Mxene nano hybrid material and application thereof in flame-retardant foaming material

Abstract

The invention relates to the field of nano materials, in particular to an Mxene nano hybrid material and application thereof in a flame-retardant foaming material, and the preparation method of the Mxene nano hybrid material comprises the following steps: step 1, obtaining an aminated MXene nanosheet; step 2, obtaining a sulfhydrylated halloysite nanotube; step 3, obtaining a modified MXene nanosheet; and step 4, obtaining the MXene nano hybrid material. The MXene nano hybrid material prepared by the invention not only has good compatibility with polyurethane foam, but also provides a large number of nucleation sites for a polyurethane foaming system to play a role of a foam stabilizer, so that the finally prepared polyurethane foam material has multiple advantages of high strength, high flame retardance, high thermal conductivity and the like.

Description

Technical Field

[0001] The invention relates to the field of nano materials, and in particular to a Mxene nano hybrid material and application thereof in flame retardant foaming materials. Background Art

[0002] Polyurethane foam is one of the most important varieties of polyurethane materials. It has a porous structure and presents advantages such as low density, high strength and high thermal insulation. It is widely used in many fields such as shockproof, shock absorption, soft cushioning materials and building thermal insulation. However, polyurethane foam has a large number of hydrocarbon segments, which makes it highly flammable, and its limiting oxygen index (LOI) is only 17%-19%. After ignition, it will burn quickly and release a lot of heat, accompanied by the release of smoke and toxic gases (CO, HCN, NO, etc.), posing a serious threat to people's lives and property. With the high-tech industry introducing higher fire safety standards for polyurethane foam materials, the preparation and research of polyurethane foam with high flame retardant performance is very urgent and necessary. However, traditional polyurethane foam surface coating flame retardant strategies such as in-situ deposition, plasma technology, sol-gel process and layer-by-layer self-assembly technology still have problems such as poor coating durability and complex process. Additive flame retardants have poor compatibility with substrates, are easy to leach, and are very easy to deteriorate the mechanical properties of foams, especially under extreme natural conditions such as wet heat erosion, high and low temperature alternation during the day and night, and high-frequency compression recovery. Long-term flame retardancy cannot be achieved. Therefore, the development of polyurethane foam flame retardant technology with long-lasting flame retardancy and enhanced flame retardancy is more favored in future industrial applications and has a bright future.

[0003] MXene is a type of two-dimensional transition metal carbide / nitride / carbonitride, which is widely used in polymer composites due to its excellent anti-permeability, rich surface chemical properties, excellent mechanical properties, and metal-like electrical and thermal conductivity. In recent years, the high-efficiency flame retardant system designed based on the two-dimensional transition metal carbonitride MXene has broad application prospects due to its good smoke suppression performance and adjustable surface functional groups. However, the current development of MXene-based synergistic flame retardants still cannot meet the high demand for flame retardancy of polymer materials. In addition, the synergistic flame retardant effect between MXene and traditional flame retardants is not clear, and it is still a challenge to achieve a high flame retardant level when only a small amount of MXene is added to the synergistic flame retardant formula. Summary of the invention

[0004] In view of the problems existing in the prior art, the purpose of the present invention is to provide a MXene nano-hybrid material and a reinforced flame-retardant polyurethane foam material to overcome the deficiencies in the prior art and improve the flame retardant, mechanical and other properties of the polyurethane foam material.

[0005] The purpose of the present invention is achieved by the following technical solutions: In a first aspect, the present invention provides a method for preparing a MXene nanohybrid material, comprising the following steps: Step 1: MXene nanosheets (Ti3C2T x ) is added to deionized water, fully dispersed under ultrasonic conditions, polyamine is added, the temperature is raised to 40-60°C, treated for 2-6 hours, filtered, washed and dried to obtain aminated MXene nanosheets; Step 2, adding the halloysite nanotubes to an ethanol aqueous solution, fully dispersing under ultrasonic conditions, then adding 3-mercaptopropyltriethoxysilane, heating to 55-75° C., reflux treatment for 3-8 hours, filtering, washing and drying to obtain thiolated halloysite nanotubes; Step 3, weigh glycidyl methacrylate and dissolve it in anhydrous ethanol, then add aminated MXene nanosheets, heat to 70-80°C, reflux and stir for 2-6h, and remove the solvent by rotary evaporation to obtain modified MXene nanosheets; Step 4, adding thiolated halloysite nanotubes and modified MXene nanosheets to toluene, uniformly dispersing them by ultrasonication, adding a photosensitizer under the protection of nitrogen, stirring and treating under ultraviolet light for 0.5-2.5h, and after the treatment, filtering, washing and drying to obtain a MXene nanohybrid material.

