An emulsifier, a polyetheretherketone aqueous sizing agent, and a carbon fiber prepreg

Abstract

The present invention relates to the technical field of fiber sizing, and specifically relates to an emulsifier, a polyetheretherketone aqueous emulsion sizing agent, and a carbon fiber prepreg. The emulsifier is obtained by reacting a hydroxyl-terminated polyetheretherketone, a bisphenol A diglycidyl ether epoxy resin, and polyethylene glycol under the action of a catalyst. The structure of the emulsifier is a hydroxyl-terminated bisphenol A epoxy resin bridging polyetheretherketone. Using this emulsifier, a polyetheretherketone aqueous emulsion sizing agent is prepared. The sizing agent prepared is used to size carbon fibers to obtain a carbon fiber prepreg, which can be subsequently used to prepare composite materials. The emulsion particle size of the polyetheretherketone aqueous emulsion sizing agent obtained in the present invention is below 10 μm, the emulsion is uniformly dispersed, and has good stability, which can effectively improve the interfacial bonding strength between the carbon fiber prepreg and the matrix resin, especially polyaryletherketone resin.

Description

Technical Field

[0001] The present invention relates to the technical field of fiber sizing, and particularly relates to an emulsifier, a polyether ether ketone aqueous emulsion sizing agent, and a carbon fiber prepreg. Background Art

[0002] Due to advantages such as high strength, high modulus, low density, high thermal conductivity, and high temperature resistance, carbon fiber has become one of the most commonly used reinforcing fibers for high-performance thermoplastic resin-based composites. However, carbon fiber itself has large brittleness and electrostatic action, is not easy to bundle during production, weaving, and transportation, and is prone to generating fuzz or even breaking. In addition, the surface of carbon fiber is smooth and has low surface energy, which is not conducive to the infiltration of resin, and the interfacial bonding strength of the composite material needs to be improved. Therefore, carbon fiber often needs to be sized in actual production to form a polymer coating layer on the fiber surface to isolate dust and moisture, improve the fiber bundling performance, make up for fiber surface defects, and improve the application processability of the fiber, etc. The sizing agent and the matrix resin can also be tightly combined through methods such as similar compatibility and physicochemical action to improve the interfacial performance of the composite material.

[0003] However, traditional epoxy resin-based carbon fiber sizing agents are not suitable for thermoplastic resin-based composites. Thermoplastic resins do not contain active cross-linking groups, have a large difference in chemical structure from traditional sizing agents, have poor compatibility between resin molecular chains and sizing agents, and have low interfacial bonding strength and matching. In addition, thermoplastic resins usually have a long-chain linear molecular structure, which makes them have high melt viscosity while showing excellent toughness and requires a high processing temperature. The forming temperature of most high-performance thermoplastic resin-based composites can reach above 300°C, which is much higher than the temperature resistance limit of traditional epoxy-based sizing agents (usually not exceeding 250°C). Sizing agents with low thermal stability are prone to decomposition during the processing of composite materials and cause the volatilization of small molecules, forming pore defects, seriously affecting the interfacial performance and comprehensive performance of composite materials, and greatly restricting the further expansion of the application of thermoplastic resin-based composites. Therefore, developing new carbon fiber sizing agents suitable for thermoplastic resin-based composites has become a research hotspot in recent years. Summary of the Invention

[0004] In order to solve the above technical problems, an emulsifier, a polyether ether ketone aqueous emulsion sizing agent, and a carbon fiber prepreg are provided. The polyether ether ketone aqueous emulsion sizing agent obtained by the present invention has a particle size below 10 μm, the emulsion is uniformly dispersed and has good stability, and can effectively improve the interfacial bonding strength between the carbon fiber prepreg and the matrix resin, especially polyaryletherketone resin.

[0005] To achieve the above object, the present invention is realized through the following technical solutions:

[0006] An emulsifier is obtained by reacting a hydroxyl-terminated polyether ether ketone, a bisphenol A diglycidyl ether epoxy resin, and polyethylene glycol under the action of a catalyst. The emulsifier is a hydroxyl-terminated bisphenol A epoxy resin-bridged polyether ether ketone and has the following structure of Formula I:

[0007]

[0008] Wherein m and n represent the number of repeating units. The value range of m is 20 - 40, and the value range of n is 10 - 40. The number-average molecular weight of the emulsifier is 15,000 g / mol to 40,000 g / mol.

