Radiation resistant composite epoxy film and method of making same

Abstract

The present application belongs to the technical field of composite materials, and particularly relates to a kind of radiation resistant composite epoxy resin film and its preparation method, which is composed of modified epoxy resin matrix, carbon fiber, modified nano-silica and curing agent.The mass ratio of carbon fiber in the radiation resistant composite epoxy resin film is 0.5%~5%, the mass ratio of modified nano-silica in the radiation resistant composite epoxy resin film is 1%~8%, and the mass ratio of curing agent to modified epoxy resin matrix is 5~8:10.The present application improves the dielectric properties and mechanical properties of the radiation resistant composite epoxy resin film by double modification of bisphenol A epoxy resin matrix and the addition of carbon fiber and modified nano-silica filler, and improves the radiation resistance of the material.After high-intensity irradiation, the performance of the composite epoxy resin film before irradiation can be basically maintained.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of composite materials, and particularly relates to a radiation-resistant composite epoxy resin film and a preparation method thereof. BACKGROUND

[0002] Epoxy resin is widely used in various fields such as electronics, electrical engineering and aerospace as a composite material matrix in the form of structural parts or functional parts, and has good heat resistance, moisture resistance, impact resistance, bonding performance and interface performance. However, the insulation and mechanical properties of the epoxy resin matrix composite material decrease after being irradiated, thereby affecting the application of the epoxy resin composite material. SUMMARY

[0003] In order to solve the above technical problems, the present application provides a radiation-resistant composite epoxy resin film and a preparation method thereof. The bisphenol A epoxy resin matrix is modified twice, and carbon fibers and modified nano-silica fillers are added. After high-intensity irradiation, the performance before irradiation can be basically maintained.

[0004] The present application is realized by the following technical solutions.

[0005] A radiation-resistant composite epoxy resin film is formed by a modified epoxy resin matrix, carbon fibers, modified nano-silica and a curing agent. The mass ratio of the carbon fibers in the radiation-resistant composite epoxy resin film is 0.5% to 5%, the mass ratio of the modified nano-silica in the radiation-resistant composite epoxy resin film is 1% to 8%, the balance is the curing agent and the modified epoxy resin matrix, and the mass ratio of the curing agent to the modified epoxy resin matrix is 5 to 8:10, and the total is 100%.

[0006] The preparation method of the modified epoxy resin matrix comprises the following steps:

[0007] Under an inert gas atmosphere, in an organic solvent, using bisphenol A type epoxy resin, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and eugenol as raw materials, and under the catalysis of triphenylphosphine, addition reaction and substitution reaction occur to prepare a modified epoxy resin.

[0008] The preparation method of the modified nano-silica is as follows: a mixed dispersion system of nano-silica and oil acid imidazoline quaternary ammonium salt is prepared by using water as a dispersant; the mixed dispersion system is kept at 75-85 DEG C to prepare the modified nano-silica; more specifically, the nano-silica is uniformly dispersed in deionized water and ultrasonically treated for 30-60 minutes, then the oil acid imidazoline quaternary ammonium salt aqueous solution is added dropwise within 20-30 minutes after the temperature is raised to 75-85 DEG C, and the temperature is kept at 75-85 DEG C for 2.5-3.5 hours after the dropwise addition is completed; after the solid phase particles are separated, the deionized washing is performed, and the solid phase particles are collected to obtain the modified nano-silica.

[0009] The chemical structure of the oil acid imidazoline quaternary ammonium salt is as follows:

[0010] .

[0011] The above-mentioned radiation-resistant composite epoxy resin film improves the dielectric properties and mechanical properties of the radiation-resistant composite epoxy resin film by double modification of the bisphenol A epoxy resin matrix and addition of carbon fibers and modified nano-silica fillers, and improves the radiation resistance of the material, and after high-intensity irradiation, the performance of the composite epoxy resin film before irradiation can be basically maintained, and the performance decline is not obvious.

