Radiation resistant composite resin insulating adhesive and preparation method thereof

Abstract

The present application relates to the technical field of insulating glue, more particularly to a kind of radiation-resistant composite resin insulating glue and preparation method thereof, and the radiation-resistant composite resin insulating glue includes the following components: modified polycyanate, modified graphene and curing agent;The amount of modified graphene is 0.5%~5% of the weight of modified polycyanate, and the amount of curing agent is 1%~10% of the weight of modified polycyanate.The present application modifies bisphenol A type cyanate ester chemically, modifies 4,4'-diamino diphenyl sulfone and p-hydroxy phenol acrylate monomer into bisphenol A type cyanate ester polymer, and the prepared modified polycyanate is used as a matrix to match modified graphene and curing agent, and after curing, the radiation-resistant composite resin insulating glue maintains excellent dielectric properties and bonding properties, improves the radiation resistance, toughness and insulation performance of the radiation-resistant composite resin insulating glue, and is conducive to biodegradation, and is an excellent environmentally friendly electronic material insulating glue.

Description

Technical Field

[0001] This invention relates to the field of insulating adhesive technology, and more specifically to a radiation-resistant composite resin insulating adhesive and its preparation method. Background Technology

[0002] Cyanate ester resins possess excellent dielectric, mechanical, and heat resistance properties, making them suitable for use in radiation-resistant adhesives for electronic materials. However, the structural characteristics of cyanate esters result in significant brittleness. Current technologies often employ epoxy resins, bismaleimide resins, and thermoplastic resins to improve their toughness and processability. While these methods can increase toughness to some extent, they also lead to increased dielectric properties, decreased radiation resistance, and poor biodegradability, which is detrimental to environmental protection. Summary of the Invention

[0003] To address the aforementioned problems, this invention provides a radiation-resistant composite resin insulating adhesive and its preparation method. The prepared radiation-resistant composite resin insulating adhesive maintains excellent dielectric and adhesive properties, improves the radiation resistance, toughness, and insulation properties of the composite resin insulating adhesive, and is also beneficial for biodegradation.

[0004] The present invention is specifically implemented through the following technical solutions.

[0005] A radiation-resistant composite resin insulating adhesive, comprising the following components: modified polycyanate, modified graphene, and a curing agent; wherein the amount of modified graphene is 0.5% to 5% of the weight of the modified polycyanate, and the amount of the curing agent is 1% to 10% of the weight of the modified polycyanate.

[0006] The preparation method of the modified polycyanate includes the following steps:

[0007] Modified polycyanate was prepared by polymerization reaction at 80℃~120℃ using tetrahydrofuran as solvent and bisphenol A cyanate, 4,4'-diaminodiphenyl sulfone and p-hydroxyphenol acrylate as raw materials under an inert gas atmosphere.

[0008] The chemical structure of p-hydroxyphenol acrylate is shown in Formula II:

[0009]

[0010] II.

[0011] The method for preparing the modified graphene includes the following steps:

[0012] Ce 3+ An intermediate product was prepared from graphene under hydrothermal conditions at 115-125°C. The intermediate product was then impregnated in an octacyclic polyhedral oligomeric silsesquioxane solution to prepare the modified graphene.

[0013] More specifically, it includes the following steps:

[0014] (1) Graphene is ultrasonically dispersed in deionized water, and cerium chloride or its hydrate is added to obtain the first reaction solution. The weight ratio of graphene to cerium chloride is 1:1.5~2.5.

[0015] (2) After the first reaction liquid is hydrothermally heated at 115~125℃ for 8~15 hours under magnetic stirring, it is vacuum filtered, washed with deionized water until neutral, the liquid phase is removed, the solid phase is collected and dried in an anaerobic environment to obtain the intermediate product; the purpose of drying in an anaerobic environment is to prevent oxidation.

[0016] (3) The intermediate product is ultrasonically dispersed in a 1.5%~3% mass concentration octacyclic polyhedral oligomeric silsesquioxane solution and ultrasonically impregnated for 20s~60s. The solvent of the octacyclic polyhedral oligomeric silsesquioxane solution is acetone.