[0009] Furthermore, the bisphenol A diglycidyl ether epoxy resin is selected from one or more of E-20, E-44, and E-51. The molecular structure of the bisphenol A diglycidyl ether epoxy resin is shown in the following Formula III:

[0010]

[0011] The polyethylene glycol is selected from one or more of PEG-1000, PEG-2000, PEG-4000, PEG-6000, and PEG-8000; the catalyst is selected from one or more of potassium persulfate, ammonium persulfate, boron trifluoride ethylamine, boron trifluoride diethyl ether, triphenyl phosphate, and trifluoromethanesulfonic acid.

[0012] Still further, the specific method for obtaining the emulsifier is as follows: Put the hydroxyl-terminated polyether ether ketone and the bisphenol A diglycidyl ether epoxy resin into a reaction kettle, heat to 120 - 140 °C, continuously stir, and after dissolving evenly, add part of the catalyst and continue to react for 1 - 2 h;

[0013] Then add polyethylene glycol, continuously stir evenly, add the remaining part of the catalyst, and continue to react for 1 - 2 h;

[0014] Pour out the product while it is hot, wait until it cools to a solid state, crush it for later use, and obtain the emulsifier.

[0015] Preferably, the molar ratio of the hydroxyl-terminated polyether ether ketone to the bisphenol A diglycidyl ether epoxy resin is 1:2, and the hydroxyl-terminated polyether ether ketone and the polyethylene glycol are in an equal mass ratio; the dosage of the catalyst is 0.1% - 0.3% of the total mass of the hydroxyl-terminated polyether ether ketone, the bisphenol A diglycidyl ether epoxy resin, and the polyethylene glycol.

[0016] Furthermore, the molecular structure of the hydroxyl-terminated polyether ether ketone is shown in the following Formula II:

[0017]

[0018] The hydroxyl-terminated polyether ether ketone is obtained by polymerizing tert-butyl hydroquinone and 4,4'-difluorobenzophenone. The number-average molecular weight of the hydroxyl-terminated polyether ether ketone is in the range of 4500-15000 g / mol, preferably 5000-12000 g / mol.

[0019] Preferably, the specific method for obtaining the hydroxyl-terminated polyether ether ketone is as follows: First, place tert-butyl hydroquinone, a salt-forming agent, a part of organic solvent, and a water-carrying agent in a reaction kettle, introduce a protective gas to discharge oxygen in the reaction kettle, and then carry out reflux condensation at 120-160 °C, and continuously stir and react for 2-5 h;

[0020] Cool down to below 100 °C, add 4,4'-difluorobenzophenone and the remaining part of the organic solvent, and raise the temperature to 190-220 °C for polymerization reaction for 2-4 h;

[0021] After cooling to room temperature, wash the product with water, extract the product with methanol to remove the solvent, and then dry to obtain the hydroxyl-terminated polyether ether ketone.

[0022] More preferably, the molar ratio of tert-butyl hydroquinone to 4,4'-difluorobenzophenone is 1:0.8-1; the salt-forming agent is anhydrous sodium carbonate and / or anhydrous potassium carbonate, and the molar ratio of the salt-forming agent to tert-butyl hydroquinone is 1:1; the water-carrying agent is one of benzene, toluene, and xylene, and the dosage of the water-carrying agent is 10-20% of the weight of the organic solvent; the organic solvent is selected from one of N,N-dimethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone, and dimethyl sulfoxide, and the dosage of the organic solvent is 3-6 times the total weight of the monomers.

[0023] A sizing agent for polyether ether ketone aqueous emulsion comprises the following raw materials in parts by weight: 5-40 parts of an emulsifier with the above structure, 20-80 parts of polyether ether ketone sizing agent, and 80-120 parts of water, and emulsify to an emulsion particle size of less than 10 μm.

[0024] Further, the mass fraction of the polyether ether ketone sizing agent is 0.5%-2%, and the solvent therein is a solvent that can dissolve polyether ether ketone but is immiscible or slightly miscible with water, such as dichloromethane, chloroform, chlorobenzene, benzene, toluene, xylene, acetone, ethers, esters, etc.

[0025] Further, the method for obtaining the sizing agent comprises the following steps: Heat and stir the polyether ether ketone sizing agent and the emulsifier at a speed of 800-1200 rpm and at 90-100 °C until evenly dispersed, and then add water dropwise at a speed of 1-5 drops per second at a speed of more than 2500 rpm, and at the same time carry out emulsification for 30-60 min.

