Bromine-containing epoxy resin composite material with high heat resistance and preparation method thereof

Abstract

The invention relates to the technical field of epoxy resin, and particularly discloses a high-heat-resistance bromine-containing epoxy resin composite material and a preparation method thereof. The high-heat-resistance bromine-containing epoxy resin composite material is prepared from the following raw materials in parts by weight: 90-100 parts of bromine-containing epoxy resin; 10-15 parts of a curing agent; 0.4 to 1 part of a curing accelerator; 20 to 30 parts of a diluent; 15 to 25 parts of filler; 0.1 to 0.5 part of a defoaming agent; 4-6 parts of a dispersant; 2 to 5 parts of a modified PZS micro / nano tube; 1-4 parts of modified glass fiber; the preparation method comprises the following steps: putting the bromine-containing epoxy resin into a reaction container, then adding the diluent, the filler, the defoaming agent, the dispersing agent, the modified PZS micro-nano tube and the modified glass fiber, uniformly mixing, and then adding the curing agent and the curing accelerator to obtain a mixture; and putting the mixture into a mold for high-temperature curing, and cooling and demolding after curing. The high-heat-resistance bromine-containing epoxy resin composite material disclosed by the invention not only shows excellent heat resistance, but also is not easy to crack under impact or severe deformation, and the overall performance is remarkably improved.

Description

Technical Field

[0001] The present application relates to the technical field of epoxy resins, and more specifically, to a high heat-resistant brominated epoxy resin composite material and a preparation method thereof. Background Art

[0002] Brominated epoxy resin is an epoxy resin containing bromine element (Br) in its molecular structure and having a self-extinguishing function, also known as brominated epoxy resin and brominated phenolic epoxy resin. Its important varieties include brominated bisphenol A epoxy resin, brominated phenolic aldehyde type, and dibromoneopentyl glycol type epoxy resins. The common characteristics of these epoxy resins are self-extinguishing property and good heat resistance. They are mainly used as flame-retardant composite materials, structural materials, adhesives, and coatings, and are used in the fields of construction, aviation, shipbuilding, and electronic appliances.

[0003] A composite material is a material with excellent properties composed of multiple materials. The components of the brominated epoxy resin composite material mainly include brominated epoxy resin, curing agent, accelerator, and filler, etc. Brominated epoxy resin is the basic component of the composite material, which not only has excellent electrical insulation and adhesiveness, but also has self-extinguishing property and heat resistance, and can maintain good physical and chemical properties in a high-temperature environment. It can usually withstand temperatures up to above 200°C and is suitable for applications with high-temperature operations. The curing agent can make the brominated epoxy resin form a strong cross-linked network. The accelerator can accelerate the curing reaction and shorten the curing time. The filler can increase the volume and weight of the material and at the same time improve some physical properties of the material, such as hardness, wear resistance, etc. And the above-mentioned brominated epoxy resin composite material can fully combine and utilize the advantages of brominated epoxy resin, and thus can bring more extensive applications in various fields.

[0004] Regarding the above related technologies, the inventor believes that although brominated epoxy resin has excellent heat resistance, its material brittleness is relatively obvious, and it is easy to crack under impact or severe deformation, and cannot meet the requirements of some special fields.

[0005] Therefore, there is an urgent need to propose a solution to solve the above technical problems. Summary of the Invention

[0006] In order to make the brominated epoxy resin composite material not only exhibit excellent heat resistance, but also not easily crack under impact or severe deformation, the present application provides a high heat-resistant brominated epoxy resin composite material and a preparation method thereof.