[0012] In the preferred embodiment of the present application, in the preparation method of the modified nano-silica, the mass ratio of the nano-silica to the oil acid imidazoline quaternary ammonium salt is 2:0.8-1.5.

[0013] The above-mentioned radiation-resistant composite epoxy resin film has more excellent radiation resistance and dielectric properties.

[0014] In the preferred embodiment of the present application, the mass ratio of the carbon fibers in the composite epoxy resin film is 1%-3%, and the mass ratio of the modified nano-silica in the composite epoxy resin film is 2.5%-6%.

[0015] Preferably, 10-(2, 5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and eugenol are added to an organic solvent containing bisphenol A type epoxy resin at 140-160 DEG C, then triphenyl phosphine is added at 185-195 DEG C and kept for 2.5-3.5 hours.

[0016] Specifically, the following steps are included:

[0017] (1) The bisphenol A type epoxy resin is heated to 140-160°C under inert gas protection, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and eugenol are slowly added, the molar ratio of 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and eugenol is 1-4:1-4, and the mass ratio of bisphenol A type epoxy resin to 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide is 100:25-30.

[0018] (2) The temperature is further increased to 185-195°C, triphenylphosphine as a catalyst is added, and the reaction is kept for 2.5-3.5 hours; preferably, the temperature is 190°C, and the reaction time is 3h. The amount of triphenylphosphine is 0.8-1.2% of the mass of the bisphenol A type epoxy resin. The preparation mechanism of the modified epoxy resin is as follows:

[0019] .

[0020] (3) The reaction solvent is removed to obtain the modified epoxy resin.

[0021] In the preferred embodiment of the present application, the reaction in the preparation method of the modified epoxy resin is carried out in dichloromethane solvent.

[0022] In the preferred embodiment of the present application, the curing agent is 4,4'-diaminodiphenyl methane, abbreviated as DDM.

[0023] In the preferred embodiment of the present application, the length of the carbon fiber is not more than 3mm.

[0024] In the preferred embodiment of the present application, the preparation method of the radiation-resistant composite epoxy resin film comprises the following steps:

[0025] (1) The modified epoxy resin, modified nano-silicon dioxide, and carbon fiber with a length not more than 3mm are mixed according to the weight ratio, and then the curing agent is added and uniformly mixed to obtain a mixed solution.

[0026] (2) The mixed solution is degassed in a vacuum oven at 85-90°C, and then heated to 98-105°C for curing for 2-5 hours to obtain the radiation-resistant composite epoxy resin film.

[0027] More specifically, the preparation method of the radiation-resistant composite epoxy resin film comprises the following steps:

[0028] (a) The modified epoxy resin, modified nano-silicon dioxide, and carbon fiber with a length not more than 3mm are mixed according to the weight ratio, and then the curing agent is added and uniformly mixed to obtain a mixed solution.

[0029] The preparation method of the modified epoxy resin matrix comprises the following steps:

[0030] The modified epoxy resin is prepared by addition reaction and substitution reaction of bisphenol A type epoxy resin, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and eugenol as raw materials in an organic solvent under the catalysis of triphenyl phosphine in an inert gas atmosphere.

[0031] The preparation method of the modified nanosilica comprises the following steps: preparing a mixed dispersion system of nanosilica and oleic acid imidazoline quaternary ammonium salt by taking water as a dispersant; and preparing the modified nanosilica by keeping the mixed dispersion system at 75-85 DEG C.

[0032] The chemical structure of the oleic acid imidazoline quaternary ammonium salt is as follows:

[0033] .

[0034] The curing agent is 4,4'-diaminodiphenyl methane.

[0035] (b) After the mixed solution is degassed in a vacuum oven at 85-90 DEG C, the temperature is increased to 98-105 DEG C for curing for 2-5 hours, and the radiation-resistant composite epoxy resin film is obtained.