[0026] Carbon fiber prepreg, including a polyether ether ketone (PEEK) aqueous emulsion sizing agent with a uniform film formed on the surface of carbon fibers. The specific obtaining process can be to size the fibers by immersing them in the PEEK aqueous emulsion sizing agent, and then drying at 100 - 250 °C for 30 - 120 min to obtain the carbon fiber prepreg; compounding the carbon fiber prepreg with PEEK can obtain a PEEK-based composite material with better cross-sectional bonding.

[0027] Beneficial technical effects:

[0028] In the present invention, an emulsifier is obtained through molecular structure design, and it is made into a sizing agent with PEEK for sizing the fiber surface. The sizing agent uses PEEK as the main sizing material, and an emulsifier with a structure similar to PEEK is used as a bridge to effectively improve the roughness and wettability of the carbon fiber surface, effectively improve the compatibility between the carbon fiber and the PEEK matrix resin, and improve the interfacial bonding strength between the carbon fiber and the PEEK matrix resin;

[0029] The PEEK aqueous emulsion sizing agent provided by the present invention has a particle size below 10 μm, a polydispersity coefficient less than 1.5, is uniformly dispersed, and has high stability;

[0030] The PEEK aqueous emulsion sizing agent provided by the present invention has a wide temperature range, and the processing temperature can reach 300 - 400 °C. It is suitable for carbon fiber reinforced PEEK thermoplastic composites and does not affect the mechanical properties and long-term service life of the products. Description of the drawings

[0031] Figure 1 Infrared spectrum diagram of the emulsifier-α obtained in Example 1;

[0032] Figure 2 Particle size distribution diagrams of the PEEK aqueous emulsion sizing agent obtained in Example 1 and Example 2;

[0033] Figure 3 Photos of the PEEK aqueous emulsion sizing agent obtained in Example 1 and Comparative Example 2 after centrifugation;

[0034] Figure 4 Comparison of the sizing effects of the PEEK aqueous emulsion sizing agent obtained in Example 1 and Comparative Example 1 on carbon fiber bundles. Detailed implementation manners

[0035] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and in no way limits the present invention and its application or use. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0036] Unless otherwise specifically stated, the numerical values set forth in these embodiments do not limit the scope of the present invention. Technologies and methods known to those of ordinary skill in the relevant art may not be discussed in detail, but where appropriate, such technologies and methods should be regarded as part of the specification. In all examples shown and discussed herein, any specific value should be construed as merely exemplary and not as a limitation. Thus, other examples of the exemplary embodiments may have different values.

[0037] For the experimental methods without specific conditions noted in the following embodiments, they are generally determined according to national standards; if there is no corresponding national standard, they are carried out according to general standard requirements or general methods.

[0038] Preparation Example 1

[0039] This example is the preparation of hydroxyl-terminated polyether ether ketone, and the molecular structure of the hydroxyl-terminated polyether ether ketone is shown in Formula II below:

[0040]

[0041] S1. Add 40 g (0.24 mol) of tert-butylhydroquinone, 39.9 g (0.29 mol) of potassium carbonate, 360 mL of N-methyl-2-pyrrolidone, and 150 mL of toluene into a reaction kettle. After bubbling with nitrogen for 10 min, heat to 120 - 160 °C, condense and reflux, and continuously stir and react for 2 - 5 h under a nitrogen atmosphere;

[0042] S2. When the temperature drops to 100 °C, add 46.6 g (0.21 mol) of 4,4'-difluorobenzophenone and 100 mL of N-methyl-2-pyrrolidone, and heat to 190 - 220 °C for polymerization reaction for 2 - 4 h; cool to room temperature, filter and wash repeatedly with deionized water for 3 - 5 times, then extract with methanol, and vacuum dry the obtained solid at 120 °C for 24 h.

[0043] The preparation parameters and the obtained hydroxyl-terminated polyether ether ketone are shown in Table 1 below.

[0044] Table 1 Preparation Parameters

[0045]

[0046] Preparation Example 2

[0047] PEEK-OH-⑤: The addition amount of 4,4'-difluorobenzophenone in Preparation Example 1 was adjusted to 42.3 g (0.20 mol), and the preparation parameters remained unchanged according to PEEK-OH-①, obtaining PEEK-OH-⑤ with a molecular weight Mn = 3702.

