High-performance carbon fiber / epoxy resin composite material and preparation method thereof

Abstract

The invention belongs to the technical field of composite material preparation, and particularly discloses a high-performance carbon fiber / epoxy resin composite material and a preparation method thereof. The preparation method comprises the following steps: heating and refluxing 3, 4, 9, 10-perylenetetracarboxylic dianhydride, amine-terminated polyether D230, triethylamine and N, N-dimethylformamide in a nitrogen atmosphere, so as to prepare perylene naphthalene diimide; mixing the precursor with graphene oxide in N, N-dimethylformamide, and carrying out a heating reaction to obtain lt; pDI, GOgt; the preparation method comprises the following steps: dissolving the raw materials in an acetone solution, mixing with bisphenol A epoxy resin and 4, 4 '-methylenebis (2-ethyl) aniline, and carrying out vacuumizing defoaming and curing reaction to obtain 1t; pDI, GOgt; modified epoxy resin; removing a sizing agent from the carbon fibers to obtain DCF, and then immersing the DCF into lt; pDI, GOgt; drying the N, N-dimethylformamide solution to obtain modified carbon fibers; immersing the mixture at the temperature of 1t; pDI, GOgt; and carrying out pressurizing and heating reaction in modified epoxy resin, and cooling to obtain the high-performance carbon fiber / epoxy resin composite material. The high-performance carbon fiber / epoxy resin composite material has the characteristics of high strength, high toughness and excellent stress concentration resistance, and has remarkable industrial application value.

Description

Technical Field

[0001] The present invention belongs to the technical field of composite material preparation, and in particular relates to a high-performance carbon fiber / epoxy resin composite material and a preparation method thereof. Background Art

[0002] High-performance fibers combine ultra-high strength, lightweight, high-temperature and corrosion resistance, and adaptability to extreme environments, along with multifunctional properties such as electrical conductivity, flame retardancy, and bulletproofing. As reinforcements, they are used in composite materials for a wide range of applications in aerospace, military protection, industrial manufacturing, and medical technology. Their exceptional performance continues to drive innovation in high-end materials technology, expanding into cutting-edge fields such as new energy and smart wearables, becoming a core driver of modern industrial upgrading.

[0003] However, the interfacial bonding performance between carbon fiber and epoxy resin matrix in traditional composite materials is insufficient, which easily leads to stress concentration and interface failure, limiting the further improvement of its mechanical properties. In the prior art, a single modification method is usually adopted, such as chemically treating the fiber surface or adding reinforcing particles to the resin matrix, but such methods are often difficult to achieve modulus matching and interface synergistic optimization between the fiber and the resin. In addition, the fiber surface is smooth and chemically inert, resulting in poor resin wettability. The interface bonding is mainly mechanical anchoring, and it is difficult to form a stable chemical bond; and the brittle characteristics of the resin matrix easily induce crack propagation, reducing the fracture toughness of the composite material. Although the introduction of nanomaterials such as graphene oxide (GO) can partially improve the performance of the resin, its poor dispersibility and easy aggregation still restrict the reinforcement effect. Summary of the Invention

[0004] The present invention aims to provide a high-performance carbon fiber / epoxy resin composite material and a preparation method thereof. The high-performance carbon fiber / epoxy resin composite material has significantly enhanced interface properties and mechanical properties.

[0005] In order to solve the above technical problems, the technical solutions adopted by the present invention are as follows:

[0006] A method for preparing a high-performance carbon fiber / epoxy resin composite material comprises the following steps:

[0007] S1. Place 3,4,9,10-perylenetetracarboxylic dianhydride, amino-terminated polyether D230, triethylamine, and N,N-dimethylformamide in a three-necked flask, heat under reflux under a nitrogen atmosphere, cool to room temperature, wash with deionized water, vacuum dry, and grind to obtain perylene naphthalene diimide;

[0008] S2. Mix the PDI obtained in S1 with graphene oxide, add N,N-dimethylformamide, and heat to react to obtain organic-inorganic particles.<PDI,GO> ;

[0009] S3, the organic-inorganic particles obtained in S2<PDI,GO> Dissolve in acetone solution, add bisphenol A epoxy resin, stir evenly, add 4,4'-methylenebis(2-ethyl)aniline, mix evenly, vacuum to remove bubbles, and perform curing reaction to obtain<PDI,GO> Modified epoxy resin;

[0010] S4, placing the carbon fiber in a Soxhlet extractor to extract and obtain carbon fiber DCF with the sizing agent removed;

[0011] S5, the organic-inorganic particles obtained in S2<PDI,GO> Dissolve in N,N-dimethylformamide, immerse the carbon fiber DCF obtained in S4 after removing the sizing agent, take out, and dry at room temperature to obtain modified carbon fiber;

[0012] S6, fully impregnate the modified carbon fiber obtained in S5 into the<PDI,GO> Place the modified epoxy resin in the preheated mold tank and continue to pour the S3 obtained<PDI,GO> The modified epoxy resin is placed on a hot press plate, pressurized for reaction, and cooled to obtain a high-performance carbon fiber / epoxy resin composite material.

[0013] Preferably, the heating reflux temperature is 80° C., and the heating reflux time is 10 h.

[0014] Preferably, the vacuum drying temperature is 90° C., the vacuum drying time is 24 h, and the vacuum degree is -0.1 MPa.

[0015] Preferably, in S2, the heating temperature is 90° C. and the heating reaction time is 6 h.

[0016] Preferably, in S3, the mass ratio of bisphenol A epoxy resin to 4,4'-methylenebis(2-ethyl)aniline is 100:32.

