A high temperature resistant cyanate ester resin for carbon fiber composite core and preparation method thereof

Abstract

The present invention relates to the technical field of polymer material preparation, and in particular to a high-temperature resistant cyanate resin for a carbon fiber composite core and a preparation method thereof. The high-temperature resistant cyanate resin for the carbon fiber composite core, in parts by weight, comprises the following raw materials: 45 to 60 parts of bisphenol A dicyanate, 25 to 35 parts of bisphenol E dicyanate, 4 to 8 parts of nano-aluminum nitride, 8 to 10 parts of modified polyetheretherketone microspheres, 5 to 10 parts of tris(4-cyanophenyl) borate, and 2 to 5 parts of molybdenum disulfide nanosheets; the tris(4-cyanophenyl) borate is made from the following raw materials: trimethyl borate, p-hydroxybenzonitrile, and potassium carbonate; the modified polyetheretherketone microspheres use chitosan and γ-methacryloxypropyltrimethoxysilane as modifiers. The carbon fiber composite core made of the high-temperature resistant cyanate resin prepared by the present invention has excellent high-temperature resistance and aging resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer material preparation, and in particular to a high-temperature resistant cyanate resin for a carbon fiber composite core and a preparation method thereof. Background Art

[0002] Carbon fiber composite core conductors are a new type of conductor. Due to their low dielectric loss, they are particularly suitable for use in electromagnetically sensitive areas or extreme environments, such as near aircraft engine components and deep-sea exploration equipment. Once primarily used in aerospace equipment and space stations, they are now increasingly used as conductors for overhead power transmission lines. Carbon fiber composite core conductors consist of a single core rod made of a carbon fiber composite core coated with glass fiber as the core layer, and trapezoidal aluminum strands as the outer layer. Compared to traditional steel-core aluminum stranded conductors, carbon fiber composite core conductors offer reduced loads and significantly lower sag, making them suitable for capacity expansion and retrofit projects.

[0003] The technology behind carbon fiber composite core conductors currently faces the following technical challenges: First, the core resin in the conductors is susceptible to aging and even brittle fracture when operated at high temperatures for extended periods. Second, the carbon fiber composite cores' high-temperature resistance is suboptimal, with transient operating temperatures generally not exceeding 300°C. A search revealed prior art with publication number CN103819898A, which discloses a carbon fiber composite core capable of long-term operating temperatures exceeding 260°C and transient operating temperatures reaching 290°C, but exhibits poor aging resistance. Furthermore, prior art with publication number CN112151206A discloses a carbon fiber composite core conductor, which achieves high tensile strength but fails to address the issue of poor high-temperature resistance.

[0004] In summary, the existing carbon fiber composite core resin has the problems of easy aging and insufficient high temperature resistance. Summary of the Invention

[0005] In view of the above technical problems, the purpose of the present invention is to provide a high-temperature resistant cyanate ester resin for carbon fiber composite core and a preparation method thereof, so as to improve the high-temperature resistance and aging resistance of the resin for carbon fiber composite core.

[0006] To achieve the above objectives, the technical solutions adopted are as follows:

[0007] A high-temperature resistant cyanate resin for a carbon fiber composite core comprises raw materials including bisphenol A dicyanate, bisphenol E dicyanate, nano-aluminum nitride, modified polyetheretherketone microspheres, tris (4-cyanophenyl) borate, and molybdenum disulfide nanosheets.

[0008] The weight ratio of the above raw materials is: 45-60 parts of bisphenol A dicyanate, 25-35 parts of bisphenol E dicyanate, 4-8 parts of nano-aluminum nitride, 8-10 parts of modified polyetheretherketone microspheres, 5-10 parts of tris(4-cyanophenyl)borate, and 2-5 parts of molybdenum disulfide nanosheets.

[0009] A method for preparing a high-temperature resistant cyanate ester resin for a carbon fiber composite core comprises the steps of preparing modified polyetheretherketone microspheres, preparing tris(4-cyanophenyl)borate, and synthesizing the cyanate ester resin.

[0010] The modified polyetheretherketone microspheres are prepared from the following raw materials, calculated in parts by weight: 10-15 parts of polyetheretherketone microspheres, 0.5-1 part of γ-methacryloxypropyltrimethoxysilane, 2-5 parts of chitosan, 1-2 parts of glacial acetic acid, and 60-100 parts of deionized water.

