Basalt fiber reinforced polyphenyl ether composite material and preparation method thereof
By introducing amino functional groups onto the surface of basalt fibers and using a mixed sizing agent that is covalently fixed by PPO-MAH/CNTs-COOH and constrained by a nano-network, the problem of poor interfacial compatibility between basalt fibers and polyphenylene ether matrix was solved, resulting in a significant improvement in the interfacial bonding strength and mechanical properties of the composite material.
Patent Information
- Application Number
- CN202511251335.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-03
- Publication Date
- 2025-12-09
Smart Images
Figure CN121086286A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application belongs to the technical field of composite materials, and particularly relates to a basalt fiber reinforced polyphenylene ether composite material and a preparation method thereof. BACKGROUND
[0002] Basalt fiber reinforced thermoplastic polymer composites (BFRTPs) are widely used in aerospace, automotive, construction and marine engineering fields due to their high specific strength and excellent impact resistance. Basalt fiber is a new type of inorganic and environmentally friendly high-performance fiber made by melting natural volcanic rock at high temperature. It has high tensile strength, elastic modulus and thermal stability, and is one of the four fibers that China focuses on developing.
[0003] Polyphenylene ether (PPO) is a high-performance engineering plastic with excellent heat resistance and dimensional stability, but its combination with inorganic fibers is poor. Due to the poor interfacial compatibility between basalt fiber and organic polyphenylene ether matrix, the stress transfer efficiency is low, and the mechanical properties of the composite material are limited. Although existing modification methods such as acid and alkali etching, silane coupling agent treatment, plasma modification and surface sizing can improve the interfacial properties to some extent, they generally have problems such as possible damage to the fiber structure and insufficient enhancement effect. Moreover, the existing interface modification methods are often limited to a single mode, making it difficult to balance the strength and stability of the fiber and resin interface. In order to achieve firm bonding and structural constraint in the interface layer at the same time, a functional sizing system that can form a covalently fixed structure on the fiber surface and further construct a nano-scale network constraint is needed to improve the interface stability and effectively promote load transfer at the micro level, thereby improving the overall mechanical performance of the composite material. SUMMARY
[0004] The purpose of the present application is to overcome the shortcomings of the prior art and provide a basalt fiber reinforced polyphenylene ether composite material and a preparation method thereof. The interfacial bonding force and mechanical properties of the composite material are significantly improved.
[0005] To achieve the above purpose, the technical solution adopted by the present application is:
[0006] A preparation method of a basalt fiber reinforced polyphenylene ether composite material, comprising the following steps:
[0007] Step S1, preparation of covalently fixed and nano-network constrained mixed sizing agent
[0008] First, dissolve the dried polyphenylene ether grafted maleic anhydride in tetrahydrofuran to obtain a polyphenylene ether grafted maleic anhydride sizing agent; then add carboxylated multi-walled carbon nanotubes, ultrasonically disperse to form a uniform and stable suspension, and obtain a covalently fixed and nano-network constrained mixed sizing agent;
[0009] Step S2, preparation of modified basalt fiber
[0010] S21, pretreatment of basalt fiber: basalt fiber cloth is refluxed with acetone to remove the original pulp and impurities, washed with deionized water and dried to obtain desized basalt fiber;
[0011] S22, preparation of amino-functionalized basalt fiber: the desized basalt fiber is immersed in a KH550 solution hydrolyzed by glacial acetic acid, taken out after immersion, dried at room temperature, and then placed in an oven for reaction, forming a stable amino-containing silane functional layer on the surface of the fiber, i.e. obtaining amino-functionalized basalt fiber;
[0012] S23, preparation of modified basalt fiber by covalently fixing and nano-network-constrained mixed sizing agent: the amino-functionalized basalt fiber is immersed in the covalently fixed and nano-network-constrained mixed sizing agent, taken out and dried, and then hot-pressed in a hot press to obtain modified basalt fiber by covalently fixing and nano-network-constrained mixed sizing agent;
[0013] Step S3, preparation of modified basalt fiber reinforced polyphenyl ether composite material
[0014] The modified basalt fiber by covalently fixing and nano-network-constrained mixed sizing agent and polyphenyl ether resin powder are alternately layered to form a prepreg, and the prepreg is hot-pressed to form a composite board, which is taken out and slowly cooled at room temperature to obtain a modified basalt fiber by covalently fixing and nano-network-constrained mixed sizing agent reinforced polyphenyl ether composite material.
[0015] Preferably, in step S1, the drying conditions of the polyphenyl ether grafted maleic anhydride are vacuum drying at 80-120℃ for 1-3h.
[0016] Preferably, in step S1, the concentration of the polyphenyl ether grafted maleic anhydride sizing agent is 0.89-8.9g / L.
