High-elastic environment-friendly shoe sole and preparation method thereof

Abstract

The preparation method comprises the following steps: soaking a modified base material in a mixed solution of a modified ligand and ferric chloride to prepare a pretreated base material, mixing castor oil, methyl methacrylate, n-butyl acrylate, modified graphene and benzoin diethyl ether, coating the surface of the pretreated base material with the mixture, and performing ultraviolet curing to obtain the high-elastic environment-friendly shoe sole. According to the high-elasticity environment-friendly shoe sole, the pretreated base material can be cross-linked and cured with castor oil, methyl methacrylate and n-butyl acrylate, the cross-linking degree of a surface polymer is increased by adding the castor oil, then the wear resistance of the material is improved, and after the shoe sole is soaked in water, siloxane on modified graphene is hydrolyzed and grafted with hydroxyl on castor oil molecules, so that the wear resistance of the shoe sole is improved. According to the shoe sole material, the cross-linking sites of the polymer are further increased, the cross-linking sites are matched with the structure of the graphene, the wear resistance is further improved, and the shoe sole material has good elasticity due to the fact that disulfide bonds, a B-O six-membered ring dynamic cross-linking network and a pyridine iron structure are contained in molecules of the modified base material and are matched with micropores of the material.

Description

Technical Field

[0001] The invention relates to the technical field of sole material preparation, and in particular to a high-elasticity environmentally friendly sole and a preparation method thereof. Background Art

[0002] Sports shoes are shoes specially used for sports. During intense sports, the soles will be bent frequently and intensely, and at the same time, the soles will be subjected to severe tensile force due to the force applied by the feet. Although the existing polyurethane materials are relatively comfortable, their strength cannot meet the requirements when applied to sports shoe soles, which can easily lead to cracking of the soles due to sudden force during intense sports. Once cracking fine lines appear, they will quickly develop into severe cracks during subsequent force application, making the soles unusable. At the same time, after long-term use, the soles will show obvious wear, which greatly reduces the anti-slip property of the soles and affects their normal use. Summary of the invention

[0003] The purpose of the present invention is to provide a high-elastic environmentally friendly sole and a preparation method thereof, which solves the problem of poor wear resistance of the current high-elastic sole.

[0004] The purpose of the present invention can be achieved through the following technical solutions:

[0005] A method for preparing a high-elastic environmentally friendly sole comprises the following steps:

[0006] Step A1: 4-hydroxypyridine-2,6-dicarboxylic acid, potassium carbonate and tetrahydrofuran are mixed uniformly, stirred at a speed of 120-150 r / min and a temperature of 25-30° C., allyl chloride is added, and the reaction is carried out for 2-3 hours, and the pH value is adjusted to 5-6 to obtain a modified ligand, the modified ligand is dissolved in tetrahydrofuran, and the modified substrate is immersed therein, and ferric chloride is added, and the mixture is immersed for 1-1.5 hours at a temperature of 30-40° C., and then taken out and dried at a temperature of 80-100° C. for 8-10 hours to obtain a pretreated substrate;

[0007] Step A2: Graphene oxide, KH550, dicyclohexylcarbodiimide and toluene are mixed, and reacted for 3-5 hours at a rotation speed of 150-200 r / min and a temperature of 30-40°C to obtain modified graphene. Castor oil, methyl methacrylate, n-butyl acrylate, modified graphene and benzoin ethyl ether are evenly mixed to obtain a treatment liquid, and the treatment liquid is applied to the surface of the pretreated substrate. Under the condition of 365nm ultraviolet light irradiation, the substrate is treated with light for 10-15 minutes, and then immersed in water for 1-1.5 hours to obtain a highly elastic and environmentally friendly sole.

[0008] Furthermore, the molar ratio of 4-hydroxypyridine-2,6-dicarboxylic acid, potassium carbonate and allyl chloride in step A1 is 1:3.1:1, and the amount ratio of the modified ligand, tetrahydrofuran and ferric chloride is 10 mmol:100 mL:8 mmol.