[0011] Furthermore, the polyetheretherketone microspheres have a molecular weight distribution (PDI) of less than 2.0 and a particle size of 50 to 100 μm; the chitosan has a degree of deacetylation (DD) of 50 to 80% and a molecular weight distribution (PDI) of less than 1.5.

[0012] The modified polyetheretherketone microspheres are prepared by acid-washing the polyetheretherketone microspheres, adding the acid-washed polyetheretherketone microspheres, γ-methacryloxypropyltrimethoxysilane, and deionized water into a reactor, and stirring and reacting at 80-90° C. for 1-2 hours; after the reaction, cooling the temperature to 50-60° C., adding glacial acetic acid and chitosan into the reactor, and continuing to stir and react for 2-3 hours; after the reaction, filtering the materials in the reactor to retain the solids to obtain the modified polyetheretherketone microspheres.

[0013] Furthermore, the acid washing: using 3wt% H2SO4 solution, stirring and immersing the polyetheretherketone microspheres for 20-30 minutes.

[0014] The method for preparing tris(4-cyanophenyl)borate comprises the following steps: first, adding trimethyl borate and p-hydroxybenzonitrile to dimethyl sulfoxide for pre-reaction; then, adding potassium carbonate, heating to 140-160° C., and reacting for 12-18 hours to obtain a reaction solution; extracting the reaction solution to obtain an organic phase; and then subjecting the organic phase to atmospheric and reduced pressure distillation to obtain a solid, which is tris(4-cyanophenyl)borate.

[0015] The molar ratio of trimethyl borate, p-hydroxybenzonitrile and potassium carbonate is 1: (3.1-3.4): (2-3).

[0016] Furthermore, the pre-reaction temperature is 120-130° C., and the pre-reaction time is 6-8 h.

[0017] Furthermore, the dimethyl sulfoxide is used in an amount 20 to 25 times the volume of trimethyl borate.

[0018] Furthermore, the extraction is as follows: adding ice water at 0-5°C to the reaction solution, the amount of ice water being 100 times the volume of trimethyl borate, and stirring for 30 minutes; then adding dichloromethane, the amount of dichloromethane being 50 times the volume of trimethyl borate, stirring for 1 hour, standing to separate the layers, and retaining the lower organic phase.

[0019] Furthermore, the atmospheric distillation temperature is 60-65°C.

[0020] Furthermore, the reduced pressure distillation is carried out at a temperature of 35-40° C. and a pressure of less than -0.080 MPa.

[0021] The synthetic cyanate resin comprises, in parts by weight, 45-60 parts of bisphenol A dicyanate, 20-35 parts of bisphenol E dicyanate, 4-8 parts of nano-aluminum nitride, 8-10 parts of modified polyetheretherketone microspheres, 5-10 parts of tris(4-cyanophenyl)borate, and 2-5 parts of molybdenum disulfide nanosheets.

[0022] Furthermore, the nano-aluminum nitride has a particle size of 50-200 nm; the molybdenum disulfide nanosheet has a diameter of 2-10 μm and a thickness of 10-30 nm.

[0023] The method for synthesizing a cyanate ester resin involves first adding bisphenol A dicyanate and bisphenol E dicyanate to a reactor and heating to 90°C for 10-20 minutes. Then, nano-aluminum nitride, modified polyetheretherketone microspheres, tris(4-cyanophenyl)borate, and molybdenum disulfide nanosheets are added. A two-step temperature reaction is performed to obtain a high-temperature resistant cyanate ester resin.

[0024] Furthermore, the two-step temperature-raising reaction is as follows: first, the temperature is raised to 130°C at a rate of 7-10°C / min for the first step reaction, and the reaction time is 2-3 hours; then the temperature is raised to 170°C at a rate of 4-8°C / min for the second step reaction, and the reaction time is 3-4 hours.

[0025] The beneficial effects of the present invention are as follows:

[0026] (1) The carbon fiber composite core made of the high-temperature resistant cyanate ester resin prepared in the present invention has excellent high-temperature resistance, with a heat deformation temperature greater than 360°C and a glass transition temperature greater than 320°C.

[0027] (2) The carbon fiber composite core made of the high-temperature resistant cyanate ester resin prepared by the present invention has good mechanical properties, with a tensile strength of 2683~2711MPa and an interlaminar shear strength of 93~101MPa.

