Thermoset epoxy resin composite material and preparation method and recycling method, recycled thermoset epoxy resin composite material and application

Abstract

The application provides a thermosetting epoxy resin composite material and a preparation method and a recovery method, a recovered thermosetting epoxy resin composite material and application, and belongs to the technical field of composite materials.The thermosetting epoxy resin composite material provided by the application comprises the following preparation raw materials in mass fractions: 30-60 parts of epoxy resin; 6-11 parts of 4,4'-dithiodianiline; 6-10 parts of 4-aminobenzoic acid pinacol ester; 0.5-5 parts of hydroxylated reinforcing filler; and 6-12 parts of organic solvent.The epoxy resin is used as a matrix material, the 4-aminobenzoic acid pinacol ester and the 4,4'-dithiodianiline containing a disulfide bond are used as curing agents, and the hydroxylated reinforcing filler is used in cooperation, so that the prepared thermosetting epoxy resin composite material has double dynamic covalent bonds (disulfide bonds and boron ester bonds), and the recyclability of the thermosetting epoxy resin composite material is given.

Description

Technical Field

[0001] This invention relates to the field of composite material technology, and in particular to thermosetting epoxy resin composite materials, their preparation and recycling methods, recycled thermosetting epoxy resin composite materials, and their applications. Background Technology

[0002] Since the large-scale production of plastics began in 1950, the output of polymer-based materials has grown at a compound annual growth rate of 8.4%, reaching 348 million tons in 2017. Currently, polymer-based materials have replaced many traditional metal and ceramic parts, becoming sliding components in various industries such as automobiles and aircraft, reducing weight, enhancing corrosion resistance, and possessing excellent tribological properties. Thermosetting epoxy resins are an important class of polymer-based materials, playing an irreplaceable role in coatings, adhesives, and composite materials. However, traditional epoxy resins, after curing, form a three-dimensional network of strongly covalently cross-linked molecular chains, which cannot be reprocessed or reshaped by heating or solvents, resulting in solid waste that places a heavy burden on the environment. Summary of the Invention

[0003] The purpose of this invention is to provide a thermosetting epoxy resin composite material, its preparation method, its recycling method, the recycling of thermosetting epoxy resin composite materials, and their applications. This invention introduces dual dynamic covalent bonds (disulfide bonds and boron ester bonds) into the thermosetting epoxy resin system. By designing the cured crosslinked network structure, the material is endowed with recyclability, and based on this property, the tribological redesign of the thermosetting resin is achieved.

[0004] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0005] This invention provides a thermosetting epoxy resin composite material, comprising the following raw materials in parts by weight:

[0006] 30-60 parts epoxy resin;

[0007] 6–11 parts of 4,4'-dithiodiphenylamine;

[0008] 6-10 parts of 4-aminophenylboronic acid pinacol ester;

[0009] 0.5–5 parts of hydroxylated reinforcing filler;

[0010] 6 to 12 parts of organic solvent.

[0011] Preferably, the hydroxylated reinforcing filler includes one or more of hydroxylated nano-silica, hydroxylated nano-alumina, hydroxylated carbon nanotubes, nano-cellulose, and polydopamine nanoparticles.

[0012] Preferably, the epoxy resin includes epoxy resins E54, E51, E44, or E42.

[0013] This invention provides a method for preparing the thermosetting epoxy resin composite material described in the above technical solution, comprising the following steps:

[0014] Epoxy resin, 4,4'-dithiodiphenylamine, pinacol ester of 4-aminophenylboronic acid, hydroxylated reinforcing filler, and organic solvent are mixed and cured to obtain a thermosetting epoxy resin composite material.

[0015] Preferably, the curing process includes sequentially performing a first curing, a second curing, and a third curing.

[0016] The first curing temperature is 110-130℃, and the holding time is 10-14h;

[0017] The second curing temperature is 140–160°C, and the holding time is 2–4 hours;

[0018] The third curing temperature is 160-180℃, and the holding time is 1-3 hours.