[0017] Preferably, in step S1, the concentration of the carboxylated multi-walled carbon nanotube is 0.25-0.75wt%.
[0018] Preferably, in step S1, the ultrasonic dispersion conditions are 40kHz, 300W ultrasonic dispersion for 30min.
[0019] Preferably, in step S21, the refluxing temperature of acetone is 70-90℃, and the refluxing time is 32-40h.
[0020] Preferably, in step S21, the deionized water washing is performed 4-5 times.
[0021] Preferably, in step S21, the drying condition is: drying in an oven at 70-90℃ for 8-16h.
[0022] Preferably, in step S22, the preparation process of the KH550 solution is: preparing a 1-5wt% solution of KH550 silane coupling agent, the solvent is a mixture of anhydrous ethanol and deionized water in a volume ratio of 9:1, and the solution pH is adjusted to 4-5 with glacial acetic acid to obtain the KH550 hydrolysis solution.
[0023] Preferably, in step S22, the dipping temperature is room temperature, and the dipping time is 6-18h.
[0024] Preferably, in step S22, the room temperature drying time is 20-40min.
[0025] Preferably, in step S22, the reaction temperature is 50-150℃, and the reaction time is 0.5-1.5h.
[0026] Preferably, in step S23, the dipping time is 4-6min, and the drying method is to evaporate the solvent at room temperature.
[0027] Preferably, in step S23, the temperature of the hot press is 260-280℃, and the hot pressing time is 20-40s.
[0028] Preferably, in step S3, the mass ratio of the basalt fiber modified by the covalently fixed and nanometer network constrained mixed sizing agent to the polyphenyl ether resin powder is 7:3, and the number of layers of the basalt fiber modified by the covalently fixed and nanometer network constrained mixed sizing agent is 6 layers.
[0029] Preferably, in step S3, the hot pressing forming condition is: the prepreg is first hot pressed at 260-280℃ under a pressure of 2MPa for 4-6min, and then 5 times of air exhaust is performed to remove bubbles, and then the hot pressing is continued at 5MPa for 4-6min.
[0030] The application also discloses a basalt fiber reinforced polyphenyl ether composite material prepared by the preparation method.
[0031] Compared with the prior art, the basalt fiber reinforced polyphenyl ether composite material has the following beneficial effects:
[0032] 1. The application uses polyphenyl ether (PPO) as the base resin, which has excellent heat resistance and dimensional stability, uses KH550 as the interface bridging agent to modify basalt fibers, introduces amino reactive sites on the surface of the basalt fibers to obtain amino-functionalized basalt fibers, and uses covalent fixation and nano-network constraint mixed sizing agent PPO-MAH / CNTs to treat the amino-functionalized basalt fibers, PPO-MAH reacts with the amino groups on the surface of the fibers to form a firm interface fixed layer, realizing the covalent fixation of the fibers and the matrix, and also promoting the formation of a uniform and continuous nano-scale network structure of CNTs-COOH on the surface of the fibers, thereby constructing a composite reinforcing interface with covalent fixation and nano-network constraint at the fiber / matrix interface, that is, the covalent fixation and nano-network constraint mixed sizing agent realizes the interface enhancement between the basalt fibers and the polyphenyl ether matrix, so that the interfacial bonding force and the mechanical properties of the composite material are significantly improved.
[0033] 2. The preparation method of the application has mild conditions, and the operation steps include fiber desizing, surface functionalization, sizing treatment and hot pressing, and has good reproducibility, providing a feasible process for further expanding the application of basalt fiber composites.
[0034] 3. The basalt fiber reinforced polyphenyl ether composite material prepared by the application has an interlaminar shear strength of 30.2-34.3 MPa, a bending strength of 195.9-210.2 MPa, and a tensile strength of 136.1-148.8 MPa, and the composite material has achieved a substantial improvement in a plurality of mechanical indicators, providing a solid performance support for high-strength structural applications. BRIEF DESCRIPTION OF DRAWINGS
[0035] Figure 1 The infrared spectra of the basalt fibers before and after modification in the application. In the figure, DBF is desized basalt fiber, DBF-K is amino-functionalized basalt fiber, DBF-KP is basalt fiber modified by PPO-MAH sizing agent only, and DBF-KPC is basalt fiber modified by covalent fixation and nano-network constraint mixed sizing agent.
[0036] Figure 2 The SEM images of the desized basalt fiber and the basalt fiber modified by covalent fixation and nano-network constraint mixed sizing agent in Example 1 of the application.
[0037] Figure 3 The SEM images of the interlaminar shear test section of the composite material prepared in Example 1 and Comparative Example 1 of the application. DETAILED DESCRIPTION
[0038] The application will be described in more detail below with reference to the drawings and specific embodiments, and the raw materials used in the embodiments of the application are all commercially available unless otherwise specified.