[0028] (3) After 1000h of xenon lamp aging treatment, the carbon fiber composite core made of high-temperature resistant cyanate resin prepared by the present invention has a tensile strength performance attenuation of less than 2% and a glass transition temperature attenuation of less than 3.5%, and has good aging resistance. DETAILED DESCRIPTION

[0029] To make the purpose, technical solutions and advantages of the present invention clearer, the embodiments of the present invention will be described in further detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention and are not intended to limit the present invention.

[0030] Example 1 A high temperature resistant cyanate resin for carbon fiber composite core

[0031] Step 1: Preparation of modified polyetheretherketone microspheres

[0032] The raw materials include, by weight, 12 parts of polyetheretherketone microspheres, 1 part of γ-methacryloxypropyltrimethoxysilane, 2.5 parts of chitosan, 1.5 parts of glacial acetic acid, and 70 parts of deionized water.

[0033] The polyetheretherketone (PEEK) microspheres were acid-washed with a 3wt% H2SO4 solution, stirred and soaked for 30 minutes, and then removed. The acid-washed PEEK microspheres, γ-methacryloxypropyltrimethoxysilane, and deionized water were placed in a reactor and stirred at 90°C for 1 hour. After the reaction, the temperature was lowered to 60°C, and glacial acetic acid and chitosan were added to the reactor, and the stirring reaction continued for 2 hours. After the reaction, the contents of the reactor were filtered to retain the solids, obtaining modified PEEK microspheres. The modified PEEK microspheres were washed with water and vacuum-dried at 60°C for 24 hours before use.

[0034] The polyetheretherketone microspheres used in this step have a molecular weight distribution (PDI) of <2.0 and a particle size of 50-100 μm; the chitosan has a degree of deacetylation (DD) of 50-80% and a molecular weight distribution (PDI) of <1.5.

[0035] Step 2: Preparation of tris(4-cyanophenyl)borate

[0036] The raw materials include trimethyl borate, p-hydroxybenzonitrile and potassium carbonate, wherein the molar ratio of trimethyl borate, p-hydroxybenzonitrile and potassium carbonate is 1:3.2:2.5.

[0037] Trimethyl borate and p-hydroxybenzonitrile were added to dimethyl sulfoxide (DMSO), nitrogen was introduced, and the mixture was stirred at 120°C for 8 hours. Potassium carbonate was then added, the temperature was raised to 160°C, and the reaction was continued with stirring for 12 hours to obtain a reaction solution. Ice water was added to the reaction solution and stirred for 30 minutes. Dichloromethane was then added to extract tris(4-cyanophenyl)borate. The mixture was stirred for 1 hour and allowed to stand until demixed. The lower organic phase was retained. The extraction process was repeated three times. The organic phase obtained from the extraction was distilled at 60°C under atmospheric pressure. After the atmospheric distillation was completed, the temperature was adjusted to 40°C and the pressure was <-0.080 MPa, and the organic phase was further distilled under reduced pressure. After the distillation was completed, tris(4-cyanophenyl)borate was obtained as a solid.

[0038] In this step, the amount of dimethyl sulfoxide used is 20 times the volume of trimethyl borate; the temperature range of the ice water used is 0~5°C, and the amount of ice water used is 100 times the volume of trimethyl borate; the amount of dichloromethane used is 50 times the volume of trimethyl borate.

[0039] Step 3: Synthesis of cyanate resin

[0040] The raw materials include, by weight, 45 parts of bisphenol A dicyanate, 35 parts of bisphenol E dicyanate, 8 parts of nano-aluminum nitride, 9 parts of modified polyetheretherketone microspheres, 7 parts of tris(4-cyanophenyl)borate, and 5 parts of molybdenum disulfide nanosheets.

[0041] Bisphenol A dicyanate and bisphenol E dicyanate were first added to a reactor, heated to 90°C, and stirred for 10 minutes. Nanoaluminum nitride, modified polyetheretherketone microspheres, tris(4-cyanophenyl)borate, and molybdenum disulfide nanosheets were then added to the reactor. The temperature was then raised to 130°C at a rate of 7°C / min, and the mixture was stirred for 2 hours. The temperature was then raised to 170°C at a rate of 8°C / min, and the mixture was stirred for 4 hours. The reaction was completed to yield a high-temperature cyanate ester resin.

[0042] The MoS2 nanosheets used in this step have a diameter of 2-10 μm and a thickness of 10-30 nm; the Aluminum Nitride nanosheets have a particle size of 50-200 nm.

