A waterproof and breathable shoe and its preparation method

Abstract

The invention relates to the field of footwear, and in particular to a waterproof and breathable shoe and a preparation method thereof, which are used to solve the problem that the waterproof and breathable performance of the existing waterproof and breathable shoes cannot be taken into account at the same time; the preparation method uses a yarn modification liquid to process a mixed spinning yarn to form a waterproof and breathable yarn, and the waterproof and breathable shoe upper prepared by the waterproof and breathable yarn can form a large number of breathable but non-water-permeable micropores, allowing air molecules to pass freely, thereby achieving a good ventilation effect in the shoe, avoiding the problem that the wearer's feet are prone to sweating and dampness after long-term exercise, improving the wearing comfort, and effectively blocking the invasion of external moisture, so that the wearer can wear the shoes comfortably and worry-free in rainy days or humid environments, and keep the feet dry; moreover, the preparation method has a simple process, is easy to operate, and has low cost, which is conducive to large-scale industrial production.

Description

Technical Field

[0001] The invention relates to the field of footwear, and in particular to a waterproof and breathable shoe and a preparation method thereof. Background Art

[0002] As people's living standards improve, the demand for footwear products is also increasing. In outdoor sports, work and other scenarios, people need to wear shoes with waterproof and breathable functions to protect their feet from external moisture and humidity while keeping their feet dry and comfortable.

[0003] However, the waterproof and breathable shoes currently on the market generally have the problem of not being able to balance waterproof performance and breathability. Some shoes use waterproof membranes to achieve waterproof function, but the breathability of such shoes is poor, which leads to excessive sweating of the feet and difficulty in moisture removal. Long-term wearing will cause the feet to be stuffy and airtight, affecting wearing comfort and health; other shoes use breathable materials to achieve breathability, but the waterproof performance of such shoes is poor and cannot effectively block the entry of external moisture. When encountering rain or humid environment, moisture can easily penetrate into the shoes, affecting the wearing experience. Therefore, it is of great significance to develop a waterproof and breathable shoe that is both waterproof and breathable and a preparation method thereof. Summary of the invention

[0004] In order to overcome the above-mentioned technical problems, the object of the present invention is to provide a waterproof and breathable shoe and a preparation method thereof: by blending cotton fiber and nylon fiber to obtain a mixed yarn, by evenly mixing a yarn modifier and deionized water to obtain a yarn modification liquid, by immersing the mixed yarn in the yarn modification liquid, then taking it out and draining it, and then placing it in a vacuum drying oven for baking to obtain a waterproof and breathable yarn, by weaving the waterproof and breathable yarn into an upper to obtain a waterproof and breathable upper, by sewing the waterproof and breathable upper on the sole to obtain a waterproof and breathable shoe, thereby solving the problem that the existing waterproof and breathable shoes cannot take into account both waterproof performance and breathability performance.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] A method for preparing waterproof and breathable shoes comprises the following steps:

[0007] Step 1: Weigh 45-55 parts of cotton fiber and 10-15 parts of nylon fiber according to weight and set aside;

[0008] Step 2: blending cotton fiber and nylon fiber to obtain blended yarn;

[0009] Step 3: Weigh 0.5-2.5 parts of yarn modifier and 100 parts of deionized water according to weight, and set aside;

[0010] Step 4: Evenly mix the yarn modifier and deionized water to obtain a yarn modification liquid;

[0011] Step Five: Immerse the blended yarn in the yarn modifier solution at a mass ratio of 1:20 for 2 - 3 hours, then take it out and drain, and then place it in a vacuum drying oven. Pre-dry it for 3 - 5 minutes at a temperature of 90 - 95°C, and then bake it for 1 - 2 minutes at a temperature of 130 - 135°C to obtain the waterproof and breathable yarn.

[0012] Step Six: Weave the waterproof and breathable yarn into a shoe upper to obtain a waterproof and breathable shoe upper.

[0013] Step Seven: Sew the waterproof and breathable shoe upper onto the sole to obtain a waterproof and breathable shoe.