[0039] The polyphenyl ether grafted maleic anhydride is purchased from Jiaiyirong Polymer (Shanghai) Co., Ltd., with a brand of FB820 and a grafting rate of 0.5-1.0 wt%, and a processing temperature of 240-300℃;
[0040] The carboxylated multi-walled carbon nanotubes are purchased from Chengdu Zhongke Times Nanometer Technology Co., Ltd., with a tube diameter of 10-20 nm, a length of 0.5-2 μm, and a carboxyl content of 2.0 wt%.
[0041] Example 1
[0042] A preparation method of a basalt fiber reinforced polyphenyl ether composite material, comprising the following steps:
[0043] Step S1, preparation of covalently fixed and nano-network constrained mixed sizing agent
[0044] (1) After the polyphenyl ether grafted maleic anhydride is vacuum dried at 100℃ for 2 h, it is dissolved in tetrahydrofuran to obtain a PPO-MAH sizing agent, with a solution concentration of 4.45 g / L;
[0045] (2) 0.5 wt% carboxylated multi-walled carbon nanotubes are added to the prepared PPO-MAH sizing agent, and ultrasonic dispersion is performed at 40 kHz and 300 W for 30 min to form a uniform and stable suspension, thereby obtaining a covalently fixed and nano-network constrained mixed sizing agent (PPO-MAH / CNTs sizing agent).
[0046] Step S2, preparation of modified basalt fiber
[0047] S21, pretreatment of basalt fiber
[0048] (1) Commercial basalt fiber cloth is cut into samples with a size of 60 mm×60 mm, and is placed in a Soxhlet extractor to be refluxed with acetone at 80℃ for 36 h to remove the original commercial sizing agent and impurities;
[0049] (2) The basalt fiber sample after acetone reflux is taken out, washed with deionized water for 4 times, and dried in an oven at 80℃ for 12 h to obtain desized basalt fiber DBF;
[0050] S22, preparation of basalt fiber with amino functional groups
[0051] (1) A 3 wt% solution of KH550 silane coupling agent is prepared, with a mixed solution of anhydrous ethanol and deionized water in a volume ratio of 9:1 as the solvent, and the solution pH is adjusted to 4.5 with glacial acetic acid to obtain a KH550 hydrolysis solution;
[0052] (2) The desized basalt fiber DBF sample is immersed in the solution, taken out after soaking at room temperature for 12 h, dried in air for 30 min, and then placed in an oven at 100 ℃ for 1 h to obtain modified basalt fiber containing amino active groups, i.e., amino-functionalized basalt fiber DBF-K;
[0053] S23, Preparation of basalt fiber modified by covalently fixed and nanonetwork-constrained mixed sizing agent
[0054] The amino-functionalized basalt fiber DBF-K is immersed in the covalently fixed and nanonetwork-constrained mixed sizing agent for 5 min, taken out, and dried after the solvent is volatilized at room temperature, and then hot-pressed in a hot press at 270 ℃ for 30 s to obtain basalt fiber DBF-KPC modified by the covalently fixed and nanonetwork-constrained mixed sizing agent.
[0055] Step S3, Preparation of modified basalt fiber reinforced polyphenyl ether composite material
[0056] (1) 6 layers of basalt fiber DBF-KPC modified by the covalently fixed and nanonetwork-constrained mixed sizing agent and polyphenyl ether (PPO) resin powder are alternately laid according to a fiber-to-resin mass ratio of 7:3 to form a prepreg.
[0057] (2) The prepreg is hot-pressed at 270 ℃ under a pressure of 2 MPa for 5 min, and air is discharged for 5 times to remove bubbles, and then the pressure is continuously maintained at 5 MPa for 5 min, and the composite plate is taken out and slowly cooled at room temperature to obtain a covalently fixed and nanonetwork-constrained mixed sizing agent modified basalt fiber reinforced polyphenyl ether composite material DBF-KPC / PPO with a thickness of 3 mm.
[0058] Example 2
[0059] A method for preparing a basalt fiber reinforced polyphenyl ether composite material, comprising the following steps:
[0060] Step S1, Preparation of covalently fixed and nanonetwork-constrained mixed sizing agent
[0061] (1) Polyphenyl ether grafted maleic anhydride is dried at 80 ℃ under vacuum for 3 h, and then dissolved in tetrahydrofuran to obtain PPO-MAH sizing agent with a solution concentration of 4.45 g / L.
[0062] (2) 0.5 wt% of carboxylated multi-walled carbon nanotubes is added to the prepared PPO-MAH sizing agent, and ultrasonically dispersed at 40 kHz and 300 W for 30 min to form a uniform and stable suspension, thereby obtaining a covalently fixed and nanonetwork-constrained mixed sizing agent.