[0009] Furthermore, the molar ratio of carboxyl groups on the graphene oxide described in step A2, KH550 and dicyclohexylcarbodiimide is 1:1:1.2, and the mass ratio of castor oil, methyl methacrylate, n-butyl acrylate, modified graphene and benzoin ethyl ether is 10-15:25-30:20-25:4-8:0.5-0.8.

[0010] Further, the modified substrate is prepared by the following steps:

[0011] Step B1: dissolving 4,4'-diaminodiphenyl sulfide in dichloromethane, introducing nitrogen protection, reacting for 2-3 hours at a speed of 60-80 r / min and a temperature of 0°C, adding 2,6-pyridinedicarbonyl chloride, reacting for 2-3 hours, raising the temperature to 20-25°C, and reacting for 20-25 hours to obtain a modified monomer;

[0012] Step B2: 4-vinylbenzeneboronic acid, anhydrous sodium sulfate and tetrahydrofuran are mixed evenly, nitrogen is introduced for protection, and the reaction is carried out for 20-25 hours at a speed of 120-150 r / min and a temperature of 50-60° C. to obtain intermediate 1; intermediate 1, 2-mercaptoethanol, benzophenone and toluene are mixed evenly, and the reaction is carried out for 20-25 minutes at a speed of 60-80 r / min, a temperature of 25-30° C. and irradiation with 365 nm ultraviolet light to obtain a reinforced monomer;

[0013] Step B3: polycarbonate diol, diphenylmethane diisocyanate, dibutyltin dilaurate and DMF are mixed, nitrogen protection is introduced, and the reaction is carried out for 2-3 hours at a speed of 60-80r / min and a temperature of 75-80°C. Modified monomers and reinforcing monomers are added, and the reaction is carried out for 3-4 hours. The temperature is then reduced to 30-40°C, 1,4-butanediol and deionized water are added, and the mixture is placed in a mold, heated to 50-55°C, and kept warm for 10-15 minutes. The mold is demolded and kept warm for 10-15 hours at a temperature of 80-85°C to obtain a modified substrate.

[0014] Furthermore, the molar ratio of 4,4'-diaminodiphenyl sulfide to 2,6-pyridinedicarbonyl chloride in step B1 is n+1:n, where n is a natural number greater than 0.

[0015] Further, the amount ratio of 4-vinylbenzeneboronic acid, anhydrous sodium sulfate and tetrahydrofuran in step B2 is 3mmol:10mmo l:4mL, the molar ratio of intermediate 1 and 2-mercaptoethanol is 1:3, and the amount of benzophenone is 1.5% of the mass of intermediate 1.

[0016] Furthermore, the dosage ratio of the polycarbonate diol, diphenylmethane diisocyanate, modified monomer, reinforcing monomer, 1,4-butanediol and deionized water described in step B3 is 3 mol:7.5 mol:1 mol:1 mol:2 mol:100 mL, the dosage of dibutyltin dilaurate is 5‰ of the mass of diphenylmethane diisocyanate, and the molecular weight of the polycarbonate diol is 2000.

[0017] The beneficial effects of the present invention are as follows: a highly elastic and environmentally friendly sole disclosed by the present invention is prepared by reacting 4-hydroxypyridine-2,6-dicarboxylic acid and allyl chloride under the action of potassium carbonate to obtain a modified ligand, immersing a modified substrate in a mixed solution of the modified ligand and ferric chloride to form a pyridine iron structure on the surface to obtain a pretreated substrate, reacting graphene oxide with KH550 to dehydrate the carboxyl groups on the graphene oxide and the amino groups on the KH550 to obtain modified graphene, and mixing castor oil, methyl methacrylate, n-butyl acrylate, the modified graphene and benzoin ethyl ether, coating the mixture on the surface of the pretreated substrate and UV curing to obtain a highly elastic and environmentally friendly sole.