[0043] Example 2 A high temperature resistant cyanate resin for carbon fiber composite core

[0044] Step 1: Preparation of modified polyetheretherketone microspheres

[0045] The raw materials include, by weight, 15 parts of polyetheretherketone microspheres, 1 part of γ-methacryloxypropyltrimethoxysilane, 5 parts of chitosan, 2 parts of glacial acetic acid, and 100 parts of deionized water.

[0046] The polyetheretherketone (PEEK) microspheres were acid-washed with a 3wt% H2SO4 solution, stirred and soaked for 30 minutes, and then removed. The acid-washed PEEK microspheres, γ-methacryloxypropyltrimethoxysilane, and deionized water were placed in a reactor and stirred at 90°C for 1 hour. After the reaction, the temperature was lowered to 50°C, and glacial acetic acid and chitosan were added to the reactor, and the stirring reaction continued for 3 hours. After the reaction, the contents of the reactor were filtered to retain the solids, obtaining modified PEEK microspheres. The modified PEEK microspheres were washed with water and vacuum-dried at 60°C for 24 hours before use.

[0047] The polyetheretherketone microspheres used in this step have a molecular weight distribution (PDI) of <2.0 and a particle size of 50-100 μm; the chitosan has a degree of deacetylation (DD) of 50-80% and a molecular weight distribution (PDI) of <1.5.

[0048] Step 2: Preparation of tris(4-cyanophenyl)borate

[0049] The raw materials include trimethyl borate, p-hydroxybenzonitrile and potassium carbonate, wherein the molar ratio of trimethyl borate, p-hydroxybenzonitrile and potassium carbonate is 1:3.4:3.

[0050] Trimethyl borate and p-hydroxybenzonitrile were added to dimethyl sulfoxide, nitrogen was introduced, and the mixture was stirred at 130°C for 6 hours. Potassium carbonate was then added, the temperature was raised to 140°C, and the reaction was continued with stirring for 18 hours to obtain a reaction solution. Ice water was added to the reaction solution and stirred for 30 minutes. Dichloromethane was then added to extract tris(4-cyanophenyl)borate. The mixture was stirred for 1 hour and allowed to stand until stratification occurred, retaining the lower organic phase. The extraction operation was repeated three times. The organic phase obtained by extraction was distilled at 65°C under atmospheric pressure. After the atmospheric distillation was completed, the temperature was adjusted to 40°C and the pressure was less than -0.080 MPa, and the organic phase was further distilled under reduced pressure. After the distillation was completed, tris(4-cyanophenyl)borate solid was obtained.

[0051] In this step, the amount of dimethyl sulfoxide used is 25 times the volume of trimethyl borate; the ice water temperature range used is 0~5°C, and the amount of ice water used is 100 times the volume of trimethyl borate; the amount of dichloromethane used is 50 times the volume of trimethyl borate.

[0052] Step 3: Synthesis of cyanate resin

[0053] The raw materials include, by weight, 60 parts of bisphenol A dicyanate, 20 parts of bisphenol E dicyanate, 4 parts of nano-aluminum nitride, 10 parts of modified polyetheretherketone microspheres, 10 parts of tris(4-cyanophenyl)borate, and 2 parts of molybdenum disulfide nanosheets.

[0054] Bisphenol A dicyanate and bisphenol E dicyanate were first added to a reactor, heated to 90°C, and stirred for 10 minutes. Nanoaluminum nitride, modified polyetheretherketone microspheres, tris(4-cyanophenyl)borate, and molybdenum disulfide nanosheets were then added to the reactor. The temperature was then raised to 130°C at a rate of 10°C / min and stirred for 3 hours. The reaction was then continued at a rate of 4°C / min to 170°C, stirred for 3 hours, and the reaction was completed to yield a high-temperature cyanate resin.

[0055] The MoS2 nanosheets used in this step have a diameter of 2-10 μm and a thickness of 10-30 nm; the Aluminum Nitride nanosheets have a particle size of 50-200 nm.

[0056] Example 3 A high temperature resistant cyanate resin for carbon fiber composite core

[0057] Step 1: Preparation of modified polyetheretherketone microspheres

[0058] The raw materials include, by weight, 10 parts of polyetheretherketone microspheres, 0.5 parts of γ-methacryloxypropyltrimethoxysilane, 2 parts of chitosan, 1 part of glacial acetic acid, and 60 parts of deionized water.

