A highly elastic and environmentally friendly shoe sole and its preparation method

Abstract

The present invention discloses a highly elastic and environmentally friendly sole and a preparation method thereof. The modified substrate is immersed in a mixed solution of a modified ligand and ferric chloride to obtain a pretreated substrate. Castor oil, methyl methacrylate, n-butyl acrylate, modified graphene and benzoin ethyl ether are mixed and then coated on the surface of the pretreated substrate and cured by ultraviolet light to obtain a highly elastic and environmentally friendly sole. The pretreated substrate can crosslink and cure with castor oil, methyl methacrylate and n-butyl acrylate. The addition of castor oil increases the crosslinking degree of the surface polymer, thereby increasing the wear resistance of the material. After soaking in water, the siloxane on the modified graphene hydrolyzes and grafts with the hydroxyl group on the castor oil molecule, further increasing the crosslinking sites of the polymer, and cooperating with the structure of graphene itself to further improve the wear resistance. The modified substrate molecule contains disulfide bonds, a B-O six-membered ring dynamic crosslinking network and a pyridine iron structure, which cooperate with the micropores of the material itself to make the sole material have good elasticity.

Description

Technical Field

[0001] The present invention relates to the technical field of sole material preparation, and particularly relates to a highly elastic and environmentally friendly sole and a preparation method thereof. Background Art

[0002] Sports shoes are specifically designed for sports. During intense sports activities, the soles are subjected to frequent and intense bending, and at the same time, due to the force exerted by the feet during bending, the soles are also subjected to severe tensile forces. Although existing polyurethane materials have relatively high comfort, when applied to sports shoe soles, their strength is still difficult to meet the requirements, and it is easy for the soles to crack due to sudden stress during intense sports. Once cracks or fine lines appear, they will quickly develop into serious cracks during subsequent stress, resulting in the soles being unable to be used continuously. At the same time, after long-term use, the soles will show obvious wear, greatly reducing the anti-slip performance of the soles and affecting normal use. Summary of the Invention

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

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

[0005] A preparation method of a highly elastic and environmentally friendly sole specifically includes the following steps:

[0006] Step A1: Mix 4-hydroxypyridine-2,6-dicarboxylic acid, potassium carbonate, and tetrahydrofuran evenly. Under the conditions of a rotation speed of 120 - 150 r / min and a temperature of 25 - 30 °C, stir and add allyl chloride, and react for 2 - 3 h. Then adjust the pH value to 5 - 6 to obtain a modified ligand. Dissolve the modified ligand in tetrahydrofuran, immerse the modified substrate in it, add ferric chloride, and under the condition of a temperature of 30 - 40 °C, soak for 1 - 1.5 h, then take it out and dry it at a temperature of 80 - 100 °C for 8 - 10 h to obtain a pretreated substrate;

[0007] Step A2: Mix graphene oxide, KH550, dicyclohexylcarbodiimide, and toluene, and react for 3 - 5 h under the conditions of a rotation speed of 150 - 200 r / min and a temperature of 30 - 40 °C to obtain modified graphene. Mix castor oil, methyl methacrylate, n-butyl acrylate, modified graphene, and benzoin ethyl ether evenly to obtain a treatment solution. Coat the treatment solution on the surface of the pretreated substrate, and under the irradiation of 365 nm ultraviolet light, perform light treatment for 10 - 15 min, and then soak it in water for 1 - 1.5 h to obtain a highly elastic and environmentally friendly sole.

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

[0009] Further, the molar ratio of the carboxyl group on graphene oxide, KH550, and dicyclohexylcarbodiimide described in step A2 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: Dissolve 4,4'-diaminodiphenyl sulfide in dichloromethane, introduce nitrogen protection, and react for 2-3 h at a rotation speed of 60-80 r / min and a temperature of 0 °C. Then add 2,6-pyridinedicarbonyl chloride and react for 2-3 h. After that, raise the temperature to 20-25 °C and react for 20-25 h to obtain the modified monomer.

[0012] Step B2: Mix 4-vinylphenylboronic acid, anhydrous sodium sulfate, and tetrahydrofuran evenly, introduce nitrogen protection, and react for 20-25 h at a rotation speed of 120-150 r / min and a temperature of 50-60 °C to obtain intermediate 1. Then mix intermediate 1, 2-mercaptoethanol, benzophenone, and toluene evenly and react for 20-25 min at a rotation speed of 60-80 r / min, a temperature of 25-30 °C, and under the irradiation of 365 nm ultraviolet light to obtain the strengthened monomer.