[0017] Preferably, in S3, the specific process parameters of the curing reaction are: heating at 90° C. for 1 hour, heating to 120° C. for 2 hours, and then heating to 150° C. for 3 hours.

[0018] Preferably, in S4, the extraction solvent is acetone solution, and the extraction time is 48 hours.

[0019] Preferably, in S5, the immersion time is 15 minutes.

[0020] Preferably, in S6, the specific conditions of the pressurized reaction are: heating at 90°C for 1 h under a pressure of 5 MPa, increasing the pressure to 10 MPa, heating at 120°C for 2 h, and heating at 150°C for 3 h.

[0021] The present invention also provides a high-performance carbon fiber / epoxy resin composite material prepared by the preparation method.

[0022] The principle of the present invention is: the present invention improves the interface performance of fiber-resin-based composite materials through modulus, toughness matching and gradient interface synergy strategy.<PDI,GO> , modifying the fiber and resin simultaneously. When added to the resin matrix, the rigid structure and flexible terminal amino chain of PDI synergistically participate in the curing and cross-linking of the epoxy resin with GO, thereby improving the strength and elongation at break; used as a sizing agent coated on the fiber surface,<PDI,GO> The abundant amino and oxygen-containing groups on the surface enhance the fiber's surface activity. Furthermore, the three-dimensional structure composed of naphthalene rings and GO sheets increases the fiber's surface roughness, thereby improving resin wettability. Importantly, this reduces stress concentration in the composite material by forming a gradient interface between the fiber and the resin.

[0023] Compared with the prior art, the present invention has the following advantages and technical effects:

[0024] The present invention discloses a high-performance carbon fiber / epoxy resin composite material and a preparation method thereof.<PDI,GO> Hybrid particles bidirectionally modify carbon fibers and epoxy resins to create a gradient interface layer. This increases the carbon fiber's surface energy, reduces the contact angle, enhances interlaminar shear strength, and significantly enhances interfacial load transfer efficiency. Furthermore, the gradient structure mitigates interfacial stress concentration, preventing brittle fracture. Bidirectional modification improves transverse strength compared to single-modification systems, providing a new path for the preparation of high-performance composite materials. This composite material combines high strength, high toughness, and resistance to stress concentration, meeting the demanding requirements for high-performance structural materials in aerospace, automotive lightweighting, and other fields, and has significant potential for industrial application.

[0025] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 Provided for Examples 1-5<PDI,GO> The modified epoxy resin and comparative example 1 provide polarizing microscope results of pure resin, wherein, Figure 1 (a) is the polarizing microscope result of comparative example 1, the scale is 50 μm, Figure 1 (b) is the polarizing microscope result of Example 1, the scale is 50 μm, Figure 1 (c) is the polarizing microscope result of Example 2, the scale is 50 μm, Figure 1 (d) is the polarizing microscope result of Example 3, the scale is 50 μm, Figure 1 (e) is the polarizing microscope result of Example 4, the scale is 50 μm, Figure 1 (f) is the polarizing microscope result of Example 5, and the scale bar is 50 μm;

[0027] Figure 2 Provided for Examples 1-5<PDI,GO> The modified epoxy resin and comparative example 1 provide load-displacement curves and strength-elongation at break statistical graphs of pure resin, wherein: Figure 2 (a) is the load-displacement curve, Figure 2 (b) is the statistical diagram of strength-elongation at break;

[0028] Figure 3 Provided for Example 6-Example 10<PDI,GO> Storage modulus and loss factor curves of the modified epoxy resin and the pure resin provided in Comparative Example 1, wherein, Figure 3 (a) is the storage modulus curve. Figure 3 (b) is the loss factor curve;

[0029] Figure 4 Provided for Example 6-Example 10<PDI,GO> The load-displacement curve and strength-elongation at break statistical graph of the modified epoxy resin and the pure resin provided in Comparative Example 1, wherein: Figure 4 (a) is the load-displacement curve, Figure 4 (b) is the statistical diagram of strength-elongation at break;

[0030] Figure 5 Electron microscope images of the composite materials provided in Examples 11 to 13 and the DCF provided in Comparative Example 2, wherein: Figure 5 (a) is the SEM image of Comparative Example 2, with a scale of 10 μm. Figure 5 (b) is the SEM image of Example 11, the scale is 10 μm, Figure 5 (c) is the SEM image of Example 12, with a scale of 10 μm. Figure 5 (d) is the SEM image of Example 13, the scale is 10 μm, Figure 5 (e) is the SEM image of Comparative Example 2, with a scale of 1 μm. Figure 5 (f) is the SEM image of Example 11, the scale is 1 μm, Figure 5 (g) is the SEM image of Example 12, the scale is 1 μm, Figure 5 (h) is the SEM image of Example 13, the scale bar is 1 μm;

[0031] Figure 6 The contact angle and surface energy results of the carbon fibers of the composite materials provided in Examples 11 to 13 and the DCF provided in Comparative Example 2, wherein: Figure 6 (a) is the contact angle statistics diagram. Figure 6 (b) is the surface energy statistics diagram;

[0032] Figure 7The load-displacement curves, TFBT strength, and ILSS strength results of the composite materials provided in Examples 11 to 13 and the DCF provided in Comparative Example 2 are shown, wherein: Figure 7 (a) is the load-displacement curve of the transverse tensile test of different carbon fiber composite materials. Figure 7 (b) is the TFBT strength result. Figure 7 (c) is the load-displacement curve of the interlaminar shear test of different carbon fiber composite materials. Figure 7 (d) in the figure is the ILSS intensity. DETAILED DESCRIPTION

[0033] The technical solution of the present invention is further described below with reference to the accompanying drawings and embodiments.