[0063] Step S2, Preparation of modified basalt fiber
[0064] S21, Pretreatment of basalt fiber
[0065] (1) Commercial basalt fiber cloth was cut into 60mm x 60mm samples and placed in a Soxhlet extractor to reflux with acetone at 70°C for 40h to remove the original commercial sizing and impurities;
[0066] (2) The basalt fiber sample after refluxing with acetone was taken out, washed with deionized water for 5 times, and dried in an oven at 70°C for 16h to obtain desized basalt fiber DBF;
[0067] S22, Preparation of amino-functionalized basalt fiber
[0068] (1) A 3wt% solution of KH550 silane coupling agent was prepared with anhydrous ethanol and deionized water in a volume ratio of 9:1 as solvent, and the solution pH was adjusted to 4 with glacial acetic acid to obtain a KH550 hydrolysis solution;
[0069] (2) The desized basalt fiber DBF sample was immersed in the solution, taken out after soaking at room temperature for 12h, dried in air for 20min, and then placed in an oven at 100°C for 1h to obtain modified basalt fiber with amino active groups on the surface, i.e. amino-functionalized basalt fiber DBF-K;
[0070] S23, Preparation of basalt fiber modified by covalently immobilized and nano-network constrained mixed sizing agent
[0071] The amino-functionalized basalt fiber DBF-K was immersed in the covalently immobilized and nano-network constrained mixed sizing agent for 4min, taken out, and dried at room temperature after the solvent evaporated, and then hot-pressed in a hot press at 260°C for 40s to obtain basalt fiber modified by covalently immobilized and nano-network constrained mixed sizing agent DBF-KPC;
[0072] Step S3, Preparation of modified basalt fiber reinforced polyphenyl ether composite material
[0073] (1) Six layers of basalt fiber DBF-KPC modified by covalently immobilized and nano-network constrained mixed sizing agent and polyphenyl ether resin powder were alternately laid according to a fiber to resin mass ratio of 7:3 to form a prepreg;
[0074] (2) The prepreg was hot-pressed at 260°C under a pressure of 2MPa for 6min, and degassed 5 times to remove bubbles, and then kept under a pressure of 5MPa for another 6min, and the composite plate was taken out and slowly cooled at room temperature to obtain a covalently immobilized and nano-network constrained mixed sizing agent modified basalt fiber reinforced polyphenyl ether composite material DBF-KPC / PPO with a thickness of 3mm.
[0075] Example 3
[0076] A method for preparing basalt fiber reinforced polyphenylene ether composite material, comprising the following steps:
[0077] Step S1, preparation of covalently immobilized and nano-network constrained mixed sizing agent
[0078] (1) After polyphenylene ether grafted maleic anhydride is dried at 120°C for 1h, it is dissolved in tetrahydrofuran, and the solution concentration is 4.45g / L, to obtain PPO-MAH sizing agent;
[0079] (2) 0.5wt% carboxylated multi-walled carbon nanotubes are added to the prepared PPO-MAH sizing agent, and are dispersed under the condition of 40kHz and 300W ultrasonic for 30min to form a uniform and stable suspension, to obtain covalently immobilized and nano-network constrained mixed sizing agent.
[0080] Step S2, preparation of modified basalt fiber
[0081] S21, pretreatment of basalt fiber
[0082] (1) Commercial basalt fiber cloth is cut into 60mm×60mm samples, and is placed in a Soxhlet extractor, and is refluxed with acetone at 90°C for 32h to remove original commercial sizing and impurities;
[0083] (2) The basalt fiber sample after acetone reflux is taken out, washed with deionized water for 4 times, and is dried in an oven at 90°C for 8h to obtain desized basalt fiber DBF;
[0084] S22, preparation of amino-functionalized basalt fiber
[0085] (1) KH550 silane coupling agent is prepared into a 3wt% solution, the solvent is a mixture of anhydrous ethanol and deionized water in a volume ratio of 9:1, and the solution pH is adjusted to 5 with glacial acetic acid to obtain KH550 hydrolysis solution;
[0086] (2) The desized basalt fiber DBF sample is immersed in the solution, taken out after soaking at room temperature for 12h, dried in air for 40min, and then placed in an oven at 100°C for 1h to obtain modified basalt fiber containing amino active groups, i.e. amino-functionalized basalt fiber DBF-K;
[0087] S23, preparation of covalently immobilized and nano-network constrained mixed sizing agent modified basalt fiber
[0088] The amino-functional basalt fiber DBF-K is immersed in the covalently immobilized and nanonetwork-restrained hybrid sizing agent for 6 min, taken out, and after the solvent is volatilized at room temperature, hot-pressed in a hot press at 280°C for 20 s to obtain the basalt fiber DBF-KPC modified by the covalently immobilized and nanonetwork-restrained hybrid sizing agent.