[0017] (4) Separate the solid phase material and dry it in an oxygen-free environment (this is to prevent oxidation) to obtain modified graphene.

[0018] The aforementioned radiation-resistant composite resin insulating adhesive is prepared by chemically modifying bisphenol A cyanate by incorporating 4,4'-diaminodiphenyl sulfone and p-hydroxyphenol acrylate monomers into the bisphenol A cyanate polymer. The modified polycyanate is then used as a matrix, combined with modified graphene, and cured with a curing agent. The modified graphene enhances the insulating properties of the adhesive. The radiation-resistant composite resin insulating adhesive maintains excellent dielectric and adhesive properties, improves its radiation resistance, toughness, and insulation properties, and is also biodegradable, making it an excellent environmentally friendly electronic material insulating adhesive.

[0019] In a preferred embodiment of the present invention, the method for preparing the modified polycyanate includes the following steps:

[0020] S1. Under an inert gas atmosphere, dissolve bisphenol A cyanate in tetrahydrofuran solvent.

[0021] S2. Under an inert gas atmosphere, a mixed solution of 4,4'-diaminodiphenyl sulfone and p-hydroxyphenol acrylate is added dropwise over 20-40 minutes while maintaining stirring. Tetrahydrofuran is used as the solvent for the mixed solution. The chemical structure of p-hydroxyphenol acrylate is shown in Formula II.

[0022]

[0023] II.

[0024] S3. Under an inert gas atmosphere, the polymerization reaction is carried out at 80~120℃ for 2~4 hours, and the solvent is removed by vacuum evaporation below 75℃ to obtain modified polycyanate.

[0025] In a preferred embodiment of the present invention, the p-hydroxyphenol acrylate is prepared by an esterification reaction of p-hydroxybenzyl alcohol and acrylic acid, and the preparation method includes the following steps:

[0026] p-Hydroxybenzyl alcohol was dissolved in methanol, concentrated sulfuric acid was added, and acrylic acid was added and heated to induce an esterification reaction. After extraction with dichloromethane, unreacted hydroxybenzyl alcohol, methanol, and acrylic acid were removed by vacuum evaporation. The reaction byproduct methyl acrylate yielded p-hydroxyphenol acrylate.

[0027] In a preferred embodiment of the present invention, the weight ratio of bisphenol A cyanate, 4,4'-diaminodiphenyl sulfone, and p-hydroxyphenol acrylate is 18~71:70~165:50~100.

[0028] In a preferred embodiment of the present invention, the weight ratio of bisphenol A cyanate, 4,4'-diaminodiphenyl sulfone, and p-hydroxyphenol acrylate is 25~50:80~120:60~90.

[0029] In a preferred embodiment of the present invention, the curing agent is N,N-diethyl-p-toluidine.

[0030] In a preferred embodiment of the present invention, the amount of modified graphene is 1.5% to 4% of the weight of the modified polycyanate, and the amount of curing agent is 3% to 8% of the weight of the modified polycyanate.

[0031] In a preferred embodiment of the present invention, the method for preparing the radiation-resistant composite resin insulating adhesive is as follows: modified graphene is ultrasonically and uniformly dispersed in modified polycyanate, a curing agent is added and mixed, and then the mixture is vacuum degassed at 95~105℃ for 50~90 minutes, and then heated to 160~180℃ for 1.5~3 hours for curing.

[0032] This invention also provides a method for preparing any of the above-described radiation-resistant composite resin insulating adhesives, comprising the following steps:

[0033] Preparation of modified graphene:

[0034] (1) Graphene of no more than 3 mm is ultrasonically dispersed in deionized water, and cerium chloride or its hydrate is added to obtain the first reaction solution. The weight ratio of graphene to cerium chloride is 1:1.5~2.5.

[0035] (2) After the first reaction liquid is hydrothermally heated at 115~125℃ for 8~15 hours under magnetic stirring, it is vacuum filtered, washed with deionized water until neutral, the liquid phase is removed, the solid phase is collected and dried in an oxygen-free environment to obtain the intermediate product.