[0034] Unless otherwise defined, technical or scientific terms used in the present invention shall have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs.

[0035] Source of test materials:

[0036] In the present invention, unless otherwise specified, other test materials and instruments and equipment are conventional test materials in this field and can be purchased through commercial channels.

[0037] Example 1

[0038] This embodiment provides a<PDI,GO> Modified epoxy resin, preparation method is as follows:

[0039] S1. Place 2.5 mmol, 0.98 g, 3,4,9,10-perylenetetracarboxylic dianhydride, 10 mmol, 2.3 g of amino-terminated polyether D230, 3 mL of triethylamine, and 80 mL of N,N-dimethylformamide in a three-necked flask. Heat to 80°C under a nitrogen atmosphere and reflux for 10 h. Cool to room temperature, wash with deionized water, and vacuum dry at 90°C for 24 h, wherein the vacuum degree is -0.1 MPa. Grind to obtain dark red powder of perylene naphthalene diimide (PDI).

[0040] S2: Mix 0.5 g of PDI obtained in S1 with 0.5 g of graphene oxide, add 100 mL of N,N-dimethylformamide, and heat at 90 °C for 6 h to obtain organic-inorganic particles.<PDI,GO> 1:1 ;

[0041] S3, get S2<PDI,GO> 1:1Dissolve it in 10 mL of acetone solution at a mass fraction of 0.5 wt%, add 45 g of bisphenol A epoxy resin, stir evenly, add 14.4 g of 4,4'-methylenebis(2-ethyl)aniline, mix evenly, vacuum to remove bubbles, heat at 90 ° C for 1 h, heat to 120 ° C for 2 h, and continue to heat to 150 ° C for 3 h to perform curing reaction.<PDI,GO> 1:1 Modified epoxy resin EP 1:1 .

[0042] Example 2

[0043] This embodiment provides a<PDI,GO> Modified epoxy resin, preparation method is as follows:

[0044] S1. Place 2.5 mmol, 0.98 g, 3,4,9,10-perylenetetracarboxylic dianhydride, 10 mmol, 2.3 g, amino-terminated polyether D230, 3 mL, triethylamine, and 80 mL, N,N-dimethylformamide, in a three-necked flask. Heat to 80°C under a nitrogen atmosphere and reflux for 10 h. Cool to room temperature, wash with deionized water, and vacuum dry at 90°C for 24 h, with a vacuum degree of -0.1 MPa. Grind to obtain dark red powder PDI.

[0045] S2: Mix 0.5 g of PDI obtained in S1 with 0.1 g of graphene oxide, add 100 mL of N,N-dimethylformamide, and heat at 90 °C for 6 h to obtain organic-inorganic particles.<PDI,GO> 5:1 ;

[0046] S3, get S2<PDI,GO> 5:1 Dissolve it in 10 mL of acetone solution at a mass fraction of 0.5 wt%, add 45 g of bisphenol A epoxy resin, stir evenly, add 14.4 g of 4,4'-methylenebis(2-ethyl)aniline, mix evenly, vacuum and remove bubbles, heat at 90 ° C for 1 h, heat to 120 ° C for 2 h, and continue to heat to 150 ° C for 3 h to perform curing reaction.<PDI,GO> 5:1 Modified epoxy resin EP 5:1 .

[0047] Example 3

[0048] This embodiment provides a<PDI,GO> Modified epoxy resin, preparation method is as follows:

[0049] S1. Place 2.5 mmol, 0.98 g, 3,4,9,10-perylenetetracarboxylic dianhydride, 10 mmol, 2.3 g, amino-terminated polyether D230, 3 mL, triethylamine, and 80 mL, N,N-dimethylformamide, in a three-necked flask. Heat to 80°C under a nitrogen atmosphere and reflux for 10 h. Cool to room temperature, wash with deionized water, and vacuum dry at 90°C for 24 h, with a vacuum degree of -0.1 MPa. Grind to obtain dark red powder PDI.

[0050] S2: Mix 0.5 g of PDI obtained in S1 with 0.05 g of graphene oxide, add 100 mL of N,N-dimethylformamide, and heat at 90 °C for 6 h to obtain organic-inorganic particles.<PDI,GO> 10:1 ;

[0051] S3, get S2<PDI,GO> 10:1 Dissolve it in 10 mL of acetone solution at a mass fraction of 0.5 wt%, add 45 g of bisphenol A epoxy resin, stir evenly, add 14.4 g of 4,4'-methylenebis(2-ethyl)aniline, mix evenly, vacuum to remove bubbles, heat at 90 ° C for 1 h, heat to 120 ° C for 2 h, and continue to heat to 150 ° C for 3 h to perform curing reaction.<PDI,GO> 10:1 Modified epoxy resin EP 10:1 .

[0052] Example 4

[0053] This embodiment provides a<PDI,GO> Modified epoxy resin, preparation method is as follows:

[0054] S1. Place 2.5 mmol, 0.98 g, 3,4,9,10-perylenetetracarboxylic dianhydride, 10 mmol, 2.3 g, amino-terminated polyether D230, 3 mL, triethylamine, and 80 mL, N,N-dimethylformamide, in a three-necked flask. Heat to 80°C under a nitrogen atmosphere and reflux for 10 h. Cool to room temperature, wash with deionized water, and vacuum dry at 90°C for 24 h, with a vacuum degree of -0.1 MPa. Grind to obtain dark red powder PDI.

