CN110698817A - Wear-resistant anti-ultraviolet aging epoxy composite material and preparation method thereof - Google Patents
Wear-resistant anti-ultraviolet aging epoxy composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a wear-resistant anti-ultraviolet aging epoxy composite material and a preparation method thereof, wherein the epoxy composite material comprises an epoxy resin matrix material and TiO uniformly dispersed in the epoxy resin matrix material2/Ti3C2Nanocomposite of said TiO2/Ti3C2The nano composite material accounts for 0.1 to 3 weight percent of the epoxy resin matrix material; the epoxy composite material is prepared by mixing TiO2/Ti3C2The nano composite material and the epoxy resin are obtained by curing in the presence of quaternary ammonium salt. The preparation method of the epoxy composite material is simple, and raw materials are easy to obtain. Compared with the common epoxy material, the wear-resistant anti-ultraviolet aging epoxy composite material prepared by the invention has lower wear rate, excellent anti-ultraviolet aging performance and certain improved tensile strength, and is particularly suitable for being used as wear-resistant devices, such as wear-resistant automobile parts and wear-resistant sports equipment.
Description
Technical Field
The invention belongs to the field of epoxy resin composite materials, and particularly relates to a wear-resistant anti-ultraviolet aging epoxy composite material and a preparation method thereof.
Background
Epoxy resin is a thermosetting polymer with excellent mechanical property, electrical insulation and chemical stability, is used as matrix resin of an enhanced composite material, and is widely used in the engineering fields of aerospace, automobiles, electronics and electricity and the like. However, the inherent three-dimensional network structure of epoxy resins makes them exhibit poor abrasion resistance. Moreover, epoxy resins are susceptible to aging degradation if used in ultraviolet light environments for a long period of time. Therefore, the improvement of the abrasion resistance and the ultraviolet aging resistance is of great significance for the practical application of the epoxy resin.
The addition of organic or inorganic abrasion resistant fillers to epoxy resins is the primary approach to improve abrasion resistance. The wear-resistant filler can reduce the friction coefficient of the epoxy resin or improve the strength of a cross-linked network, thereby improving the wear resistance of the epoxy resin. Research proves that the nano rubber, PTFE, graphite powder and nano TiO2、Al2O3And the like, can effectively improve the wear resistance of the epoxy resin. Improving the ultraviolet aging resistance of epoxy resinThe curing is mainly achieved by adding organic or inorganic UV absorbers. Generally, organic uv absorbers have poor photo-thermal stability and can be slowly destroyed and consumed in polymers, thereby gradually losing uv resistance of the protected polymer material; and inorganic UV absorbers, e.g. ZnO, TiO2And the like, so that the composite material has better photo-thermal stability and stronger ultraviolet absorption capacity, and can improve the mechanical strength of the polymer material.
In recent years, a class of two-dimensional transition metal carbonitride materials known as MXene has attracted increasing attention by researchers. They have excellent electrical, thermal, mechanical and optical properties and can be represented by the general formula Mn+1Xn(n-1-3), wherein M represents an early transition metal, X is one or a combination of carbon and nitrogen, and the surface of the compound contains abundant termination groups such as-OH, -F and the like. Wherein, Ti3C2Is a typical and widely studied MXene material. Ti3C2The lubricating oil has high mechanical strength and low friction coefficient, and shows good application prospect in the fields of solid lubrication, polymer reinforcement and the like. Studies by Zhang et al have found that Ti is added to Ultra High Molecular Weight Polyethylene (UHMWPE)3C2The particles can effectively reduce the friction coefficient of UHMWPE and improve the wear resistance of the UHMWPE. Thus, by adding Ti3C2The particles are expected to be effective in improving the abrasion resistance of the epoxy resin.
TiO2Is a common ultraviolet absorption material and has the characteristics of strong ultraviolet absorption capacity, high stability, safety, no toxicity and the like. Nano TiO 22Has a small size and a large specific surface area, and thus exhibits a strong ultraviolet absorbing ability, and has been widely used as a sunscreen additive in the cosmetic field. Meanwhile, the research proves that the nano TiO2The abrasion resistance of the epoxy resin can also be improved. However, nano TiO2The epoxy resin is easy to agglomerate, so that the improvement effect on the wear resistance and the ultraviolet aging resistance of the epoxy material is greatly reduced. Thus, nano TiO is improved2The dispersion degree in the epoxy resin is made of the wear-resistant anti-ultraviolet aging epoxy composite materialOne of the key problems in the preparation process.