[0036] The mass ratio of the carbon fiber in the radiation-resistant composite epoxy resin film is 0.5-5%, the mass ratio of the modified nanosilica in the radiation-resistant composite epoxy resin film is 1-8%, the rest is the curing agent and the modified epoxy resin matrix, and the mass ratio of the curing agent to the modified epoxy resin matrix is 5-8:10, and the total is 100%.

[0037] Compared with the prior art, the present application has the following beneficial effects:

[0038] The radiation-resistant composite epoxy resin film provided by the present application improves the dielectric properties and mechanical properties of the composite epoxy resin film by double modification of the bisphenol A epoxy resin matrix and addition of carbon fiber and modified nanosilica filler, and improves the radiation resistance of the material, and can basically maintain the performance of the composite epoxy resin film before radiation after high-intensity radiation, and can be used as an insulating material. DETAILED DESCRIPTION

[0039] In order to enable those skilled in the art to better understand the technical solutions of the present application and implement them, the present application will be further described below in combination with specific examples and data, but the examples are not limiting to the present application. The experimental methods and detection methods described in the following examples are all conventional methods unless otherwise specified; and the reagents and materials described are all commercially available unless otherwise specified.

[0040] In order to improve the radiation resistance of the epoxy resin, the application provides a kind of radiation resistance composite epoxy resin film, which is composed of modified epoxy resin matrix, carbon fiber, modified nano-silica and curing agent;Wherein, the mass ratio of carbon fiber in the radiation resistance composite epoxy resin film is 0.5%~5%, the mass ratio of modified nano-silica in the radiation resistance composite epoxy resin film is 1%~8%, the rest is curing agent and modified epoxy resin matrix, and the mass ratio of curing agent to modified epoxy resin matrix is 5~8:10, and the total is 100%.

[0041] The preparation method of the modified epoxy resin matrix comprises the following steps:

[0042] Under the atmosphere of inert gas, in organic solvent, with bisphenol A type epoxy resin, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and eugenol as raw materials, under the catalysis of triphenyl phosphorus, addition reaction and substitution reaction occur, and modified epoxy resin is prepared. The mass ratio of bisphenol A type epoxy resin to 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide is 100:25~30, the molar ratio of 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide to eugenol is 1~4:1~4, and the amount of triphenyl phosphorus is 0.8%~1.2% of the mass of bisphenol A type epoxy resin. The chemical structure of the modified epoxy resin matrix obtained by the above preparation method is shown as formula (I):

[0043] (I);

[0044] Wherein, x, y are natural numbers, 5≤x≤40, 5≤y≤40, x, y are controlled by the proportion of bisphenol A epoxy resin, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and eugenol in the modified epoxy resin. Among them, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, abbreviated as DOPO-HQ. It should be noted that the degree of reaction of each molecular chain is different during preparation, so the product obtained by one specific preparation process includes a large number of molecular chains of different lengths, so x and y in the above structure are numerical ranges. That is, by the preparation method of the application, products with x and y in the above range can be obtained.

[0045] The preparation method of the modified nano-silica comprises the following steps:

[0046] A mixed dispersion system of nano-silica and oleic acid-based imidazoline quaternary ammonium salt is prepared with water as dispersant;The mixed dispersion system is incubated at 75℃~85℃ to prepare modified nano-silica.

[0047] The chemical structure of the oleic acid imidazoline quaternary ammonium salt is shown in formula (II):

[0048] (II).

[0049] In addition, it should be noted that the present application modifies the bisphenol A epoxy resin matrix twice, and after adding carbon fibers and modified nanosilica fillers, the dielectric properties and mechanical properties of the composite epoxy resin film are improved, and the radiation resistance of the material is improved. Among them, the bisphenol A epoxy resin matrix is modified twice, which means that 10-(2, 5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and eugenol are used to modify the main chain of the epoxy resin. In order to illustrate the advantages of the above-mentioned double modification strategy, the present application also provides a single modified bisphenol A epoxy resin matrix, which is single modified by 10-(2, 5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide or eugenol on the main chain of the epoxy resin, respectively, as a comparison.