[0013] Step B3: Mix polycarbonate diol, diphenylmethane diisocyanate, dibutyltin dilaurate, and DMF, introduce nitrogen protection, and react for 2-3 h at a rotation speed of 60-80 r / min and a temperature of 75-80 °C. Then add the modified monomer and the strengthened monomer and react for 3-4 h. After that, cool down to 30-40 °C, add 1,4-butanediol and deionized water, and place them in a mold. Raise the temperature to 50-55 °C, keep warm for 10-15 min, then demold and perform heat preservation treatment at a temperature of 80-85 °C for 10-15 h to obtain the modified substrate.

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

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

[0016] Further, the dosage ratio of the polycarbonate diol, diphenylmethane diisocyanate, modified monomer, strengthening 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] Beneficial effects of the present invention: A highly elastic and environmentally friendly sole disclosed by the present invention is prepared by reacting 4-hydroxypyridine-2,6-dicarboxylic acid with allyl chloride under the action of potassium carbonate to obtain a modified ligand, soaking the 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 so that the carboxyl group on the graphene oxide and the amino group on KH550 undergo a dehydration reaction to obtain modified graphene, mixing castor oil, methyl methacrylate, n-butyl acrylate, modified graphene, and benzoin ethyl ether, coating the mixture on the surface of the pretreated substrate, and subjecting it to ultraviolet curing to obtain the highly elastic and environmentally friendly sole.

[0018] The modified substrate uses 4,4'-diaminodiphenyl sulfide and 2,6-pyridinedicarbonyl chloride as raw materials, so that the amino group on 4,4'-diaminodiphenyl sulfide reacts with the acyl chloride on 2,6-pyridinedicarbonyl chloride to obtain a modified monomer. 4-vinylbenzeneboronic acid forms a B-O six-membered ring dynamic crosslinking network under the action of anhydrous sodium sulfate to obtain intermediate 1. Intermediate 1 reacts with 2-mercaptoethanol so that the double bond on intermediate 1 reacts with the mercapto group on 2-mercaptoethanol to obtain a strengthening monomer. The polycarbonate diol, diphenylmethane diisocyanate, modified monomer, strengthening monomer, and 1,4-butanediol react, and deionized water is used as a foaming agent to form a microporous polyurethane material to obtain the modified substrate.

[0019] When the modified substrate is immersed in the mixed solution of the modified ligand and iron chloride, the pyridine structure in the molecular chain of the modified substrate can coordinate with the pyridine structure and iron ions on the modified ligand to form a pyridine-iron structure on the surface of the modified substrate. At the same time, unsaturated double bonds are grafted on the surface. When the mixture of castor oil, methyl methacrylate, n-butyl acrylate, modified graphene and benzoin ethyl ether is coated on the surface of the pretreated substrate and cured by ultraviolet light, the unsaturated double bonds on the surface of the pretreated substrate can crosslink and cure with castor oil, methyl methacrylate and n-butyl acrylate. The addition of castor oil increases the crosslinking degree of the surface polymer, thereby increasing the wear resistance of the material. After soaking in water, the siloxane on the modified graphene hydrolyzes and grafts with the hydroxyl groups on the castor oil molecules, further increasing the crosslinking sites of the polymer. Combined with the structure of graphene itself, the wear resistance is further improved. The modified substrate molecule contains disulfide bonds, a B-O six-membered ring dynamic crosslinking network and a pyridine-iron structure, which cooperate with the micropores of the material itself, making the sole material have good elasticity. Detailed implementation mode

[0020] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0021] Example 1. A preparation method of a highly elastic and environmentally friendly sole specifically includes the following steps:

[0022] Step A1: Mix 4-hydroxypyridine-2,6-dicarboxylic acid, potassium carbonate and tetrahydrofuran evenly. Under the conditions of a rotation speed of 120 r / min and a temperature of 25 °C, stir and add allyl chloride. After reacting for 2 h, adjust the pH value to 5 to obtain the modified ligand. Dissolve the modified ligand in tetrahydrofuran, immerse the modified substrate therein, add iron chloride, and soak for 1 h under the condition of a temperature of 30 °C. Then take it out and dry it at a temperature of 80 °C for 8 h to obtain the pretreated substrate.