[0019] This invention provides a method for recycling waste thermosetting epoxy resin composite materials, comprising the following steps:

[0020] Waste thermosetting epoxy resin composite material is pulverized and mixed with reinforcing filler, and then subjected to a first hot pressing treatment to obtain a precursor material; the thermosetting epoxy resin composite material is the thermosetting epoxy resin composite material described in the above technical solution or the thermosetting epoxy resin composite material prepared by the preparation method described in the above technical solution; the reinforcing filler includes graphene oxide and / or hydroxylated nanofiller.

[0021] The precursor material is pulverized and mixed with lubricating filler, and then subjected to a second hot pressing treatment to obtain a recycled thermosetting epoxy resin composite material; the lubricating filler includes one or more of polytetrafluoroethylene, nano-graphite, molybdenum disulfide and boron nitride.

[0022] Preferably, the mass ratio of the waste thermosetting epoxy resin composite material, reinforcing filler and lubricating filler is 100:2.5~7.5:7.5~2.5.

[0023] Preferably, the pressure of the first hot pressing treatment and the second hot pressing treatment are independently 18-22 MPa, the temperature is independently 160-180°C, and the time is independently 0.75-1.5 h.

[0024] The present invention provides a recycled thermosetting epoxy resin composite material prepared by the method described in the above technical solution.

[0025] This invention provides the application of the thermosetting epoxy resin composite material described in the above technical solution, the thermosetting epoxy resin composite material prepared by the preparation method described in the above technical solution, or the recycled thermosetting epoxy resin composite material described in the above technical solution as a tribological material.

[0026] This invention provides a thermosetting epoxy resin composite material, comprising, by weight, the following raw materials: 30-60 parts epoxy resin; 6-10 parts 4,4'-dithiodiphenylamine; 6-10 parts 4-aminophenylboronic acid pinacol ester; 0.5-5 parts hydroxylated reinforcing filler; and 6-12 parts organic solvent. This invention uses epoxy resin as the matrix material, 4-aminophenylboronic acid pinacol ester and 4,4'-dithiodiphenylamine containing disulfide bonds as curing agents, and simultaneously incorporates hydroxylated reinforcing filler. The resulting thermosetting epoxy resin composite material possesses dual dynamic covalent bonds (disulfide bonds and boron ester bonds), endowing it with recyclability.

[0027] This invention provides a method for recycling waste thermosetting epoxy resin composite materials, comprising the following steps: pulverizing the waste thermosetting epoxy resin composite material and mixing it with reinforcing fillers, then performing a first hot-pressing treatment to obtain a precursor material; the thermosetting epoxy resin composite material is the thermosetting epoxy resin composite material described in the above-mentioned technical solution or a thermosetting epoxy resin composite material prepared by the preparation method described in the above-mentioned technical solution; the reinforcing fillers include graphene oxide and / or hydroxylated nanofillers; pulverizing the precursor material and mixing it with lubricating fillers, then performing a second hot-pressing treatment to obtain a recycled thermosetting epoxy resin composite material; the lubricating fillers include one or more of polytetrafluoroethylene, nano-graphite, molybdenum disulfide, and boron nitride. This invention introduces new lubricating fillers into the recycling process of waste thermosetting epoxy resin composite materials, enabling multiple recycling processes. Each recycling process can be modified by adding new reinforcing fillers, achieving multiple redesigns of lubrication and wear resistance (i.e., tribological properties). Existing technologies typically employ mechanical recycling methods to recover waste thermosetting epoxy resins. Specifically, this involves mechanically pulverizing the waste thermosetting epoxy resin to obtain epoxy resin powder, which is then mixed with other thermoplastic resins or adhesives and processed using mechanical means (extruders or hydraulic presses) to obtain new material. Theoretically, this method only recovers the material and does not restore the covalently cross-linked three-dimensional molecular chain structure of the epoxy resin itself. Therefore, with each mechanical pulverization cycle, the mechanical properties of the resulting material gradually decrease. The method of this invention introduces two types of dynamic covalent bonds into the epoxy resin. During the recycling process, it is not necessary to mix with other resins or adhesives; the recycling and restoration of the three-dimensional molecular chain network can be achieved solely through the dynamic covalent bonds within the epoxy cross-linked network. Furthermore, during the recycling process, the epoxy resin can also form new dynamic covalent bonds with lubricating fillers, which not only does not reduce the mechanical properties of the material but also enhances and modifies it. Attached Figure Description