[0050] Specifically, when 10-(2, 5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide is used to modify the bisphenol A epoxy resin matrix, the obtained structure is shown in formula (III):

[0051] (III);

[0052] Wherein, x, y are natural numbers, 5≤x≤40, 5≤y≤40.

[0053] When eugenol is used to modify the bisphenol A epoxy resin matrix, the obtained structure is shown in formula (IV):

[0054] (IV);

[0055] Wherein x, y are natural numbers, 5≤x≤40, 5≤y≤40.

[0056] The preparation method of the radiation-resistant composite epoxy resin film comprises the following steps:

[0057] The modified epoxy resin matrix, modified nanosilica and carbon fibers are mixed according to the weight ratio, and then the curing agent is added and uniformly mixed to obtain a mixed solution.

[0058] The mixed solution is degassed in a vacuum oven at 85℃~90℃, and then heated to 98℃~105℃ for 2~5 hours to obtain a radiation-resistant composite epoxy resin film.

[0059] The radiation-resistant composite epoxy resin film provided by the present application improves the dielectric properties and mechanical properties of the radiation-resistant composite epoxy resin film by double modification of the bisphenol A epoxy resin matrix and the addition of carbon fibers and modified nano-silica fillers, and improves the radiation resistance of the material, and after high-intensity irradiation, the performance of the composite epoxy resin film before irradiation can be basically maintained, and the performance does not decrease significantly.

[0060] The content of the present application will be specifically described below through the following examples and comparative examples.

[0061] Example 1

[0062] As a radiation-resistant composite epoxy resin film according to an embodiment of the present application, the composite epoxy resin film is made of a modified epoxy resin matrix, carbon fibers, modified nano-silica, and a curing agent, the curing agent is 4,4'-diaminodiphenyl methane, abbreviated as DDM, and the length of the carbon fibers is not more than 3 mm.

[0063] The mass ratio of the carbon fibers in the radiation-resistant composite epoxy resin film is 3%, the mass ratio of the modified nano-silica in the radiation-resistant composite epoxy resin film is 4%, and the mass ratio of the curing agent to the modified epoxy resin matrix is 5:10.

[0064] The preparation method of the modified epoxy resin matrix represented by the above formula (I) includes the following steps:

[0065] (1) Bisphenol A type epoxy resin is added to a four-necked flask containing dichloromethane solvent, provided with a stirrer and a thermometer, dissolved at 90℃ for 20 min, heated to 150℃ under argon protection, and 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and eugenol are slowly added, the mass ratio of bisphenol A type epoxy resin to 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide is 100:25, and the molar ratio of 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide to eugenol is 1:1; stir for 15 minutes to mix evenly.

[0066] (2) Heat to 190℃, add triphenylphosphine as a catalyst, and keep the reaction for 3 hours; the amount of catalyst is 1% of the weight of bisphenol A type epoxy resin.

[0067] (3) Remove the reaction solvent to obtain the modified epoxy resin.

[0068] The preparation method of the modified nano-silica is as follows: uniformly dispersing the nano-silica in deionized water, ultrasonic treatment for 40 minutes, the mass ratio of the nano-silica to the deionized water being 1:10, adding the oil-alkyl imidazoline quaternary ammonium salt aqueous solution dropwise within 25 minutes after being heated to 80°C, the mass concentration of the oil-alkyl imidazoline quaternary ammonium salt aqueous solution being 20%, the mass ratio of the oil-alkyl imidazoline quaternary ammonium salt to the nano-silica being 2:1, keeping the temperature at 80°C for 3 hours after the dropwise addition is completed, separating the solid-phase particles, washing with deionized water, collecting the solid-phase particles and drying to obtain the modified nano-silica.

[0069] The chemical structure of the oil-alkyl imidazoline quaternary ammonium salt is as follows:

[0070] .