[0023] Step A2: Mix graphene oxide, KH550, dicyclohexylcarbodiimide and toluene, and react for 3 h under the conditions of a rotation speed of 150 r / min and a temperature of 30 °C to obtain modified graphene. Mix castor oil, methyl methacrylate, n-butyl acrylate, modified graphene and benzoin ethyl ether evenly to obtain the treatment liquid. Coat the treatment liquid on the surface of the pretreated substrate, and under the condition of ultraviolet light irradiation at 365 nm, after light treatment for 10 min, soak it in water for 1 h to obtain the highly elastic and environmentally friendly sole.

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

[0025] The molar ratio of the carboxyl group on graphene oxide, KH550 and dicyclohexylcarbodiimide described in step A2 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: Dissolve 4,4'-diaminodiphenyl sulfide in dichloromethane, protect it by introducing nitrogen, react for 2 h under the conditions of a rotation speed of 60 r / min and a temperature of 0 °C, add 2,6-pyridinedicarbonyl chloride, react for 2 h, then raise the temperature to 20 °C and react for 20 h to obtain a modified monomer.

[0028] Step B2: Mix 4-vinylphenylboronic acid, anhydrous sodium sulfate and tetrahydrofuran evenly, protect it by introducing nitrogen, react for 20 h under the conditions of a rotation speed of 120 r / min and a temperature of 50 °C to obtain intermediate 1. Mix intermediate 1, 2-mercaptoethanol, benzophenone and toluene evenly, and react for 20 min under the conditions of a rotation speed of 60 r / min, a temperature of 25 °C and ultraviolet irradiation at 365 nm to obtain a strengthened monomer.

[0029] Step B3: Mix polycarbonate diol, diphenylmethane diisocyanate, dibutyltin dilaurate and DMF, protect it by introducing nitrogen, react for 2 h under the conditions of a rotation speed of 60 r / min and a temperature of 75 °C, add the modified monomer and the strengthened monomer, react for 3 h, then cool down to 30 °C, add 1,4-butanediol and deionized water, place it in a mold, raise the temperature to 50 °C, keep it warm for 10 min, then demold and keep it warm at 80 °C for 10 h to obtain the modified substrate.

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

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

[0032] The dosage ratio of the polycarbonate diol, diphenylmethane diisocyanate, modified monomer, strengthening 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] Example 2. A preparation method of a highly elastic and environmentally friendly shoe sole, which specifically includes the following steps:

[0034] Step A1: Mix 4-hydroxypyridine-2,6-dicarboxylic acid, potassium carbonate and tetrahydrofuran evenly. Under the conditions of a rotation speed of 120 r / min and a temperature of 30 °C, stir and add allyl chloride. After reacting for 2 h, adjust the pH value to 6 to obtain a modified ligand. Dissolve the modified ligand in tetrahydrofuran, soak the modified substrate therein, add ferric chloride, and soak for 1.5 h under the condition of a temperature of 35 °C. Then take it out and dry it at a temperature of 90 °C for 9 h to obtain a pretreated substrate.

[0035] Step A2: Mix graphene oxide, KH550, dicyclohexylcarbodiimide and toluene, and react for 4 h under the conditions of a rotation speed of 150 r / min and a temperature of 35 °C to obtain modified graphene. Mix castor oil, methyl methacrylate, n-butyl acrylate, modified graphene and benzoin ethyl ether evenly to obtain a treatment liquid. Coat the treatment liquid on the surface of the pretreated substrate, and under the condition of 365 nm ultraviolet light irradiation, after light treatment for 10 min, soak it in water for 1.5 h to obtain a highly elastic and environmentally friendly shoe sole.

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

[0037] The molar ratio of the carboxyl group on graphene oxide, KH550 and dicyclohexylcarbodiimide described in step A2 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: Dissolve 4,4'-diaminodiphenyl sulfide in dichloromethane, protect it by introducing nitrogen. Under the conditions of a rotation speed of 60 r / min and a temperature of 0 °C, react for 3 h, then add 2,6-pyridinedicarbonyl chloride, react for 2 h, and then raise the temperature to 25 °C and react for 20 h to obtain a modified monomer.