[0028] Figure 1 This is a schematic diagram of the recovery process of sample ADEP2 in Example 1;

[0029] Figure 2 The graph shows the friction coefficient and wear rate results for samples ADEP2, rADEP2, rADEP2-1, and rADEP2-2 in Example 1. Detailed Implementation

[0030] This invention provides a thermosetting epoxy resin composite material, comprising the following raw materials in parts by weight:

[0031] 30-60 parts epoxy resin;

[0032] 6–11 parts of 4,4'-dithiodiphenylamine;

[0033] 6-10 parts of 4-aminophenylboronic acid pinacol ester;

[0034] 0.5–5 parts of hydroxylated reinforcing filler;

[0035] 6 to 12 parts of organic solvent.

[0036] Unless otherwise specified, all raw materials used in this invention are commercially available products well known to those skilled in the art.

[0037] The raw materials for preparing the thermosetting epoxy resin composite material of the present invention, by weight, include 30-60 parts of epoxy resin, preferably 35-55 parts, more preferably 40-50 parts, and even more preferably 46-50 parts. In the present invention, the epoxy resin preferably includes epoxy resin E54, E51, E44 or E42, more preferably epoxy resin E44 (i.e., the international designation of epoxy resin is E44).

[0038] Based on the mass fraction of the epoxy resin, the raw materials for preparing the thermosetting epoxy resin composite material of the present invention include 6 to 11 parts of 4,4'-dithiodiphenylamine (DTDA), preferably 8 to 10.5 parts.

[0039] Based on the mass fraction of the epoxy resin, the raw materials for preparing the thermosetting epoxy resin composite material of the present invention include 6 to 10 parts of 4-aminophenylboronic acid pinacol ester (ABAPE), preferably 6 to 8 parts.

[0040] Based on the mass fraction of the epoxy resin, the raw materials for preparing the thermosetting epoxy resin composite material of the present invention include 0.5 to 5 parts of hydroxylated reinforcing filler, preferably 1.5 to 3.5 parts, and more preferably 2.5 parts. In the present invention, the particle size of the hydroxylated reinforcing filler is preferably 10 to 50 nm, more preferably 15 to 30 nm. In the present invention, the hydroxylated reinforcing filler preferably includes one or more of hydroxylated nano-silica, hydroxylated nano-alumina, hydroxylated carbon nanotubes, nanocellulose, and polydopamine nanoparticles, more preferably hydroxylated nano-silica (hydroxylated nano-SiO2), and the particle size of the hydroxylated nano-silica is preferably 15 to 30 nm.

[0041] Based on the mass fraction of the epoxy resin, the raw materials for preparing the thermosetting epoxy resin composite material of the present invention include 6 to 12 parts of organic solvent, preferably 8 to 11 parts, and more preferably 9.5 parts. In the present invention, the organic solvent preferably includes one or more of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), N-methylpyrrolidone (NMP), and acetone, more preferably N,N-dimethylformamide.

[0042] In this invention, the epoxy resin is used as the matrix material, and hydroxylation is used as a reinforcing filler. The hydroxyl group can serve as a dynamic covalent bond reaction site. 4-aminophenylboronic acid pinacol ester and 4,4'-dithiodiphenylamine containing disulfide bonds are used as curing agents. The resulting thermosetting epoxy resin composite material is a dual dynamic covalent thermosetting epoxy resin composite material with "intelligent friction behavior". It has the characteristics of being reusable, and the tribological properties of the material can be redesigned by adding functional lubricating fillers during the recycling process.