[0071] The preparation method of the radiation-resistant composite epoxy resin film in the embodiment includes the following steps:

[0072] After the modified epoxy resin, the modified nano-silica and the carbon fibers with a length of not more than 3 mm are mixed according to the weight ratio, a curing agent is added and uniformly mixed to obtain a mixed solution.

[0073] After the mixed solution is degassed in a vacuum oven at 90°C, the temperature is increased to 100°C for curing for 2.5 hours to obtain the radiation-resistant composite epoxy resin film.

[0074] Example 2

[0075] As a radiation-resistant composite epoxy resin film according to the embodiment of the present application, the embodiment is different from the embodiment 1 in that the mass ratio of the bisphenol A type epoxy resin to 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide is 100:30, and the molar ratio of 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide to eugenol is 1:1.

[0076] Example 3

[0077] As a radiation-resistant composite epoxy resin film according to the embodiment of the present application, the embodiment is different from the embodiment 1 in that the mass ratio of the bisphenol A type epoxy resin to 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide is 100:25, and the molar ratio of 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide to eugenol is 3:2.

[0078] Example 4

[0079] As a kind of radiation resistant composite epoxy resin film of the embodiment of the application, the embodiment is different from embodiment 1 in that the mass ratio of bisphenol A type epoxy resin to 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide is 100:25, and the molar ratio of 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide to eugenol is 3:4.5.

[0080] Example 5

[0081] As a kind of radiation resistant composite epoxy resin film of the embodiment of the application, the embodiment is different from embodiment 1 in that the mass ratio of carbon fiber in the radiation resistant composite epoxy resin film is 3%, and the mass ratio of modified nanosilica in the radiation resistant composite epoxy resin film is 1%.

[0082] Example 6

[0083] As a kind of radiation resistant composite epoxy resin film of the embodiment of the application, the embodiment is different from embodiment 1 in that the mass ratio of carbon fiber in the radiation resistant composite epoxy resin film is 3%, and the mass ratio of modified nanosilica in the radiation resistant composite epoxy resin film is 2.5%.

[0084] Example 7

[0085] As a kind of radiation resistant composite epoxy resin film of the embodiment of the application, the embodiment is different from embodiment 1 in that the mass ratio of carbon fiber in the radiation resistant composite epoxy resin film is 3%, and the mass ratio of modified nanosilica in the radiation resistant composite epoxy resin film is 6%.

[0086] Example 8

[0087] As a kind of radiation resistant composite epoxy resin film of the embodiment of the application, the embodiment is different from embodiment 1 in that the mass ratio of carbon fiber in the radiation resistant composite epoxy resin film is 3%, and the mass ratio of modified nanosilica in the radiation resistant composite epoxy resin film is 8%.

[0088] Comparative Example 1

[0089] As a kind of composite epoxy resin film of the comparative example of the application, the comparative example is different from embodiment 1 in that:

[0090] The modified epoxy resin shown in the above formula (III) is used to replace the modified epoxy resin in embodiment 1, and the preparation of the modified epoxy resin shown in formula (III) refers to the preparation method of the modified epoxy resin shown in formula (I) in embodiment 1, and the difference is that eugenol is not added, and the molar amount of eugenol is supplemented with 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide.

[0091] Comparative Example 2

[0092] As a composite epoxy resin film of the present application, the comparative example is different from Example 1 in that:

[0093] The modified epoxy resin shown in formula (IV) is used to replace the modified epoxy resin in Example 1, and the preparation of the modified epoxy resin shown in formula (IV) refers to the preparation method of the modified epoxy resin shown in formula (I) in Example 1, except that 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide is not added, and the molar amount of 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide is supplemented with the molar amount of eugenol.

[0094] Comparative Example 3

[0095] As a composite epoxy resin film of the present application, the comparative example is different from Example 1 in that: nano-silica is used to replace the modified nano-silica.

[0096] Comparative Example 4

[0097] As a composite epoxy resin film of the present application, the comparative example is different from Example 1 in that: no carbon fiber is added.