[0040] Step B2: Mix 4-vinylbenzeneboronic acid, anhydrous sodium sulfate, and tetrahydrofuran evenly, introduce nitrogen for protection, and react for 25 h under the conditions of a rotation speed of 150 r / min and a temperature of 55 °C to obtain Intermediate 1. Mix Intermediate 1, 2-mercaptoethanol, benzophenone, and toluene evenly, and react for 25 min under the conditions of a rotation speed of 60 r / min, a temperature of 25 °C, and irradiation with 365 nm ultraviolet light to obtain a strengthened monomer;

[0041] Step B3: Mix polycarbonate diol, diphenylmethane diisocyanate, dibutyltin dilaurate, and DMF, introduce nitrogen for protection, and react for 3 h under the conditions of a rotation speed of 80 r / min and a temperature of 75 °C. Add a modified monomer and a strengthened monomer, react for 3 h, then cool down to 35 °C, add 1,4-butanediol and deionized water, and place them in a mold. Heat up to 50 °C, keep warm for 15 min, then demold and perform heat preservation treatment at 85 °C for 10 h to obtain a modified substrate.

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

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

[0044] The dosage ratio of polycarbonate diol, diphenylmethane diisocyanate, modified monomer, strengthened 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 polycarbonate diol is 2000.

[0045] Example 3. A preparation method of a highly elastic and environmentally friendly shoe sole specifically includes the following steps:

[0046] Step A1: Mix 4-hydroxypyridine-2,6-dicarboxylic acid, potassium carbonate, and tetrahydrofuran evenly, stir and add allyl chloride under the conditions of a rotation speed of 150 r / min and a temperature of 30 °C, react for 3 h, then adjust the pH value to 6 to obtain a modified ligand. Dissolve the modified ligand in tetrahydrofuran, soak the modified substrate in it, add ferric chloride, soak for 1.5 h at 40 °C, then take it out and dry it at 100 °C for 10 h to obtain a pretreated substrate;

[0047] Step A2: Mix graphene oxide, KH550, dicyclohexylcarbodiimide, and toluene, and react them for 5 h under the conditions of a rotation speed of 200 r / min and a temperature of 40 °C to obtain modified graphene. Mix castor oil, methyl methacrylate, n-butyl acrylate, modified graphene, and benzoin ethyl ether evenly to obtain a treatment liquid. Coat the treatment liquid on the surface of the pretreated substrate, and under the condition of ultraviolet light irradiation at 365 nm, after 15 min of light treatment, soak it in water for 1.5 h to obtain a highly elastic and environmentally friendly shoe sole.

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

[0049] The molar ratio of the carboxyl group on the graphene oxide, KH550, and dicyclohexylcarbodiimide described in Step A2 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: Dissolve 4,4'-diaminodiphenyl sulfide in dichloromethane, protect it by introducing nitrogen, and react it for 3 h under the conditions of a rotation speed of 80 r / min and a temperature of 0 °C. Then add 2,6-pyridinedicarbonyl chloride and react for 3 h. After that, raise the temperature to 25 °C and react for 25 h to obtain a modified monomer.

[0052] Step B2: Mix 4-vinylphenylboronic acid, anhydrous sodium sulfate, and tetrahydrofuran evenly, protect it by introducing nitrogen, and react it for 25 h under the conditions of a rotation speed of 150 r / min and a temperature of 60 °C to obtain Intermediate 1. Mix Intermediate 1, 2-mercaptoethanol, benzophenone, and toluene evenly, and react it for 25 min under the conditions of a rotation speed of 80 r / min, a temperature of 30 °C, and ultraviolet light irradiation at 365 nm to obtain a strengthened monomer.

[0053] Step B3: Mix polycarbonate diol, diphenylmethane diisocyanate, dibutyltin dilaurate, and DMF, protect it by introducing nitrogen, and react it for 3 h under the conditions of a rotation speed of 80 r / min and a temperature of 80 °C. Then add the modified monomer and the strengthened monomer and react for 4 h. After that, lower the temperature to 40 °C, add 1,4-butanediol and deionized water, and place it in a mold. Raise the temperature to 55 °C, keep it warm for 15 min, then demold and keep it warm at 85 °C for 15 h to obtain the modified substrate.