[0018] The modified substrate uses 4,4'-diaminodiphenyl sulfide and 2,6-pyridine dicarboxylic acid chloride as raw materials, and the amino group on the 4,4'-diaminodiphenyl sulfide reacts with the acyl chloride on the 2,6-pyridine dicarboxylic acid chloride to obtain a modified monomer, 4-vinyl phenylboronic acid is reacted with anhydrous sodium sulfate to form a BO six-membered ring dynamic cross-linking network to obtain an intermediate 1, the intermediate 1 is reacted with 2-mercaptoethanol, so that the double bond on the intermediate 1 reacts with the thiol group on the 2-mercaptoethanol to obtain a reinforcing monomer, polycarbonate diol, diphenylmethane diisocyanate, the modified monomer, the reinforcing monomer and 1,4-butanediol are reacted, and deionized water is used as a foaming agent to form a microporous polyurethane material to obtain a modified substrate.

[0019] When the modified substrate is immersed in a mixed solution of modified ligand and ferric chloride, the pyridine structure in the molecular chain of the modified substrate can cooperate with the pyridine structure and iron ions on the modified ligand to form a pyridine iron structure on the surface of the modified substrate, and unsaturated double bonds are grafted on the surface. When castor oil, methyl methacrylate, n-butyl acrylate, modified graphene and benzoin ethyl ether are mixed and coated on the surface of the pretreated substrate and UV-cured, the unsaturated double bonds on the surface of the pretreated substrate can be cross-linked and cured with castor oil, methyl methacrylate and n-butyl acrylate. The addition of castor oil increases the cross-linking degree of the surface polymer, thereby increasing the wear resistance of the material. After soaking in water, the siloxane on the modified graphene is hydrolyzed and grafted with the hydroxyl groups on the castor oil molecules, further increasing the cross-linking sites of the polymer, cooperating with the graphene's own structure to further improve the wear resistance. The modified substrate molecules contain disulfide bonds, BO six-membered ring dynamic cross-linking networks and pyridine iron structures, which cooperate with the material's own micropores to make the sole material have good elasticity. DETAILED DESCRIPTION

[0020] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0021] Embodiment 1: A method for preparing a highly elastic and environmentally friendly sole, comprising the following steps:

[0022] Step A1: 4-hydroxypyridine-2,6-dicarboxylic acid, potassium carbonate and tetrahydrofuran are mixed uniformly, stirred at a speed of 120 r / min and a temperature of 25° C., allyl chloride is added, and the reaction is carried out for 2 hours, and the pH value is adjusted to 5 to obtain a modified ligand, and the modified ligand is dissolved in tetrahydrofuran, and the modified substrate is immersed therein, and ferric chloride is added, and after being immersed for 1 hour at a temperature of 30° C., it is taken out and dried at a temperature of 80° C. for 8 hours to obtain a pretreated substrate;

[0023] Step A2: Graphene oxide, KH550, dicyclohexylcarbodiimide and toluene are mixed, and the reaction is carried out at a speed of 150 r / min and a temperature of 30°C for 3 hours to obtain modified graphene. Castor oil, methyl methacrylate, n-butyl acrylate, modified graphene and benzoin ethyl ether are evenly mixed to obtain a treatment liquid, and the treatment liquid is applied to the surface of the pretreated substrate. Under the condition of 365nm ultraviolet light irradiation, the substrate is treated with light for 10 minutes and then immersed in water for 1 hour to obtain a highly elastic and environmentally friendly sole.

[0024] The molar ratio of 4-hydroxypyridine-2,6-dicarboxylic acid, potassium carbonate and allyl chloride in step A1 is 1:3.1:1, and the amount ratio of modified ligand, tetrahydrofuran and ferric chloride is 10 mmol:100 mL:8 mmol.

[0025] The molar ratio of carboxyl groups on the graphene oxide described in step A2, KH550 and dicyclohexylcarbodiimide is 1:1:1.2, and the mass ratio of castor oil, methyl methacrylate, n-butyl acrylate, modified graphene and benzoin ethyl ether is 10:25:20:4:0.5.