[0055] S2: Mix 0.5 g of PDI obtained in S1 with 0.025 g of graphene oxide, add 100 mL of N,N-dimethylformamide, and heat at 90 °C for 6 h to obtain organic-inorganic particles.<PDI,GO> 20:1 ;

[0056] S3, get S2<PDI,GO> 20:1Dissolve it in 10 mL of acetone solution at a mass fraction of 0.5 wt%, add 45 g of bisphenol A epoxy resin, stir evenly, add 14.4 g of 4,4'-methylenebis(2-ethyl)aniline, mix evenly, vacuum to remove bubbles, heat at 90 ° C for 1 h, heat to 120 ° C for 2 h, and continue to heat to 150 ° C for 3 h to perform curing reaction.<PDI,GO> 20:1 Modified epoxy resin EP 20:1 .

[0057] Example 5

[0058] This embodiment provides a<PDI,GO> Modified epoxy resin, preparation method is as follows:

[0059] S1. Place 2.5 mmol, 0.98 g, 3,4,9,10-perylenetetracarboxylic dianhydride, 10 mmol, 2.3 g, amino-terminated polyether D230, 3 mL, triethylamine, and 80 mL, N,N-dimethylformamide, in a three-necked flask. Heat to 80°C under a nitrogen atmosphere and reflux for 10 h. Cool to room temperature, wash with deionized water, and vacuum dry at 90°C for 24 h, with a vacuum degree of -0.1 MPa. Grind to obtain dark red powder PDI.

[0060] S2: 0.5 g of PDI obtained in S1 was mixed with 0.016 g of graphene oxide, 100 mL of N,N-dimethylformamide was added, and the mixture was heated at 90°C for 6 h to obtain organic-inorganic particles.<PDI,GO> 30:1 ;

[0061] S3, get S2<PDI,GO> 30:1 Dissolve it in 10 mL of acetone solution at a mass fraction of 0.5 wt%, add 45 g of bisphenol A epoxy resin, stir evenly, add 14.4 g of 4,4'-methylenebis(2-ethyl)aniline, mix evenly, vacuum to remove bubbles, heat at 90 ° C for 1 h, heat to 120 ° C for 2 h, and continue to heat to 150 ° C for 3 h to perform curing reaction.<PDI,GO> 30:1 Modified epoxy resin EP 30:1 .

[0062] Example 6

[0063] This embodiment provides a<PDI,GO> Modified epoxy resin, preparation method is as follows:

[0064] S1. Place 2.5 mmol, 0.98 g, 3,4,9,10-perylenetetracarboxylic dianhydride, 10 mmol, 2.3 g, amino-terminated polyether D230, 3 mL, triethylamine, and 80 mL, N,N-dimethylformamide, in a three-necked flask. Heat to 80°C under a nitrogen atmosphere and reflux for 10 h. Cool to room temperature, wash with deionized water, and vacuum dry at 90°C for 24 h, with a vacuum degree of -0.1 MPa. Grind to obtain dark red powder PDI.

[0065] S2: 0.5 g of PDI obtained in S1 was mixed with 0.025 g of graphene oxide, 100 mL of N,N-dimethylformamide was added, and the mixture was heated at 90 °C for 6 h to obtain organic-inorganic particles.<PDI,GO> 20:1 ;

[0066] S3, get S2<PDI,GO> 20:1 Dissolve it in 10 mL of acetone solution at a mass fraction of 0.1 wt%, add 45 g of bisphenol A epoxy resin, stir evenly, add 14.4 g of 4,4'-methylenebis(2-ethyl)aniline, mix evenly, vacuum to remove bubbles, heat at 90 ° C for 1 h, heat to 120 ° C for 2 h, and continue to heat to 150 ° C for 3 h to perform curing reaction, and obtain 0.1 wt% of<PDI,GO> 20:1 Modified epoxy resin EP 0.1wt％ .

[0067] Example 7

[0068] This embodiment provides a<PDI,GO> Modified epoxy resin, preparation method is as follows:

[0069] S1. Place 2.5 mmol, 0.98 g, 3,4,9,10-perylenetetracarboxylic dianhydride, 10 mmol, 2.3 g, amino-terminated polyether D230, 3 mL, triethylamine, and 80 mL, N,N-dimethylformamide, in a three-necked flask. Heat to 80°C under a nitrogen atmosphere and reflux for 10 h. Cool to room temperature, wash with deionized water, and vacuum dry at 90°C for 24 h, with a vacuum degree of -0.1 MPa. Grind to obtain dark red powder PDI.

[0070] S2: 0.5 g of PDI obtained in S1 was mixed with 0.025 g of graphene oxide, 100 mL of N,N-dimethylformamide was added, and the mixture was heated at 90 °C for 6 h to obtain organic-inorganic particles.<PDI,GO> 20:1 ;

[0071] S3, get S2<PDI,GO> 20:1Dissolve it in 10 mL of acetone solution at a mass fraction of 0.3 wt%, add 45 g of bisphenol A epoxy resin, stir evenly, add 14.4 g of 4,4'-methylenebis(2-ethyl)aniline, mix evenly, vacuum to remove bubbles, heat at 90 ° C for 1 h, heat to 120 ° C for 2 h, and continue to heat to 150 ° C for 3 h to perform curing reaction, and obtain 0.3 wt% of<PDI,GO> 20:1 Modified epoxy resin EP 0.3wt％ .

[0072] Example 8

[0073] This embodiment provides a<PDI,GO> Modified epoxy resin, preparation method is as follows:

[0074] S1. Place 2.5 mmol, 0.98 g, 3,4,9,10-perylenetetracarboxylic dianhydride, 10 mmol, 2.3 g, amino-terminated polyether D230, 3 mL, triethylamine, and 80 mL, N,N-dimethylformamide, in a three-necked flask. Heat to 80°C under a nitrogen atmosphere and reflux for 10 h. Cool to room temperature, wash with deionized water, and vacuum dry at 90°C for 24 h, with a vacuum degree of -0.1 MPa. Grind to obtain dark red powder PDI.