[0043] This invention provides a method for preparing the thermosetting epoxy resin composite material described in the above technical solution, comprising the following steps:

[0044] Epoxy resin, 4,4'-dithiodiphenylamine, pinacol ester of 4-aminophenylboronic acid, hydroxylated reinforcing filler, and organic solvent are mixed and cured to obtain a thermosetting epoxy resin composite material.

[0045] In this invention, 4,4'-dithiodiphenylamine, 4-aminophenylboronic acid pinacol ester, hydroxylated reinforcing filler are mixed with an organic solvent. The mixture is stirred and sonicated to fully dissolve or disperse the 4,4'-dithiodiphenylamine, 4-aminophenylboronic acid pinacol ester and hydroxylated reinforcing filler in the organic solvent. Then, epoxy resin is added and stirred to obtain a mixture.

[0046] After obtaining the mixture, the present invention preferably places the mixture in a mold for curing, and then demolds it to obtain a thermosetting epoxy resin composite material. In the present invention, the mold is preferably a Teflon mold. In the present invention, the curing preferably includes sequentially performing a first curing, a second curing, and a third curing; the temperature of the first curing is preferably 110-130℃, more preferably 120℃, and the holding time is preferably 10-14h, more preferably 12h; the temperature of the second curing is preferably 140-160℃, more preferably 150℃, and the holding time is preferably 2-4h, more preferably 3h; the temperature of the third curing is preferably 160-180℃, more preferably 170℃, and the holding time is preferably 1-3h, more preferably 2h. The preferred staged curing method of this invention facilitates the full cross-linking of the three-dimensional network. During curing, the epoxy groups undergo ring-opening and chemical cross-linking with the amino groups. After the methyl group is deactivated, the 4-aminophenylboronic acid pinacol ester reacts with the hydroxyl groups on the hydroxylated reinforcing filler to form a boronic ester dynamic covalent bond. Simultaneously, during curing, the polymer segments also undergo physical cross-linking through thermal motion. The 4,4'-dithiodiphenylamine molecule contains a disulfide bond, serving as both a curing agent and a carrier of the disulfide dynamic covalent bond. Therefore, the thermosetting epoxy resin composite material prepared by the method of this invention possesses dual dynamic covalent bonds (disulfide bond and boronic ester bond), endowing it with recyclability.

[0047] This invention provides a method for recycling waste thermosetting epoxy resin composite materials, comprising the following steps:

[0048] Waste thermosetting epoxy resin composite material is pulverized and mixed with reinforcing filler, and then subjected to a first hot pressing treatment to obtain a precursor material; the thermosetting epoxy resin composite material is the thermosetting epoxy resin composite material described in the above technical solution or the thermosetting epoxy resin composite material prepared by the preparation method described in the above technical solution; the reinforcing filler includes graphene oxide and / or hydroxylated nanofiller.

[0049] The precursor material is pulverized and mixed with lubricating filler, and then subjected to a second hot pressing treatment to obtain a recycled thermosetting epoxy resin composite material; the lubricating filler includes one or more of polytetrafluoroethylene, nano-graphite, molybdenum disulfide and boron nitride.

[0050] This invention involves pulverizing waste thermosetting epoxy resin composite materials and mixing them with reinforcing fillers, followed by a first hot-pressing treatment to obtain a precursor material. The waste thermosetting epoxy resin composite materials are pulverized to obtain a powder material; the pulverization method is preferably ball milling, with a preferred milling speed of 400–800 rpm, more preferably 500–600 rpm; the preferred milling time is 6–24 h, more preferably 10–12 h. This invention preferably uses high-energy ball milling under the above conditions to pulverize the waste thermosetting epoxy resin composite materials, which can significantly reduce the particle size of the waste thermosetting epoxy resin composite materials and facilitate the full utilization of the dynamic bond exchange effect in the system during recycling. In this invention, the reinforcing filler includes graphene oxide and / or hydroxylated nanofillers, preferably graphene oxide (GO); the preferred sheet size of the graphene oxide is 200–400 μm, and the preferred thickness is 1–4 layers. In this invention, the hydroxylated nanofiller preferably includes hydroxylated carbon nanotubes. In this invention, the mass ratio of the waste thermosetting epoxy resin composite material to the reinforcing filler is preferably 100:(2-8), more preferably 100:5. In this invention, the pressure of the first hot-pressing treatment is preferably 18-22 MPa, more preferably 20 MPa; the temperature is preferably 160-180°C, more preferably 170°C; and the time is preferably 0.75-1.5 h, more preferably 1 h.