The prior art discloses composites with epoxy and MXene. Patent document CN10980290A discloses an MXene/epoxy resin composite material, wherein the MXene material is prepared by sintering, grinding, etching and ultrasonic layering metal of Ti, Nb, V, Cr or Ta, aluminum powder and carbon powder to obtain a single layer of MXene, mixing with methyl tetrahydrophthalic anhydride, a curing agent, an accelerator and epoxy resin, and heating and curing. However, the method is complex, the yield of the single-layer MXene after ultrasonic treatment is generally low, the obtained MXene is a single-layer/multi-layer mixture, and the mass ratio of the single-layer/multi-layer MXene is extremely difficult to control, so that the performance stability of the finally prepared MXene/epoxy resin composite material product is poor. Patent CN110105711A discloses a method for improving friction performance of epoxy resin by MXene, which is to mix Ti3C2Preparing uniform Ti by nano-sheets and nano-cellulose3C2MXene/cellulose solution, freezing in single direction to obtain Ti3C2A three-dimensional network structure block of the nano-sheet. The epoxy resin is added and fully immersed into the three-dimensional structure to prepare the epoxy resin composite material, and the friction coefficient, the wear rate and the wear volume of the obtained material are greatly improved. However, the method has the defects of complex process flow, difficult industrial production and the like, and does not have large-scale industrial production conditions. In addition, in these methods, the epoxy resin and MXene are simply physically mixed or impregnated, and the two materials cannot be effectively compounded, and thus, various performances of the epoxy resin cannot be effectively improved.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a wear-resistant anti-ultraviolet aging epoxy composite material and a preparation method thereof. The inventors have unexpectedly discovered TiO2/Ti3C2The nano composite particles and the epoxy resin are cured in the presence of the quaternary ammonium salt to obtain the material, so that the wear resistance and the ultraviolet resistance of the material are greatly improved, and the tensile strength is also improved to a certain extent.
Ti3C2Having a unique accordion-like sheet structureThe surface area of the lamella is large, a certain gap exists between the lamellae, and the surface of the lamella has rich-OH functional groups and the like, so that the nano TiO nano composite material is suitable for nano TiO2Growth on the surface thereof. Directly adding nano TiO by hydrothermal method2Uniformly grow on Ti3C2On lamellar structure, simultaneously on the TiO obtained2/Ti3C2The nano composite particles are subjected to surface modification to improve the dispersibility of the nano composite particles in the epoxy resin, so that the wear resistance and the ultraviolet aging resistance of the epoxy resin are improved. By using TiO2/Ti3C2The research of modifying epoxy resin by the nano composite particles has not been reported in a public way.
The invention aims to provide a wear-resistant ultraviolet aging-resistant epoxy composite material which comprises an epoxy resin matrix material and TiO uniformly dispersed in the epoxy resin matrix material2/Ti3C2Nanocomposite of said TiO2/Ti3C2The nano composite material accounts for 0.1 to 3 weight percent of the epoxy resin matrix material; the epoxy composite material is prepared by mixing TiO2/Ti3C2The nano composite material and the epoxy resin are obtained by curing in the presence of quaternary ammonium salt.
Preferably, the TiO is2/Ti3C2The nano composite material accounts for 0.5-1 wt% of the epoxy resin matrix material.
The invention provides a wear-resistant anti-ultraviolet aging epoxy composite material which is prepared from TiO2/Ti3C2The nano composite material is used as filler, firstly TiO is added2/Ti3C2The nano composite material is treated by quaternary ammonium salt, fully mixed with liquid epoxy, mixed with a curing agent and an accelerant to obtain pre-cured epoxy precursor mixed liquid, and then the epoxy composite material is obtained by curing and crosslinking the epoxy precursor mixed liquid at high temperature.
The epoxy resin matrix material is a mixture of liquid epoxy, a curing agent and an accelerator.
Preferably, the liquid epoxy is selected from at least one of E-51, E-55, E-44, E-42; and/or
The curing agent is an anhydride curing agent and is selected from at least one of tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, phthalic anhydride and maleic anhydride; and/or
The accelerator is an amine accelerator and is selected from at least one of tetraethylammonium bromide, dimethylbenzylamine, 2-ethyl-4-methylimidazole, 2,4, 6-tri (dimethylaminomethyl) phenol, triethanolamine, N-dimethylformamide, N-dimethylacetamide, N-dimethylaniline and N, N-dimethylbenzylamine.