[0075] S2: 0.5 g of PDI obtained in S1 was mixed with 0.025 g of graphene oxide, 100 mL of N,N-dimethylformamide was added, and the mixture was heated at 90 °C for 6 h to obtain organic-inorganic particles.<PDI,GO> 20:1 ;

[0076] S3, get S2<PDI,GO> 20:1 Dissolve it in 10 ml of acetone solution at a mass fraction of 0.5 wt%, add 45 g of bisphenol A epoxy resin, stir evenly, add 14.4 g of 4,4'-methylenebis(2-ethyl)aniline, mix evenly, vacuum to remove bubbles, heat at 90 ° C for 1 hour, heat to 120 ° C for 2 hours, and continue to heat to 150 ° C for 3 hours to perform curing reaction, and obtain 0.5 wt% of<PDI,GO> 20:1 Modified epoxy resin EP 0.5wt％ .

[0077] Example 9

[0078] This embodiment provides a<PDI,GO> Modified epoxy resin, preparation method is as follows:

[0079] S1. Place 2.5 mmol, 0.98 g, 3,4,9,10-perylenetetracarboxylic dianhydride, 10 mmol, 2.3 g, amino-terminated polyether D230, 3 mL, triethylamine, and 80 mL, N,N-dimethylformamide, in a three-necked flask. Heat to 80°C under a nitrogen atmosphere and reflux for 10 h. Cool to room temperature, wash with deionized water, and vacuum dry at 90°C for 24 h, with a vacuum degree of -0.1 MPa. Grind to obtain dark red powder PDI.

[0080] S2: 0.5 g of PDI obtained in S1 was mixed with 0.025 g of graphene oxide, 100 mL of N,N-dimethylformamide was added, and the mixture was heated at 90 °C for 6 h to obtain organic-inorganic particles.<PDI,GO> 20:1 ;

[0081] S3, get S2<PDI,GO> 20:1 Dissolve it in 10 mL of acetone solution at a mass fraction of 0.7 wt%, add 45 g of bisphenol A epoxy resin, stir evenly, add 14.4 g of 4,4'-methylenebis(2-ethyl)aniline, mix evenly, vacuum to remove bubbles, heat at 90 ° C for 1 h, heat to 120 ° C for 2 h, and continue to heat to 150 ° C for 3 h to perform curing reaction to obtain 0.7 wt% of<PDI,GO> 20:1 Modified epoxy resin EP 0.7wt％ .

[0082] Example 10

[0083] This embodiment provides a<PDI,GO> Modified epoxy resin, preparation method is as follows:

[0084] S1. Place 2.5 mmol, 0.98 g, 3,4,9,10-perylenetetracarboxylic dianhydride, 10 mmol, 2.3 g, amino-terminated polyether D230, 3 mL, triethylamine, and 80 mL, N,N-dimethylformamide, in a three-necked flask. Heat to 80°C under a nitrogen atmosphere and reflux for 10 h. Cool to room temperature, wash with deionized water, and vacuum dry at 90°C for 24 h, with a vacuum degree of -0.1 MPa. Grind to obtain dark red powder PDI.

[0085] S2: Mix 0.5 g of PDI obtained in S1 with 0.025 g of graphene oxide, add 100 mL of N,N-dimethylformamide, and heat at 90 °C for 6 h to obtain organic-inorganic particles.<PDI,GO> 20:1 ;

[0086] S3, get S2<PDI,GO> 20:1Dissolve it in 10 ml of acetone solution at a mass fraction of 0.9 wt%, add 45 g of bisphenol A epoxy resin, stir evenly, add 14.4 g of 4,4'-methylenebis(2-ethyl)aniline, mix evenly, vacuum to remove bubbles, heat at 90 ° C for 1 h, heat to 120 ° C for 2 h, and continue to heat to 150 ° C for 3 h to perform curing reaction, and obtain 0.9 wt% of<PDI,GO> 20:1 Modified epoxy resin EP 0.9wt％ .

[0087] Example 11

[0088] This embodiment provides a carbon fiber / epoxy resin composite material, and the preparation method includes the following steps:

[0089] S1. Place 2.5 mmol, 0.98 g, 3,4,9,10-perylenetetracarboxylic dianhydride, 10 mmol, 2.3 g, amino-terminated polyether D230, 3 mL, triethylamine, and 80 mL, N,N-dimethylformamide, in a three-necked flask. Heat to 80°C under a nitrogen atmosphere and reflux for 10 h. Cool to room temperature, wash with deionized water, and vacuum dry at 90°C for 24 h, with a vacuum degree of -0.1 MPa. Grind to obtain dark red powder PDI.

[0090] S2: Mix 0.5 g of PDI obtained in S1 with 0.025 g of graphene oxide, add 100 mL of N,N-dimethylformamide, and heat to react to obtain organic-inorganic particles.<PDI,GO> 20:1 ;

[0091] S3, get S2<PDI,GO> 20:1 Dissolve it in 10 mL of acetone solution at a mass fraction of 0.7 wt%, add 45 g of bisphenol A epoxy resin, stir evenly, add 14.4 g of 4,4'-methylenebis(2-ethyl)aniline, mix evenly, vacuum to remove bubbles, heat at 90 ° C for 1 h, heat to 120 ° C for 2 h, and continue to heat to 150 ° C for 3 h to perform curing reaction to obtain 0.7 wt% of<PDI,GO> 20:1 Modified epoxy resin EP 0.7wt％ .

