Graphene fiber insole material and application thereof

Abstract

The invention relates to the field of insole materials, in particular to a graphene fiber insole material and application thereof, and a preparation method of the graphene fiber insole material comprises the following steps: S1, preparing carboxylated graphene; s2, preparing thiolated graphene; s3, catechol lignin is prepared; s4, preparing vinyl phenylboronic acid esterified lignin; s5, carrying out a reaction on the sulfhydrylated graphene and the vinyl phenylboronic acid esterified lignin to obtain modified graphene; s6, spinning to obtain the graphene fiber insole material. The graphene fiber insole material prepared by the preparation method disclosed by the invention is prepared by compounding modified graphene and polyamide resin and then carrying out electrostatic spinning. The graphene fiber material prepared by the method not only has higher strength and wear resistance, but also has better moisture absorption and air permeability, and also has very excellent long-term antibacterial property.

Description

Technical Field

[0001] The invention relates to the field of insole materials, and in particular to a graphene fiber insole material and application thereof. Background Art

[0002] As the direct contact layer between the shoe and the foot, the insole not only bears the heavy responsibility of support, cushioning and comfort, but is also directly related to the health and hygiene of the foot. An excellent insole should be able to effectively absorb sweat discharged from the foot, prevent bacterial growth, thereby reducing the problem of foot odor and providing the wearer with a dry and comfortable wearing experience. As a new type of two-dimensional carbon nanomaterial, graphene has a strict two-dimensional structure of honeycomb-like carbon atoms and rich and excellent physical properties (high carrier mobility, ultra-large specific surface area, excellent mechanical properties and chemical stability). Once discovered, it quickly set off a huge research boom in the fields of physics and materials science. Graphene has unique physical, chemical and electrical properties, and has been applied in various fields, including electronics, optoelectronics, energy, biology, etc.

[0003] Graphene is a very light and thin material. Its advantages are first of all that it is very light, weighing only about a quarter of that of ordinary insoles, which can reduce the weight of insoles, provide more free movement space for the feet, and increase comfort; secondly, graphene has good thermal conductivity, electrical conductivity and air permeability, so that graphene insoles can keep feet dry and reduce the adverse effects of bacteria and sweat; in addition, graphene also has high hardness and strength, and the degree of wear is lower than that of ordinary materials, which can extend the service life of insoles. However, due to the high price of graphene materials, graphene is usually used to prepare composite materials after blending with polymers such as polyamide. However, due to the poor compatibility of graphene and polyamide, graphene is unevenly dispersed, and composite materials also have many defects when used as insole materials. For example, in actual use, they may encounter problems such as durability, long-term antibacterial properties, and insufficient moisture absorption and air permeability. Summary of the invention

[0004] In view of the problems existing in the prior art, the object of the present invention is to provide a graphene fiber insole material and application thereof.

[0005] The purpose of the present invention is achieved by the following technical solutions:

[0006] In a first aspect, the present invention provides a method for preparing a graphene fiber insole material, comprising the following steps:

[0007] S1. Graphene carboxylation:

[0008] The graphene powder and the nitric acid solution are mixed, stirred for 8-12 hours, centrifuged, washed and dried to obtain carboxylated graphene;

[0009] S2. Graphene thiolation:

[0010] The carboxylated graphene and anhydrous ethanol are mixed and dispersed uniformly, and then a silane coupling agent KH-580 is added dropwise, and the mixture is refluxed at 65-85° C. for 3-10 hours, centrifuged, washed and dried to obtain the thiol-modified graphene;

[0011] S3, catechol lignin:

[0012] Mix lignin and dimethyl sulfoxide, heat-treat at 80-120°C for 10-20 minutes, then add cyclohexyl bromide, continue to heat-treat and stir for 8-12 hours, and after the reaction is completed, purify, wash and dry to obtain catecholized lignin;

[0013] S4, preparation of vinylbenzene borate esterified lignin:

[0014] Mixing 4-vinylbenzene boronic acid and catecholated lignin in tetrahydrofuran, stirring and treating at 20-40° C. for 12-24 hours, and removing the solvent under reduced pressure after the treatment to obtain vinylbenzene borate esterified lignin;

[0015] S5. Preparation of modified graphene:

[0016] The thiolated graphene, vinylbenzene borate lignin and tetrahydrofuran are mixed, a photoinitiator is added, and the mixture is stirred under ultraviolet light for 1-3 hours. After the reaction is completed, the mixture is centrifuged, washed and dried to obtain modified graphene.