[0007] In the first aspect, the present application provides a high heat-resistant brominated epoxy resin composite material, adopting the following technical solution:

[0008] The high heat-resistant brominated epoxy resin composite material is made from raw materials comprising the following parts by weight:

[0009] 90 - 100 parts of brominated epoxy resin;

[0010] 10 - 15 parts of curing agent;

[0011] 0.4 - 1 part of curing accelerator;

[0012] 20 - 30 parts of diluent;

[0013] 15 - 25 parts of filler;

[0014] 0.1 - 0.5 part of defoamer;

[0015] 4 - 6 parts of dispersant;

[0016] 2 - 5 parts of modified PZS micro - nano tubes;

[0017] 1 - 4 parts of modified glass fibers;

[0018] The said modified PZS micro - nano tubes are obtained by the following method:

[0019] S1. After mixing hexachlorocyclotriphosphazene and tetrahydrofuran, triethylamine is added and mixed evenly to obtain a mixed solution; 4,4'-dihydroxydiphenyl sulfone is dissolved in tetrahydrofuran and then dropped into the mixed solution. After the reaction ends, the obtained reaction product is washed and dried to obtain the PZS micro - nano tube raw material;

[0020] S2. Cerium dioxide particles and the PZS micro - nano tube raw material in step S1 are mixed, then ethanol is added and ultrasonically mixed evenly. After adding a silane coupling agent and reacting, it is centrifuged, washed and dried to obtain the modified PZS micro - nano tubes;

[0021] The said modified glass fibers are obtained by the following method:

[0022] 5,5'-carbonylbis(1,3 - isobenzofurandione) and 4,4'-diaminodiphenyl ether are dissolved in N,N'-dimethylformamide, mixed evenly and then dropped into deionized water to obtain an amic acid emulsion. Then the glass fiber raw material is subjected to surface immersion treatment and dried to obtain the modified glass fibers.

[0023] By adopting the above technical solutions, in the preparation of the modified PZS micro-nanotubes, the raw materials of the PZS micro-nanotubes with a highly cross-linked chemical structure and the presence of micropores and mesopores on the surface are first prepared, and then surface modification and compounding are carried out with cerium dioxide; it has good dispersibility in the high heat-resistant brominated epoxy resin composite material, and can enhance the structural toughness, improve the thermal stability and flame retardancy. The modified glass fiber is obtained by surface modification of the proportional fiber raw materials with the prepared amic acid emulsion. It has excellent interfacial adhesion performance with the brominated epoxy resin, can effectively transfer the load in the high heat-resistant brominated epoxy resin composite material, reduce stress concentration, and thus bring a significant improvement in the impact resistance. At the same time, in addition to being able to play the above excellent self-role, the modified PZS micro-nanotubes and the modified glass fiber can also play an excellent compounding and synergistic effect with each other. In a high-temperature environment, the modified PZS micro-nanotubes will partially form a lamellar structure under the catalysis of CeO2, and the main components of the lamellar structure are carbon and CeO2. Its diffusion in the brominated epoxy resin can combine with the modified glass fiber to form an interpenetrating network structure, and this structure can stably exist and form excellent interfacial adhesion with the brominated epoxy resin. As a result, the brominated epoxy resin composite material not only exhibits excellent heat resistance, but also is not prone to cracking under impact or severe deformation, and the overall performance is significantly improved.

[0024] Preferably, in the preparation of the modified PZS micro-nanotubes, the weight ratio of the cerium dioxide particles to the PZS micro-nanotube raw materials is 1:(8 - 10).

[0025] By adopting the above technical solutions, when the cerium dioxide particles and the PZS micro-nanotube raw materials with the above weight ratio are combined, the cerium dioxide particles can be more fully combined at the micropores and mesopores of the PZS micro-nanotube raw materials, thereby bringing a relatively excellent surface modification effect. And during the application process of the modified PZS micro-nanotubes, when affected by high heat, the formed lamellar structure mainly composed of carbon and CeO2 can also form a better cooperative structure system with the modified glass fiber. In this way, a high heat-resistant brominated epoxy resin composite material with relatively excellent application quality can be obtained.

[0026] Preferably, in the preparation of the modified glass fiber, the particle size of the amic acid emulsion is 60 - 100 nm.

[0027] By adopting the above technical solution, during the application process, the amic acid emulsion with the above particle size can be relatively evenly dispersed in the modified glass fiber, and strong hydrogen bond interactions are formed with the silicon-oxygen bonds on the surface of the glass fiber by using groups such as hydroxyl and amino groups rich in itself. A stable surface layer structure can be formed during the subsequent treatment process, which not only forms a stable interfacial adhesion with the bromine-containing epoxy resin, but also exhibits excellent compound synergistic effects with the modified PZS micro-nano tubes. Furthermore, a bromine-containing epoxy resin composite material with high heat resistance and excellent application quality is obtained.