[0036] (3) The intermediate product is ultrasonically dispersed in a 1.5%~3% mass concentration octacyclic polyhedral oligomeric silsesquioxane solution and ultrasonically impregnated for 20s~60s. The solvent of the octacyclic polyhedral oligomeric silsesquioxane solution is acetone.

[0037] (4) The solid phase material was separated and dried in an oxygen-free environment to obtain modified graphene.

[0038] Preparation of modified polycyanate:

[0039] S1. Under an inert gas atmosphere, dissolve bisphenol A cyanate in tetrahydrofuran solvent.

[0040] S2. Under an inert gas atmosphere, a mixed solution of 4,4'-diaminodiphenyl sulfone and p-hydroxyphenol acrylate is added dropwise over 20-40 minutes while maintaining stirring. Tetrahydrofuran is used as the solvent for the mixed solution. The chemical structure of p-hydroxyphenol acrylate is shown in Formula II.

[0041]

[0042] II.

[0043] S3. Under an inert gas atmosphere, the polymerization reaction is carried out at 80~120℃ for 2~4 hours, and the solvent is removed by vacuum evaporation below 75℃ to obtain modified polycyanate.

[0044] Modified graphene was ultrasonically and uniformly dispersed in modified polycyanate. After adding curing agent and mixing, the mixture was vacuum degassed at 95~105℃ for 50~90 minutes and then cured at 160~180℃.

[0045] For those skilled in the art, it is clear that there is no logical order required for the preparation of modified polycyanate and the preparation of modified graphene.

[0046] In a preferred embodiment of the present invention, in the preparation of modified polycyanate, the weight ratio of bisphenol A cyanate, 4,4'-diaminodiphenyl sulfone and p-hydroxyphenol acrylate is 18~71:70~165:50~100.

[0047] Compared with the prior art, the present invention has the following beneficial effects:

[0048] The radiation-resistant composite resin insulating adhesive of this invention comprises modified polycyanate, modified graphene, and a curing agent. Modified polycyanate is prepared by modifying and incorporating 4,4'-diaminodiphenyl sulfone and p-hydroxyphenol acrylate monomers into a bisphenol A type cyanate polymer. Using the modified polycyanate as a matrix, after filling the matrix with modified graphene and adding a curing agent for curing, the composite resin insulating adhesive maintains excellent dielectric and adhesive properties, improves its radiation resistance, toughness, and insulation properties, and is biodegradable, making it an excellent environmentally friendly electronic material insulating adhesive. Detailed Implementation

[0049] The technical solutions of the present invention will be clearly and completely described below with reference to the data in the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0050] Unless otherwise specified, the experimental methods described in the various embodiments of this invention are all conventional methods.

[0051] The present invention first provides a radiation-resistant composite resin insulating adhesive, which is formed by curing modified polycyanate, modified graphene and curing agent, wherein the amount of modified graphene is 0.5% to 5% of the weight of modified polycyanate, and the amount of curing agent is 1% to 10% of the weight of modified polycyanate.

[0052] The preparation method of the modified polycyanate includes the following steps:

[0053] Modified polycyanate was prepared by polymerization reaction at 80℃~120℃ using tetrahydrofuran as solvent and bisphenol A cyanate, 4,4'-diaminodiphenyl sulfone and p-hydroxyphenol acrylate as raw materials under an inert gas atmosphere.

[0054] The chemical structure of p-hydroxyphenol acrylate is shown in Formula II:

[0055]

[0056] II.

[0057] The chemical structure of the modified polycyanate obtained by the above preparation method is shown in Formula I:

[0058] Ⅰ

[0059] Where a, b, and c are natural numbers, 10 ≤ a ≤ 40, 25 ≤ b ≤ 60, and 20 ≤ c ≤ 40. The values ​​of a, b, and c in the modified polycyanate formula I are controlled by the weight ratio of bisphenol A cyanate, 4,4'-diaminodiphenyl sulfone, and p-hydroxyphenol acrylate. Modified polycyanate with a weight ratio of 18~71:70~165:50~100 yields a radiation-resistant composite resin insulating adhesive with superior overall performance. It should be noted that during the polymerization reaction, the degree of reaction varies among each molecular chain, and the product is composed of molecular chains of different lengths. Therefore, after one reaction, the values ​​of a, b, and c in the obtained product are range values. That is, the modified polycyanate with the structure shown in Formula I can be obtained through the method described above in this invention.