[0059] The polyetheretherketone (PEEK) microspheres were acid-washed with a 3wt% H2SO4 solution, stirred and soaked for 30 minutes, and then removed. The acid-washed PEEK microspheres, γ-methacryloxypropyltrimethoxysilane, and deionized water were placed in a reactor and stirred at 80°C for 2 hours. After the reaction, the temperature was lowered to 55°C, and glacial acetic acid and chitosan were added to the reactor, and the stirring reaction continued for another 2 hours. After the reaction, the contents of the reactor were filtered to retain the solids, yielding modified PEEK microspheres. The modified PEEK microspheres were then washed with water and vacuum-dried at 60°C for 24 hours before use.

[0060] The polyetheretherketone microspheres used in this step have a molecular weight distribution (PDI) of <2.0 and a particle size of 50-100 μm; the chitosan has a degree of deacetylation (DD) of 50-80% and a molecular weight distribution (PDI) of <1.5.

[0061] Step 2: Preparation of tris(4-cyanophenyl)borate

[0062] The raw materials include trimethyl borate, p-hydroxybenzonitrile, and potassium carbonate, wherein the molar ratio of trimethyl borate, p-hydroxybenzonitrile, and potassium carbonate is 1:3.1:2.

[0063] Trimethyl borate and p-hydroxybenzonitrile were added to dimethyl sulfoxide (DMSO), purged with nitrogen, and stirred at 125°C for 7 hours. Potassium carbonate was then added, the temperature was raised to 150°C, and the reaction was continued with stirring for 15 hours to obtain a reaction solution. Ice water was added to the reaction solution and stirred for 30 minutes. Dichloromethane was then added to extract tris(4-cyanophenyl)borate. The mixture was stirred for 1 hour and allowed to stand until demixed. The lower organic phase was retained. The extraction process was repeated three times. The organic phase obtained from the extraction was distilled at 65°C under atmospheric pressure. After the atmospheric distillation was completed, the temperature was adjusted to 35°C and the pressure was <-0.080 MPa, and the organic phase was further distilled under reduced pressure. After the distillation was completed, tris(4-cyanophenyl)borate was obtained as a solid.

[0064] In this step, the amount of dimethyl sulfoxide used is 20 times the volume of trimethyl borate; the temperature range of the ice water used is 0~5°C, and the amount of ice water used is 100 times the volume of trimethyl borate; the amount of dichloromethane used is 50 times the volume of trimethyl borate.

[0065] Step 3: Synthesis of cyanate resin

[0066] The raw materials include, by weight, 50 parts of bisphenol A dicyanate, 35 parts of bisphenol E dicyanate, 5 parts of nano-aluminum nitride, 8 parts of modified polyetheretherketone microspheres, 5 parts of tris(4-cyanophenyl)borate, and 3 parts of molybdenum disulfide nanosheets.

[0067] Bisphenol A dicyanate and bisphenol E dicyanate were first added to a reactor, heated to 90°C, and stirred for 20 minutes. Nanoaluminum nitride, modified polyetheretherketone microspheres, tris(4-cyanophenyl)borate, and molybdenum disulfide nanosheets were then added to the reactor. The temperature was then raised to 130°C at a rate of 9°C / min and stirred for 3 hours. The reaction was then continued at a rate of 6°C / min to 170°C, stirred for 3 hours, and the reaction was completed to yield a high-temperature cyanate resin.

[0068] The MoS2 nanosheets used in this step have a diameter of 2-10 μm and a thickness of 10-30 nm; the Aluminum Nitride nanosheets have a particle size of 50-200 nm.

[0069] Comparative Example 1: A cyanate resin for carbon fiber composite core

[0070] Step 1: Synthesis of cyanate resin

[0071] Calculated in parts by weight, the raw materials include: 50 parts of bisphenol A dicyanate, 35 parts of bisphenol E dicyanate, 6 parts of nano-aluminum nitride, and 3 parts of molybdenum disulfide nanosheets.

[0072] First, bisphenol A dicyanate and bisphenol E dicyanate were added to a reactor, heated to 90°C, and stirred for 10 minutes. Then, nano-aluminum nitride and molybdenum disulfide nanosheets were added to the reactor. The temperature was then raised to 130°C at a rate of 10°C / min, with stirring for 3 hours. The temperature was then raised to 170°C at a rate of 4°C / min, with stirring for 3 hours. The reaction was completed to yield a cyanate resin.