[0028] Preferably, 2-5 parts by weight of a functional auxiliary agent are further added to the raw materials. The functional auxiliary agent is composed of a polyimide-siloxane copolymer and graphene oxide, and the weight ratio of the polyimide-siloxane copolymer to graphene oxide is 1:(2.4-3.2).

[0029] By adopting the above technical solution, the polyimide-siloxane copolymer has excellent high and low temperature resistance, can maintain stable performance in extreme temperature environments, and has high flexibility and impact resistance, thereby bringing corresponding functional improvements to the bromine-containing epoxy resin composite material with high heat resistance; the use of graphene oxide can significantly enhance the mechanical properties such as fracture toughness, strength and tensile modulus of the bromine-containing epoxy resin composite material with high heat resistance, and also can bring an improvement in heat resistance by using its excellent photothermal conversion advantage; when the polyimide-siloxane copolymer and graphene oxide are compounded and used as a functional auxiliary agent, the graphene oxide is fixed by using the self-adhesion of the polyimide-siloxane copolymer in the interpenetrating network structure formed by the cooperation of the modified PZS micro-nano tubes and the modified glass fiber, and an adaptive adjustment system is built through the interfacial self-lubrication effect of graphene, so that the bromine-containing epoxy resin composite material with high heat resistance can exert excellent adaptive adjustment effects under impact or severe deformation, the overall structure is more difficult to be damaged, and the corresponding performance is significantly improved.

[0030] Preferably, the weight ratio of the polyimide-siloxane copolymer to graphene oxide is 1:2.8.

[0031] By adopting the above technical solution, when the polyimide-siloxane copolymer and graphene oxide with the above weight ratio are used in combination, the corresponding effects brought by their application are better, so that during the application process of the bromine-containing epoxy resin composite material with high heat resistance, the improvement of the impact resistance or severe deformation performance is better, that is, the overall application performance of the functional auxiliary agent is better.

[0032] Preferably, the curing agent is one or a combination of several of dicyandiamide curing agents, linear phenolic resin curing agents, aromatic amine curing agents, acid anhydride curing agents and phenolic curing agents.

[0033] Preferably, the curing accelerator is one or a combination of imidazole-based curing accelerators, organic amine-based accelerators, acid anhydride-based accelerators, phenol-based accelerators, and organic phosphine curing accelerators.

[0034] Preferably, the diluent is one or a combination of acetone, ethylene glycol monomethyl ether, 1,4-butanediol diglycidyl ether, butyl glycidyl ether, and propylene glycol monomethyl ether.

[0035] Preferably, the filler is one or a combination of barium sulfate, kaolin, talc powder, mica powder, zinc oxide, boron nitride, and calcium carbonate.

[0036] By adopting the above technical solutions, the curing agent reacts chemically with epoxy groups, and the formed crosslinked network enhances the mechanical strength, hardness, wear resistance, chemical corrosion resistance, and other physical properties of the material; the curing accelerator accelerates the reaction rate of epoxy resin and the curing agent by reducing the activation energy of the curing reaction; the introduction of the diluent can significantly reduce the viscosity of epoxy resin, thereby improving its fluidity and wettability; the filler can improve the mechanical properties of the resin, improve the processing performance of the resin, provide fire protection and heat insulation, reduce costs, etc.; and the above types of curing agents, curing accelerators, diluents, and fillers are all applicable to the preparation of high heat-resistant brominated epoxy resin composites and can be selected and combined according to actual needs, showing strong adaptability as a whole.

[0037] In a second aspect, the present application provides a method for preparing a high heat-resistant brominated epoxy resin composite, adopting the following technical solution:

[0038] A method for preparing a high heat-resistant brominated epoxy resin composite, comprising the following steps:

[0039] (1) Prepare raw materials including brominated epoxy resin, curing agent, curing accelerator, diluent, filler, defoaming agent, dispersant, modified PZS micro-nanotubes, and modified glass fibers according to the ratio.