[0006] Preferably, in step 1, the particle size of the MXene nanosheets is 3-6 μm.

[0007] Preferably, in step 1, the method for preparing MXene nanosheets comprises: Add LiF to the hydrochloric acid solution, stir thoroughly to dissolve in an ice-water bath, and then slowly add the precursor Ti3AlC2 to the solution. After all the addition, continue to keep warm and stir for 1-2 hours, then raise the temperature to 30-40°C, keep warm and stir for 20-50 hours. After the treatment is completed, filter, wash and dry to obtain MXene nanosheets.

[0008] More preferably, the mass fraction of the hydrochloric acid solution is 28%-33%, and the mass volume ratio of the precursor Ti3AlC2, LiF and the hydrochloric acid solution is (4-6) g: (6-12) g: (100-200) mL.

[0009] Preferably, in step 1, the polyamine is one or more of ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.

[0010] Preferably, in step 1, the mass volume ratio of MXene nanosheets, polyamine and deionized water is (0.1-0.3) g: (0.01-0.04) g: (10-30) mL.

[0011] Preferably, in step 2, the particle size of the halloysite nanotubes is 100-300 nm.

[0012] Preferably, in step 2, the mass fraction of the ethanol aqueous solution is 20%-80%.

[0013] Preferably, in step 2, the mass volume ratio of the halloysite nanotubes, 3-mercaptopropyltriethoxysilane and the ethanol aqueous solution is 1 g: (0.1-0.3) g: (10-30) mL.

[0014] Preferably, in step 3, the mass volume ratio of aminated MXene nanosheets, glycidyl methacrylate and anhydrous ethanol is 1 g: (0.3-0.7) g: (10-30) mL.

[0015] Preferably, in step 4, the mass volume ratio of the modified MXene nanosheets, the thiolated halloysite nanotubes and toluene is 1 g: (0.5-1) g: (20-30) mL.

[0016] Preferably, in step 4, the photosensitizer is one or more of benzoin methyl ether, benzoin ethyl ether, benzoin dimethyl ether and benzoin diethyl ether.

[0017] Preferably, in step 4, the amount of photosensitizer added is 1%-5% of the mass of the thiolated halloysite nanotubes.

[0018] Preferably, in step 4, the wavelength of the ultraviolet light is 365 nm, and the light intensity is 50-250 mW / cm 2 .

[0019] In a second aspect, the present invention provides an application of a MXene nano-hybrid material in a polyurethane foam material, wherein the polyurethane foam material comprises the following components in parts by weight: 100 parts of a polyether polyol, 50-250 parts of a polyisocyanate, 5-15 parts of a MXene nano-hybrid material, 2-6 parts of a catalyst and 3-10 parts of water.

[0020] Preferably, the polyether polyol is one or more of castor oil polyether polyol (hydroxyl value, 190-220 mgKOH / g), glycerol polyether polyol (hydroxyl value, 185-200 mgKOH / g), sorbitol polyether polyol (hydroxyl value, 300-320 mgKOH / g) and sucrose polyether polyol (hydroxyl value, 750-770 mgKOH / g).

[0021] Preferably, the polyisocyanate is polymethylene polyphenyl polyisocyanate, and the isocyanate content is 30%.

[0022] Preferably, the catalyst is catalyst T12.

[0023] Preferably, the preparation method of the polyurethane foam material comprises: (1) Mixing polyether polyol, MXene nano-hybrid material, catalyst and water at a speed of 300-500 r / min for 5-10 min to obtain a mixture; (2) Add polyisocyanate to the mixture of step (1) at a stirring speed of 300-500 r / min, mix and stir for 10-15 seconds, then immediately pour into a mold for foaming to obtain a flame retardant foam material.