[0092] S4, placing the carbon fiber in a Soxhlet extractor, adding acetone solution and extracting for 48 hours to obtain carbon fiber DCF with the sizing agent removed;

[0093] S5, 0.1gS2 obtained<PDI,GO> Dissolve in 100 mL N,N-dimethylformamide, immerse the DCF obtained in S4 for 15 min, take it out, and dry it at room temperature to obtain modified carbon fiber CF 1％ ;

[0094] S6, the modified carbon fiber CF obtained in S5 1％ Fully immersed in S3<PDI,GO> Modified epoxy resin EP 0.7wt％ Place in the preheated mold tank and continue to pour the S3<PDI,GO> Modified epoxy resin EP 0.7wt％ The mold groove was placed on a hot press plate, heated at 90 ° C for 1 h under a pressure of 5 MPa, increased to 10 MPa, heated at 120 ° C for 2 h, heated at 150 ° C for 3 h, and cooled for 12 h to obtain a carbon fiber / epoxy resin composite material CF 1％ @EP 0.7％ .

[0095] Example 12

[0096] This embodiment provides a carbon fiber / epoxy resin composite material, and the preparation method includes the following steps:

[0097] S1. Place 2.5 mmol, 0.98 g, 3,4,9,10-perylenetetracarboxylic dianhydride, 10 mmol, 2.3 g, amino-terminated polyether D230, 3 mL, triethylamine, and 80 mL, N,N-dimethylformamide, in a three-necked flask. Heat to 80°C under a nitrogen atmosphere and reflux for 10 h. Cool to room temperature, wash with deionized water, and vacuum dry at 90°C for 24 h, with a vacuum degree of -0.1 MPa. Grind to obtain dark red powder PDI.

[0098] S2: Mix 0.5 g of PDI obtained in S1 with 0.025 g of graphene oxide, add 100 mL of N,N-dimethylformamide, and heat to react to obtain organic-inorganic particles.<PDI,GO> 20:1 ;

[0099] S3, the result from S2<PDI,GO> 20:1 Dissolve it in 10 mL of acetone solution at a mass fraction of 0.7 wt%, add 45 g of bisphenol A epoxy resin, stir evenly, add 14.4 g of 4,4'-methylenebis(2-ethyl)aniline, mix evenly, vacuum to remove bubbles, heat at 90 ° C for 1 h, heat to 120 ° C for 2 h, and continue to heat to 150 ° C for 3 h to perform curing reaction to obtain 0.7 wt% of<PDI,GO> 20:1 Modified epoxy resin EP 0.7wt％ .

[0100] S4, placing the carbon fiber in a Soxhlet extractor, adding acetone solution and extracting for 48 hours to obtain carbon fiber DCF with the sizing agent removed;

[0101] S5, 0.3g S2 obtained<PDI,GO> Dissolve in 100 mL N,N-dimethylformamide, immerse the DCF obtained in S4 for 15 min, take it out, and dry it at room temperature to obtain modified carbon fiber CF 3％ ;

[0102] S6, the modified carbon fiber CF obtained in S5 3％ Fully immersed in S3<PDI,GO> Modified epoxy resin EP 0.7wt％ Place in the preheated mold tank and continue to pour the S3<PDI,GO> Modified epoxy resin EP 0.7wt％ The mold groove was placed on a hot press plate, heated at 90 ° C for 1 h under a pressure of 5 MPa, increased to 10 MPa, heated at 120 ° C for 2 h, heated at 150 ° C for 3 h, and cooled for 12 h to obtain a carbon fiber / epoxy resin composite material CF 3％ @EP 0.7％ .

[0103] Example 12

[0104] This embodiment provides a carbon fiber / epoxy resin composite material, and the preparation method includes the following steps:

[0105] S1. Place 2.5 mmol, 0.98 g, 3,4,9,10-perylenetetracarboxylic dianhydride, 10 mmol, 2.3 g, amino-terminated polyether D230, 3 mL, triethylamine, and 80 mL, N,N-dimethylformamide, in a three-necked flask. Heat to 80°C under a nitrogen atmosphere and reflux for 10 h. Cool to room temperature, wash with deionized water, and vacuum dry at 90°C for 24 h, with a vacuum degree of -0.1 MPa. Grind to obtain dark red powder PDI.

[0106] S2: 0.5 g of PDI obtained in S1 was mixed with 0.025 g of graphene oxide, 100 mL of N,N-dimethylformamide was added, and the mixture was heated at 90 °C for 6 h to obtain organic-inorganic particles.<PDI,GO> 20:1 ;

[0107] S3, get S2<PDI,GO> 20:1 Dissolve it in 10 mL of acetone solution at a mass fraction of 0.7 wt%, add 45 g of bisphenol A epoxy resin, stir evenly, add 14.4 g of 4,4'-methylenebis(2-ethyl)aniline, mix evenly, vacuum to remove bubbles, heat at 90 ° C for 1 h, heat to 120 ° C for 2 h, and continue to heat to 150 ° C for 3 h to perform curing reaction to obtain 0.7 wt% of<PDI,GO> 20:1 Modified epoxy resin EP 0.7wt％ .