[0014] As a further solution of the present invention: The yarn modifier is prepared by the following steps:

[0015] Step s1: Add triphenylamine, N-bromosuccinimide, and anhydrous tetrahydrofuran into a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube. Protect it by introducing nitrogen. Stir and react for 20 - 30 minutes at a temperature of -5 - 0°C and a stirring rate of 300 - 400 r / min, then raise the temperature to 50 - 55°C and continue to stir and react for 2 - 3 hours. After the reaction is completed, cool the reaction product to room temperature, then pour it into a saturated sodium thiosulfate solution, and then extract it with dichloromethane 2 - 3 times. Combine the extraction solutions and dry them with anhydrous magnesium sulfate, then perform vacuum filtration. Rotate and evaporate the filtrate to remove the solvent, and then recrystallize it with a mixed solution to obtain Intermediate 1.

[0016] Step s2: Add Intermediate 1, ethyl 3,4-dihydroxybenzoate, anhydrous potassium carbonate, toluene, and N,N-dimethylformamide into a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube. Protect it by introducing nitrogen. Stir and react for 30 - 50 minutes at a temperature of 25 - 30°C and a stirring rate of 300 - 400 r / min, then raise the temperature to 130 - 135°C and continue to stir and react for 3 - 4 hours, and then raise the temperature to 150 - 155°C and continue to stir and react for 2 - 3 hours. After the reaction is completed, cool the reaction product to room temperature, then pour it into ice water, and then let it stand for liquid separation. Rotate and evaporate the organic phase to remove the solvent to obtain Intermediate 2.

[0017] Step s3: Add intermediate 2 and anhydrous tetrahydrofuran into a three-necked flask equipped with a stirrer, a thermometer, a gas pipe, and a reflux condenser. Introduce nitrogen for protection. Stir and react for 1 - 1.5 h under the conditions of a temperature of 25 - 30 °C and a stirring rate of 300 - 400 r / min. Then add potassium hydroxide solution and continue to stir and react for 20 - 30 min. After that, raise the temperature to reflux and continue to stir and react for 15 - 20 h. After the reaction is completed, cool the reaction product to room temperature. Then adjust the pH to 3 - 4 with hydrochloric acid solution. Then let it stand to precipitate. Then centrifuge. Wash the precipitate with distilled water 2 - 3 times. Then place it in a vacuum drying oven and dry it for 3 - 4 h under the condition of a temperature of 50 - 55 °C to obtain intermediate 3;

[0018] Step s4: Add intermediate 3, perfluorohexyl ethanol, p-toluenesulfonic acid, and anhydrous tetrahydrofuran into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Stir and react for 20 - 30 min under the conditions of a temperature of 25 - 30 °C and a stirring rate of 300 - 400 r / min. Then raise the temperature to 90 - 95 °C and continue to stir and react for 6 - 7 h. After the reaction is completed, cool the reaction product to room temperature. Then wash it 2 - 3 times with saturated brine. Then rotate and evaporate to remove the solvent to obtain intermediate 4;

[0019] Step s5: Add intermediate 4, isophorone diisocyanate, dibutyltin dilaurate, and anhydrous tetrahydrofuran into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Stir and react for 20 - 30 min under the conditions of a temperature of 25 - 30 °C and a stirring rate of 300 - 400 r / min. Then raise the temperature to 70 - 75 °C and continue to stir and react for 3 - 4 h. After the reaction is completed, cool the reaction product to room temperature. Then rotate and evaporate to remove the solvent to obtain the yarn modifier.

[0020] As a further scheme of the present invention: The dosage ratio of the triphenylamine, N-bromosuccinimide, and anhydrous tetrahydrofuran in step s1 is 10 mmol: 30 - 35 mmol: 40 - 50 mL.

[0021] As a further scheme of the present invention: The mixed solution in step s1 is a mixture of ethyl acetate and petroleum ether in a volume ratio of 1:5.

[0022] As a further scheme of the present invention: The dosage ratio of the intermediate 1, ethyl 3,4-dihydroxybenzoate, anhydrous potassium carbonate, toluene, and N,N-dimethylformamide in step s2 is 10 mmol: 30 mmol: 35 - 45 mmol: 35 - 40 mL: 50 - 55 mL.