[0051] After obtaining the precursor material, the present invention pulverizes the precursor material and mixes it with a lubricating filler, then performs a second hot-pressing treatment to obtain a recycled thermosetting epoxy resin composite material. In this invention, the pulverization method of the precursor material is preferably the same as the pulverization method of the waste thermosetting epoxy resin composite material in the above-mentioned technical solution, and will not be repeated here. In this invention, the lubricating filler preferably includes one or more of polytetrafluoroethylene (PTFE), nano-graphite, molybdenum disulfide, and boron nitride, preferably polytetrafluoroethylene (PTFE); the diameter of the PTFE is preferably 230 nm. In this invention, the mass ratio of the waste thermosetting epoxy resin composite material to the lubricating filler is preferably 100:(2-8), more preferably 100:5. In this invention, the pressure of the second hot-pressing treatment is preferably 18-22 MPa, more preferably 20 MPa; the temperature is preferably 160-180℃, more preferably 170℃; and the time is preferably 0.75-1.5 h, more preferably 1 h.

[0052] This invention provides a recycled thermosetting epoxy resin composite material prepared by the above-described technical solution.

[0053] This invention provides the application of the thermosetting epoxy resin composite material described in the above technical solution, the thermosetting epoxy resin composite material prepared by the preparation method described in the above technical solution, or the recycled thermosetting epoxy resin composite material described in the above technical solution as a friction material.

[0054] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0055] The sources of the raw materials used in the following embodiments and comparative examples of this invention are as follows:

[0056] Graphene oxide (GO) has a sheet diameter of 200–400 μm and a thickness of 1–4 layers;

[0057] The polytetrafluoroethylene (PTFE) particles supplied by DuPont are used, with a diameter of 230 nm.

[0058] The epoxy resin used is provided by Yueyang Baling Petrochemical Industry Co., Ltd., with the international grade E44.

[0059] 4,4'-dithiodiphenylamine (DTDA) supplied by China Energy Chemical Corporation was used.

[0060] The 4-aminophenylboronic acid pinacol ester (ABAPE) supplied by China Energy Chemical Co., Ltd. was used.

[0061] N,N-dimethylformamide (DMF) provided by Liancheng Longbohua Pharmaceutical Chemical Co., Ltd., analytical grade;

[0062] Nano-SiO2 particles with a particle size of 15–30 nm are used, provided by Beijing Deco Shimadzu.

[0063] Example 1

[0064] 1.02g DTDA, 0.6g ABAPE and 0.25g nano-SiO2 particles were dispersed into 10mL DMF under thorough stirring and ultrasonic treatment. Then 5g E44 was added and the mixture was magnetically stirred for 0.5h. The resulting mixture was then transferred into a Teflon mold and cured sequentially at 120℃ for 12h, 150℃ for 3h and 170℃ for 2h to obtain sample ADEP2.

[0065] The sample ADEP2 was ball-milled at a rate of 600 rpm for 12 hours to obtain the first powder sample.

[0066] The first powdered sample was hot-pressed at 20 MPa and 170 °C for 1 h to obtain sample rADEP2.

[0067] By mass fraction, 100 parts of the first powdered sample were mechanically mixed with 5 parts of GO powder, and then hot-pressed at 20 MPa and 170°C for 1 hour to obtain sample rADEP2-1; sample rADEP2-1 was ball-milled at 600 rpm for 12 hours to obtain the second powdered sample; the second powdered sample was mechanically mixed with 5 parts of PTFE powder, and then hot-pressed at 20 MPa and 170°C for 1 hour to obtain sample rADEP2-2.