[0040] (2) Place the brominated epoxy resin in step (1) in a reaction vessel, then add the diluent, filler, defoaming agent, dispersant, modified PZS micro-nanotubes, and modified glass fibers and mix evenly, and then add the curing agent and curing accelerator to obtain a mixture.

[0041] (3) Put the mixture in step (2) into a mold for high-temperature curing, and after curing is completed, cool and demold to obtain a high heat-resistant brominated epoxy resin composite.

[0042] By adopting the above technical scheme, the operation of the above preparation method is relatively simple, and it only needs to mix the raw materials, which can enable the modified PZS micro-nanotubes and modified glass fibers to exert excellent and stable coordination effects during the application process, which is conducive to obtaining high-quality and stable high-heat-resistant bromine-containing epoxy resin composite materials, and is more suitable for large-scale industrial production as a whole.

[0043] In summary, this application has the following beneficial effects:

[0044] 1. The present application forms a network interpenetrating structure in a high-temperature environment by compounding modified PZS micro-nanotubes and modified glass fibers, and the structure can stably exist and form an excellent interface bonding with the bromine-containing epoxy resin, thereby making the bromine-containing epoxy resin composite material not only exhibit excellent heat resistance, but also not easily cracked under impact or severe deformation, and the overall performance is significantly improved;

[0045] 2. The present application uses functional additives composed of polyimide-siloxane copolymer and graphene oxide, and builds an adaptive adjustment system in the network interpenetrating structure formed by the modified PZS micro-nanotubes and modified glass fibers, so that the high heat-resistant bromine-containing epoxy resin composite material can play an excellent adaptive adjustment role under impact or severe deformation, the overall structure is less likely to be destroyed, and the overall application performance is significantly improved. DETAILED DESCRIPTION

[0046] The present application is further described in detail below in combination with preparation examples, embodiments and comparative examples.

[0047] Unless otherwise specified, the raw materials used in the preparation examples, embodiments and comparative examples of the present application are commercially available.

[0048] Brominated epoxy resin was purchased from Nan Ya NPEB 460A80 brominated bisphenol A epoxy resin;

[0049] The curing agent is a dicyandiamide curing agent purchased from Huntsman Omicure U-52M;

[0050] The curing accelerator is an imidazole curing accelerator, which is 1-cyanoethyl-2-ethyl-4-methylimidazole 2E4MZ-CN from Shikoku Chemical of Japan;

[0051] The diluent is acetone;

[0052] The filler is barium sulfate, purchased from Aoda BD-702;

[0053] The defoamer was purchased from BYK-A535;

[0054] The dispersant was purchased from EFKA-5210;

[0055] The glass fiber raw material is chopped glass fiber purchased from Tai'an Songze Composite Materials Co., Ltd., with a specification of 3 mm;

[0056] The polyimide-siloxane copolymer was prepared by oneself according to the content in "Yu Xinhai. Synthesis of Polyimide Siloxane Copolymer [J] New Chemical Materials in Chemical Industry. 2002, (9). DOI: 10.3969 / j.issn.1006 - 3536.2002.09.001". Its number-average molecular weight is 2840, and the degree of polymerization is 35.0.

[0057] Graphene oxide was purchased from Shanghai Hanlang New Materials Technology Co., Ltd. Single-layer Graphene Oxide HL-GO high-purity grade 99.9%.

[0058] Preparation examples of raw materials and / or intermediates

[0059] Preparation Example 1

[0060] A kind of modified PZS micro-nano tube was obtained by the following method:

[0061] S1. After mixing hexachlorocyclotriphosphazene and tetrahydrofuran in a ratio of 1 g:125 mL, triethylamine was added and mixed evenly. The volume ratio of triethylamine to tetrahydrofuran was 14:100 to obtain a mixed solution; after dissolving 4,4'-dihydroxydiphenyl sulfone in tetrahydrofuran, the ratio of 4,4'-dihydroxydiphenyl sulfone to tetrahydrofuran was 1.72:100 mL, and then it was added dropwise to the mixed solution according to a weight ratio of 1:1. After reacting for 10 h, the obtained reaction product was washed and dried to obtain the PZS micro-nano tube raw material;

[0062] S2. After taking cerium dioxide particles and the PZS micro-nano tube raw material obtained in step S1 and mixing them, they were added to ethanol according to a ratio of 1 g:50 mL and ultrasonically mixed evenly. Then, 10% of the volume of ethanol of silane coupling agent was added and reacted at 60 °C for 6 h. After centrifugation, washing and drying, the modified PZS micro-nano tube was obtained.