[0017] S6. Preparation of insole materials:

[0018] The polyamide resin is dissolved in N,N-dimethylformamide, and then the modified graphene is added and mixed thoroughly to obtain a spinning solution, which is then subjected to an electrostatic spinning treatment to obtain a graphene fiber insole material.

[0019] Preferably, during the graphene carboxylation process of S1, the particle size of the graphene powder is 1-3 μm, and the concentration of the nitric acid solution is 5-10 mol / L.

[0020] Preferably, in S1, the mass volume ratio of graphene powder to nitric acid solution is 1 g:(10-30) mL.

[0021] Preferably, in S2, the mass volume ratio of carboxylated graphene, silane coupling agent KH-580 and anhydrous ethanol is 1 g: (0.1-0.5) g: (10-30) mL.

[0022] Preferably, in S3, the lignin is alkaline lignin, with a particle size of 100-200 nm and a purity of ≥98%.

[0023] Preferably, in S3, the mass volume ratio of lignin, cyclohexyl bromide and dimethyl sulfoxide is 1 g: (6.2-12.4) g: (30-80) mL.

[0024] Preferably, in S4, the mass volume ratio of 4-vinylbenzeneboric acid, catecholated lignin and tetrahydrofuran is (2.4-4.8) g: 1 g: (20-50) mL.

[0025] Preferably, in S5, the light intensity of the ultraviolet lamp is 10-15W / cm 2 The photoinitiator is dimethyl benzoate (DMPA), and the added amount is 1.5%-6.5% of the mass of the thiol-modified graphene.

[0026] Preferably, in S5, the mass volume ratio of thiolated graphene, vinylbenzene borate lignin and tetrahydrofuran is 1 g: (7.3-14.6) g: (40-80) mL.

[0027] Preferably, in S6, the polyamide resin is at least one of PA6, PA66 and PA12, and has a molecular weight of 10,000-50,000.

[0028] Preferably, in S6, the mass volume ratio of the modified graphene, the polyamide resin and the N,N-dimethylformamide is 0.2-1:10:40-60.

[0029] Preferably, in S6, the parameters of electrospinning are: spinning voltage is 10-30 kV, propulsion speed is 0.3-0.8 mL / h, and receiving distance is 10-30 cm.

[0030] In a second aspect, the present invention provides a graphene fiber insole material prepared by the above-mentioned preparation method.

[0031] In a third aspect, the present invention provides an application of a graphene fiber insole material in the insoles of sports shoes and casual shoes.

[0032] The beneficial effects of the present invention are:

[0033] 1. The graphene fiber insole material prepared by the present invention is prepared by electrostatic spinning after compounding modified graphene and polyamide resin. The graphene fiber material prepared by this method not only has high strength and wear resistance, but also has good moisture absorption and air permeability, and also has very excellent long-term antibacterial properties.

[0034] 2. The modified graphene is made of thiol-modified graphene and vinylbenzene borate-modified lignin as raw materials, and is obtained by combining the thiol-ene click reaction under the initiation of light. Lignin and borate groups are introduced into the prepared modified graphene, and sulfide groups are also generated, thereby giving the modified graphene very good antibacterial properties. In addition, it has better compatibility with polyamide materials, and has obvious improvements in moisture absorption, air permeability and mechanical strength.

[0035] 3. The present invention prepares catecholated lignin by using an in-situ demethylation method for alkaline lignin, and then uses 4-vinylbenzeneboric acid as a reactant to combine with the catecholated lignin to form a borate ester bond, thereby obtaining vinylbenzene borate esterified lignin. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] 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.

[0037] Figure 1 Schematic diagram of SEM of the graphene fiber insole material prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0038] 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.

[0039] 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.

[0040] The present invention will be further described below in conjunction with the following examples.

[0041] Example 1

[0042] A method for preparing a graphene fiber insole material comprises the following steps:

[0043] S1. Graphene carboxylation:

[0044] Graphene powder with a particle size of 1-3 μm and 6 mol / L nitric acid solution are mixed, the mass volume ratio of graphene powder to nitric acid solution is 1 g: 20 mL, stirred overnight (about 10 h) at 25° C., then centrifuged in a centrifuge, the lower layer of precipitate is collected, washed with distilled water until the washing liquid is neutral, and then the precipitate is collected and placed in a vacuum drying oven for drying to obtain carboxylated graphene;

[0045] S2. Graphene thiolation:

[0046] The carboxylated graphene and anhydrous ethanol were mixed and dispersed uniformly, and then a silane coupling agent KH-580 (γ-mercaptopropyltriethoxysilane) was added dropwise, and the mass volume ratio of the carboxylated graphene, the silane coupling agent KH-580 and the anhydrous ethanol was 1g:0.3g:20mL. The mixture was placed in a water bath, heated to 75°C, and refluxed for 8h. After the treatment was completed, the mixture was cooled to room temperature, and the precipitate was collected by centrifugation in a centrifuge, washed with anhydrous ethanol for 3 times, and then dried in a vacuum oven to obtain thiolated graphene.