[0024] The beneficial effects of the present invention are: 1. The present invention prepares a MXene nano-hybrid material, and uses the MXene nano-hybrid material to obtain an enhanced flame-retardant polyurethane foam material. The MXene nano-hybrid material prepared by the present invention not only has good compatibility with polyurethane foam, but also provides a large number of nucleation sites for the polyurethane foam system to act as a foam stabilizer, so that the finally prepared polyurethane foam material has multiple advantages such as high strength, high flame retardancy, and high thermal conductivity.

[0025] 2. The present invention utilizes the -NH2 of polyamine and the -OH, -F and other functional groups on the MXene interface to form a self-healing hydrogen bond network through self-assembly to construct a stable MXene-based sandwich structure. On the one hand, the MXene interlayer spacing can be adjusted through the hydrogen bond network, and on the other hand, the rich amino groups provide additional cross-linking active sites. Then, the aminated MXene nanosheets are reacted with glycidyl methacrylate to react the amino-epoxy groups to obtain modified MXene nanosheets. The halloysite nanotubes are activated with a mercaptosilane coupling agent to give the halloysite nanotubes mercapto groups, and then the mercapto-double bond click chemistry reaction occurs with the modified MXene nanosheets containing unsaturated bonds, and finally the MXene nanohybrid material is obtained.

[0026] 3. The present invention modifies the polyurethane foam material with MXene nano-hybrid material to obtain a reinforced flame-retardant polyurethane foam material. The polyurethane foam material of the present invention has the characteristics of high strength, excellent flame retardancy and thermal conductivity, etc. The prepared polyurethane foam material can be used in fuel vehicles, electric vehicle shock absorber blocks, 3C product device sealing, shock absorption, dust prevention, new energy battery cell protection, box insulation, module protection and other fields.

[0027] 4. The MXene nano-hybrid material and polyurethane foam material described in the present invention have simple preparation processes, no environmental pollution, and are suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The present invention is further described using the accompanying drawings, but the embodiments in the accompanying drawings do not constitute any limitation to the present invention. A person skilled in the art can obtain other drawings based on the following drawings without creative work.

[0029] Figure 1 This is a SEM schematic diagram of the product prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0030] The technical solution of the present invention is described below through specific examples. It should be understood that the one or more method steps mentioned in the present invention do not exclude the existence of other method steps before and after the combination step or the insertion of other method steps between these explicitly mentioned steps; it should also be understood that these embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention. Moreover, unless otherwise specified, the numbering of each method step is only a convenient tool for identifying each method step, and is not intended to limit the order of arrangement of each method step or to limit the scope of the present invention. The change or adjustment of the relative relationship thereof shall also be regarded as the scope of the present invention without substantially changing the technical content.

[0031] In order to better understand the above technical scheme, the exemplary embodiments of the present invention are described in more detail below. Although exemplary embodiments of the present invention are shown, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments set forth herein. On the contrary, these embodiments are provided in order to enable a more thorough understanding of the present invention and to enable the scope of the present invention to be fully communicated to those skilled in the art.

[0032] The present invention will be further described below in conjunction with the following examples.