[0026] The modified substrate is prepared by the following steps:

[0027] Step B1: 4,4'-diaminodiphenyl sulfide was dissolved in dichloromethane, nitrogen was introduced for protection, and the reaction was carried out for 2 hours at a speed of 60 r / min and a temperature of 0°C. Then, 2,6-pyridinedicarbonyl chloride was added and the reaction was carried out for 2 hours. The temperature was raised to 20°C and the reaction was carried out for 20 hours to obtain a modified monomer;

[0028] Step B2: 4-vinylbenzeneboronic acid, anhydrous sodium sulfate and tetrahydrofuran were mixed evenly, nitrogen was introduced for protection, and the reaction was carried out for 20 hours at a speed of 120 r / min and a temperature of 50° C. to obtain intermediate 1. Intermediate 1, 2-mercaptoethanol, benzophenone and toluene were mixed evenly, and the reaction was carried out for 20 minutes at a speed of 60 r / min, a temperature of 25° C. and irradiation with 365 nm ultraviolet light to obtain a reinforced monomer;

[0029] Step B3: polycarbonate diol, diphenylmethane diisocyanate, dibutyltin dilaurate and DMF are mixed, nitrogen is introduced for protection, and the reaction is carried out at a speed of 60r / min and a temperature of 75°C for 2h. Modified monomers and reinforcing monomers are added, and the reaction is carried out for 3h. The temperature is then reduced to 30°C, 1,4-butanediol and deionized water are added, and the mixture is placed in a mold, heated to 50°C, and kept warm for 10min. The mold is demolded and kept warm for 10h at 80°C to obtain a modified substrate.

[0030] The molar ratio of 4,4'-diaminodiphenyl sulfide to 2,6-pyridinedicarbonyl chloride in step B1 is 2:1.

[0031] The amount ratio of 4-vinylbenzeneboronic acid, anhydrous sodium sulfate and tetrahydrofuran in step B2 is 3mmol:10mmol:4mL, the molar ratio of intermediate 1 and 2-mercaptoethanol is 1:3, and the amount of benzophenone is 1.5% of the mass of intermediate 1.

[0032] The dosage ratio of the polycarbonate diol, diphenylmethane diisocyanate, modified monomer, reinforcing monomer, 1,4-butanediol and deionized water described in step B3 is 3 mol:7.5 mol:1 mol:1 mol:2 mol:100 mL, the dosage of dibutyltin dilaurate is 5‰ of the mass of diphenylmethane diisocyanate, and the molecular weight of the polycarbonate diol is 2000.

[0033] Embodiment 2: A method for preparing a highly elastic and environmentally friendly sole, comprising the following steps:

[0034] Step A1: 4-hydroxypyridine-2,6-dicarboxylic acid, potassium carbonate and tetrahydrofuran are mixed uniformly, stirred at a speed of 120 r / min and a temperature of 30° C., allyl chloride is added, and the reaction is carried out for 2 hours, and the pH value is adjusted to 6 to obtain a modified ligand, and the modified ligand is dissolved in tetrahydrofuran, and the modified substrate is immersed therein, and ferric chloride is added, and the mixture is immersed for 1.5 hours at a temperature of 35° C., and then taken out and dried at a temperature of 90° C. for 9 hours to obtain a pretreated substrate;

[0035] Step A2: Graphene oxide, KH550, dicyclohexylcarbodiimide and toluene are mixed, and the reaction is carried out at a speed of 150 r / min and a temperature of 35°C for 4 hours to obtain modified graphene. Castor oil, methyl methacrylate, n-butyl acrylate, modified graphene and benzoin ethyl ether are evenly mixed to obtain a treatment liquid, and the treatment liquid is applied to the surface of the pretreated substrate. Under the condition of 365nm ultraviolet light irradiation, after light treatment for 10 minutes, it is immersed in water for 1.5 hours to obtain a highly elastic and environmentally friendly sole.

[0036] The molar ratio of 4-hydroxypyridine-2,6-dicarboxylic acid, potassium carbonate and allyl chloride in step A1 is 1:3.1:1, and the amount ratio of modified ligand, tetrahydrofuran and ferric chloride is 10 mmol:100 mL:8 mmol.

[0037] The molar ratio of carboxyl groups on the graphene oxide described in step A2, KH550 and dicyclohexylcarbodiimide is 1:1:1.2, and the mass ratio of castor oil, methyl methacrylate, n-butyl acrylate, modified graphene and benzoin ethyl ether is 13:28:23:6:0.7.