[0063] Note: The weight ratio of cerium dioxide particles to the PZS micro-nano tube raw material is 1:9; the silane coupling agent is KH550 type silane coupling agent.

[0064] Preparation Example 2

[0065] A kind of modified PZS micro-nano tube, the difference from Preparation Example 1 is that the weight ratio of cerium dioxide particles to the PZS micro-nano tube raw material is 1:8.

[0066] Preparation Example 3

[0067] A kind of modified PZS micro-nano tube, the difference from Preparation Example 1 is that the weight ratio of cerium dioxide particles to the PZS micro-nano tube raw material is 1:10.

[0068] Preparation Example 4

[0069] A modified glass fiber is prepared by the following method:

[0070] Dissolve 5,5'-carbonylbis(1,3-isobenzofurandione) and 4,4'-diaminodiphenyl ether in N,N'-dimethylformamide. After mixing evenly, drop the solution into deionized water to obtain an amic acid emulsion. Then, perform surface immersion treatment on the glass fiber raw material. After drying, the modified glass fiber is obtained.

[0071] Note: In the above operation, the molar ratio of 5,5'-carbonylbis(1,3-isobenzofurandione) to 4,4'-diaminodiphenyl ether is 7:6, the volume ratio of N,N'-dimethylformamide to ionic water is 1:6, and the particle size of the obtained amic acid emulsion is 80 nm.

[0072] Preparation Example 5

[0073] A modified glass fiber, which is different from Preparation Example 4 in that the particle size of the amic acid emulsion is 60 nm.

[0074] Preparation Example 6

[0075] A modified glass fiber, which is different from Preparation Example 4 in that the particle size of the amic acid emulsion is 100 nm.

[0076] Examples

[0077] Example 1

[0078] A high heat-resistant brominated epoxy resin composite material, the components required for its preparation and their corresponding weights are shown in Table 1, and it is prepared by the following steps:

[0079] (1) Prepare raw materials including brominated epoxy resin, curing agent, curing accelerator, diluent, filler, defoaming agent, dispersant, modified PZS micro-nanotubes and modified glass fiber according to the ratio;

[0080] (2) Place the brominated epoxy resin in step (1) in a reaction vessel, then add the diluent, filler, defoaming agent, dispersant, modified PZS micro-nanotubes and modified glass fiber and mix evenly, and then add the curing agent and curing accelerator to obtain a mixture;

[0081] (3) Put the mixture in step (2) into a mold for high-temperature curing. After curing is completed, cool and demold to obtain a high heat-resistant brominated epoxy resin composite material.

[0082] Note: In the above operation, the modified PZS micro-nanotubes are obtained from Preparation Example 1; the modified glass fiber is obtained from Preparation Example 4.

[0083] Example 2-3

[0084] A high heat-resistant brominated epoxy resin composite material, which is different from that of Example 1 in that the components required for its preparation and their corresponding weights are shown in Table 1.

[0085] Table 1 Components required for the preparation of Examples 1-3 and their weight parts (kg / part)

[0086]

[0087]

[0088] Example 4

[0089] A high heat-resistant brominated epoxy resin composite material, which is different from that of Example 1 in that the modified PZS micro-nano tubes are obtained from Preparation Example 2.

[0090] Example 5

[0091] A high heat-resistant brominated epoxy resin composite material, which is different from that of Example 1 in that the modified PZS micro-nano tubes are obtained from Preparation Example 3.

[0092] Example 6

[0093] A high heat-resistant brominated epoxy resin composite material, which is different from that of Example 1 in that the modified glass fibers are obtained from Preparation Example 5.

[0094] Example 7

[0095] A high heat-resistant brominated epoxy resin composite material, which is different from that of Example 1 in that the modified glass fibers are obtained from Preparation Example 6.