[0073] The molybdenum disulfide nanosheets used in this comparative example have a diameter of 2 to 10 μm and a thickness of 10 to 30 nm; the nano-aluminum nitride used has a particle size of 50 to 200 nm.

[0074] Example 4 Application of a high temperature resistant cyanate ester resin for carbon fiber composite core

[0075] Add trihydroxypropane glycidyl ether to the cyanate resin, with the mass ratio of the cyanate resin to the trihydroxypropane glycidyl ether being 50:9, and stir thoroughly to form a uniform adhesive solution.

[0076] The T700-24K carbon fiber bundle is immersed in the glue solution, and the carbon fiber bundle is pulled through a pultrusion machine for pultrusion. The pultrusion speed is controlled at 1m / min, and it is dried with hot air at 100°C for preliminary curing to obtain a prepreg.

[0077] The prepreg is laid up using an 8-layer layup design, with the inter-layer angle controlled at ±15°. After the layup is completed, it is transferred to an autoclave for curing to obtain a carbon fiber composite core.

[0078] Performance Test (I)

[0079] The resins prepared in Examples 1 to 3 and Comparative Example 1 were respectively used to prepare carbon fiber composite cores according to the method of Example 4, and performance tests were performed. The test results are shown in Table 1.

[0080] Performance testing method:

[0081] Tensile strength and elongation at break tests: The carbon fiber composite core was processed into a standard specimen with a length of 700 mm and a diameter of 10 mm. The specimen was placed in the test environment for 24 hours and tested according to the GB / T 29324-2024 standard.

[0082] Interlaminar shear strength test: The carbon fiber composite core was processed into a standard specimen with a length of 17 mm, a width of 15 mm, and a thickness of 4 mm. The specimen was placed in the test environment for 24 hours and tested according to the GB / T 1450.1-2005 standard.

[0083] Heat deformation temperature test: The carbon fiber composite core was processed into a standard specimen with a length of 127 mm, a width of 13 mm, and a thickness of 10 mm. The specimen was placed at 23±2°C and a relative humidity of 50±5% for 40 hours and tested using ASTM D648-21.

[0084] Glass transition temperature test: The carbon fiber composite core is processed into a standard specimen with a length of 60 mm, a width of 10 mm, and a thickness of 2 mm. The specimen is placed in the test environment for 24 hours and tested according to the GB / T 40396-2021 standard.

[0085] Table 1

[0086] The carbon fiber composite core made of the high-temperature resistant cyanate ester resin prepared by the present invention has an elongation at break of 3.2~3.5%, a tensile strength of 2683~2711MPa, an interlaminar shear strength of 93~101MPa, a heat deformation temperature greater than 360°C, and a glass transition temperature greater than 320°C, indicating that it has good mechanical properties and high-temperature resistance.

[0087] Performance Test (2)

[0088] The resins prepared in Examples 1 to 3 and Comparative Example 1 were respectively used to prepare carbon fiber composite cores according to the method of Example 4, and then subjected to light aging treatment.

[0089] The parameters of the xenon lamp aging chamber used for light aging treatment are: irradiation intensity: 0.65 W / m² @ 340nm, chamber temperature: 80℃±2℃, relative humidity: 70%±10%, irradiation time: 1000h.

[0090] After irradiation, the performance of the carbon fiber composite core was tested. The test results are shown in Table 2.

[0091] Table 2

[0092] The carbon fiber composite core made of the high-temperature resistant cyanate ester resin prepared by the present invention has a tensile strength performance of 2675~2702 MPa, which is attenuated by less than 2% compared with before aging treatment, and a glass transition temperature of 314~319°C, which is attenuated by less than 3.5% compared with before aging treatment, after being photoaged for 1000 hours.

[0093] From the above test results, it can be seen that the mechanical properties and glass transition temperature decay slightly after aging treatment, indicating that the carbon fiber composite core made of the high-temperature resistant cyanate ester resin prepared by the present invention has excellent high-temperature resistance and aging resistance.

[0094] Obviously, there are many specific implementation methods that can be changed under the concept of the present invention. It should be stated here that any changes made under the inventive concept of the present invention will fall within the scope of protection of the present invention.