[0048] PEEK-OH-⑥: The addition amount of 4,4'-difluorobenzophenone in Preparation Example 1 was adjusted to 48.8 g (0.22 mol), and the preparation parameters remained unchanged according to PEEK-OH-①, obtaining PEEK-OH-⑥ with a molecular weight Mn = 11906.

[0049] Example 1

[0050] (1) Preparation of emulsifier

[0051] An emulsifier is obtained by reacting hydroxy-terminated polyether ether ketone, bisphenol A diglycidyl ether epoxy resin, and polyethylene glycol under the action of a catalyst to obtain hydroxy-terminated bisphenol A epoxy resin-bridged polyether ether ketone, having the molecular structure of Formula Ⅰ as follows:

[0052]

[0053] The specific method for obtaining the above-structured emulsifier is as follows: Put 66.9 g of PEEK-OH-① (0.01 mol) and 7.0 g of bisphenol A diglycidyl ether epoxy resin E-20 (0.02 mol) into a reaction kettle, heat to 140 °C, stir at 200 r / min for 10 min until dissolved uniformly, add 0.5 g of triphenyl phosphate, and continue to react for 2 h;

[0054] Then add 20 g of PEG-2000 (0.01 mol), stir at 200 r / min for 10 min until dissolved uniformly, add 0.25 g of triphenyl phosphate, and continue to react for 2 h;

[0055] After the reaction is completed, pour out the product while it is hot. After cooling, it becomes solid and is broken for use to obtain emulsifier-α.

[0056] The infrared spectrum of the obtained emulsifier-α is as shown in Figure 1 shown, 1647 cm -1 is the stretching vibration of C=O; 1589 cm -1 is the in-plane vibration of Ar-O-Ar (Ar is the benzene ring); 1304 cm -1 is the in-plane vibration of Ar-CO-Ar; 1275, 1225, 1181 cm -1 is the asymmetric stretching vibration of Ar-O-Ar; 1149 cm -1 is the in-plane bending vibration of C-H; 922 cm -1are the symmetric stretching vibration of Ar-CO-Ar and the stretching vibration of epoxy group; 832, 761 cm -1 is the out-of-plane bending vibration of C-H; 3407 cm -1 is the stretching vibration of -OH.

[0057] (2) Preparation of sizing agent

[0058] The emulsifier-α with the obtained structure is made into a sizing agent as follows:

[0059] A polyetheretherketone aqueous emulsion sizing agent, comprising raw materials in the following weight parts:

[0060] 20 parts of the emulsifier-α with the above structure, 50 parts of polyetheretherketone sizing, and 120 parts of deionized water

[0061] Among them, the mass fraction of polyetheretherketone sizing is 0.5%, and the solvent is dichloromethane;

[0062] Obtaining method: Mix the emulsifier-α and polyetheretherketone sizing in a high-speed dispersion kettle, heat to 90 °C, stir and disperse evenly at a rotation speed of 1000 rpm, then adjust the rotation speed to 3000 rpm and drop deionized water at a speed of 3-5 drops / second, while performing high-speed dispersion emulsification for 60 min until the emulsion particle size is below 10 μm, and the liquid material inside the dispersion kettle gradually changes from transparent to milky white. After the emulsion is stable, take it out, that is, polyetheretherketone aqueous emulsion sizing agent-α.

[0063] The particle size distribution of the prepared polyetheretherketone aqueous emulsion sizing agent-α is as Figure 2 shown, and the emulsion particle size distribution is in the range of 1-5 microns.

[0064] Centrifuge the prepared polyetheretherketone aqueous emulsion sizing agent-α at 3000 rpm for 30 minutes, and the photo after centrifugation is as Figure 3 shown, it can be seen that the sizing agent has good stability, the polydispersity coefficient is less than 1.5, and the dispersion is uniform.

[0065] Size the carbon fiber bundle with the prepared polyetheretherketone aqueous emulsion sizing agent-α, and the result is as Figure 4 shown, it can be seen that the sizing agent in this case has good bundling ability for the carbon fiber bundle, and basically no bundle disorder occurs, while the carbon fiber bundle without sizing agent in Comparative Example 1 shows obvious bundle disorder.

