hours, and slowly cooling after the reaction is finished to obtain polyamide;
step S23, heating 150g of the thermoplastic bisphenol S type epoxy resin to 160 ℃, then adding 30g of the polyamide and 0.005g of stannous octoate to react for 6 hours, and adding 0.005g of stannous octoate to react for 8 hours to obtain the polyamide grafted thermoplastic epoxy resin.
2. The grafted thermoplastic epoxy resin is characterized by comprising polyurethane grafted thermoplastic epoxy resin, and the preparation method of the polyurethane grafted thermoplastic epoxy resin comprises the following steps:
step S31, mixing 1000g of bisphenol A epoxy resin E51 with 250g of benzylamine, uniformly stirring, and heating to 150 ℃ for 2 hours to obtain thermoplastic epoxy resin B;
step S32, under the protection of nitrogen, adding 10g of polyether glycol, a few drops of dibutyltin dilaurate and 10g of 2, 2-dimethylolpropionic acid dissolved by a small amount of N, N-dimethylformamide into a flask, stirring and heating to 50 ℃, dropwise adding 10g of isophorone diisocyanate, heating to 80 ℃ after the dropwise adding is finished, and reacting for 2 hours to obtain polyurethane;
step S33, dissolving 150g of the thermoplastic epoxy resin B in chloroform, adding 3g of butyl glycidyl ether active diluent, stirring uniformly to obtain a thermoplastic epoxy resin solution, dropwise adding the polyurethane into the thermoplastic epoxy resin solution under the protection of nitrogen at 65 ℃, and reacting for 2 hours after the dropwise adding is finished to obtain the polyurethane grafted thermoplastic epoxy resin.
3. The grafted thermoplastic epoxy resin is characterized by comprising a polyester grafted thermoplastic epoxy resin, and the preparation method of the polyester grafted thermoplastic epoxy resin comprises the following steps:
step S41, mixing 1000g of bisphenol A epoxy resin E51 with 250g of benzylamine, uniformly stirring, and heating to 150 ℃ for 2 hours to obtain thermoplastic epoxy resin B;
step S42, heating 20g of tetradecanoic dibasic acid and 13g of 1, 6-hexanediol to 230 ℃ under the protection of nitrogen, adding 0.04g of tetraisopropyl titanate, and reacting for 4 hours to obtain polyester;
step S43, heating 150g of the thermoplastic epoxy resin B to 160 ℃, adding 30g of the polyester and 0.005g of stannous octoate to react for 6 hours, adding 0.005g of stannous octoate, and reacting for 8 hours to obtain the polyester grafted thermoplastic epoxy resin.
4. Use of the grafted thermoplastic epoxy resin according to any of claims 1-3 for treating carbon fibers.
5. A surface modifier for carbon fibers, characterized by comprising the grafted thermoplastic epoxy resin according to any one of claims 1 to 3.
6. The surface modifier for carbon fiber according to claim 5, further comprising a solvent.
7. The surface modifier for carbon fiber according to claim 6, wherein the solvent is at least one selected from toluene, hexane, propanol, acetone, methanol, ethylene glycol, butanone, and ether.
8. The surface modifier for carbon fiber according to claim 5, further comprising an emulsifier.
9. A modified carbon fiber characterized by being obtained by treating a carbon fiber with the surface modifier for carbon fiber according to any one of claims 5 to 8.
10. A carbon fiber thermoplastic composite comprising a thermoplastic matrix resin and the modified carbon fiber of claim 9.
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CN103788322B (en) * 2012-10-26 2016-09-14 中国石油化工股份有限公司 The bisphenol A epoxide resin compositions modified by polyurethane structural and preparation thereof and application
CN105484041A (en) * 2016-01-21 2016-04-13 中复神鹰碳纤维有限责任公司 Composite water-based emulsion sizing agent for carbon fibers, and preparation method for sizing agent
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CN106498740A (en) * 2016-11-11 2017-03-15 北京化工大学 A kind of polyurethane modified epoxy resin sizing agent and preparation method thereof
CN106633086A (en) * 2016-12-28 2017-05-10 北京光华纺织集团有限公司 Preparation method for polyamide-modified epoxy resin emulsion
CN109810414A (en) * 2018-12-17 2019-05-28 会通新材料股份有限公司 A kind of isocyanates surface modified carbon fibers-polypropylene composite material and preparation method

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