[0060] The method for preparing the modified graphene includes the following steps:

[0061] Ce 3+ An intermediate product was prepared from graphene under hydrothermal conditions at 115-125°C. The intermediate product was then impregnated in an octacyclic polyhedral oligomeric silsesquioxane solution to prepare the modified graphene.

[0062] The aforementioned radiation-resistant composite resin insulating adhesive is prepared by chemically modifying bisphenol A cyanate by incorporating 4,4'-diaminodiphenyl sulfone and p-hydroxyphenol acrylate monomers into the bisphenol A cyanate polymer. The modified polycyanate is then used as a matrix, combined with modified graphene, and cured with a curing agent. The radiation-resistant composite resin insulating adhesive maintains excellent dielectric and adhesive properties, improves radiation resistance, toughness, and insulation properties, and is also biodegradable, making it an excellent environmentally friendly electronic material insulating adhesive.

[0063] In a preferred embodiment of the present invention, the method for preparing the modified polycyanate includes the following steps:

[0064] S1. Under an inert gas atmosphere, dissolve bisphenol A cyanate in tetrahydrofuran solvent.

[0065] S2. Under an inert gas atmosphere, a mixed solution of 4,4'-diaminodiphenyl sulfone and p-hydroxyphenol acrylate is added dropwise over 20-40 minutes while maintaining stirring. Tetrahydrofuran is used as the solvent for the mixed solution. The chemical structure of p-hydroxyphenol acrylate is shown in Formula II.

[0066]

[0067] II.

[0068] S3. Under an inert gas atmosphere, the polymerization reaction is carried out at 80~120℃ for 2~4 hours, and the solvent is removed by vacuum evaporation below 75℃ to obtain modified polycyanate.

[0069] It should be noted that the above method modifies bisphenol A cyanate polymers by incorporating 4,4'-diaminodiphenyl sulfone and p-hydroxyphenol acrylate monomers to prepare modified polycyanate. This invention also provides a method for modifying polycyanate using only 4,4'-diaminodiphenyl sulfone or p-hydroxyphenol acrylate monomers, with the prepared products used as a comparison. Specifically:

[0070] When only 4,4'-diaminodiphenyl sulfone is used, the product prepared is shown in Formula III:

[0071] III.

[0072] When modified with only p-hydroxyphenol acrylate, the product prepared is shown in Formula IV:

[0073]

[0074] IV.

[0075] In a preferred embodiment of the present invention, the method for preparing the modified graphene includes the following steps:

[0076] (1) Graphene of no more than 3 mm is ultrasonically dispersed in deionized water, and cerium chloride or its hydrate is added to obtain the first reaction solution. The weight ratio of graphene to cerium chloride is 1:1.5~2.5.

[0077] (2) After the first reaction liquid is hydrothermally heated at 115~125℃ for 8~15 hours under magnetic stirring, it is vacuum filtered, washed with deionized water until neutral, the liquid phase is removed, the solid phase is collected and dried in an oxygen-free environment to obtain the intermediate product.

[0078] (3) The intermediate product is ultrasonically dispersed in a 1.5%~3% mass concentration octacyclic polyhedral oligomeric silsesquioxane solution and ultrasonically impregnated for 20~60s. The solvent of the octacyclic polyhedral oligomeric silsesquioxane solution is acetone.

[0079] (4) The solid phase material was separated and dried in an oxygen-free environment to obtain modified graphene.

[0080] The present invention also provides a method for preparing the radiation-resistant composite resin insulating adhesive, comprising the following steps:

[0081] Modified graphene was ultrasonically and uniformly dispersed in modified polycyanate. After adding curing agent and mixing, the mixture was vacuum degassed at 95~105℃ for 50~90 minutes and then cured at 160~180℃.

[0082] The invention will now be described in detail through the following embodiments and comparative examples.