[0033] Example 1 A method for preparing a MXene nanohybrid material comprises the following steps: Step 1, add LiF to a hydrochloric acid solution with a mass fraction of 31%, stir and dissolve it in an ice water bath, and then slowly add the precursor Ti3AlC2 into the solution. The mass volume ratio of the precursor Ti3AlC2, LiF and hydrochloric acid solution is 5g:9g:150mL. After all are added, continue to keep warm and stir for 1.5h, then heat to 35°C, keep warm and stir for 30h. After the treatment is completed, filter, wash and dry to obtain MXene nanosheets with a particle size of 3-6μm; Step 2: MXene nanosheets (Ti3C2T x) was added to deionized water, fully dispersed under ultrasonic conditions, triethylenetetramine was added, the mass volume ratio of MXene nanosheets, triethylenetetramine and deionized water was 0.2g:0.03g:20mL, the temperature was raised to 50°C, treated for 4h, filtered, washed and dried to obtain aminated MXene nanosheets; Step 3, adding halloysite nanotubes with a particle size of 100-300 nm to a 50% ethanol aqueous solution by mass fraction, fully dispersing under ultrasonic conditions, and then adding 3-mercaptopropyltriethoxysilane, the mass volume ratio of halloysite nanotubes, 3-mercaptopropyltriethoxysilane and ethanol aqueous solution is 1g:0.2g:20mL, heating to 65°C, reflux treatment for 5h, filtering, washing and drying to obtain thiolated halloysite nanotubes; Step 4, weigh glycidyl methacrylate and dissolve it in anhydrous ethanol, then add aminated MXene nanosheets, the mass volume ratio of aminated MXene nanosheets, glycidyl methacrylate and anhydrous ethanol is 1g:0.5g:20mL, heat to 75°C, reflux and stir for 4h, and remove the solvent by rotary evaporation to obtain modified MXene nanosheets; Step 5: Add the thiolated halloysite nanotubes and modified MXene nanosheets to toluene, the mass volume ratio of the modified MXene nanosheets, the thiolated halloysite nanotubes and toluene is 1 g:0.6 g:25 mL, and ultrasonic dispersion is uniform. Under the protection of nitrogen, benzoin dimethyl ether is added in an amount of 3% of the mass of the thiolated halloysite nanotubes, the wavelength is 365 nm, and the illumination intensity is 150 mW / cm 2 The mixture was stirred and treated under ultraviolet light for 1.5 h. After the treatment, the mixture was filtered, washed and dried to obtain a MXene nanohybrid material.

[0034] The MXene nano-hybrid material is applied in a polyurethane foam material, which includes the following components in parts by weight: 100 parts of castor oil polyether polyol, 57.3 parts of polymethylene polyphenyl polyisocyanate, 10 parts of MXene nano-hybrid material, 4 parts of catalyst T12 and 4 parts of water.

[0035] Wherein, the preparation method of polyurethane foam material comprises: (1) Castor oil polyether polyol (hydroxyl value, 190-220 mgKOH / g), MXene nanohybrid material, catalyst and water were mixed and stirred at a speed of 400 r / min for 8 min to obtain a mixture; (2) Add polymethylene polyphenyl polyisocyanate (isocyanate content: 30%) to the mixture of step (1), stir at a speed of 400 r / min, mix and stir for 12 seconds, and then immediately pour into a mold for foaming to obtain a flame retardant foam material.

[0036] Example 2 A method for preparing a MXene nanohybrid material comprises the following steps: Step 1, add LiF to a hydrochloric acid solution with a mass fraction of 28%, stir and dissolve it in an ice water bath, and then slowly add the precursor Ti3AlC2 into the solution. The mass volume ratio of the precursor Ti3AlC2, LiF and hydrochloric acid solution is 4g:6g:100mL. After all are added, continue to keep warm and stir for 1h, then heat to 30°C, keep warm and stir for 20h. After the treatment is completed, filter, wash and dry to obtain MXene nanosheets with a particle size of 3-6μm; Step 2: MXene nanosheets (Ti3C2T x ) was added to deionized water, fully dispersed under ultrasonic conditions, ethylenediamine was added, the mass volume ratio of MXene nanosheets, ethylenediamine and deionized water was 0.1g:0.01g:10mL, the temperature was raised to 40°C, treated for 2h, filtered, washed and dried to obtain aminated MXene nanosheets; Step 3, adding halloysite nanotubes with a particle size of 100-300 nm to a 20% ethanol aqueous solution by mass fraction, fully dispersing under ultrasonic conditions, and then adding 3-mercaptopropyltriethoxysilane, the mass volume ratio of halloysite nanotubes, 3-mercaptopropyltriethoxysilane and ethanol aqueous solution is 1g:0.1g:10mL, heating to 55°C, reflux treatment for 3h, filtering, washing and drying to obtain thiolated halloysite nanotubes; Step 4, weigh glycidyl methacrylate and dissolve it in anhydrous ethanol, then add aminated MXene nanosheets, the mass volume ratio of aminated MXene nanosheets, glycidyl methacrylate and anhydrous ethanol is 1g:0.3g:10mL, heat to 70°C, reflux and stir for 2h, and remove the solvent by rotary evaporation to obtain modified MXene nanosheets; Step 5: Add the thiolated halloysite nanotubes and modified MXene nanosheets to toluene, the mass volume ratio of the modified MXene nanosheets, the thiolated halloysite nanotubes and toluene is 1 g:0.5 g:20 mL, and ultrasonically disperse them uniformly. Under the protection of nitrogen, add benzoin methyl ether in an amount of 1% of the mass of the thiolated halloysite nanotubes, the wavelength is 365 nm, and the illumination intensity is 50 mW / cm 2 The mixture was stirred and treated under ultraviolet light for 2.5 h. After the treatment, the MXene nanohybrid material was obtained by filtration, washing and drying.