[0096] Example 8

[0097] A high heat-resistant brominated epoxy resin composite material, which is different from that of Example 1 in that 3.5 parts by weight of a functional additive are further added to the raw materials. The functional additive is composed of a polyimide-siloxane copolymer and graphene oxide in a weight ratio of 1:2.8, and the functional additive is added and used together with the modified PZS micro-nano tubes and the modified glass fibers.

[0098] Example 9

[0099] A high heat-resistant brominated epoxy resin composite material, which is different from that of Example 8 in that the added weight part of the functional additive is 5 parts.

[0100] Example 10

[0101] A high heat-resistant brominated epoxy resin composite material, which is different from that of Example 8 in that the added weight part of the functional additive is 2 parts.

[0102] Example 11

[0103] A high heat-resistant brominated epoxy resin composite, which is different from Example 8 in that the functional additive is composed of a polyimide-siloxane copolymer and graphene oxide in a weight ratio of 1:2.4.

[0104] Example 12

[0105] A high heat-resistant brominated epoxy resin composite, which is different from Example 8 in that the functional additive is composed of a polyimide-siloxane copolymer and graphene oxide in a weight ratio of 1:3.2.

[0106] Example 13

[0107] A high heat-resistant brominated epoxy resin composite, which is different from Example 8 in that the polyimide-siloxane copolymer is not added to the preparation raw materials.

[0108] Example 14

[0109] A high heat-resistant brominated epoxy resin composite, which is different from Example 8 in that graphene oxide is not added to the preparation raw materials.

[0110] Comparative Example

[0111] Comparative Example 1

[0112] A high heat-resistant brominated epoxy resin composite, which is different from Example 1 in that the modified PZS micro-nanotubes are not added to the preparation raw materials.

[0113] Comparative Example 2

[0114] A high heat-resistant brominated epoxy resin composite, which is different from Example 1 in that the modified glass fibers are not added to the preparation raw materials.

[0115] Comparative Example 3

[0116] A high heat-resistant brominated epoxy resin composite, which is different from Example 1 in that the modified PZS micro-nanotubes and modified glass fibers are not added to the preparation raw materials.

[0117] Comparative Example 4

[0118] A high heat-resistant brominated epoxy resin composite, which is different from Example 1 in that the modified PZS micro-nanotubes are replaced with PZS micro-nanotube raw materials of equal mass.

[0119] Comparative Example 5

[0120] A high heat-resistant brominated epoxy resin composite, which is different from Comparative Example 2 in that the modified PZS micro-nano tubes are replaced with PZS micro-nano tube raw materials in equal mass.

[0121] Comparative Example 6

[0122] A high heat-resistant brominated epoxy resin composite, which is different from Example 1 in that the modified glass fiber is replaced with glass fiber raw materials in equal mass.

[0123] Comparative Example 7

[0124] A high heat-resistant brominated epoxy resin composite, which is different from Comparative Example 1 in that the modified glass fiber is replaced with glass fiber raw materials in equal mass.

[0125] Performance detection test

[0126] Test samples: The high heat-resistant brominated epoxy resin composites obtained in Examples 1-14 were used as Test Samples 1-14, and the high heat-resistant brominated epoxy resin composites obtained in Comparative Examples 1-7 were used as Control Samples 1-7.

[0127] Test method: (1) Thermogravimetric analysis is a test method for testing high-temperature resistance by heating the sample to cause weight loss. In this process, the sample will gradually lose weight until most of the volatile components are completely volatilized. By analyzing the amount of weight loss, the physical and chemical properties of the sample at high temperature can be obtained, so as to evaluate its high-temperature resistance.

[0128] The high heat-resistant brominated epoxy resin composite was placed at 300 °C for 30 min, and the weight loss rate was measured. The test results of Test Samples 1-14 and Control Samples 1-7 were correspondingly recorded in Table 2.