[0083] The sources of raw materials in the following examples and comparative examples are:

[0084] Bisphenol A cyanate was purchased from Shandong Xiya Chemical Co., Ltd., and 4,4'-diaminodiphenyl sulfone, p-hydroxybenzyl alcohol, acrylic acid, and N,N-diethyl-p-toluidine were purchased from Aladdin. p-Hydroxyphenol acrylate was prepared by esterification of 4,4'-diaminodiphenyl sulfone and p-hydroxybenzyl alcohol.

[0085] Example 1

[0086] An embodiment of the present invention provides a radiation-resistant composite resin insulating adhesive comprising the following components: modified polycyanate, modified graphene, and a curing agent; the amount of modified graphene is 3% of the weight of the modified polycyanate, the amount of the curing agent is 5% of the weight of the modified polycyanate, and the curing agent is N,N-diethyl-p-toluidine.

[0087] The method for preparing the modified graphene includes the following steps:

[0088] (1) Graphene was ultrasonically dispersed in deionized water for 5 minutes, with a weight ratio of graphene to deionized water of 10:100; cerium chloride hexahydrate was added to obtain the first reaction solution, with a weight ratio of graphene to cerium chloride of 1:2.

[0089] (2) After the first reaction liquid was hydrothermally heated at 120°C for 10 hours under magnetic stirring, it was vacuum filtered, washed with deionized water until neutral, the liquid phase was removed, the solid phase was collected and dried in an oxygen-free environment to obtain the intermediate product.

[0090] (3) Disperse 2g of intermediate product in 20mL of 2% (w / w) octacyclic polyhedral oligomeric silsesquioxane (POSS) solution and ultrasonically impregnate for 45s. The solvent of the octacyclic polyhedral oligomeric silsesquioxane solution is acetone.

[0091] (4) The solid phase material was separated and dried in an oxygen-free environment to obtain modified graphene.

[0092] The method for preparing the modified polycyanate shown in Formula I above includes the following steps:

[0093] S1. Under a nitrogen atmosphere, bisphenol A cyanate is dissolved in tetrahydrofuran solvent; the mass concentration is 15%.

[0094] S2. Under a nitrogen atmosphere, a mixed solution of 4,4'-diaminodiphenyl sulfone and p-hydroxyphenol acrylate is added dropwise over 30 minutes while maintaining stirring. Tetrahydrofuran is used as the solvent for the mixed solution. The mass concentration of 4,4'-diaminodiphenyl sulfone and p-hydroxyphenol acrylate in the mixed solution is 10%. The chemical structure of p-hydroxyphenol acrylate is shown in Formula II. The weight ratio of bisphenol A cyanate, 4,4'-diaminodiphenyl sulfone, and p-hydroxyphenol acrylate is 30:120:75.

[0095]

[0096] II.

[0097] Under a nitrogen atmosphere, the polymerization reaction was carried out at 100°C for 3 hours, followed by vacuum evaporation at a temperature below 75°C to remove the solvent and obtain modified polycyanate.

[0098] p-Hydroxyphenol acrylate is prepared by esterification reaction of p-hydroxybenzyl alcohol and acrylic acid. p-Hydroxybenzyl alcohol is dissolved in methanol with a mass concentration of 60%. After adding concentrated sulfuric acid, acrylic acid is added and heated to 80°C with stirring to carry out esterification reaction for 1 hour. p-Hydroxybenzyl alcohol and acrylic acid are fed in a molar ratio of 1:1.1. After extraction with dichloromethane, the extract phase is removed. The residue is evaporated under vacuum at 50°C. After two steps of extraction and vacuum evaporation, unreacted hydroxybenzyl alcohol, methanol, and acrylic acid are removed. The reaction byproduct methyl acrylate is obtained as p-hydroxyphenol acrylate.

[0099] The preparation method of the radiation-resistant composite resin insulating adhesive is as follows: modified graphene is ultrasonically and uniformly dispersed in modified polycyanate, N,N-diethyl-p-toluidine curing agent is added and mixed, and then vacuum degassed at 100℃ for 60 minutes and heated to 160℃ for 2 hours for curing.