[0038] The modified substrate is prepared by the following steps:

[0039] Step B1: 4,4'-diaminodiphenyl sulfide was dissolved in dichloromethane, nitrogen was introduced for protection, and the reaction was carried out for 3 hours at a speed of 60 r / min and a temperature of 0°C. Then, 2,6-pyridinedicarbonyl chloride was added and the reaction was carried out for 2 hours. The temperature was raised to 25°C and the reaction was carried out for 20 hours to obtain a modified monomer;

[0040] Step B2: 4-vinylbenzeneboronic acid, anhydrous sodium sulfate and tetrahydrofuran were mixed evenly, nitrogen was introduced for protection, and the reaction was carried out for 25 hours at a speed of 150 r / min and a temperature of 55° C. to obtain intermediate 1. Intermediate 1, 2-mercaptoethanol, benzophenone and toluene were mixed evenly, and the reaction was carried out for 25 minutes at a speed of 60 r / min, a temperature of 25° C. and irradiation with 365 nm ultraviolet rays to obtain a reinforced monomer;

[0041] Step B3: polycarbonate diol, diphenylmethane diisocyanate, dibutyltin dilaurate and DMF are mixed, nitrogen is introduced for protection, and the reaction is carried out at a speed of 80r / min and a temperature of 75°C for 3 hours. Modified monomers and reinforcing monomers are added, and the reaction is carried out for 3 hours. The temperature is then reduced to 35°C, 1,4-butanediol and deionized water are added, and the mixture is placed in a mold, heated to 50°C, and kept warm for 15 minutes. The mold is demolded and kept warm for 10 hours at a temperature of 85°C to obtain a modified substrate.

[0042] The molar ratio of 4,4'-diaminodiphenyl sulfide to 2,6-pyridinedicarbonyl chloride in step B1 is 3:2.

[0043] The amount ratio of 4-vinylbenzeneboronic acid, anhydrous sodium sulfate and tetrahydrofuran in step B2 is 3mmol:10mmol:4mL, the molar ratio of intermediate 1 and 2-mercaptoethanol is 1:3, and the amount of benzophenone is 1.5% of the mass of intermediate 1.

[0044] The dosage ratio of the polycarbonate diol, diphenylmethane diisocyanate, modified monomer, reinforcing monomer, 1,4-butanediol and deionized water described in step B3 is 3 mol:7.5 mol:1 mol:1 mol:2 mol:100 mL, the dosage of dibutyltin dilaurate is 5‰ of the mass of diphenylmethane diisocyanate, and the molecular weight of the polycarbonate diol is 2000.

[0045] Embodiment 3: A method for preparing a highly elastic and environmentally friendly sole, comprising the following steps:

[0046] Step A1: 4-hydroxypyridine-2,6-dicarboxylic acid, potassium carbonate and tetrahydrofuran are mixed uniformly, stirred at a speed of 150 r / min and a temperature of 30° C., allyl chloride is added, and the reaction is carried out for 3 hours, and the pH value is adjusted to 6 to obtain a modified ligand, and the modified ligand is dissolved in tetrahydrofuran, and the modified substrate is immersed therein, and ferric chloride is added, and the substrate is immersed at a temperature of 40° C. for 1.5 hours, and then taken out and dried at a temperature of 100° C. for 10 hours to obtain a pretreated substrate;

[0047] Step A2: Graphene oxide, KH550, dicyclohexylcarbodiimide and toluene are mixed, and the reaction is carried out at a speed of 200 r / min and a temperature of 40°C for 5 hours to obtain modified graphene. Castor oil, methyl methacrylate, n-butyl acrylate, modified graphene and benzoin ethyl ether are evenly mixed to obtain a treatment liquid, and the treatment liquid is applied to the surface of the pretreated substrate. Under the condition of 365nm ultraviolet light irradiation, the substrate is treated with light for 15 minutes and then immersed in water for 1.5 hours to obtain a highly elastic and environmentally friendly sole.