[0108] S4, placing the carbon fiber in a Soxhlet extractor, adding acetone solution and extracting for 48 hours to obtain carbon fiber DCF with the sizing agent removed;

[0109] S5, 0.5gS2 obtained<PDI,GO> Dissolve in 100 mL N,N-dimethylformamide, immerse the DCF obtained in S4 for 15 min, take it out, and dry it at room temperature to obtain modified carbon fiber CF 5％ ;

[0110] S6, the modified carbon fiber CF obtained in S5 5％ Fully immersed in S3<PDI,GO> Modified epoxy resin EP 0.7wt％ Place in the preheated mold tank and continue to pour the S3<PDI,GO> Modified epoxy resin EP 0.7wt％ The mold groove was placed on a hot press plate, heated at 90 ° C for 1 h under a pressure of 5 MPa, increased to 10 MPa, heated at 120 ° C for 2 h, heated at 150 ° C for 3 h, and cooled for 12 h to obtain a carbon fiber / epoxy resin composite material CF 5％ @EP 0.7％ .

[0111] Comparative Example 1

[0112] The test material of this comparative example is pure resin, purchased from Wuxi Morui Electronic Technology Co., Ltd.

[0113] The test material of this comparative example is DCF, and the specific preparation method is: placing the carbon fiber in a Soxhlet extractor, adding acetone solution and extracting for 48 hours to obtain the carbon fiber DCF with the sizing agent removed.

[0114] The effects of the above examples and comparative examples were verified by the following experiments.

[0115] 1. The polarizing microscope provided in the above examples 1-5<PDI,GO> Modified epoxy resin and comparative example 1 provide pure resin for observation, the results are as follows Figure 1 .

[0116] exist Figure 1 As shown in (a), some bubbles can be seen in EP. As the relative content of PDI increases,<PDI,GO> The degree of aggregation in the resin gradually decreases. When PDI:GO=20:1,<PDI,GO> In EP 20:1 The dispersion in EP 30:1 Relatively speaking, it is good.

[0117] 2. Determine the above examples 1-5 provided<PDI,GO> The modified epoxy resin and comparative example 1 provide the load-displacement and strength-elongation of pure resin. The test scheme is as follows: According to ASTM D638 standard, the tensile strength is measured using a universal testing machine (GT-7000-A2X, Taiwan, China). The value is calculated by the average of five valid data of each sample. The results are shown in Figure 2. Figure 2 .

[0118] Depend on Figure 2 (a) and Figure 2 As shown in (b), with the increase of the relative content of PDI, the stress and elongation at break of the modified epoxy resins with different proportions show a trend of first decreasing, then increasing, and then decreasing. 1:1 and EP 5:1 The strength of<PDI,GO> The relatively high content of graphene oxide (GO) in the resin matrix aggregates, resulting in a decrease in mechanical properties. When the ratio of PDI to GO is 20:1, EP 20:1 The stress value reaches the maximum (68.83MPa), which is 15.8% higher than that of EP, and the elongation at break also reaches the highest (4.03%), which is 24.77% higher than that of EP.

[0119] 3. Determination of the values ​​provided in Examples 6-10<PDI,GO> The storage modulus and loss factor of the modified epoxy resin and the pure resin provided in Comparative Example 1 were tested as follows: The storage modulus and loss factor of the epoxy resin before and after modification were measured using a dynamic mechanical analyzer (DMA, Perkin Elmer DMA8000). The results are shown in Figure 2. Figure 3 .

[0120] Depend on Figure 3 (a) and Figure 3 From (b) in the figure, we can see that as<PDI,GO> With the increase of concentration, the E' and glass transition temperature (Tg) of the modified resin showed an upward trend. E' increased from 1800MPa to 2250MPa, an increase of 25%.

[0121] 4. Determination of the values ​​provided in Examples 6-10<PDI,GO> The load-displacement and strength-elongation at break of the modified epoxy resin and the pure resin provided in Comparative Example 1 were tested using the following test protocol. The tensile strength was measured using a universal testing machine (GT-7000-A2X, Taiwan, China) according to ASTM D638. The value was calculated by averaging five valid data points for each sample. The results are shown in Table 1. Figure 4 .

[0122] Depend on Figure 4 (a) and Figure 4From (b) in the figure, we can see that as<PDI,GO> With the increase of EP content, the stress and elongation at break of the sample are also enhanced. When the mass fraction reaches 0.7wt%, the mechanical properties are optimized. It is worth noting that compared with EP, 0.7wt％ The elongation at break increased by 44.58%.

[0123] 5. Electron microscope scanning was performed on the composite materials provided in Examples 11 to 13 and the DCF provided in Comparative Example 2. The results are as follows: Figure 5 .

[0124] Depend on Figure 5 It can be seen that the surface of untreated carbon fiber is smooth and the mechanical locking effect should be poor when combined with the resin matrix. After coating treatment, the surface roughness of CFs increases and a layered structure of varying degrees appears. 1％ On the surface, a small amount of layered structure is attached, which is unevenly distributed. 3％ There are many flaky structures on the surface, which almost covers the entire fiber surface. This will allow the fiber and resin to have more active sites to form chemical bonds, and the roughness is significantly increased, which is conducive to enhancing the mechanical interaction with the resin matrix. 5％ Aggregation occurs on the surface.<PDI,GO> Larger clusters were formed on the fiber surface. The above results show that the coating<PDI,GO> The CF can increase the surface roughness and active sites.

[0125] 6. Determination of the contact angle and surface energy of the composite materials provided in Examples 11 to 13 and the DCF provided in Comparative Example 2. The test protocol is as follows: a dynamic contact angle meter (DCAT21, Germany) was used to measure the contact angle of CF in polar deionized water (γp = 51.0 mN·m -1 ,γd=21.8mN·m -1 ) and nonpolar diiodomethane (γd=50.8mN·m -1 ) and calculated the surface energy. The results are as follows Figure 6 .