[0129] (2) Take the high heat-resistant brominated epoxy resin composite and use an impact strength testing machine to test the impact strength. Evaluate the anti-fracture ability of the epoxy resin when it is impacted according to the size of the impact strength. The obtained impact strength value is denoted as A; then the high heat-resistant brominated epoxy resin composite is placed at 200 °C for 2 h, and then the impact strength is tested in the same way. The obtained impact strength value is denoted as B; finally, calculate the impact strength loss rate. The impact strength loss rate = (A - B) / A. The larger the impact strength loss rate, the more likely the high heat-resistant brominated epoxy resin composite is to crack under impact or severe deformation when applied in a high-temperature environment.

[0130] After the above tests were sequentially completed on Test Samples 1-14 and Control Samples 1-7, the corresponding results were correspondingly recorded in Table 2.

[0131] Table 2 Test results of Test Samples 1-14 and Control Samples 1-7

[0132]

[0133]

[0134] Combined with Example 1 and Comparative Examples 1-3 and Table 2, it can be seen that using the modified PZS micro-nanotubes and modified glass fibers in combination in the high heat-resistant brominated epoxy resin composite can bring about a significant improvement in heat resistance, and the anti-cracking performance shown during application in a high-temperature environment is also more excellent; at the same time, if it is found that only one of the modified PZS micro-nanotubes and modified glass fibers is used, although there are improvements in the weight loss rate (%) and impact strength loss rate (%) in the above tests, the improvement effect brought is limited, and the sum of the improvement effects brought by their respective single use is also far less excellent than their combined use. Combining Comparative Examples 4-7 and Table 2, it can be seen that if the modified PZS micro-nanotubes are replaced with PZS micro-nanotube raw materials of equal mass, or the modified glass fibers are replaced with glass fiber raw materials of equal mass, it is found that the heat resistance of the high heat-resistant brominated epoxy resin composite and its anti-cracking performance at high temperatures both show significant losses, and the combination between the PZS micro-nanotube raw materials and the modified glass fibers and the combination between the glass fiber raw materials and the modified PZS micro-nanotubes can only bring about a simple superposition of the corresponding effects, rather than bringing about the exertion of an excellent combined effect.

[0135] Combined with Example 1 and Examples 4-5 and Table 2, it can be seen that in the preparation of the modified PZS micro-nanotubes, the weight ratio of cerium dioxide particles to PZS micro-nanotube raw materials is 1:(8-10), and all can enable the obtained modified PZS micro-nanotubes to exhibit excellent and stable effect, and thus a high heat-resistant brominated epoxy resin composite with relatively excellent application quality is obtained.

[0136] Combined with Example 1 and Examples 6-7 and Table 2, it can be seen that in the preparation of the modified glass fibers, the particle size of the amic acid emulsion is 60-100 nm, and all can enable the obtained modified glass fibers to exhibit excellent and stable effect, and thus a high heat-resistant brominated epoxy resin composite with relatively excellent application quality is obtained.

[0137] Combined with Example 1 and Examples 8 - 12 and Table 2, it can be seen that using the functional additive composed of polyimide - siloxane copolymer and graphene oxide can further reduce both the weight loss rate (%) and impact strength loss rate (%) obtained from the test, indicating that the heat resistance of the high - heat - resistant brominated epoxy resin composite material and its anti - cracking performance when applied in a high - temperature environment have been significantly improved. Further combined with Examples 13 - 14 and Table 2, it can be seen that if the polyimide - siloxane copolymer or graphene oxide is added and used alone, although it can bring corresponding improvement in effects, the improvement amplitude is limited, and the sum of the improvement effects brought by their respective single use is far less excellent than that of their compound use, indicating that the combination between the polyimide - siloxane copolymer and graphene oxide can bring a significant improvement effect of 1 + 1 > 2.

[0138] This specific embodiment is only an interpretation of the present application, and it does not limit the present application. After reading this specification, those skilled in the art can make modifications without creative contributions to this embodiment as needed, but as long as it is within the scope of the claims of the present application, it is protected by the patent law.