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

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

[0056] The dosage ratio of 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 polycarbonate diol is 2000.

[0057] Comparative example 1: In this comparative example, compared with Example 1, pyridine-2,6-dicarboxylic acid was used instead of the modified ligand, and the remaining steps were the same.

[0058] Comparative example 2: In this comparative example, compared with Example 1, modified graphene was not added, and the remaining steps were the same.

[0059] Comparative example 3: In this comparative example, compared with Example 1, the modified monomer was not added, and the remaining steps were the same.

[0060] Comparative example 4: In this comparative example, compared with Example 1, the reinforcing monomer was not added, and the remaining steps were the same.

[0061] The sole materials prepared in Examples 1-3 and Comparative examples 1-4 were tested for abrasion resistance 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 abrasion resistance.

[0066] The above content is only an example and illustration of the concept of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the specific embodiments described, or use similar methods to replace them. As long as they do not deviate from the concept of the invention or exceed the scope defined by this claim book, they should all belong to the protection scope of the present invention.

Claims

1. A preparation method of a highly elastic and environmentally friendly shoe sole, characterized in that: Specifically, it includes the following steps: Step A1: Mix 4-hydroxypyridine-2,6-dicarboxylic acid, potassium carbonate and tetrahydrofuran, stir and add allyl chloride. After reaction, adjust the pH to acidic to obtain a modified ligand. Dissolve the modified ligand in tetrahydrofuran, soak the modified substrate therein, add ferric chloride, and after soaking treatment, take it out and dry it to obtain a pretreated substrate. Step A2: React graphene oxide, KH550, dicyclohexylcarbodiimide and toluene to obtain modified graphene. Mix castor oil, methyl methacrylate, n-butyl acrylate, modified graphene and benzoin ethyl ether evenly to obtain a treatment solution. Coat the treatment solution on the surface of the pretreated substrate, and after light treatment, soak it in water to obtain a high-elastic environmental protection shoe sole. The modified substrate is prepared by the following steps: Step B1: Dissolve 4,4'-diaminodiphenyl sulfide in dichloromethane, protect it by introducing nitrogen, and after reaction, add 2,6-pyridinedicarbonyl chloride. After reaction, raise the temperature and continue the reaction to obtain a modified monomer. Step B2: Mix 4-vinylphenylboronic acid, anhydrous sodium sulfate and tetrahydrofuran evenly, protect it by introducing nitrogen, and carry out the reaction to obtain intermediate 1. React intermediate 1, 2-mercaptoethanol, benzophenone and toluene to obtain a strengthened monomer. Step B3: Mix polycarbonate diol, diphenylmethane diisocyanate, dibutyltin dilaurate and DMF, protect it by introducing nitrogen, and carry out the reaction. Add the modified monomer and the strengthened monomer, and after reaction, lower the temperature and add 1,4-butanediol and deionized water, and place it in a mold. After heating and insulation, obtain a modified substrate.

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

3. The preparation method of a highly elastic and environmentally friendly shoe sole according to claim 1, characterized in that: In step A2, the molar ratio of the carboxyl group on graphene oxide, 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 preparation method of a highly elastic and environmentally friendly shoe sole according to claim 1, characterized in that: In step B1, the molar ratio of 4,4'-diaminodiphenyl sulfide and 2,6-pyridinedicarbonyl chloride is n + 1:n, where n is a natural number greater than 0.

5. The preparation method of a highly elastic and environmentally friendly shoe sole according to claim 1, characterized in that: In step B2, the dosage ratio of 4-vinylphenylboronic acid, anhydrous sodium sulfate and tetrahydrofuran is 3 mmol:10 mmol:4 mL, and the molar ratio of intermediate 1 and 2-mercaptoethanol is 1:

3.

6. The preparation method of a highly elastic and environmentally friendly shoe sole according to claim 1, characterized in that: In step B3, the dosage ratio of polycarbonate diol, diphenylmethane diisocyanate, modified monomer, strengthened monomer, 1,4-butanediol and deionized water is 3 mol:7.5 mol:1 mol:1 mol:2 mol:100 mL.

7. A highly elastic and environmentally friendly shoe sole, characterized in that: Prepared by the preparation method according to any one of claims 1-6.

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