[0100] Example 2

[0101] As an example of a radiation-resistant composite resin insulating adhesive of the present invention, the only difference between this embodiment and Example 1 is that the weight ratio of bisphenol A cyanate, 4,4'-diaminodiphenyl sulfone and p-hydroxyphenol acrylate is 20:120:75.

[0102] Example 3

[0103] As an example of a radiation-resistant composite resin insulating adhesive of the present invention, the only difference between this embodiment and Example 1 is that the weight ratio of bisphenol A cyanate, 4,4'-diaminodiphenyl sulfone and p-hydroxyphenol acrylate is 30:120:50.

[0104] Example 4

[0105] As an example of a radiation-resistant composite resin insulating adhesive of the present invention, the only difference between this embodiment and Example 1 is that the weight ratio of bisphenol A cyanate, 4,4'-diaminodiphenyl sulfone and p-hydroxyphenol acrylate is 35:120:85.

[0106] Example 5

[0107] As an embodiment of the present invention, the only difference between this embodiment and Embodiment 1 is that the amount of modified graphene used is 1.5% of the weight of the modified polycyanate.

[0108] Example 6

[0109] As an embodiment of the present invention, the only difference between this embodiment and embodiment 1 is that the amount of modified graphene is 4% of the weight of the modified polycyanate.

[0110] Comparative Example 1

[0111] As a comparative example of the present invention, this radiation-resistant composite resin insulating adhesive differs from Example 1 only in that the modified polycyanate in Example 1 is replaced with the modified polycyanate of the structure shown in Formula III above.

[0112] The preparation method of the modified polycyanate with the structure shown in Formula III is the same as in Example 1, except that p-hydroxyphenol acrylate is not added, and the amount of 4,4'-diaminodiphenyl sulfone is increased accordingly to make up the difference.

[0113] Comparative Example 2

[0114] As a comparative example of the present invention, this radiation-resistant composite resin insulating adhesive differs from Example 1 only in that the modified polycyanate in Example 1 is replaced with the modified polycyanate of the structure shown in Formula IV above.

[0115] The preparation method of the modified polycyanate with the structure shown in Formula IV is the same as in Example 1, except that 4,4'-diaminodiphenyl sulfone is not added, and the amount of p-hydroxyphenol acrylate is increased to make up the difference.

[0116] Comparative Example 3

[0117] As a comparative example of the present invention, this radiation-resistant composite resin insulating adhesive differs from Example 1 only in that graphene is used instead of the modified graphene in Example 1.

[0118] According to Examples 1-6 and Comparative Examples 1-3, and based on the sample specification requirements of the test methods, radiation-resistant composite resin insulating adhesive samples were cured in molds to obtain test samples. Specific test items and methods are as follows:

[0119] 1. Shear strength test

[0120] Shear strength: The shear strength of a standard sheet made of a uniformly mixed sealant is tested according to ASTM D1002.

[0121] 2. Radiation resistance

[0122] After curing the sheet according to the ASTM D1002 test strip, the laser power density is 3.54 kW / cm² at 1000 W. 2 The laser irradiates the central region of the gauge length of the sample, and after irradiation for 60 seconds, the shear strength is tested according to method 1 above.

[0123] 3. Insulation performance

[0124] The volume resistivity of the composite material was tested using a three-electrode system consisting of a Keithley 6517B picoammeter and a high-voltage DC power supply. The sample thickness was 150 μm and the sample area was 2500 mm². 2 (50×50). The experimental apparatus specifications are as follows: DC high-voltage power supply, 0-10 kV; ammeter, 10-4-10-14 A; electric heating oven, 0-100℃; high-voltage electrode, main electrode, and grounding electrode are cylindrical, with a diameter of 50 mm for the high-voltage electrode, 25 mm for the main electrode, and 5 mm for the grounding electrode. The sample size is 50×50 mm, and an aluminum electrode layer is vacuum-plated onto the surface according to the three electrode dimensions. Before testing, the oven is set to the corresponding test temperature and kept at that temperature for two hours.

[0125] The experimental results are shown in Table 1.