The quaternary ammonium salt is ammonium halide with long-chain alkyl or aryl, preferably cetyl trimethyl ammonium bromide, dodecyl dimethyl benzyl ammonium bromide, N dimethyl dodecyl ammonium bromide, octadecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium bromide, didecyl dimethyl ammonium bromide, dodecyl dimethyl benzyl ammonium chloride, hexadecyl trimethyl ammonium chloride, dodecyl dimethyl phenoxy ethyl ammonium bromide, and bis (dodecyl dimethyl) ethylene ammonium bromide.
Preferably, quaternary ammonium salts and TiO2/Ti3C2The mass ratio of the nano composite material is 1:3-8, in particular to the TiO prepared2/Ti3C2The nanocomposite is added to an aqueous quaternary ammonium salt solution, and the concentration of the aqueous quaternary ammonium salt solution is not particularly limited, but the mass fraction of the aqueous quaternary ammonium salt solution is generally 0.2 to 2%.
The TiO is2/Ti3C2The nano composite material is prepared by coating Ti on the surface of the material3C2In the dispersion, tetrabutyl titanate (TBOT) is used as TiO2Precursor, in-situ hydrothermal growth of TiO2Nanoparticles in Ti3C2Obtained by the above method, nano TiO2With Ti3C2The molar ratio of (A) to (B) is 1: 1-5.
Specifically, the TiO2/Ti3C2The nanocomposite is obtained by a preparation method comprising the following steps:
1) addition of TBOT to alcoholsStirring the solution to obtain TiO2Precursor solution; mixing Ti3C2Adding the powder into a mixed solvent of alcohol and water, and performing ultrasonic dispersion to obtain Ti3C2A dispersion liquid; TiO to be obtained2Precursor solution and Ti3C2Uniformly mixing the dispersion liquid, and stirring at room temperature to obtain a uniform mixed solution of the TBOT and the Ti3C2The molar ratio of (A) to (B) is 1: 1-5;
2) transferring the mixed solution obtained in the step 1) into a polytetrafluoroethylene liner, sealing the high-pressure reaction kettle, and fully reacting at 100-220 ℃;
3) after the reaction in the step 2) is finished and naturally cooled, centrifugally collecting powder obtained by the reaction, respectively washing the powder by using deionized water and absolute ethyl alcohol, and then drying the washed powder in vacuum to obtain a powder product, namely TiO2/Ti3C2A nanocomposite material.
Wherein Ti is used3C2The particle size of the powder is not particularly limited, and Ti is obtained by a general conventional method3C2The particle size and the size can be used for preparing TiO in the application2/Ti3C2A nanocomposite material. Preferably, Ti3C2The diameter is 5-10 μm, and the thickness is 3-6 μm.
Adding TiO into the mixture2Precursor solution and Ti3C2The dispersions are mixed homogeneously, either individually or in one solution in another, in a manner known per se. TiO is preferably mixed in the invention2The precursor solution is slowly dripped into Ti3C2In the form of a dispersion.
The second purpose of the invention is to provide a preparation method of the wear-resistant ultraviolet aging resistant epoxy composite material, which comprises the following steps:
1) the obtained TiO is2/Ti3C2Adding the nano composite material into a quaternary ammonium salt aqueous solution, performing ultrasonic dispersion, then adding into liquid epoxy, and performing reduced pressure distillation to obtain TiO2/Ti3C2Adding curing agent and accelerator, stirring under vacuum to obtain epoxy mixtureIs a step of;
2) pouring the epoxy mixed system obtained in the step 1) into a stainless steel mold, and heating and curing to obtain TiO2/Ti3C2A/epoxy composite material.
Wherein the mass ratio of the liquid epoxy, the curing agent and the accelerator is 100:60-100:1-5, preferably 100:80-90: 1-2.
The beneficial effects obtained by the invention are as follows:
firstly, the invention is to mix TiO2/Ti3C2Compounding of nanocomposites with epoxy resins, Ti3C2The epoxy resin has high mechanical strength and low friction coefficient, and can improve the wear resistance of the epoxy resin; and TiO 22Has high-efficiency and stable ultraviolet absorption capacity, and can improve the ultraviolet aging resistance of the epoxy resin. At the same time, TiO2Uniformly grow on Ti3C2Surface of lamella and Ti3C2The epoxy resin matrix is uniformly dispersed.