[0037] The MXene nano-hybrid material is applied in a polyurethane foam material, which includes the following components in parts by weight: 100 parts of glycerol polyether polyol, 53.8 parts of polymethylene polyphenyl polyisocyanate, 5 parts of MXene nano-hybrid material, 2 parts of catalyst T12 and 3 parts of water.

[0038] Wherein, the preparation method of polyurethane foam material comprises: (1) Glycerol polyether polyol (hydroxyl value, 185-200 mgKOH / g), MXene nanohybrid material, catalyst and water were mixed and stirred at a speed of 300 r / min for 5 min to obtain a mixture; (2) Add polymethylene polyphenyl polyisocyanate (isocyanate content: 30%) to the mixture of step (1), stir at a speed of 300 r / min, mix and stir for 10 seconds, and immediately pour into a mold for foaming to obtain a flame retardant foam material.

[0039] Example 3 A method for preparing a MXene nanohybrid material comprises the following steps: Step 1, add LiF to a hydrochloric acid solution with a mass fraction of 33%, stir and dissolve it in an ice water bath, and then slowly add the precursor Ti3AlC2 into the solution. The mass volume ratio of the precursor Ti3AlC2, LiF and hydrochloric acid solution is 6g:12g:200mL. After all are added, continue to keep warm and stir for 2h, then heat to 40°C, keep warm and stir for 50h. After the treatment is completed, filter, wash and dry to obtain MXene nanosheets with a particle size of 3-6μm; Step 2: MXene nanosheets (Ti3C2T x ) was added to deionized water, fully dispersed under ultrasonic conditions, and diethylenetriamine was added. The mass volume ratio of MXene nanosheets, diethylenetriamine and deionized water was 0.3g:0.04g:30mL. The temperature was raised to 60°C and treated for 6h. After filtering, washing and drying, aminated MXene nanosheets were obtained; Step 3, adding halloysite nanotubes with a particle size of 100-300 nm to an ethanol aqueous solution with a mass fraction of 80%, fully dispersing under ultrasonic conditions, and then adding 3-mercaptopropyltriethoxysilane, the mass volume ratio of halloysite nanotubes, 3-mercaptopropyltriethoxysilane and ethanol aqueous solution is 1g:0.3g:30mL, heating to 75°C, reflux treatment for 8h, filtering, washing and drying to obtain thiolated halloysite nanotubes; Step 4, weigh glycidyl methacrylate and dissolve it in anhydrous ethanol, then add aminated MXene nanosheets, the mass volume ratio of aminated MXene nanosheets, glycidyl methacrylate and anhydrous ethanol is 1g:0.7g:30mL, heat to 80°C, reflux and stir for 6h, and remove the solvent by rotary evaporation to obtain modified MXene nanosheets; Step 5: Add the thiolated halloysite nanotubes and modified MXene nanosheets to toluene, the mass volume ratio of the modified MXene nanosheets, the thiolated halloysite nanotubes and toluene is 1 g:1 g:30 mL, and ultrasonic dispersion is uniform. Under the protection of nitrogen, add benzoin diethyl ether, the addition amount is 5% of the mass of the thiolated halloysite nanotubes, the wavelength is 365 nm, and the illumination intensity is 250 mW / cm 2 The mixture was stirred and treated under ultraviolet light for 0.5 h. After the treatment, the mixture was filtered, washed and dried to obtain a MXene nanohybrid material.

[0040] The MXene nano-hybrid material is applied in a polyurethane foam material, which includes the following components in parts by weight: 100 parts of sorbitol polyether polyol, 212.5 g of polymethylene polyphenyl polyisocyanate, 15 parts of MXene nano-hybrid material, 6 parts of catalyst T12 and 10 parts of water.