[0126] Table 1. Shear strength, radiation resistance, and insulation properties of radiation-resistant composite resin insulating adhesives

[0127]

[0128] As shown in Table 1, the above-mentioned radiation-resistant composite resin insulating adhesive, through chemical modification of bisphenol A cyanate, by incorporating 4,4'-diaminodiphenyl sulfone and p-hydroxyphenol acrylate monomers into the bisphenol A cyanate polymer, and using the prepared modified polycyanate as a matrix, combined with modified graphene and cured with a curing agent, maintains excellent bonding properties and improves the radiation resistance, toughness and insulation properties of the radiation-resistant composite resin insulating adhesive.

[0129] The following analysis was conducted: In Comparative Example 1, the difference from Example 1 was that p-hydroxyphenol acrylate was not added during the preparation of the modified polycyanate. As can be seen from the data in Table 1, the shear strength and volume resistivity of the sample prepared in Comparative Example 1 were significantly reduced. This indicates that the introduction of p-hydroxyphenol acrylate monomer is necessary and can improve the radiation resistance, toughness and insulation performance of the sample.

[0130] In Comparative Example 2, the difference from Example 1 is that 4,4'-diaminodiphenyl sulfone was not added during the preparation of the modified polycyanate. The shear strength and volume resistivity of the sample prepared in Comparative Example 2 were significantly reduced, which indicates that the introduction of 4,4'-diaminodiphenyl sulfone monomer is necessary and can improve the radiation resistance, toughness and insulation properties of the sample.

[0131] The difference between Comparative Example 3 and Example 1 is that graphene was used in Comparative Example 3. The shear strength and volume resistivity of the sample prepared in Comparative Example 3 were significantly reduced, indicating that modifying graphene can improve the radiation resistance, toughness, and insulation properties of the sample.

[0132] 4. Dielectric properties

[0133] Using a precision impedance analyzer (Agilent 4294A) at 25°C, at 10 4 -10 7 Dielectric properties were measured within a frequency range of Hz. The experimental results are shown in Table 2.

[0134] 5. Biodegradability test

[0135] Radiation-resistant composite resin insulating sheets were buried in soil for biodegradation. The biodegradation experiment was conducted in incubators with relative humidity of 60% in the air and 80% in the soil. The biodegradation temperature was maintained at 25–30°C. All radiation-resistant composite resin insulating sheet samples were buried 0.1 m deep in the soil. After 60 days, the samples were retrieved, cleaned, and dried in a vacuum drying oven at 50°C for 5 hours. The biodegradation rate of the film was calculated using the formula: (W1-W2) / W1×100%, where W1 and W2 are the weights of the radiation-resistant composite resin insulating sheets before and after the soil biodegradation experiment, respectively. The experimental results are shown in Table 2.

[0136] Table 2 Dielectric properties and biodegradability of radiation-resistant composite resin insulating adhesive

[0137]

[0138] As shown in Table 2, the above-mentioned radiation-resistant composite resin insulating adhesive, through chemical modification of bisphenol A cyanate, by incorporating 4,4'-diaminodiphenyl sulfone and p-hydroxyphenol acrylate monomers into the bisphenol A cyanate polymer, and using the prepared modified polycyanate as a matrix, combined with modified graphene and cured with a curing agent, maintains excellent adhesion and dielectric properties, while reducing the dielectric constant. Simultaneously, it improves the biodegradability of the radiation-resistant composite resin insulating adhesive, making it more environmentally friendly.

[0139] Detailed analysis:

[0140] In Comparative Example 1, the difference from Example 1 is that p-hydroxyphenol acrylate is not added during the preparation of the modified polycyanate. The dielectric constant of the sample prepared in Comparative Example 1 is increased and the biodegradability is reduced.

[0141] In Comparative Example 2, the difference from Example 1 is that 4,4'-diaminodiphenyl sulfone was not added during the preparation of the modified polycyanate. The dielectric constant of the sample prepared in Comparative Example 2 increased and the biodegradability decreased.

[0142] The difference between Comparative Example 3 and Example 1 is that graphene was used in Comparative Example 3. The shear strength and volume resistivity of the sample prepared in Comparative Example 3 were significantly reduced, indicating that modifying graphene can improve the radiation resistance, toughness, and insulation properties of the sample.