The inventors have also unexpectedly found that TiO2/Ti3C2After being treated by a certain amount of quaternary ammonium salt, the nano composite particles are cured with epoxy resin, so that the wear resistance and the ultraviolet aging resistance of the obtained epoxy composite material are improved, and the tensile strength is also improved to a certain degree. The chemical combination between the composite particles treated by the quaternary ammonium salt and the epoxy resin is firmer; the growth of the metal oxide particles significantly roughens the Ti3C2 surface, thereby improving the mechanical bond between the nanocomposite particles and the epoxy resin.
The preparation method of the wear-resistant anti-ultraviolet aging epoxy composite material provided by the invention is simple, the raw materials are easy to obtain, and the method is suitable for industrial large-scale production of epoxy resin.
Drawings
FIG. 1 is a schematic view of Ti in preparation example 13C2Scanning Electron Micrographs (SEM) of the nanomaterials.
FIG. 2 shows TiO obtained in preparation example 12/Ti3C2Scanning Electron Micrographs (SEM) of the nanocomposite.
Detailed Description
The technical content of the invention is further explained below with reference to specific embodiments. However, the present invention is not limited to the following examples. Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Ti used in examples of the present invention3C2Is obtained by self-making. The preparation method is widely adopted in the industry, namely commercial Ti3AlC2Adding the powder into hydrofluoric acid, stirring at normal temperature, and etching to obtain Ti3C2A powder having a diameter of about 8 μm and a thickness of about 4 μm. Epoxy resin type E51 was used as purchased from phoenix brand.
Preparation example 2 3 2Preparation of TiO/TiC nano composite material
Preparation example 1
1) Adding 1.25mmol of TBOT into 10mL of ethanol solution, and stirring for 1h to obtain TiO2Precursor solution; adding 2.5mmol of Ti3C2Adding the powder into 30mL of mixed solvent of water and ethanol (the volume ratio of the water to the ethanol is 1:1), and performing ultrasonic dispersion for 0.5h to obtain Ti3C2A dispersion liquid; TiO to be obtained2The precursor solution is slowly dripped into Ti3C2In the dispersion, vigorously stirring for 2 hours at room temperature to obtain a uniform mixed solution;
2) transferring the mixed solution obtained in the step 1) into a polytetrafluoroethylene liner, sealing the high-pressure reaction kettle, and reacting for 24 hours at 160 ℃;
3) after the reaction in the step 2) is finished and naturally cooled, centrifugally collecting powder obtained by the reaction at 6000r/min, respectively washing the powder by using deionized water and absolute ethyl alcohol, and then placing the washed powder in a vacuum drying oven for drying for 12 hours at the temperature of 60 ℃ to obtain a powder productIs TiO2/Ti3C2A nanocomposite;
FIG. 1 shows Ti used3C2SEM photograph of the nanomaterial, and FIG. 2 shows TiO prepared in preparation example 12/Ti3C2SEM photograph of the nanocomposite. As can be seen from the figure, in Ti3C2Nano-sheet in-situ growth TiO2Then, Ti3C2A large amount of TiO uniformly distributed on the nano-chip2Particles which will make TiO2Can exert excellent uvioresistant performance; at the same time Ti3C2The nanosheet surface was significantly roughened, which may render the TiO2/Ti3C2The mechanical combination between the nano composite particles and the epoxy resin matrix is firmer, and the subsequent preparation of TiO is promoted2/Ti3C2Mechanical strength and abrasion resistance of epoxy composites.
Preparation example 2
The other steps were the same as in preparation example 1 except that the amount of TBOT used in step 1) was 2.5mmol, to obtain powdered TiO2/Ti3C2A nanocomposite material.
Preparation example 3
The other steps were the same as in preparation example 1 except that TBOT was used in an amount of 0.625mmol in step 1), to obtain powdered TiO2/Ti3C2A nanocomposite material.
Examples 2 3 2Preparation of TiO/TiC/epoxy composite material
Example 1
1) TiO prepared in preparation example 1 was accurately weighed2/Ti3C2Adding 0.945g of nano composite material into 30mL of aqueous solution containing 0.25g of cetyltrimethylammonium bromide (CTAB), performing ultrasonic treatment for 1h to form dispersion, adding into 100g E-51 liquid epoxy, and distilling at 100 ℃ under reduced pressure for 6h to obtain TiO2/Ti3C2Epoxy mixed solution. Cooling to room temperature, adding 88g of methyl hexahydrophthalic anhydride solution and 1g of tetraethylammonium bromide, and stirring in vacuum for 0.5h to obtain an epoxy mixed system, wherein TiO is2/Ti3C2The dosage of the nano composite material is 0.5 wt% relative to the epoxy resin matrix (the sum of the mass of the liquid epoxy, the methyl hexahydrophthalic anhydride and the tetraethyl ammonium bromide);
2) pouring the epoxy mixed system obtained in the step 2) into a stainless steel mold, and curing for 2 hours at 150 ℃ to obtain TiO2/Ti3C2A/epoxy composite material.