[0089] Step S3, preparation of the modified basalt fiber reinforced polyphenyl ether composite material
[0090] (1) The basalt fiber DBF-KPC modified by the covalently immobilized and nanonetwork-restrained hybrid sizing agent and the polyphenyl ether resin powder are alternately laid in a fiber-to-resin mass ratio of 7:3 to form a prepreg;
[0091] (2) The prepreg is hot-pressed at 280°C under a pressure of 2 MPa for 4 min, and is subjected to 5 times of exhaust to remove bubbles, and then continues to be kept under 5 MPa for 4 min, and the composite plate is taken out and slowly cooled at room temperature to obtain the basalt fiber DBF-KPC / PPO modified by the covalently immobilized and nanonetwork-restrained hybrid sizing agent and reinforced by the polyphenyl ether composite material with a thickness of 3 mm.
[0092] Example 4
[0093] The embodiment provides a preparation method of a basalt fiber reinforced polyphenyl ether composite material, which is different from the embodiment 1 only in that in step S22, the KH550 silane coupling agent is prepared into a 1wt% solution; and other steps are consistent with the embodiment 1.
[0094] Example 5
[0095] The embodiment provides a preparation method of a basalt fiber reinforced polyphenyl ether composite material, which is different from the embodiment 1 only in that in step S22, the KH550 silane coupling agent is prepared into a 5wt% solution; and other steps are consistent with the embodiment 1.
[0096] Example 6
[0097] The embodiment provides a preparation method of a basalt fiber reinforced polyphenyl ether composite material, which is different from the embodiment 1 only in that in step S1, the PPO-MAH concentration in the covalently immobilized and nanonetwork-restrained hybrid sizing agent is 0.89g / L; and other steps are consistent with the embodiment 1.
[0098] Example 7
[0099] The embodiment provides a preparation method of a basalt fiber reinforced polyphenyl ether composite material, which is different from the embodiment 1 only in that in step S1, the PPO-MAH concentration in the covalently immobilized and nanonetwork-restrained hybrid sizing agent is 8.9g / L; and other steps are consistent with the embodiment 1.
[0100] Example 8
[0101] This example provides a preparation method of basalt fiber reinforced polyphenylene ether composite, which is only different from example 1 in that in step S1, the concentration of carboxylated multi-walled carbon nanotubes in the covalently fixed and nano-network constrained mixed sizing agent is 0.25wt%; other steps are consistent with example 1.
[0102] Example 9
[0103] This example provides a preparation method of basalt fiber reinforced polyphenylene ether composite, which is only different from example 1 in that in step S1, the concentration of carboxylated multi-walled carbon nanotubes in the covalently fixed and nano-network constrained mixed sizing agent is 0.75wt%; other steps are consistent with example 1.
[0104] Example 10
[0105] This example provides a preparation method of basalt fiber reinforced polyphenylene ether composite, which is only different from example 1 in that in step S22, the desized basalt fiber DBF sample is soaked in the prepared KH550 solution for 6h; other steps are consistent with example 1.
[0106] Example 11
[0107] This example provides a preparation method of basalt fiber reinforced polyphenylene ether composite, which is only different from example 1 in that in step S22, the desized basalt fiber DBF sample is soaked in the prepared KH550 solution for 18h; other steps are consistent with example 1.
[0108] Example 12
[0109] This example provides a preparation method of basalt fiber reinforced polyphenylene ether composite, which is only different from example 1 in that in the preparation of amino-functionalized basalt fiber in step S22, the temperature of the oven is 50℃, and the reaction time is 1.5h; other steps are consistent with example 1.
[0110] Example 13
[0111] This example provides a preparation method of basalt fiber reinforced polyphenylene ether composite, which is only different from example 1 in that in the preparation of amino-functionalized basalt fiber in step S22, the temperature of the oven is 150℃, and the reaction time is 0.5h; other steps are consistent with example 1.
[0112] Comparative Example 1
[0113] Comparative Example 1 provides a preparation method of a desized basalt fiber reinforced polyphenylene oxide composite material, which is only different from Example 1 in that steps S1, S22 and S23 are not included, step S21 is consistent with Example 1, and step S3 is the preparation of a desized basalt fiber reinforced polyphenylene oxide composite material, and the specific preparation method is as follows:
[0114] (1) 6 layers of desized basalt fiber DBF and polyphenylene oxide resin powder are used to form a prepreg by alternately laying the fibers and resins in a mass ratio of 7:3;
[0115] (2) The prepreg is hot-pressed at 270°C under a pressure of 2 MPa for 5 min, and 5 times of exhaust are performed to remove bubbles, then it is continuously kept at 5 MPa for 5 min, and the composite plate is taken out and slowly cooled at room temperature to obtain a desized basalt fiber reinforced polyphenylene oxide composite material DBF / PPO with a thickness of 3 mm.