[0068] Figure 1 The diagram shows the recycling process of sample ADEP2. Specifically, sample ADEP2 is directly ball-milled and then hot-pressed to obtain sample rADEP2 (i.e., no new lubricating filler is added), indicating that the thermosetting epoxy resin composite material prepared by the method of this invention is recyclable.

[0069] Example 2

[0070] 0.7g DTDA, 1.2g ABAPE and 0.25g nano-SiO2 particles were dispersed into 10mL DMF under thorough stirring and ultrasonic treatment. Then 5g E44 was added and the mixture was magnetically stirred for 0.5h. The resulting mixture was then transferred into a Teflon mold and cured sequentially at 120℃ for 12h, 150℃ for 3h and 170℃ for 2h to obtain sample ADEP3.

[0071] The subsequent processing method is the same as in Example 1.

[0072] Example 3

[0073] 0.34g DTDA, 1.8g ABAPE and 0.25g nano-SiO2 particles were dispersed into 10mL DMF under thorough stirring and ultrasonic treatment. Then 5g E44 was added and the mixture was magnetically stirred for 0.5h. The resulting mixture was then transferred into a Teflon mold and cured sequentially at 120℃ for 12h, 150℃ for 3h and 170℃ for 2h to obtain sample ADEP4.

[0074] The subsequent processing method is the same as in Example 1.

[0075] Comparative Example 1

[0076] 1.02g DTDA and 0.6g ABAPE were dispersed in 10mL DMF under thorough stirring and ultrasonic treatment. Then, 5g E44 was added, and the mixture was magnetically stirred for 0.5h. The resulting mixture was then transferred into a Teflon mold and cured sequentially at 120℃ for 12h, 150℃ for 3h, and 170℃ for 2h to obtain sample ADEP2-0.

[0077] Comparative Example 2

[0078] 0.7g DTDA and 1.2g ABAPE were dispersed in 10mL DMF under thorough stirring and ultrasonication. Then, 5g E44 was added, and the mixture was magnetically stirred for 0.5h. The resulting mixture was then transferred into a Teflon mold and cured sequentially at 120℃ for 12h, 150℃ for 3h, and 170℃ for 2h to obtain sample ADEP3-0.

[0079] Comparative Example 3

[0080] 0.34g DTDA and 1.8g ABAPE were dispersed in 10mL DMF under thorough stirring and ultrasonication. Then, 5g E44 was added, and the mixture was magnetically stirred for 0.5h. The resulting mixture was then transferred into a Teflon mold and cured sequentially at 120℃ for 12h, 150℃ for 3h, and 170℃ for 2h to obtain sample ADEP4-0.

[0081] Test case

[0082] The performance of the samples prepared in the examples and comparative examples was tested, as follows:

[0083] The coefficient of friction of each sample over time was recorded using a ball-and-disc friction tester (CSM, Switzerland) at room temperature. The test method was linear reciprocating motion, with a load of 3 N, a speed of 2 cm / s, a stroke of 10 mm, and a duration of 1 hour. GCr15 balls (Φ = 3 mm, Rockwell hardness 62 HRC) were used as the mating material. Before the test, the surface of all samples was polished with 2000-grit sandpaper.

[0084] Wear scars were analyzed using a surface microprofilometer (UP-Lambda, Rtec-Instruments, USA). Wear rates (WRs) were calculated using the following formula:

[0085] WRs = SL1 / PL (mm) 3 / N·m);

[0086] In the formula, S is the cross-sectional area of ​​the wear track, L1 is the length of the wear track, P is the applied load, and L is the sliding distance.

[0087] All tests should be repeated at least three times.

[0088] Table 1. Performance test results of Examples 1-3 and Comparative Examples 1-3

[0089]

[0090]

[0091] Figure 2 The graph shows the friction coefficient and wear rate results for samples ADEP2, rADEP2, rADEP2-1, and rADEP2-2. Figure 2 It can be seen that (1) the thermosetting epoxy resin composite material provided by the present invention can be recycled by hot pressing. After recycling, the friction coefficient of the material is basically the same as that of the raw material, and the wear rate increases; (2) the addition of graphene oxide during the recycling process can significantly reduce the wear rate of the material, indicating that the wear resistance is improved; (3) the addition of polytetrafluoroethylene particles can significantly reduce the friction coefficient and further reduce the wear rate.