[0047] S3, catechol lignin:

[0048] Alkaline lignin (purity ≥ 98%) with a particle size of 100-200 nm and dimethyl sulfoxide are mixed, stirred until fully dissolved, and then heated to 100° C. under the protection of nitrogen, and kept warm for 15 minutes, and then cyclohexyl bromide is added, and the mass volume ratio of lignin, cyclohexyl bromide and dimethyl sulfoxide is 1g:9.3g:50mL, and the stirring is continued for 10 hours. After the reaction is completed, it is cooled to room temperature, and then washed with n-hexane, and then poured into a saturated sodium pyrosulfite solution, the precipitate is collected, washed with water 3 times, and dried in a vacuum oven to obtain catecholized lignin;

[0049] S4, preparation of vinylbenzene borate esterified lignin:

[0050] 4-vinylbenzene boronic acid and catecholated lignin were mixed in tetrahydrofuran, the mass volume ratio of 4-vinylbenzene boronic acid, catecholated lignin and tetrahydrofuran was 3.6 g:1 g:35 mL, and the mixture was stirred at 25°C for 18 hours. After the treatment, the solvent was removed under reduced pressure to obtain vinylbenzene borate lignin;

[0051] S5. Preparation of modified graphene:

[0052] The thiolated graphene and the vinylbenzene borate lignin were mixed together in tetrahydrofuran, and the mass volume ratio of the thiolated graphene, the vinylbenzene borate lignin and the tetrahydrofuran was 1g:10.9g:60mL. Then, the photoinitiator DMPA was added, and the addition amount was 4.5% of the mass of the thiolated graphene. The reaction system was irradiated with an ultraviolet lamp, and the light intensity was 12W / cm 2 , while continuously stirring to react, the reaction time is 2h. After the reaction is completed, the precipitate is collected by centrifugation, washed with anhydrous ethanol for 3 times, and then placed in a vacuum box for drying to obtain modified graphene;

[0053] S6. Preparation of insole materials:

[0054] The polyamide resin PA6 (molecular weight 15,000) was dissolved in N,N-dimethylformamide, and then the modified graphene was added, the mass volume ratio of the modified graphene, polyamide resin and N,N-dimethylformamide was 0.6:10:50, and they were fully mixed to obtain a spinning solution; then electrospinning was performed with the following parameters: spinning voltage of 20 kV, propulsion speed of 0.5 mL / h, syringe needle of No. 8 needle, and receiving distance of 20 cm to obtain a graphene fiber insole material.

[0055] Example 2

[0056] A method for preparing a graphene fiber insole material comprises the following steps:

[0057] S1. Graphene carboxylation:

[0058] Graphene powder with a particle size of 1-3 μm and 5 mol / L nitric acid solution are mixed, the mass volume ratio of graphene powder to nitric acid solution is 1 g:10 mL, stirred overnight (8-12 h) at 20° C., then centrifuged in a centrifuge, the lower layer of precipitate is collected, washed with distilled water until the washing solution is neutral, and then the precipitate is collected and dried in a vacuum drying oven to obtain carboxylated graphene;

[0059] S2. Graphene thiolation:

[0060] The carboxylated graphene and anhydrous ethanol were mixed and dispersed uniformly, and then a silane coupling agent KH-580 (γ-mercaptopropyltriethoxysilane) was added dropwise, and the mass volume ratio of the carboxylated graphene, the silane coupling agent KH-580 and the anhydrous ethanol was 1g:0.1g:10mL. The mixture was placed in a water bath, heated to 65°C, and refluxed for 3h. After the treatment was completed, the mixture was cooled to room temperature, and the precipitate was collected by centrifugation in a centrifuge, washed with anhydrous ethanol for 4 times, and then dried in a vacuum box to obtain thiolated graphene;

[0061] S3, catechol lignin:

[0062] Alkaline lignin (purity ≥ 98%) with a particle size of 100-200 nm and dimethyl sulfoxide are mixed, stirred until fully dissolved, and then heated to 80° C. under the protection of nitrogen, and kept warm for 10 minutes, and then cyclohexyl bromide is added, and the mass volume ratio of lignin, cyclohexyl bromide and dimethyl sulfoxide is 1g:6.2g:30mL, and the stirring is continued for 8 hours. After the reaction is completed, it is cooled to room temperature, and then washed with n-hexane, and then poured into a saturated sodium pyrosulfite solution, the precipitate is collected, washed with water 4 times, and dried in a vacuum oven to obtain catecholized lignin;

[0063] S4, preparation of vinylbenzene borate esterified lignin:

[0064] 4-vinylbenzene boronic acid and catecholated lignin are mixed in tetrahydrofuran, the mass volume ratio of 4-vinylbenzene boronic acid, catecholated lignin and tetrahydrofuran is 2.4g:1g:20mL, and the mixture is stirred for 12h at a temperature of 20°C. After the treatment, the solvent is removed under reduced pressure to obtain vinylbenzene borate lignin;

[0065] S5. Preparation of modified graphene:

[0066] The thiolated graphene and the vinylbenzene borate lignin were mixed together in tetrahydrofuran, and the mass volume ratio of the thiolated graphene, the vinylbenzene borate lignin and the tetrahydrofuran was 1g:7.3g:40mL. Then, the photoinitiator DMPA was added, and the addition amount was 1.5% of the mass of the thiolated graphene. The reaction system was irradiated with an ultraviolet lamp with a light intensity of 10W / cm 2 , while continuously stirring to react, the reaction time is 1 hour, after the reaction is completed, the precipitate is collected by centrifugation, washed with anhydrous ethanol for 3 times, and then placed in a vacuum box for drying to obtain modified graphene;

[0067] S6. Preparation of insole materials:

[0068] The polyamide resin PA66 (molecular weight 25,000) was dissolved in N,N-dimethylformamide, and then the modified graphene was added. The mass volume ratio of the modified graphene, polyamide resin and N,N-dimethylformamide was 0.2:10:40. The mixture was fully mixed to obtain a spinning solution. Then, an electrospinning treatment was performed with the following parameters: the spinning voltage was 10 kV, the propulsion speed was 0.3 mL / h, and the receiving distance was 10 cm to obtain a graphene fiber insole material.

[0069] Example 3

[0070] A method for preparing a graphene fiber insole material comprises the following steps:

[0071] S1. Graphene carboxylation:

[0072] Graphene powder with a particle size of 1-3 μm and 10 mol / L nitric acid solution are mixed, the mass volume ratio of graphene powder to nitric acid solution is 1 g:30 mL, stirred overnight (about 10 h) at 40° C., then centrifuged in a centrifuge, the lower layer of precipitate is collected, washed with distilled water until the washing liquid is neutral, and then the precipitate is collected and placed in a vacuum drying oven for drying to obtain carboxylated graphene;

[0073] S2. Graphene thiolation:

[0074] The carboxylated graphene and anhydrous ethanol were mixed and dispersed uniformly, and then a silane coupling agent KH-580 (γ-mercaptopropyltriethoxysilane) was added dropwise, and the mass volume ratio of the carboxylated graphene, the silane coupling agent KH-580 and the anhydrous ethanol was 1g:0.5g:30mL. The mixture was placed in a water bath, heated to 85°C, and refluxed for 10 hours. After the treatment was completed, the mixture was cooled to room temperature, and the precipitate was collected by centrifugation in a centrifuge, washed with anhydrous ethanol for 5 times, and then dried in a vacuum box to obtain thiolated graphene;

[0075] S3, catechol lignin:

[0076] Alkaline lignin (purity ≥ 98%) with a particle size of 100-200 nm and dimethyl sulfoxide are mixed, stirred until fully dissolved, and then heated to 120° C. under the protection of nitrogen, and kept warm for 20 minutes, and then cyclohexyl bromide is added, and the mass volume ratio of lignin, cyclohexyl bromide and dimethyl sulfoxide is 1g:12.4g:80mL, and the stirring is continued for 12 hours. After the reaction is completed, it is cooled to room temperature, and then washed with n-hexane, and then poured into a saturated sodium pyrosulfite solution, the precipitate is collected, washed with water 5 times, and dried in a vacuum oven to obtain catecholized lignin;

[0077] S4, preparation of vinylbenzene borate esterified lignin:

[0078] 4-vinylbenzene boronic acid and catecholated lignin are mixed in tetrahydrofuran, the mass volume ratio of 4-vinylbenzene boronic acid, catecholated lignin and tetrahydrofuran is 4.8g:1g:50mL, and the mixture is stirred at 40°C for 24h. After the treatment, the solvent is removed under reduced pressure to obtain vinylbenzene borate lignin;

[0079] S5. Preparation of modified graphene:

[0080] The thiolated graphene and the vinylbenzene borate lignin were mixed together in tetrahydrofuran, and the mass volume ratio of the thiolated graphene, the vinylbenzene borate lignin and the tetrahydrofuran was 1g:14.6g:80mL. Then, the photoinitiator DMPA was added, and the amount added was 6.5% of the mass of the thiolated graphene. The reaction system was irradiated with an ultraviolet lamp with a light intensity of 15W / cm 2 , while continuously stirring to react, the reaction time is 3 hours, after the reaction is completed, the precipitate is collected by centrifugation, washed with anhydrous ethanol 5 times, and then placed in a vacuum box for drying to obtain modified graphene;

[0081] S6. Preparation of insole materials:

[0082] The polyamide resin PA12 (molecular weight 50,000) was dissolved in N,N-dimethylformamide, and then the modified graphene was added. The mass volume ratio of the modified graphene, polyamide resin and N,N-dimethylformamide was 1:10:60. The mixture was fully mixed to obtain a spinning solution. Then, an electrospinning treatment was performed with the following parameters: a spinning voltage of 30 kV, a propulsion speed of 0.8 mL / h, and a receiving distance of 30 cm to obtain a graphene fiber insole material.

[0083] Comparative Example 1

[0084] A method for preparing a graphene fiber insole material, which differs from Example 1 only in that the modified graphene used in Example 1 is replaced with unmodified graphene. The preparation method comprises:

[0085] Polyamide resin PA6 (molecular weight 15,000) was dissolved in N,N-dimethylformamide, and then graphene powder was added. The mass volume ratio of graphene, polyamide resin and N,N-dimethylformamide was 0.6:10:50. The mixture was fully mixed to obtain a spinning solution. Then, electrospinning was performed with the following parameters: spinning voltage of 20 kV, propulsion speed of 0.5 mL / h, syringe needle of No. 8, and receiving distance of 20 cm to obtain a graphene fiber insole material.

[0086] Comparative Example 2

[0087] A method for preparing a graphene fiber insole material, which differs from Example 1 only in that the modified graphene used in Example 1 is replaced with carboxylated graphene. The preparation method comprises:

[0088] S1, preparing carboxylated graphene, the same as in Example 1;

[0089] S2. Dissolve polyamide resin PA6 (molecular weight 15,000) in N,N-dimethylformamide, then add carboxylated graphene, the mass volume ratio of carboxylated graphene, polyamide resin and N,N-dimethylformamide is 0.6:10:50, mix them thoroughly and evenly to obtain a spinning solution; then perform electrospinning treatment, the parameters are: spinning voltage is 20 kV, propulsion speed is 0.5 mL / h, syringe needle is No. 8 needle, receiving distance is 20 cm, and graphene fiber insole material is obtained.

[0090] Comparative Example 3

[0091] A method for preparing a graphene fiber insole material, which differs from Example 1 only in that the modified graphene used in Example 1 is replaced with a mixture of graphene and vinylbenzene borate lignin. The preparation method comprises:

[0092] S1, preparing vinylbenzene borate lignin, the same as Example 1;

[0093] S2. Dissolve polyamide resin PA6 (molecular weight 15,000) in N,N-dimethylformamide, then add graphene and vinylbenzene borate lignin, the mass volume ratio of graphene, vinylbenzene borate lignin, polyamide resin and N,N-dimethylformamide is 0.05:0.55:10:50, mix them thoroughly and evenly to obtain a spinning solution; then perform electrospinning treatment, the parameters are: spinning voltage is 20 kV, propulsion speed is 0.5 mL / h, syringe needle is No. 8 needle, receiving distance is 20 cm, to obtain graphene fiber insole material.

[0094] Experimental example

[0095] In order to more clearly illustrate the content of the present invention, the present invention has carried out corresponding performance tests on the graphene fiber insole materials obtained in Example 1 and Comparative Examples 1-3, and the test results are listed in Table 1.