[0116] Comparative Example 2
[0117] Comparative Example 2 provides a preparation method of an amino-functionalized basalt fiber reinforced polyphenylene oxide composite material, which is only different from Example 1 in that steps S1 and S23 are not included, steps S21 and S22 are consistent with Example 1, and step S3 is the preparation of an amino-functionalized basalt fiber reinforced polyphenylene oxide composite material, and the specific preparation process is as follows:
[0118] (1) 6 layers of amino-functionalized basalt fiber DBF-K and polyphenylene oxide resin powder are used to form a prepreg by alternately laying the fibers and resins in a mass ratio of 7:3;
[0119] (2) The prepreg is hot-pressed at 270°C under a pressure of 2 MPa for 5 min, and 5 times of exhaust are performed to remove bubbles, then it is continuously kept at 5 MPa for 5 min, and the composite plate is taken out and slowly cooled at room temperature to obtain an amino-functionalized basalt fiber reinforced polyphenylene oxide composite material DBF-K / PPO with a thickness of 3 mm.
[0120] Comparative Example 3
[0121] Comparative Example 3 provides a preparation method of a PPO-MAH sizing agent modified basalt fiber reinforced polyphenylene oxide composite material, which is only different from Example 1 in that:
[0122] Step S1 is the preparation of a PPO-MAH sizing agent, and the specific preparation process is to dissolve polyphenylene oxide grafted maleic anhydride in tetrahydrofuran after vacuum drying at 100°C for 2 h, and the solution concentration is 4.45 g / L to obtain a PPO-MAH sizing agent;
[0123] Steps S21 and S22 are consistent with Example 1;
[0124] Step S23 is the preparation of basalt fiber modified by PPO-MAH sizing agent, and the specific preparation process is as follows: the amino-functionalized basalt fiber DBF-K is immersed in the PPO-MAH sizing agent for 5 min, taken out, and the solvent is volatilized at room temperature, and then hot-pressed at 270℃ for 30s to obtain the basalt fiber DBF-KP modified by PPO-MAH sizing agent only;
[0125] Step S3 is the preparation of basalt fiber reinforced polyphenyl ether composite material modified by PPO-MAH sizing agent, and the specific preparation process is as follows:
[0126] (1) 6 layers of basalt fiber DBF-KP modified by PPO-MAH sizing agent and polyphenyl ether resin powder are used to form a prepreg according to the mass ratio of fiber to resin of 7:3, and the layers are alternately laid;
[0127] (2) The prepreg is hot-pressed at 270℃ under a pressure of 2MPa for 5min, and 5 times of exhaust is carried out to remove bubbles, and then it is continuously kept at 5MPa for 5min, and then the composite plate is taken out and slowly cooled at room temperature to obtain a PPO-MAH sizing agent modified basalt fiber reinforced polyphenyl ether composite material DBF-KP / PPO with a thickness of 3mm.
[0128] Performance detection:
[0129] (1) Infrared spectrum detection is carried out on the desized basalt fiber DBF, amino-functionalized basalt fiber DBF-K, basalt fiber DBF-KP modified by PPO-MAH sizing agent only, and basalt fiber DBF-KPC modified by covalently fixed and nano-network constrained mixed sizing agent in Example 1 and Comparative Examples 1-3.
[0130] The infrared spectrum results of Figure 1 show that: the modified basalt fiber sample appears new absorption signals, DBF-K appears C-H asymmetric and symmetric stretching vibration peaks at 2923cm -1 and 2852cm -1 , respectively, proving that KH550 has been successfully grafted to the fiber surface. For DBF-KP and DBF-KPC, new absorption peaks appear at 1743cm -1 and 1645cm -1 , respectively, which are attributed to the formation of carbonyl and amide covalent bond, further proving that the PPO-MAH / CNTs sizing agent is chemically bonded to the basalt fiber.
[0131] (2) The desized basalt fiber DBF in Example 1 and the basalt fiber DBF-KPC modified by covalently fixed and nano-network constrained mixed sizing agent are detected by scanning electron microscope.
[0132] The scanning electron microscope images of Figure 2The SEM images of the DBF-KPC can find that compared with the untreated DBF, the basalt fiber DBF-KPC treated by covalent fixation and nano-network constraint mixed sizing agent forms a continuous network structure on the fiber surface.
[0133] (3) The interlaminar shear test sections of the basalt fiber reinforced polyphenyl ether composite DBF-KPC / PPO in Example 1 and the desized basalt fiber reinforced polyphenyl ether composite DBF / PPO in Comparative Example 1 are detected by a scanning electron microscope.