Claims

1. A high temperature resistant cyanate ester resin for carbon fiber composite core, characterized by: Ingredients include: Bisphenol A dicyanate, bisphenol E dicyanate, nano-aluminum nitride, modified polyetheretherketone microspheres, tris(4-cyanophenyl)borate, molybdenum disulfide nanosheets; The weight ratio of the above raw materials is: 45-60 parts of bisphenol A dicyanate, 25-35 parts of bisphenol E dicyanate, 4-8 parts of nano-aluminum nitride, 8-10 parts of modified polyetheretherketone microspheres, 5-10 parts of tris(4-cyanophenyl)borate, and 2-5 parts of molybdenum disulfide nanosheets; The modified polyetheretherketone microspheres use chitosan and γ-methacryloxypropyltrimethoxysilane as modifiers. The preparation method of the modified polyetheretherketone microspheres comprises: acid-washing the polyetheretherketone microspheres, adding the acid-washed polyetheretherketone microspheres, γ-methacryloxypropyltrimethoxysilane, and deionized water into a reactor, and stirring and reacting at 80-90° C. for 1-2 hours; after the reaction, cooling the reactor to 50-60° C., adding glacial acetic acid and chitosan into the reactor, and continuing to stir and react for 2-3 hours; after the reaction, filtering the materials in the reactor to retain the solids to obtain the modified polyetheretherketone microspheres. The tris(4-cyanophenyl)borate is prepared from the following raw materials: trimethyl borate, p-hydroxybenzonitrile, and potassium carbonate. The preparation method of the tris(4-cyanophenyl)borate is as follows: first, trimethyl borate and p-hydroxybenzonitrile are added to dimethyl sulfoxide for pre-reaction, then potassium carbonate is added, and the temperature is raised to 140-160°C and reacted for 12-18 hours to obtain a reaction liquid; the reaction liquid is extracted to obtain an organic phase; and the organic phase is then subjected to atmospheric distillation and reduced pressure distillation to obtain a solid tris(4-cyanophenyl)borate.

2. The high temperature resistant cyanate ester resin for carbon fiber composite core according to claim 1, characterized in that: The modified polyetheretherketone microspheres are prepared from the following raw materials in parts by weight: 10-15 parts of polyetheretherketone microspheres, 0.5-1 part of γ-methacryloxypropyltrimethoxysilane, 2-5 parts of chitosan, 1-2 parts of glacial acetic acid, and 60-100 parts of deionized water.

3. The high temperature resistant cyanate ester resin for carbon fiber composite core according to claim 1, characterized in that: The molar ratio of the raw materials for preparing the tris(4-cyanophenyl)borate is trimethyl borate: p-hydroxybenzonitrile: potassium carbonate = 1: (3.1-3.4): (2-3).

4. The method for preparing a high-temperature resistant cyanate ester resin for a carbon fiber composite core according to claim 1, wherein: The method comprises the steps of preparing modified polyetheretherketone microspheres, preparing tris(4-cyanophenyl)borate and synthesizing cyanate resin.

5. The method for preparing a high-temperature resistant cyanate ester resin for a carbon fiber composite core according to claim 1, wherein: The pickling: use Solution, stir and soak the polyetheretherketone microspheres for 20~30min.

6. The method for preparing a high-temperature resistant cyanate ester resin for a carbon fiber composite core according to claim 1, wherein: The pre-reaction temperature is 120-130° C. and the pre-reaction time is 6-8 hours.

7. The method for preparing a high-temperature resistant cyanate ester resin for a carbon fiber composite core according to claim 4, characterized in that: The method for synthesizing a cyanate ester resin comprises the following steps: firstly, adding bisphenol A dicyanate and bisphenol E dicyanate into a reactor, heating to 90° C. and maintaining the temperature for 10 to 20 minutes; then adding nano-aluminum nitride, modified polyetheretherketone microspheres, tris(4-cyanophenyl)borate, and molybdenum disulfide nanosheets, and performing a two-step temperature-raising reaction to obtain a high-temperature-resistant cyanate ester resin.

8. The method for preparing a high-temperature resistant cyanate ester resin for a carbon fiber composite core according to claim 7, characterized in that: The two-step temperature-raising reaction is as follows: first, the temperature is raised to 130°C at a rate of 7-10°C / min for the first step reaction, and the reaction time is 2-3 hours; then the temperature is raised to 170°C at a rate of 4-8°C / min for the second step reaction, and the reaction time is 3-4 hours.

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