[0126] Depend on Figure 6 (a) and Figure 6 As shown in (b), the surface energy of CF is only 28.83 mN·m due to its smooth surface and high chemical inertness. -1 , the dispersion component is only 23.47mN·m -1 , the polar component is only 5.36mN·m -1.along with<PDI,GO> As the contact angle increases, the contact angle decreases and the surface energy increases. This is because<PDI,GO> The modified CFs are distributed on the surface of the CFs. While increasing the surface roughness of the fiber, they also introduce numerous chemically active sites, increasing both polar and dispersed components. This modification increases the surface energy of the CFs, effectively promoting the penetration of epoxy resin into the CFs surface, achieving complete bonding between the CFs and epoxy resin and improving interfacial adhesion.

[0127] 7. The load-displacement curves, TFBT strength, and ILSS strength of the composite materials provided in Examples 11 to 13 and the DCF provided in Comparative Example 2 were measured. The test protocol was as follows: According to ASTM D2344, a universal testing machine (GT-7000-A2X) was used to obtain the ILSS values ​​of the composite materials. The test sample size was 25 mm × 6 mm × 2 mm, and the loading speed was adjusted to 1 mm / min. Five valid data points were collected for each sample, and the final results were averaged. The results are shown in Figure 2. Figure 7 .

[0128] Depend on Figure 5 (a) and Figure 5 As shown in (b), the TFBT of CF@EP is only 17.00MPa. When only the fiber is modified, compared with CF@EP, 1％ @EP、CF 3％ @EP and CF 5％ The TFBT of @EP has been improved. The TFBT of CF@EP is only 17.00MPa, while that of CF 5％ @EP's TFBT is lower than CF's 3％ @EP, which is due to the particles aggregated on the CF surface; when only the resin matrix is ​​modified, CF@EP 0.7％ The TFBT of CF@EP is higher than that of CF@EP, reaching 24.27MPa. When CF and EP are modified at the same time, that is, bidirectional modification, the modification effect is the best. 1％ @EP 0.7％ The TFBT of CF@EP reached 28.63MPa, which is 68.4% higher than that of CF@EP. Figure 7 (c) and Figure 7 As shown in Figure (d), the interlaminar shear strength (ILSS) of the CF / resin composite is consistent with the TFBT results, with bidirectional modification showing a more significant improvement in ILSS. Compared with single modification (fiber or resin), bidirectional structural design more effectively enhances the interfacial bond strength between CF and resin, thereby improving the mechanical properties of the composite.

[0129] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit the same. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that they can still modify or replace the technical solutions of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A method for preparing a high-performance carbon fiber / epoxy resin composite material, characterized in that: The following steps are involved: S1. Place 3,4,9,10-perylenetetracarboxylic dianhydride, amino-terminated polyether D230, triethylamine, and N,N-dimethylformamide in a three-necked flask, heat under reflux under a nitrogen atmosphere, cool to room temperature, wash with deionized water, vacuum dry, and grind to obtain perylene naphthalene diimide PDI; S2. Mix the PDI obtained in S1 with graphene oxide, add N,N-dimethylformamide, and heat to react to obtain organic-inorganic particles.<PDI,GO> ; S3, the organic-inorganic particles obtained in S2<PDI,GO> Dissolve in acetone solution, add bisphenol A epoxy resin, stir evenly, add 4,4'-methylenebis(2-ethyl)aniline, mix evenly, vacuum to remove bubbles, and perform curing reaction to obtain<PDI,GO> Modified epoxy resin; S4, placing the carbon fiber in a Soxhlet extractor to extract and obtain carbon fiber DCF with the sizing agent removed; S5, the organic-inorganic particles obtained in S2<PDI,GO> Dissolve in N,N-dimethylformamide, immerse the carbon fiber DCF obtained in S4 after removing the sizing agent, take out, and dry at room temperature to obtain modified carbon fiber; S6, fully impregnate the modified carbon fiber obtained in S5 into the<PDI,GO> Place the modified epoxy resin in the preheated mold tank and continue to pour the S3 obtained<PDI,GO> The modified epoxy resin is placed on a hot press plate, pressurized for reaction, and cooled to obtain a high-performance carbon fiber / epoxy resin composite material.

2. The preparation method according to claim 1, characterized in that In S1, the heating reflux temperature is 80° C., and the heating reflux time is 10 h.

3. The preparation method according to claim 1, characterized in that In S1, the vacuum drying temperature is 90° C., the vacuum drying time is 24 h, and the vacuum degree is -0.1 MPa.

4. The preparation method according to claim 1, characterized in that In S2, the heating temperature is 90° C., and the heating reaction time is 6 h.

5. The preparation method according to claim 1, characterized in that: In S3, the mass ratio of bisphenol A epoxy resin to 4,4'-methylenebis(2-ethyl)aniline is 100:

32.

6. The preparation method according to claim 1, characterized in that: In S3, the specific process parameters of the curing reaction are: heating at 90°C for 1 hour, heating at 120°C for 2 hours, and then heating at 150°C for 3 hours.

7. The preparation method according to claim 1, characterized in that: In S4, the extraction solvent is acetone solution, and the extraction time is 48 hours.

8. The preparation method according to claim 1, characterized in that: In S5, the immersion time is 15 minutes.

9. The preparation method according to claim 1, characterized in that: In S6, the specific conditions of the pressurized reaction are: heating at 90°C for 1 h under a pressure of 5 MPa, increasing the pressure to 10 MPa, heating at 120°C for 2 h, and heating at 150°C for 3 h.

10. A high-performance carbon fiber / epoxy resin composite material prepared by the preparation method according to any one of claims 1 to 9.

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