Example 2
Otherwise the same as in example 1, except that TiO in step 1)2/Ti3C2A nanocomposite was prepared as in preparation example 2.
Example 3
Otherwise the same as in example 1, except that TiO in step 1)2/Ti3C2A nanocomposite was prepared as in preparation example 3.
Example 4
Otherwise the same as in example 2, except that TiO in step 1)2/Ti3C2The amount of nanocomposite used was 1.42g, relative to 0.75 wt% of the epoxy resin matrix.
Example 5
Otherwise the same as in example 2, except that TiO in step 1)2/Ti3C2The amount of nanocomposite used was 1.89g, relative to 1 wt% of the epoxy resin matrix.
Example 6
Otherwise the same as in example 2, except that in step 1) the quaternary ammonium salt was replaced by dodecyltrimethylammonium bromide.
Example 7
Otherwise the same as in example 2, except that in step 1) the quaternary ammonium salt was replaced by octadecyl trimethyl ammonium bromide.
Example 8
Otherwise the same as in example 2, except that in step 1) the quaternary ammonium salt was replaced by dodecyldimethylbenzylammonium chloride.
Comparative example 1
Otherwise the same as in example 1, except that no quaternary ammonium salt was added in step 1).
Comparative example 2
The other is the same as in example 1 except that the quaternary ammonium salt is replaced with a silane coupling agent in step 1).
Comparative example 3
The other steps are the same as in example 1, except that in step 1), Sodium Dodecyl Sulfate (SDS) is used instead of quaternary ammonium salt.
Comparative example 4
Otherwise the same as example 1, except that Ti is used in step 1)3C2Replacement of TiO by nano material2/Ti3C2A nanocomposite material.
Comparative example 5
Using a commercially available E-51 type epoxy resin without the addition of TiO2/Ti3C2The nanocomposite was cured under the same curing conditions as in example 1.
Application example
The epoxy resin materials obtained by the check proportion in the above examples were tested for wear resistance and ultraviolet aging resistance, and the results are shown in table 1, and the test methods are as follows: (1) wear resistance
The abrasion resistance of the sample is tested by a friction abrasion tester: the test results were expressed as specific abrasion loss by rubbing for 1h under the conditions of a load of 8N, a rotational speed of 780r/min and a friction torque of 500N · m.
(2) Ultraviolet aging resistance
The ultraviolet aging resistance of the sample refers to GB/T16422-2006 standard: the aging is accelerated for 500h under the conditions that the wavelength of ultraviolet rays is 340nm and the temperature is 60 ℃, and the test result is expressed by the mass loss rate.
(3) Tensile strength
The test was carried out according to the national standard GB/T2568-1995.
TABLE 1
As can be seen from the data in table 1,the invention is prepared by mixing TiO2/Ti3C2After the nano composite material and the epoxy resin are modified, the wear resistance and the ultraviolet aging resistance of the obtained epoxy composite material are greatly improved compared with those of the common epoxy resin sold in the market, and the tensile strength is also improved to a certain extent. By comparing the examples with comparative examples 1 to 3, TiO could not be obtained without adding quaternary ammonium salt or adding other types of modifiers2/Ti3C2The nano composite particles and the epoxy resin are well dispersed, so that the abrasion resistance and the aging resistance of the composite material are improved to a limited extent, and the actual requirements cannot be met.
The preparation method is simple, the raw materials are cheap and easy to obtain, and the obtained epoxy resin composite material has excellent comprehensive performance compared with other epoxy resin composite materials which are not subjected to TiO2/Ti3C2The epoxy resin modified by the nano composite material has the advantages of outstanding wear resistance and ageing resistance, and has market competitiveness.
The above embodiments are merely illustrative of the present disclosure and do not represent a limitation of the present disclosure. Other variations of the specific structure of the invention will occur to those skilled in the art. The above detailed description is specific to one possible embodiment of the present invention, and the embodiment is not intended to limit the scope of the present invention, and all equivalent implementations or modifications without departing from the scope of the present invention should be included in the technical scope of the present invention.