[0096] The test of breaking strength refers to GB / T 13835.5-2009, the test of abrasion resistance (load mass is 797±7g) refers to GB / T 21196.2-2007 to test the abrasion resistance of fabrics made of fibers; the test of air permeability (test area 5cm 2 The test of moisture regain (20℃, 65RH%) shall refer to GB / T 9994-2018, and the test of antibacterial property (after washing 30 times) shall refer to QB / T 2881-2013 and T / CIAA 001-2020.

[0097] Table 1 Detection performance results display

[0098]

[0099] It can be seen from the test results in Table 1 that the graphene fiber insole material prepared in Example 1 of the present invention not only has higher strength and stronger wear resistance, but also can maintain good moisture absorption and air permeability. In addition, the inhibition effect on a variety of common harmful bacteria can reach 99%. Therefore, it can be explained that the graphene fiber insole material prepared in Example 1 of the present invention has good strength and moisture absorption and air permeability, as well as very excellent long-term antibacterial properties.

[0100] 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.

[0101] 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 graphene fiber insole material, characterized in that: The following steps are involved: S1. Mixing graphene powder and nitric acid solution, stirring for 8-12 hours, centrifuging, washing and drying to obtain carboxylated graphene; S2, mixing carboxylated graphene and anhydrous ethanol, dispersing them uniformly, adding silane coupling agent KH-580 dropwise, reflux at 65-85° C. for 3-10 h, centrifuging, washing and drying to obtain thiolated graphene; S3, mixing lignin and dimethyl sulfoxide, heat-treating at 80-120° C. for 10-20 min, then adding bromocyclohexane, and continuing to heat-treat and stir for 8-12 h. After the reaction is completed, purifying, washing and drying to obtain catecholized lignin; S4, mixing 4-vinylbenzene boronic acid and catecholated lignin in tetrahydrofuran, stirring and treating at 20-40° C. for 12-24 hours, and removing the solvent under reduced pressure after the treatment to obtain vinylbenzene borate esterified lignin; S5, mixing the thiolated graphene, the vinylbenzene borate lignin and tetrahydrofuran, adding a photoinitiator, stirring and reacting under ultraviolet light for 1-3 hours, and after the reaction is completed, centrifuging, washing and drying to obtain modified graphene; S6. Dissolve the polyamide resin in N,N-dimethylformamide, then add the modified graphene, mix thoroughly and evenly to obtain a spinning solution, and perform electrostatic spinning treatment to obtain a graphene fiber insole material.

2. The method for preparing a graphene fiber insole material according to claim 1, characterized in that: During the graphene carboxylation process of S1, the particle size of the graphene powder is 1-3 μm, the concentration of the nitric acid solution is 5-10 mol / L; the mass volume ratio of the graphene powder and the nitric acid solution is 1 g: (10-30) mL.

3. The method for preparing a graphene fiber insole material according to claim 1, characterized in that: In S2, the mass volume ratio of carboxylated graphene, silane coupling agent KH-580 and anhydrous ethanol is 1 g: (0.1-0.5) g: (10-30) mL.

4. The method for preparing a graphene fiber insole material according to claim 1, characterized in that: In S3, the mass volume ratio of lignin, cyclohexyl bromide and dimethyl sulfoxide is 1 g: (6.2-12.4) g: (30-80) mL.

5. The method for preparing a graphene fiber insole material according to claim 1, characterized in that: In S4, the mass volume ratio of 4-vinylbenzeneboric acid, catecholated lignin and tetrahydrofuran is (2.4-4.8) g: 1 g: (20-50) mL.

6. The method for preparing a graphene fiber insole material according to claim 1, characterized in that: In the S5, the mass volume ratio of thiolated graphene, vinylbenzene borate lignin and tetrahydrofuran is 1 g: (7.3-14.6) g: (40-80) mL.

7. The method for preparing a graphene fiber insole material according to claim 1, characterized in that: In S6, the polyamide resin is at least one of PA6, PA66, and PA12; and the mass volume ratio of the modified graphene, the polyamide resin, and N,N-dimethylformamide is 0.2-1:10:40-60.

8. The method for preparing a graphene fiber insole material according to claim 1, characterized in that: In the S6, the parameters of the electrospinning are: the spinning voltage is 10-30 kV, the propulsion speed is 0.3-0.8 mL / h, and the receiving distance is 10-30 cm.

9. A graphene fiber insole material, characterized in that: The preparation method according to claim 1 is used for preparation.

10. Use of the graphene fiber insole material according to claim 9 in insoles of sports shoes and casual shoes.

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