[0143] Although preferred embodiments of the invention have been described, those skilled in the art, upon learning the basic inventive concept, can make other changes and modifications to these embodiments. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments as well as all changes and modifications falling within the scope of the invention.

[0144] Obviously, those skilled in the art can make various modifications and variations to this invention without departing from its spirit and scope. Therefore, if these modifications and variations fall within the scope of the claims of this invention and their equivalents, this invention also intends to include these modifications and variations.

Claims

1. A radiation resistant composite resinous insulating compound, characterized by, The modified polycyanate is cured by a curing agent and modified graphene, wherein the amount of the modified graphene is 0.5-5% of the weight of the modified polycyanate, and the amount of the curing agent is 1-10% of the weight of the modified polycyanate. The preparation method of the modified polycyanate comprises the following steps: The modified polycyanate is prepared by polymerization reaction under an inert gas atmosphere, using tetrahydrofuran as a solvent, and using bisphenol A cyanate, 4,4'-diamino diphenyl sulfone and p-hydroxy phenol acrylate as raw materials at 80-120℃. The chemical structure of the p-hydroxy phenol acrylate is shown in Formula II: Ⅱ； The preparation method of the modified graphene comprises the following steps: Ce 3+ and graphene under hydrothermal conditions at 115 °C to 125 °C; and the intermediate product is immersed in an octa-epoxy polyhedral oligomeric silsesquioxane solution to prepare the modified graphene.

2. The radiation resistant resinous insulating compound of claim 1, wherein The Ce 3+ derived from cerium chloride or its hydrate, the weight ratio of graphene to cerium chloride is 1:1.5~2.

5.

3. The radiation resistant resinous insulating compound of claim 1, wherein The solution of octa-epoxy polyhedral oligomeric silsesquioxane has a solvent of acetone and a mass concentration of 1.5-3%, and is ultrasonically immersed for 20-60s.

4. The radiation resistant resinous insulating compound of claim 1, wherein, The weight ratio of the bisphenol A cyanate, 4,4'-diamino diphenyl sulfone and p-hydroxy phenol acrylate is 18-71:70-165:50-100.

5. The radiation resistant combined resinous insulation of claim 4, wherein, The weight ratio of the bisphenol A cyanate, 4,4'-diamino diphenyl sulfone and p-hydroxy phenol acrylate is 25-50:80-120:60-90.

6. The radiation resistant resinous insulating compound of claim 1, wherein, The amount of the modified graphene is 1.5-4% of the weight of the modified polycyanate, and the amount of the curing agent is 3-8% of the weight of the modified polycyanate.

7. The radiation resistant resinous insulating compound of claim 1, wherein, The curing agent is N,N-diethyl-p-toluidine.

8. The method for preparing the radiation-resistant composite resin insulating adhesive according to claim 1, characterized in that, The preparation method of the modified polycyanate comprises the following steps: Ce 3+ and graphene under hydrothermal conditions at 115℃-125℃ to prepare an intermediate product; the intermediate product is immersed in an octa-epoxy polyhedral oligomeric silsesquioxane solution to prepare modified graphene; The modified graphene is uniformly dispersed in the modified polycyanate, the curing agent is added and uniformly mixed, degassing treatment is performed, and then curing is performed at 160-180℃ to obtain the radiation-resistant composite resin insulating adhesive; The preparation method of the modified polycyanate comprises the following steps: The modified polycyanate is prepared by polymerization reaction under an inert gas atmosphere, using tetrahydrofuran as a solvent, and using bisphenol A cyanate, 4,4'-diamino diphenyl sulfone and p-hydroxy phenol acrylate as raw materials at 80-120℃. The chemical structure of the p-hydroxy phenol acrylate is shown in Formula II: Ⅱ； The amount of the modified graphene is 0.5-5% of the weight of the modified polycyanate, and the amount of the curing agent is 1-10% of the weight of the modified polycyanate.

9. The production method according to claim 8, characterized by, Vacuum degassing is performed at 95-105℃ for 50-90min.

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