[0066] (3) Preparation of carbon fiber prepreg

[0067] The carbon fiber fabric (T300-3k twill fabric, areal density 285 g / m 2) Impregnate it in the above-mentioned obtained polyetheretherketone aqueous emulsion sizing agent-α for more than 120 minutes for sizing, and then dry it at 150 °C for 60 minutes. The resin component in the emulsion forms a uniform film on the surface of the carbon fiber to obtain carbon fiber prepreg-α.

[0068] (4) Preparation of composite material

[0069] CF / PEEK composite material sheet: Weigh the corresponding amounts of carbon fiber prepreg-α and 0.15 mm thick PEEK film according to the mass fraction ratio of 6:4, and lay them in the order of PEEK / CF / PEEK, and prepare CF / PEEK composite material sheet-α by molding. During the molding process, select a molding temperature of 380 °C and a molding pressure of 10 MPa.

[0070] Example 2

[0071] (1) Preparation of emulsifier

[0072] The chemical structure of the emulsifier in this case is the same as that of Formula I, and the preparation is the same as that in Step (1) of Example 1. The difference is that PEEK-OH-② and PEG-4000 are used to prepare emulsifier-β.

[0073] (2) Preparation of sizing agent

[0074] The formula and preparation process of the sizing agent in this case are the same as those in Step (2) of Example 1. The difference is that the emulsifier-β of this case is used to prepare polyetheretherketone aqueous emulsion sizing agent-β.

[0075] The particle size distribution of the prepared polyetheretherketone aqueous emulsion sizing agent-β is as Figure 2 shown, and the particle size distribution of the emulsion is in the range of 1-7 microns.

[0076] Centrifuge the prepared polyetheretherketone aqueous emulsion sizing agent-β at 3000 rpm for 30 minutes. The sizing agent is stable without stratification and is uniformly dispersed. And it has good bundling ability for carbon fiber bundles and basically does not cause disordered bundles.

[0077] (3) Preparation of carbon fiber prepreg

[0078] The preparation process of the carbon fiber prepreg in this case is the same as that in Step (3) of Example 1. The difference is that the polyetheretherketone aqueous emulsion sizing agent-β of this case is used to prepare carbon fiber prepreg-β.

[0079] (4) Preparation of composite material

[0080] The preparation of CF / PEEK composite material sheet is the same as that in Step (4) of Example 1. The difference is that the carbon fiber prepreg-β of this case is used to prepare CF / PEEK composite material sheet-β.

[0081] Example 3

[0082] (1) Preparation of emulsifier

[0083] The chemical structure of the emulsifier in this case is the same as that of Formula I, and the preparation is the same as the (1) step in Example 1. The difference is that PEEK-OH-③ and PEG-6000 are used, and boron trifluoride etherate is used as the catalyst to obtain emulsifier-γ.

[0084] (2) Preparation of sizing agent

[0085] The formula and preparation process of the sizing agent in this case are the same as the (2) step in Example 1. The difference is that the emulsifier-γ of this case is used to obtain the polyether ether ketone aqueous emulsion sizing agent-γ.

[0086] The prepared polyether ether ketone aqueous emulsion sizing agent-γ was centrifuged at 3000 rpm for 30 minutes. The sizing agent was stable without stratification and was uniformly dispersed. And it has good bundling ability for carbon fiber bundles and basically does not cause disordered bundles.

[0087] (3) Preparation of carbon fiber prepreg

[0088] The preparation process of the carbon fiber prepreg in this case is the same as the (3) step in Example 1. The difference is that the polyether ether ketone aqueous emulsion sizing agent-γ of this case is used to obtain the carbon fiber prepreg-γ.

[0089] (4) Composite material preparation

[0090] The preparation of CF / PEEK composite material plates is the same as the (4) step in Example 1. The difference is that the carbon fiber prepreg-γ of this case is used to obtain the CF / PEEK composite material plates-γ.

[0091] Example 4

[0092] (1) Preparation of emulsifier

[0093] The chemical structure of the emulsifier in this case is the same as that of Formula I, and the preparation is the same as the (1) step in Example 1. The difference is that PEEK-OH-② and PEG-8000 are used, and boron trifluoride etherate is used as the catalyst to obtain emulsifier-δ.

[0094] (2) Preparation of sizing agent

[0095] The formula and preparation process of the sizing agent in this case are the same as the (2) step in Example 1. The difference is that the emulsifier-δ of this case is used to obtain the polyether ether ketone aqueous emulsion sizing agent-δ.