Claims (10)
1. An abrasion-resistant ultraviolet aging-resistant epoxy composite material comprises an epoxy resin matrix material and TiO dispersed in the epoxy resin matrix material2/Ti3C2Nanocomposite of said TiO2/Ti3C2The nano composite material accounts for 0.1 to 3 weight percent of the epoxy resin matrix material; the epoxy composite material is prepared by mixing TiO2/Ti3C2The nano composite material and the epoxy resin are obtained by curing in the presence of quaternary ammonium salt.
2. The epoxy composite material according to claim 1, characterized in thatCharacterized in that the TiO is2/Ti3C2The nano composite material accounts for 0.5-1 wt% of the epoxy resin matrix material.
3. The epoxy composite of claim 1, wherein the epoxy resin matrix material is a mixture of a liquid epoxy, a curing agent, and an accelerator.
4. The epoxy composite of claim 1, wherein the liquid epoxy is selected from at least one of E-51, E-55, E-44, E-42; and/or
The curing agent is an anhydride curing agent and is selected from at least one of tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, phthalic anhydride and maleic anhydride; and/or
The accelerator is an amine accelerator and is selected from at least one of tetraethylammonium bromide, dimethylbenzylamine, 2-ethyl-4-methylimidazole, 2,4, 6-tri (dimethylaminomethyl) phenol, triethanolamine, N-dimethylformamide, N-dimethylacetamide, N-dimethylaniline and N, N-dimethylbenzylamine.
5. The epoxy composite of claim 1, wherein the TiO is selected from the group consisting of2/Ti3C2The nanocomposite is obtained by a preparation method comprising the following steps: at Ti3C2In the dispersion, tetrabutyl titanate (TBOT) is used as TiO2Precursor, in-situ hydrothermal growth of TiO2Nanoparticles in Ti3C2Obtained by the above method, nano TiO2With Ti3C2The molar ratio of (A) to (B) is 1: 1-5.
6. The epoxy composite of claim 5, wherein the TiO is selected from the group consisting of2/Ti3C2The nanocomposite is obtained by a preparation method comprising the following steps:
1) adding TBOT into alcohol solution, stirring to obtain TiO2Precursor solution; mixing Ti3C2Adding the powder into a mixed solvent of alcohol and water, and performing ultrasonic dispersion to obtain Ti3C2A dispersion liquid; TiO to be obtained2Precursor solution and Ti3C2Uniformly mixing the dispersion liquid, and stirring at room temperature to obtain a uniform mixed solution of the TBOT and the Ti3C2The molar ratio of (A) to (B) is 1: 1-5;
2) transferring the mixed solution obtained in the step 1) into a polytetrafluoroethylene liner, sealing the high-pressure reaction kettle, and fully reacting at 100-220 ℃;
3) after the reaction in the step 2) is finished and naturally cooled, centrifugally collecting powder obtained by the reaction, respectively washing the powder by using deionized water and absolute ethyl alcohol, and then drying the washed powder in vacuum to obtain a powder product, namely TiO2/Ti3C2A nanocomposite material.
7. The epoxy composite of claim 1, wherein the quaternary ammonium salt is an ammonium halide with long chain alkyl or aryl groups, preferably cetyl trimethyl ammonium bromide, dodecyl dimethyl benzyl ammonium bromide, N dimethyl dodecyl ammonium bromide, octadecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium bromide, didecyl dimethyl ammonium bromide, dodecyl dimethyl benzyl ammonium chloride, hexadecyl trimethyl ammonium chloride, dodecyl dimethyl phenoxy ethyl ammonium bromide, bis (dodecyl dimethyl) ethylene ammonium bromide.
8. The epoxy composite of claim 1, wherein the quaternary ammonium salt and ZrO2/Ti3C2The mass ratio of the nano composite material is 1: 3-8.
9. A process for preparing an epoxy composite as claimed in any one of claims 1 to 8, comprising the steps of:
1) the obtained TiO is2/Ti3C2Adding the nano composite material into a quaternary ammonium salt aqueous solution, performing ultrasonic dispersion, and adding the solutionIn the epoxy resin, reduced pressure distillation is carried out to obtain TiO2/Ti3C2Adding a curing agent and an accelerator into the epoxy mixed solution, and stirring under vacuum to obtain an epoxy mixed system;
2) heating and curing the epoxy mixed system obtained in the step 1) to obtain TiO2/Ti3C2A/epoxy composite material.
10. The method according to claim 9, wherein the mass ratio of the liquid epoxy, the curing agent and the accelerator is 100:60-100:1-5, preferably 100:80-90: 1-2.
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