[0134] Figure 3 The SEM images of the DBF-KPC can find that compared with the untreated DBF, the basalt fiber DBF-KPC treated by covalent fixation and nano-network constraint mixed sizing agent forms a continuous network structure on the fiber surface.
[0135] (3) The mechanical properties of the composite materials prepared in Examples 1-13 and Comparative Examples 1-3 are detected, and the mechanical property detection includes interlaminar shear strength, tensile strength and bending strength tests. The interlaminar shear strength, tensile strength and bending strength are detected according to ASTM D2344, ASTM D3039 and ASTM D7264 standards, respectively. The detection results are shown in Table 1:
[0136] Table 1: Mechanical property detection results of the composite materials prepared in Examples 1-13 and Comparative Examples 1-3
[0137]
[0138]
[0139] As can be seen from the detection results in Table 1, the basalt fiber reinforced polyphenyl ether composite DBF-KPC / PPO modified by covalent fixation and nano-network constraint mixed sizing agent is prepared in Examples 1-13. The modified basalt fiber DBF-KPC is prepared from PPO-MAH / CNTs covalent fixation and nano-network constraint mixed sizing agent soaked in amino-functionalized basalt fiber DBF-K. The interlaminar shear strength of the composite material DBF-KPC / PPO prepared in Examples 1-13 is as high as 30.2-34.3 MPa, the bending strength is as high as 195.9-210.2 MPa, and the tensile strength is as high as 136.1-148.8 MPa.
[0140] Comparative Example 1 is to prepare a de-sizing basalt fiber reinforced polyphenyl ether composite material DBF / PPO, which is prepared by using only de-sizing basalt fiber DBF-KP and polyphenyl ether PPO. The interlaminar shear strength of the composite material DBF / PPO prepared in Comparative Example 1 is only 20.9 MPa, the bending strength is only 150.3 MPa, and the tensile strength is only 91.0 MPa;
[0141] Comparative Example 2 is to prepare an amino-functionalized basalt fiber reinforced polyphenyl ether composite material DBF-K / PPO, which is prepared by using only amino-functionalized basalt fiber DBF-K and polyphenyl ether PPO. The interlaminar shear strength of the composite material DBF-K / PPO prepared in Comparative Example 2 is only 25.7 MPa, the bending strength is only 173.6 MPa, and the tensile strength is only 106.7 MPa;
[0142] Comparative Example 3 is to prepare a PPO-MAH sizing agent modified basalt fiber reinforced polyphenyl ether composite material DBF-KP / PPO, which is prepared by using only PPO-MAH sizing agent modified basalt fiber DBF-KP and polyphenyl ether PPO. The interlaminar shear strength of the composite material DBF-KP / PPO prepared in Comparative Example 3 is only 27.2 MPa, the bending strength is only 182.5 MPa, and the tensile strength is only 125.8 MPa.
[0143] The test results show that: the interfacial performance of the composite material formed by only the amino-functionalized fiber and the polyphenyl ether is still limited; when only PPO-MAH sizing agent is used, the interfacial bonding force is improved but the effect is not significant; and when the PPO-MAH and the CNTs-COOH are used in combination, the interfacial performance of the composite material is significantly enhanced, which is because the chemical reaction between the amino-functionalized basalt fiber and the PPO-MAH realizes the covalent fixation of the fiber and the matrix, and the three-dimensional network constraint is formed at the interface by using the CNTs-COOH, so as to construct a composite enhanced interface with covalent fixation and nano network constraint at the fiber / matrix interface, and realize excellent interfacial bonding and stress transfer.
[0144] The composite material DBF-KPC / PPO prepared by using the covalent fixation and nano network constraint mixed sizing agent to soak the amino-functionalized basalt fiber has obvious increase in the interlaminar shear strength, the bending performance and the tensile performance, which fully shows that the interfacial bonding force and the stress transfer efficiency between the basalt fiber and the polyphenyl ether resin matrix in the embodiments 1-13 are significantly improved, and the prepared composite material DBF-KPC / PPO has stronger anti-deformation ability when bearing the bending load.
[0145] The above examples are only explanations of the present application, and are not intended to limit the present application. Any obvious modification made by those skilled in the art without departing from the principle and spirit of the present application shall be considered to be within the scope of protection of the present application.