[0041] Wherein, the preparation method of polyurethane foam material comprises: (1) Sorbitol polyether polyol (hydroxyl value, 300-320 mgKOH / g), MXene nanohybrid material, catalyst and water were mixed and stirred at a speed of 500 r / min for 10 min to obtain a mixture; (2) Add polymethylene polyphenyl polyisocyanate (isocyanate content: 30%) to the mixture of step (1), stir at a speed of 500 r / min, mix and stir for 15 seconds, and immediately pour into a mold for foaming to obtain a flame retardant foam material.

[0042] Comparative Example 1 A MXene nano-hybrid material, which differs from Example 1 in that the aminated MXene nanosheets and the halloysite nanotubes are directly compounded, and the preparation method includes: Step 1, preparing aminated MXene nanosheets, the same as in Example 1; Step 2: Add halloysite nanotubes and aminated MXene nanosheets to toluene, with the mass volume ratio of aminated MXene nanosheets, halloysite nanotubes and toluene being 1 g:0.6 g:25 mL; heat to 75° C., reflux with stirring for 4 h, and remove the solvent by rotary evaporation to obtain a MXene nanohybrid material.

[0043] The obtained MXene nano-hybrid material is applied to a polyurethane foam material, and the composition and preparation method of the polyurethane foam material are the same as those in Example 1.

[0044] Comparative Example 2 A MXene nano-hybrid material, which is different from Example 1 in that MXene nanosheets and thiolated halloysite nanotubes are directly compounded, and the preparation method includes: Step 1, preparing MXene nanosheets, the same as in Example 1; Step 2, preparing thiolated halloysite nanotubes, the same as in Example 1; Step 3, adding thiolated halloysite nanotubes and MXene nanosheets to toluene, the mass volume ratio of MXene nanosheets, thiolated halloysite nanotubes and toluene is 1g:0.6g:25mL, heating to 75°C, reflux stirring for 4h, and rotary evaporation to remove the solvent to obtain a MXene nanohybrid material.

[0045] The obtained MXene nano-hybrid material is applied to a polyurethane foam material, and the composition and preparation method of the polyurethane foam material are the same as those in Example 1.

[0046] Comparative Example 3 A MXene nano-hybrid material, which is different from Example 1 in that aminated MXene nanosheets, glycidyl methacrylate and halloysite nanotubes are directly compounded, and the preparation method includes: Step 1, preparing aminated MXene nanosheets, the same as in Example 1; Step 2: weigh glycidyl methacrylate and dissolve it in anhydrous ethanol, then add aminated MXene nanosheets and halloysite nanotubes, the mass volume ratio of aminated MXene nanosheets, halloysite nanotubes, glycidyl methacrylate and anhydrous ethanol is 1g:0.6g:0.5g:20mL, heat to 75°C, reflux with stirring for 4h, and remove the solvent by rotary evaporation to obtain a MXene nanohybrid material.

[0047] The obtained MXene nano-hybrid material is applied to a polyurethane foam material, and the composition and preparation method of the polyurethane foam material are the same as those in Example 1.

[0048] Experimental testing: The properties of the polyurethane foam materials prepared in Example 1 and Comparative Examples 1-3 were tested respectively, and the test items included compressive strength (reference standard GB / T 8813-2020), horizontal burning rate (reference standard ASTM D4986), vertical burning time (reference standard UL 94), flame retardant grade (reference standard UL 94) and thermal conductivity (reference standard GB / T10294-2008). The test results are shown in Table 1: Table 1 Performance test results of different polyurethane foam materials Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Compression strength (KPa) 278.0 193.7 211.2 234.5 Vertical burning time (s) 40.1 20.8 25.1 21.9 Horizontal burning rate (mm / min) 54.2 100.4 81.5 97.8 Flame retardant grade (UL94) V-0 V-1 V-1 V-1 <![CDATA[Thermal conductivity (W•(m•K) -1 )]]> 0.037 0.041 0.039 0.034 It can be seen from the test results in Table 1 that the strength and flame retardancy of the polyurethane foam material prepared in Example 1 of the present invention are significantly better than those of Comparative Examples 1-3, and can also maintain good thermal conductivity, indicating that the polyurethane foam material prepared in Example 1 of the present invention has multiple advantages such as high strength, high flame retardancy, and high thermal conductivity.