[0092] The above results demonstrate that the thermosetting epoxy resin composite provided by this invention has the characteristic of being reusable, and that the tribological properties of the material can be specifically redesigned by adding functional lubricating fillers during the recycling process.

[0093] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A thermosetting epoxy resin composite, raw materials for preparation are the following components in mass fraction: epoxy resin 30-60 parts; 4,4'-dithiodianiline 6-11 parts; 4-aminobenzoic acid pinacol ester 6-10 parts; hydroxylated reinforcing filler 0.5-5 parts; the hydroxylated reinforcing filler is hydroxylated nanosilica; organic solvent 6-12 parts; the organic solvent is one or more of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and acetone; the preparation method of the thermosetting epoxy resin composite comprises the following steps: mixing the epoxy resin, 4,4'-dithiodianiline, 4-aminobenzoic acid pinacol ester, hydroxylated reinforcing filler and organic solvent, and curing to obtain the thermosetting epoxy resin composite; the curing comprises sequentially performing first curing, second curing and third curing; the temperature of the first curing is 110-130 DEG C, and the holding time is 10-14 h; the temperature of the second curing is 140-160 DEG C, and the holding time is 2-4 h; the temperature of the third curing is 160-180 DEG C, and the holding time is 1-3 h. 2.The thermosetting epoxy resin composite of claim 1, wherein the epoxy resin comprises epoxy resin E54, E51, E44 or E42. 3.A preparation method of the thermosetting epoxy resin composite of claim 1 or 2, comprising the following steps: mixing the epoxy resin, 4,4'-dithiodianiline, 4-aminobenzoic acid pinacol ester, hydroxylated reinforcing filler and organic solvent, and curing to obtain the thermosetting epoxy resin composite; the curing comprises sequentially performing first curing, second curing and third curing; the temperature of the first curing is 110-130 DEG C, and the holding time is 10-14 h; the temperature of the second curing is 140-160 DEG C, and the holding time is 2-4 h; the temperature of the third curing is 160-180 DEG C, and the holding time is 1-3 h. 4.A method for recycling waste thermosetting epoxy resin composite, comprising the following steps: crushing the waste thermosetting epoxy resin composite and mixing with reinforcing filler, and performing first hot pressing treatment to obtain precursor material; the waste thermosetting epoxy resin composite is the thermosetting epoxy resin composite of claim 1 or 2 or the thermosetting epoxy resin composite prepared by the preparation method of claim 3; the reinforcing filler comprises graphene oxide and / or hydroxylated nanofiller; crushing the precursor material and mixing with lubricating filler, and performing second hot pressing treatment to obtain recycled thermosetting epoxy resin composite; the lubricating filler comprises one or more of polytetrafluoroethylene, nanographite, molybdenum disulfide and boron nitride. The mass ratio of the waste thermosetting epoxy resin composite, reinforcing filler and lubricating filler is 100:2.5-7.5:7.5-2.

5. The pressure of the first hot pressing treatment and the second hot pressing treatment is independently 18-22 MPa, the temperature is independently 160-180 DEG C, and the time is independently 0.75-1.5 h. 7.The recycled thermosetting epoxy resin composite prepared by the method of any one of claims 4-6. ​ ​ ​ ​ ​ 2. The thermoset epoxy resin composite according to claim 1, characterized in that, ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ 5. The method of claim 4, wherein, ​ 6. The method according to claim 4 or 5, characterized in that, ​ ​ 8. Use of the thermoset epoxy resin composite material according to claim 1 or 2, of the thermoset epoxy resin composite material prepared according to the method of claim 3 or of the recycled thermoset epoxy resin composite material according to claim 7 as tribological material.

Images