[0098] Experimental method

[0099] I. Sample to be tested

[0100] The composite epoxy resin films prepared in Examples 1-8 and Comparative Examples 1-4 are prepared according to the requirements of the test specifications. Bisphenol A epoxy resin is used as a control.

[0101] II. Mechanical property test

[0102] According to GB / 1943-2007, the Izod impact strength is tested by using an XJUD-5.5 cantilever beam impact testing machine, wherein the sample size is 80 mm x 10 mm x 4 mm, and the notch is 2 mm.

[0103] III. Dielectric property

[0104] The dielectric property is measured by using a precision impedance analyzer, model Agilent 4294A, at 25°C, in the frequency range of 10 4 ~10 7 Hz.

[0105] The mechanical properties and dielectric properties of Examples 1-8 and Comparative Examples 1-4 are shown in Table 1.

[0106] Table 1 Dielectric properties of the radiation resistant composite epoxy resin film

[0107]

[0108] As can be seen from Table 1, compared with the comparative sample, the above radiation resistant composite epoxy resin film improves the dielectric properties and mechanical properties of the radiation resistant composite epoxy resin film by double modification of the bisphenol A epoxy resin matrix and addition of carbon fibers and modified nano-silica fillers, has lower dielectric constant and dielectric loss, and absorbs less electrical energy under the action of alternating electric field, can be used as an insulating material for microwave communication, and exhibits higher electromagnetic wave transparency.

[0109] Among them, Comparative Example 1 does not add eugenol when preparing the modified epoxy resin, and the impact strength of the prepared sample is lower than that of Example 1, and the dielectric constant and dielectric loss are higher, which shows that the introduction of eugenol is necessary and can improve the dielectric properties and mechanical properties of the sample.

[0110] Comparative Example 2 does not add 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10- phosphaphenanthrene-10-oxide when preparing the modified epoxy resin, and the impact strength of the prepared sample is lower than that of Example 1, and the dielectric constant and dielectric loss are higher, which shows that the introduction of 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10- phosphaphenanthrene-10-oxide is necessary and can improve the dielectric properties and mechanical properties of the sample.

[0111] Comparative Example 3 uses nano-silica, and the impact strength of the prepared sample is lower than that of Example 1, and the dielectric constant and dielectric loss are higher, which shows that the modified nano-silica can improve the dielectric properties and mechanical properties of the sample.

[0112] Comparative Example 4 does not add carbon fibers, and the impact strength of the prepared sample is lower than that of Example 1, and the dielectric constant and dielectric loss are higher, which shows that the modified nano-silica can improve the dielectric properties and mechanical properties of the sample.

[0113] Four, radiation resistant performance test

[0114] The center region of the gauge length section of the sample was irradiated with a laser with a power of 1000W, i.e. a laser power density of 3.54kW / cm 2 The irradiation time was set to 20s, 60s and 5 minutes. After irradiation, the impact strength and dielectric properties of the sample under different irradiation times were tested.

[0115] The samples to be tested were the products of Example 1, Comparative Examples 1 to 4, and epoxy resin was used as a control.

[0116] Table 2. Results of irradiation resistance performance test

[0117]

[0118] As shown in Table 2, the mechanical properties of the composite epoxy resin films of Comparative Examples 1 to 4 decrease after laser irradiation, and the dielectric constant and dielectric loss increase significantly, while the irradiation resistant composite epoxy resin film of Example 1 can basically maintain the original mechanical properties and dielectric properties after laser irradiation, indicating that the irradiation resistant composite epoxy resin film of the present application improves the irradiation resistance of the material by double modification of the bisphenol A epoxy resin matrix, and addition of carbon fibers and modified nano-silica fillers.

[0119] Obviously, those skilled in the art can make various modifications and variations to the present application without departing from the spirit and scope of the present application. Thus, if these modifications and variations of the present application fall within the scope of the claims of the present application and their equivalents, these modifications and variations are also intended to be included.