[0048] The molar ratio of 4-hydroxypyridine-2,6-dicarboxylic acid, potassium carbonate and allyl chloride in step A1 is 1:3.1:1, and the amount ratio of modified ligand, tetrahydrofuran and ferric chloride is 10 mmol:100 mL:8 mmol.

[0049] The molar ratio of carboxyl groups on the graphene oxide described in step A2, KH550 and dicyclohexylcarbodiimide is 1:1:1.2, and the mass ratio of castor oil, methyl methacrylate, n-butyl acrylate, modified graphene and benzoin ethyl ether is 15:30:25:4-8:0.8.

[0050] The modified substrate is prepared by the following steps:

[0051] Step B1: 4,4'-diaminodiphenyl sulfide was dissolved in dichloromethane, nitrogen was introduced for protection, and the reaction was carried out for 3 hours at a speed of 80 r / min and a temperature of 0°C. Then, 2,6-pyridinedicarbonyl chloride was added and the reaction was carried out for 3 hours. The temperature was raised to 25°C and the reaction was carried out for 25 hours to obtain a modified monomer;

[0052] Step B2: 4-vinylbenzeneboronic acid, anhydrous sodium sulfate and tetrahydrofuran were mixed evenly, nitrogen was introduced for protection, and the reaction was carried out for 25 hours at a speed of 150 r / min and a temperature of 60° C. to obtain intermediate 1. Intermediate 1, 2-mercaptoethanol, benzophenone and toluene were mixed evenly, and the reaction was carried out for 25 minutes at a speed of 80 r / min, a temperature of 30° C. and irradiation with 365 nm ultraviolet light to obtain a reinforced monomer;

[0053] Step B3: polycarbonate diol, diphenylmethane diisocyanate, dibutyltin dilaurate and DMF are mixed, nitrogen is introduced for protection, and the reaction is carried out for 3 hours at a speed of 80 r / min and a temperature of 80°C. Modified monomers and reinforcing monomers are added, and the reaction is carried out for 4 hours. The temperature is then reduced to 40°C, 1,4-butanediol and deionized water are added, and the mixture is placed in a mold, heated to 55°C, and kept warm for 15 minutes. The mold is demolded and kept warm for 15 hours at a temperature of 85°C to obtain a modified substrate.

[0054] The molar ratio of 4,4'-diaminodiphenyl sulfide to 2,6-pyridinedicarbonyl chloride in step B1 is 4:3.

[0055] The amount ratio of 4-vinylbenzeneboronic acid, anhydrous sodium sulfate and tetrahydrofuran in step B2 is 3mmol:10mmol:4mL, the molar ratio of intermediate 1 and 2-mercaptoethanol is 1:3, and the amount of benzophenone is 1.5% of the mass of intermediate 1.

[0056] The dosage ratio of the polycarbonate diol, diphenylmethane diisocyanate, modified monomer, reinforcing monomer, 1,4-butanediol and deionized water described in step B3 is 3 mol:7.5 mol:1 mol:1 mol:2 mol:100 mL, the dosage of dibutyltin dilaurate is 5‰ of the mass of diphenylmethane diisocyanate, and the molecular weight of the polycarbonate diol is 2000.

[0057] Comparative Example 1: Compared with Example 1, this comparative example uses pyridine-2,6-dicarboxylic acid instead of the modified ligand, and the remaining steps are the same.

[0058] Comparative Example 2: Compared with Example 1, no modified graphene was added to this comparative example, and the remaining steps were the same.

[0059] Comparative Example 3: Compared with Example 1, no modified monomer was added to this comparative example, and the remaining steps were the same.

[0060] Comparative Example 4: Compared with Example 1, no reinforcing monomer was added in this comparative example, and the remaining steps were the same.

[0061] The wear resistance of the sole materials obtained in Examples 1-3 and Comparative Examples 1-4 was tested according to the standard of GB / T3960-2016, and the rebound rate was tested according to GB / T1681-2009. The test results are shown in Table 1 below.