Claims

1. A high heat-resistant bromine-containing epoxy resin composite material, characterized in that: Made from the following raw materials in parts by weight: 90-100 parts of bromine-containing epoxy resin; 10-15 parts of curing agent; 0.4-1 part of curing accelerator; 20-30 parts of diluent; 15-25 parts of filler; Defoaming agent 0.1-0.5 parts; 4-6 parts of dispersant; 2-5 parts of modified PZS micro-nanotubes; 1-4 parts of modified glass fiber; The modified PZS micro-nanotubes are prepared by the following method: S1. After mixing hexachlorocyclotriphosphazene and tetrahydrofuran, triethylamine is added and mixed evenly to obtain a mixed solution; after dissolving 4,4'-dihydroxydiphenyl sulfone in tetrahydrofuran, the mixture is added dropwise to the mixed solution; after the reaction is completed, the obtained reaction product is washed and dried to obtain a PZS micro-nanotube raw material; S2, mixing the cerium dioxide particles and the PZS micro-nanotube raw material in step S1, adding ethanol to mix evenly by ultrasonication, adding a silane coupling agent to react, centrifuging, washing and drying to obtain modified PZS micro-nanotubes; The modified glass fiber is prepared by the following method: 5,5'-Carbonylbis(1,3-isobenzofurandione) and 4,4'-diaminodiphenyl ether are dissolved in N,N'-dimethylformamide, mixed evenly and then added dropwise into deionized water to obtain an amic acid emulsion, and then the glass fiber raw material is subjected to surface immersion treatment and dried to obtain a modified glass fiber.

2. The high heat-resistant bromine-containing epoxy resin composite material according to claim 1, characterized in that: In the preparation of the modified PZS micro-nanotubes, the weight ratio of the cerium dioxide particles to the PZS micro-nanotube raw materials is 1:(8-10).

3. The high heat-resistant bromine-containing epoxy resin composite material according to claim 1, characterized in that: In the preparation of modified glass fiber, the particle size of the amic acid emulsion is 60-100 nm.

4. The high heat-resistant bromine-containing epoxy resin composite material according to claim 1, characterized in that: The raw materials are also added with 2-5 parts by weight of a functional additive, which is composed of a polyimide-siloxane copolymer and graphene oxide, and the weight ratio of the polyimide-siloxane copolymer to the graphene oxide is 1:(2.4-3.2).

5. The high heat-resistant bromine-containing epoxy resin composite material according to claim 4, characterized in that: The weight ratio of the polyimide-siloxane copolymer to graphene oxide is 1:2.

8.

6. The high heat-resistant bromine-containing epoxy resin composite material according to claim 1, characterized in that: The curing agent is one or a combination of dicyandiamide curing agent, linear phenolic resin curing agent, aromatic amine curing agent, acid anhydride curing agent and phenol curing agent.

7. The high heat-resistant bromine-containing epoxy resin composite material according to claim 1, characterized in that: The curing accelerator is one or a combination of imidazole curing accelerators, organic amine accelerators, acid anhydride accelerators, phenol accelerators and organic phosphine curing accelerators.

8. The high heat-resistant bromine-containing epoxy resin composite material according to claim 1, characterized in that: The diluent is one or a combination of acetone, ethylene glycol methyl ether, 1,4-butanediol diglycidyl ether, butyl glycidyl ether and propylene glycol methyl ether.

9. The high heat-resistant bromine-containing epoxy resin composite material according to claim 1, characterized in that: The filler is one or a combination of barium sulfate, kaolin, talcum powder, mica powder, zinc oxide, boron nitride and calcium carbonate.

10. The method for preparing the high heat-resistant bromine-containing epoxy resin composite material according to claim 1, characterized in that: The following steps are involved: (1) preparing raw materials including bromine-containing epoxy resin, curing agent, curing accelerator, diluent, filler, defoamer, dispersant, modified PZS micro-nanotubes and modified glass fiber according to a proportion; (2) placing the bromine-containing epoxy resin in step (1) in a reaction container, adding a diluent, a filler, a defoamer, a dispersant, a modified PZS micro-nanotube and a modified glass fiber, mixing them evenly, and then adding a curing agent and a curing accelerator to obtain a mixture; (3) placing the mixed material in step (2) into a mold for high temperature curing, cooling and demoulding after curing, and obtaining a high heat-resistant bromine-containing epoxy resin composite material.

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