Claims

1. A radiation-resistant composite epoxy resin film, characterized in that, It is formed by curing a modified epoxy resin matrix, carbon fiber, modified nano-silica, and a curing agent; wherein the mass proportion of carbon fiber in the composite epoxy resin film is 0.5%~5%, the mass proportion of modified nano-silica in the composite epoxy resin film is 1%~8%, and the balance is curing agent and modified epoxy resin matrix, and the mass ratio of curing agent to modified epoxy resin matrix is ​​5~8:10, totaling 100%; The preparation method of the modified epoxy resin matrix includes the following steps: In an inert gas atmosphere and in an organic solvent, bisphenol A type epoxy resin, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and eugenol were used as raw materials, and addition and substitution reactions were carried out under the catalysis of triphenylphosphine to prepare modified epoxy resin. The preparation method of modified nano-silica includes the following steps: A mixed dispersion system of nano-silica and oleic acid-based imidazoline quaternary ammonium salt was prepared using water as a dispersant; the mixed dispersion system was kept at 75℃~85℃ to prepare modified nano-silica. The chemical structure of oleic acid-based imidazoline quaternary ammonium salt is as follows: 。 2. The radiation-resistant composite epoxy resin film according to claim 1, characterized in that, The mass ratio of nano-silica to oleic acid-based imidazoline quaternary ammonium salt is 2:0.8~1.

5.

3. The radiation-resistant composite epoxy resin film according to claim 1, characterized in that, The mass ratio of carbon fiber in the composite epoxy resin film is 1%~3%, and the mass ratio of modified nano-silica in the composite epoxy resin film is 2.5%~6%.

4. The radiation-resistant composite epoxy resin film according to claim 1, characterized in that, The mass ratio of bisphenol A epoxy resin to 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide is 100:25~30, the molar ratio of 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide to eugenol is 1~4:1~4, and the amount of triphenylphosphine is 0.8%~1.2% of the mass of bisphenol A epoxy resin.

5. The radiation-resistant composite epoxy resin film according to claim 1, characterized in that, First, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and eugenol were added to an organic solvent containing bisphenol A epoxy resin and mixed at 140℃~160℃. Then, triphenylphosphine was added at 185℃~195℃ and kept at that temperature for 2.5h~3.5h.

6. The radiation-resistant composite epoxy resin film according to claim 1, characterized in that, The organic solvent is dichloromethane.

7. The radiation-resistant composite epoxy resin film according to claim 1, characterized in that, The curing agent is 4,4'-diaminodiphenylmethane, and the length of the carbon fiber does not exceed 3 mm.

8. The method for preparing the radiation-resistant composite epoxy resin film according to claim 1, characterized in that, Includes the following steps: After mixing the modified epoxy resin matrix, modified nano-silica and carbon fiber in a certain weight ratio, a curing agent is added and mixed evenly to obtain a mixture. After degassing the mixture in a vacuum environment at 85℃~90℃, the temperature is raised to 98℃~105℃ and cured for 2~5 hours to obtain a radiation-resistant composite epoxy resin film. The carbon fiber accounts for 0.5% to 5% of the mass of the composite epoxy resin film, the modified nano silica accounts for 1% to 8% of the mass of the composite epoxy resin film, and the remainder is curing agent and modified epoxy resin matrix. The mass ratio of curing agent to modified epoxy resin matrix is ​​5 to 8:10, totaling 100%. The preparation method of the modified epoxy resin matrix includes the following steps: In an inert gas atmosphere and in an organic solvent, bisphenol A type epoxy resin, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and eugenol were used as raw materials, and addition and substitution reactions were carried out under the catalysis of triphenylphosphine to prepare modified epoxy resin. The preparation method of modified nano-silica includes the following steps: A mixed dispersion system of nano-silica and oleic acid-based imidazoline quaternary ammonium salt was prepared using water as a dispersant; the mixed dispersion system was kept at 75℃~85℃ to prepare modified nano-silica. The chemical structure of oleic acid-based imidazoline quaternary ammonium salt is as follows: 。

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