[0096] The prepared polyetheretherketone aqueous emulsion sizing agent - δ was centrifuged at 3000 rpm for 30 minutes, and the sizing agent was stable without delamination and was uniformly dispersed. Moreover, it had good bundling ability for carbon fiber bundles and basically no bundle disorder occurred.

[0097] (3) Preparation of carbon fiber prepreg

[0098] The preparation process of the carbon fiber prepreg in this example was the same as that of step (3) in Example 1, except that the polyetheretherketone aqueous emulsion sizing agent - δ of this example was used to obtain the carbon fiber prepreg - δ.

[0099] (4) Preparation of composite material

[0100] The preparation of the CF / PEEK composite material plate was the same as that of step (4) in Example 1, except that the carbon fiber prepreg - δ of this example was used to obtain the CF / PEEK composite material plate - δ.

[0101] Example 5

[0102] The chemical structure of the emulsifier in this example was the same as that of Formula I, and the preparation was the same as that of step (1) in Example 1, except that PEEK - OH - ⑥ of Preparation Example 2 was used to obtain the emulsifier - ζ.

[0103] The formula and preparation process of the sizing agent in this example were the same as those of step (2) in Example 1, except that the emulsifier - ζ of this example was used to obtain the polyetheretherketone aqueous emulsion sizing agent - ζ.

[0104] The prepared polyetheretherketone aqueous emulsion sizing agent - ζ was centrifuged at 3000 rpm for 30 minutes, and the sizing agent was stable without delamination and was uniformly dispersed. Moreover, it had good bundling ability for carbon fiber bundles and basically no bundle disorder occurred.

[0105] The preparation process of the carbon fiber prepreg in this example was the same as that of step (3) in Example 1, except that the polyetheretherketone aqueous emulsion sizing agent - ζ of this example was used to obtain the carbon fiber prepreg - ζ.

[0106] The preparation of the CF / PEEK composite material plate was the same as that of step (4) in Example 1, except that the carbon fiber prepreg - ζ of this example was used to obtain the CF / PEEK composite material plate - ζ.

[0107] Comparative Example 1

[0108] The carbon fiber fabric in this example was not sized with a sizing agent, and a CF / PEEK composite material plate was made according to step (4) of Example 1.

[0109] Comparative Example 2

[0110] The chemical structure of the emulsifier in this example is the same as that of Formula I. The preparation is the same as the first step in Example 1, except that PEEK-OH-⑤ of Preparation Example 2 is used to obtain emulsifier-ε.

[0111] The formulation and preparation process of the sizing agent in this example are the same as the second step in Example 1, except that the emulsifier-ε of this example is used to obtain the polyetheretherketone aqueous emulsion sizing agent-ε.

[0112] The prepared polyetheretherketone aqueous emulsion sizing agent-ε was centrifuged at 3000 rpm for 30 minutes. The photo after centrifugation is as Figure 3 shown. It can be seen that the stability of the sizing agent-ε is poor and layering has occurred.

[0113] The preparation process of the carbon fiber prepreg in this example is the same as the third step in Example 1, except that the polyetheretherketone aqueous emulsion sizing agent-ε of this example is used to obtain the carbon fiber prepreg-ε.

[0114] The preparation of the CF / PEEK composite material plate is the same as the fourth step in Example 1, except that the carbon fiber prepreg-ε of this example is used to obtain the CF / PEEK composite material plate-ε.

[0115] The CF / PEEK composite material plates were prepared from the carbon fiber fabrics obtained in Examples 1-5 and Comparative Examples 1-2, and the performance test results are shown in Table 2.

[0116] Table 2 Performance of CF / PEEK Composite Material Plates

[0117]

[0118] As can be seen from Table 2, the sizing agent made of the emulsifier is used to modify the carbon fiber, which has a great influence on the interlayer interface strength of the composite material. The tensile strength and interlaminar shear strength of the laminated composite material prepared without using the sizing agent are relatively low, while the laminated products obtained by the method of the present invention have better mechanical properties and high interface strength.

[0119] The above is only the preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and inventive concept of the present invention, makes equivalent substitutions or changes, and should be covered by the protection scope of the present invention.