[0049] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms should not be understood as necessarily being directed to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine different embodiments or examples described in this specification.

[0050] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations of the present invention. A person skilled in the art may change, modify, replace and vary the above embodiments within the scope of the present invention.

Claims

1. A method for preparing a MXene nanohybrid material, characterized in that: The following steps are involved: Step 1: MXene nanosheets (Ti3C2T x ) is added to deionized water, fully dispersed under ultrasonic conditions, polyamine is added, the temperature is raised to 40-60°C, treated for 2-6 hours, filtered, washed and dried to obtain aminated MXene nanosheets; Step 2, adding the halloysite nanotubes to an ethanol aqueous solution, fully dispersing under ultrasonic conditions, then adding 3-mercaptopropyltriethoxysilane, heating to 55-75° C., reflux treatment for 3-8 hours, filtering, washing and drying to obtain thiolated halloysite nanotubes; Step 3, weigh glycidyl methacrylate and dissolve it in anhydrous ethanol, then add aminated MXene nanosheets, heat to 70-80°C, reflux and stir for 2-6h, and remove the solvent by rotary evaporation to obtain modified MXene nanosheets; Step 4, adding thiolated halloysite nanotubes and modified MXene nanosheets to toluene, uniformly dispersing them by ultrasonication, adding a photosensitizer under the protection of nitrogen, stirring and treating under ultraviolet light for 0.5-2.5h, and after the treatment, filtering, washing and drying to obtain a MXene nanohybrid material.

2. The method for preparing a MXene nanohybrid material according to claim 1, characterized in that: In step 1, the method for preparing MXene nanosheets comprises: LiF is added to the hydrochloric acid solution, fully stirred and dissolved in an ice-water bath, and then the precursor Ti3AlC2 is slowly added to the solution. After all the addition, the solution is kept warm and stirred for 1-2 hours, and then the temperature is raised to 30-40°C and kept warm and stirred for 20-50 hours. After the treatment, MXene nanosheets are obtained by filtering, washing and drying; wherein the mass fraction of the hydrochloric acid solution is 28%-33%, and the mass volume ratio of the precursor Ti3AlC2, LiF and the hydrochloric acid solution is (4-6) g:(6-12) g:(100-200) mL.

3. The method for preparing a MXene nanohybrid material according to claim 1, characterized in that: In the step 1, the polyamine is one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine.

4. The method for preparing a MXene nanohybrid material according to claim 1, characterized in that: In step 1, the mass volume ratio of MXene nanosheets, polyamine and deionized water is (0.1-0.3) g: (0.01-0.04) g: (10-30) mL.

5. The method for preparing a MXene nanohybrid material according to claim 1, characterized in that: In the step 2, the mass volume ratio of the halloysite nanotubes, 3-mercaptopropyltriethoxysilane and the ethanol aqueous solution is 1 g: (0.1-0.3) g: (10-30) mL.

6. The method for preparing a MXene nanohybrid material according to claim 1, characterized in that: In the step 3, the mass volume ratio of the aminated MXene nanosheets, glycidyl methacrylate and anhydrous ethanol is 1 g: (0.3-0.7) g: (10-30) mL.

7. The method for preparing a MXene nanohybrid material according to claim 1, characterized in that: In the step 4, the mass volume ratio of the modified MXene nanosheets, the thiolated halloysite nanotubes and toluene is 1 g: (0.5-1) g: (20-30) mL.

8. A MXene nanohybrid material, characterized in that: The MXene nanohybrid material is prepared by the preparation method described in claim 1.

9. Use of the MXene nano-hybrid material according to claim 8 in a polyurethane foam material.

10. The use of the MXene nano-hybrid material in a polyurethane foam material according to claim 9, characterized in that: The polyurethane foaming material comprises the following components in parts by weight: 100 parts of polyether polyol, 50-250 parts of polyisocyanate, 5-15 parts of MXene nano hybrid material, 2-6 parts of catalyst and 3-10 parts of water.

Images