[0062] Table 1

[0063]

[0064]

[0065] It can be seen from the above table that the present application has good elasticity and wear resistance.

[0066] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

Claims

1. A method for preparing a highly elastic and environmentally friendly sole, characterized in that: The specific steps include: Step A1: 4-hydroxypyridine-2,6-dicarboxylic acid, potassium carbonate and tetrahydrofuran are mixed and stirred, and allyl chloride is added to react, and the pH is adjusted to be acidic to obtain a modified ligand, and the modified ligand is dissolved in tetrahydrofuran, and the modified substrate is immersed therein, and ferric chloride is added. After the immersion treatment, the substrate is taken out and dried to obtain a pretreated substrate; Step A2: Graphene oxide, KH550, dicyclohexylcarbodiimide and toluene are mixed and reacted to obtain modified graphene, castor oil, methyl methacrylate, n-butyl acrylate, modified graphene and benzoin ethyl ether are evenly mixed to obtain a treatment liquid, the treatment liquid is coated on the surface of the pretreated substrate, and after light treatment, it is immersed in water to obtain a highly elastic and environmentally friendly sole.

2. The method for preparing a highly elastic and environmentally friendly sole according to claim 1, characterized in that: The molar ratio of 4-hydroxypyridine-2,6-dicarboxylic acid, potassium carbonate and allyl chloride in step A1 is 1:3.1:1, and the amount ratio of the modified ligand, tetrahydrofuran and ferric chloride is 10mmol:100mL:8mmol.

3. The method for preparing a highly elastic and environmentally friendly sole according to claim 1, characterized in that: The molar ratio of carboxyl groups on the graphene oxide described in step A2, KH550 and dicyclohexylcarbodiimide is 1:1:1.2, and the mass ratio of castor oil, methyl methacrylate, n-butyl acrylate, modified graphene and benzoin ethyl ether is 10-15:25-30:20-25:4-8:0.5-0.

8.

4. The method for preparing a highly elastic and environmentally friendly sole according to claim 1, characterized in that: The modified substrate is prepared by the following steps: Step B1: dissolving 4,4'-diaminodiphenyl sulfide in dichloromethane, introducing nitrogen for protection, and reacting, then adding 2,6-pyridinedicarbonyl chloride, reacting, and heating to continue the reaction to obtain a modified monomer; Step B2: 4-vinylbenzeneboronic acid, anhydrous sodium sulfate and tetrahydrofuran are uniformly mixed, nitrogen is introduced for protection, and the reaction is carried out to obtain intermediate 1, and intermediate 1, 2-mercaptoethanol, benzophenone and toluene are mixed for reaction to obtain a reinforcing monomer; Step B3: polycarbonate diol, diphenylmethane diisocyanate, dibutyltin dilaurate and DMF are mixed, nitrogen is introduced for protection, a modified monomer and a reinforcing monomer are added, the reaction is carried out, the temperature is lowered, 1,4-butanediol and deionized water are added, and the mixture is placed in a mold. After heating and heat preservation, a modified substrate is obtained.

5. The method for preparing a highly elastic and environmentally friendly sole according to claim 4, characterized in that: The molar ratio of 4,4'-diaminodiphenyl sulfide and 2,6-pyridinedicarbonyl chloride in step B1 is n+1:n, where n is a natural number greater than 0.

6. The method for preparing a highly elastic and environmentally friendly sole according to claim 4, characterized in that: The amount ratio of 4-vinylbenzeneboronic acid, anhydrous sodium sulfate and tetrahydrofuran in step B2 is 3mmol:10mmol:4mL, and the molar ratio of intermediate 1 and 2-mercaptoethanol is 1:

3.

7. The method for preparing a highly elastic and environmentally friendly sole according to claim 4, characterized in that: The amount ratio of the polycarbonate diol, diphenylmethane diisocyanate, modified monomer, reinforcing monomer, 1,4-butanediol and deionized water described in step B3 is 3 mol: 7.5 mol: 1 mol: 1 mol: 2 mol: 100 mL.

8. A highly elastic and environmentally friendly sole, characterized in that: Prepared according to any one of claims 1 to 7.

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