Claims
1. A method for producing a basalt fiber-reinforced polyphenylene ether composite material, characterized by, Comprising the following steps: Step S1, preparation of covalently immobilized and nano-network constrained mixed sizing agent First, the dried polyphenyl ether grafted maleic anhydride is dissolved in tetrahydrofuran to obtain a polyphenyl ether grafted maleic anhydride sizing agent; then carboxylated multi-walled carbon nanotubes are added, and a uniform and stable suspension is formed after ultrasonic dispersion to obtain a covalently immobilized and nano-network constrained mixed sizing agent; Step S2, preparation of modified basalt fiber S21, pretreatment of basalt fiber: basalt fiber cloth is refluxed with acetone to remove the original sizing agent and impurities, washed with deionized water and dried to obtain desized basalt fiber; S22, preparation of amino-functionalized basalt fiber: the desized basalt fiber is immersed in a solution of KH550 hydrolyzed by glacial acetic acid catalysis, taken out after immersion, dried at room temperature, and then placed in an oven for reaction, forming a stable amino-containing silane functional layer on the surface of the fiber, i.e. obtaining amino-functionalized basalt fiber; S23, preparation of basalt fiber modified by covalently immobilized and nano-network constrained mixed sizing agent: the amino-functionalized basalt fiber is immersed in the covalently immobilized and nano-network constrained mixed sizing agent, taken out and dried, and then hot-pressed in a hot press to obtain basalt fiber modified by covalently immobilized and nano-network constrained mixed sizing agent; Step S3, preparation of modified basalt fiber reinforced polyphenyl ether composite material The basalt fiber modified by covalently immobilized and nano-network constrained mixed sizing agent and polyphenyl ether resin powder are alternately layered to form a prepreg, and the prepreg is hot-pressed to form a composite board, which is slowly cooled at room temperature to obtain a basalt fiber reinforced polyphenyl ether composite material modified by covalently immobilized and nano-network constrained mixed sizing agent.
2. The preparation method of the basalt fiber reinforced polyphenylene ether composite material as described in claim 1, characterized in that: In step S1, the drying conditions of the polyphenyl ether grafted maleic anhydride are: vacuum drying at 80-120℃ for 1-3h; The concentration of the polyphenyl ether grafted maleic anhydride sizing agent is 0.89-8.9g / L; The concentration of the carboxylated multi-walled carbon nanotubes is 0.25-0.75wt%; The ultrasonic dispersion conditions are: 40kHz, 300W ultrasonic dispersion for 30min.
3. The preparation method of the basalt fiber reinforced polyphenylene ether composite material as described in claim 1, characterized in that, In step S21, the refluxing temperature of acetone is 70-90℃, and the refluxing time is 32-40h; The deionized water washing is performed 4-5 times; The drying conditions are: drying in an oven at 70-90℃ for 8-16h.
4. The preparation method of the basalt fiber reinforced polyphenylene ether composite material as described in claim 1, characterized in that, In step S22, the preparation process of the KH550 solution is: KH550 silane coupling agent is prepared into a 1-5wt% solution, the solvent is a mixture of anhydrous ethanol and deionized water in a volume ratio of 9:1, and the solution pH is adjusted to 4-5 with glacial acetic acid to obtain the KH550 hydrolysis solution.
5. The preparation method of the basalt fiber reinforced polyphenylene ether composite material as described in claim 4, characterized in that, In step S22, the immersion temperature is room temperature, and the immersion time is 6-18h; The room temperature drying time is 20-40min; The reaction temperature is 50-150℃, and the reaction time is 0.5-1.5h.
6. The preparation method of the basalt fiber reinforced polyphenylene ether composite material as described in claim 1, characterized in that, In step S23, the immersion time is 4-6min, and the drying method is to evaporate the solvent at room temperature; The temperature of the hot press is 260-280℃, and the hot pressing time is 20-40s.
7. The preparation method of the basalt fiber reinforced polyphenylene ether composite material as described in claim 1, characterized in that, In step S3, the mass ratio of the covalently fixed and nano-network constrained mixed sizing agent modified basalt fiber to the polyphenyl ether resin powder is 7:3, and the number of layers of the covalently fixed and nano-network constrained mixed sizing agent modified basalt fiber is 6 layers.
8. The method for preparing basalt fiber reinforced polyphenylene ether composite material as described in claim 7, characterized in that, In step S3, the hot-pressing forming condition is that the prepreg is first hot-pressed at 260-280℃ under a pressure of 2MPa for 4-6min, and 5 times of exhaust are performed to remove bubbles, and then the hot-pressing is continued under 5MPa for 4-6min.
9. A basalt fiber reinforced polyphenyl ether composite material prepared by the preparation method of any one of claims 1-8.
10. The basalt fiber reinforced PPE composite of claim 9, wherein, The interlaminar shear strength of the composite material is 30.2-34.3MPa, the bending strength is 195.9-210.2MPa, and the tensile strength is 136.1-148.8MPa. The interlaminar shear strength of the composite material is 30.2-34.3MPa, the bending strength is 195.9-210.2MPa, and the tensile strength is 136.1-148.8MPa.