Claims

1. An emulsifier, characterized in that The emulsifier is obtained by reacting terminal hydroxyl polyether ether ketone, bisphenol A diglycidyl ether epoxy resin, and polyethylene glycol under the action of a catalyst. The specific method for obtaining the emulsifier is as follows: the terminal hydroxyl polyether ether ketone and bisphenol A diglycidyl ether epoxy resin are put into a reaction kettle, heated to 120-140° C., continuously stirred, and after being uniformly dissolved, a portion of triphenyl phosphate is added, and the reaction is continued for 1-2 hours; Then add polyethylene glycol, continue stirring until evenly mixed, then add the remaining triphenyl phosphate, and continue the reaction for 1-2 hours; Pour out the product while it is hot, cool it to a solid state, and then crush it for standby use to obtain an emulsifier, wherein the number average molecular weight of the emulsifier is 15,000 g / mol to 40,000 g / mol; The bisphenol A diglycidyl ether epoxy resin is selected from one or more of E-20, E-44, and E-51; The polyethylene glycol is selected from one or more of PEG-1000, PEG-2000, PEG-4000, PEG-6000, and PEG-8000; The molar ratio of the terminal hydroxyl polyether ether ketone and the bisphenol A diglycidyl ether epoxy resin is 1:2, and the terminal hydroxyl polyether ether ketone and the polyethylene glycol are in an equal mass ratio; the amount of the triphenyl phosphate is 0.1%-0.3% of the total mass of the terminal hydroxyl polyether ether ketone, the bisphenol A diglycidyl ether epoxy resin and the polyethylene glycol.

2. An emulsifier according to claim 1, characterized in that The molecular structure of the hydroxy-terminated polyetheretherketone is shown in the following formula II: The hydroxy-terminated polyetheretherketone is obtained by polymerizing tert-butylhydroquinone and 4,4'-difluorobenzophenone, and the number average molecular weight of the hydroxy-terminated polyetheretherketone is in the range of 4500-15000 g / mol.

3. An emulsifier according to claim 2, characterized in that, The specific method for obtaining the hydroxy-terminated polyetheretherketone is as follows: firstly, tert-butylhydroquinone, a salt-forming agent, and part of an organic solvent and a water-carrying agent are placed in a reaction kettle, a protective gas is introduced to discharge oxygen in the reaction kettle, and then condensation reflux is performed at 120-160° C., and the reaction is continuously stirred for 2-5 hours; Cool down to below 100°C, add 4,4'-difluorobenzophenone and the remaining organic solvent, and heat up to 190-220°C to carry out polymerization reaction for 2-4h; After cooling to room temperature, the product is washed with water, extracted with methanol to remove the solvent, and then dried to obtain terminal hydroxyl polyetheretherketone.

4. An emulsifier according to claim 3, characterized in that The molar ratio of tert-butylhydroquinone to 4,4'-difluorobenzophenone is 1:0.8-1; the salt-forming agent is anhydrous sodium carbonate and / or anhydrous potassium carbonate, and the molar ratio of the salt-forming agent to tert-butylhydroquinone is 1:1; the water-carrying agent is one of benzene, toluene and xylene, and the amount of the water-carrying agent is 10-20% of the weight of the organic solvent; the organic solvent is selected from one of N,N-dimethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone and dimethyl sulfoxide, and the amount of the organic solvent is 3-6 times the total weight of the monomer.

5. A polyetheretherketone aqueous emulsion sizing agent, characterized in that: The method comprises the following raw materials in parts by weight: 5-40 parts of the emulsifier according to any one of claims 1 to 4, 20-80 parts of polyetheretherketone slurry, and 80-120 parts of water, and is emulsified to an emulsion particle size of less than 10 μm.

6. A polyetheretherketone aqueous emulsion sizing agent according to claim 5, characterized in that: The mass fraction of the polyetheretherketone slurry is 0.5%-2%, and the solvent therein is a solvent that can dissolve polyetheretherketone but is immiscible or slightly soluble in water; The polyetheretherketone aqueous emulsion sizing agent is obtained by heating and stirring the polyetheretherketone slurry and the emulsifier at a speed of 800-1200 rpm and 90-100° C. until they are evenly dispersed, then dripping water at a speed of 1-5 drops / second at a speed of more than 2500 rpm, and emulsifying for 30-60 minutes.

7. Carbon fiber prepreg, characterized in that: The polyetheretherketone aqueous emulsion sizing agent according to claim 5 or 6 has a uniform film on the surface of the carbon fiber.

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