[0023] As a further solution of the present invention: the dosage ratio of the intermediate 2, anhydrous tetrahydrofuran and potassium hydroxide solution in step s3 is 10 mmol: 20 - 25 mL: 30 - 35 mL.

[0024] As a further solution of the present invention: the mass fraction of the potassium hydroxide solution in step s3 is 10 - 15%; the mass fraction of the hydrochloric acid solution is 25 - 30%.

[0025] As a further solution of the present invention: the dosage ratio of the intermediate 3, perfluorohexyl ethanol, p - toluenesulfonic acid and anhydrous tetrahydrofuran in step s4 is 10 mmol: 30 mmol: 0.01 - 0.03 g: 80 - 100 mL.

[0026] As a further solution of the present invention: the dosage ratio of the intermediate 4, isophorone diisocyanate, dibutyltin dilaurate and anhydrous tetrahydrofuran in step s5 is 10 mmol: 30 mmol: 0.02 - 0.06 g: 100 - 120 mL.

[0027] As a further solution of the present invention: a waterproof and breathable shoe, which is prepared according to the preparation method of the waterproof and breathable shoe.

[0028] The beneficial effects of the present invention:

[0029] For the waterproof and breathable shoe and its preparation method of the present invention, by blending cotton fiber and nylon fiber, a mixed spun yarn is obtained. By mixing a yarn modifier and deionized water evenly, a yarn modification liquid is obtained. By impregnating the mixed spun yarn in the yarn modification liquid, then taking it out and draining, and then placing it in a vacuum drying oven for baking, a waterproof and breathable yarn is obtained. By weaving the waterproof and breathable yarn into a shoe upper, a waterproof and breathable shoe upper is obtained. By sewing the waterproof and breathable shoe upper onto a shoe sole, a waterproof and breathable shoe is obtained; this preparation method uses the yarn modification liquid to treat the mixed spun yarn to form a waterproof and breathable yarn, and the waterproof and breathable shoe upper prepared from the waterproof and breathable yarn can form a large number of micropores that are breathable but not water - permeable, allowing air molecules to pass freely, achieving a good air - permeability effect inside the shoe, avoiding the problems that the feet of the wearer are prone to sweating and getting wet after long - term exercise, improving the wearing comfort, and also effectively blocking the intrusion of external moisture, so that it is comfortable to wear in rainy or humid environments and keeps the feet dry; moreover, this preparation method has a simple process, is easy to operate, and has a low cost, which is conducive to large - scale industrial production.

[0030] In the process of preparing a waterproof and breathable shoe, a yarn modifier was first prepared. First, triphenylamine and N-bromosuccinimide were reacted. N-bromosuccinimide was used as a brominating agent to introduce bromine atoms onto the benzene ring of triphenylamine to obtain intermediate 1. Then, intermediate 1 and ethyl 3,4-dihydroxybenzoate were reacted. The bromine atom on intermediate 1 reacted with the hydroxyl group on ethyl 3,4-dihydroxybenzoate, thereby introducing a hydroxyl group and an ester group to obtain intermediate 2. Then, the ester group on intermediate 2 was hydrolyzed to form a carboxyl group to obtain intermediate 3. Then, intermediate 3 and perfluorohexyl ethanol were reacted. The carboxyl group on intermediate 3 reacted with the hydroxyl group on perfluorohexyl ethanol to carry out an esterification reaction, introducing a large number of C-F bonds to obtain intermediate 4. Then, intermediate 4 and isophorone diisocyanate were reacted. The hydroxyl group on intermediate 4 reacted with the isocyanate group on isophorone diisocyanate, and at the same time, an isocyanate group was introduced to obtain the yarn modifier; a large number of isocyanate groups are contained in the molecular structure of the yarn modifier. During the process of treating the blended yarn, the isocyanate group reacts with the hydroxyl group thereon, and a large number of C-F bonds are grafted onto the surface of the blended yarn in the form of chemical bonds, endowing it with high hydrophobicity, greatly improving the waterproof performance, and the yarn modifier wraps the blended yarn to form a hydrophobic layer, making it difficult for adjacent blended yarns to adhere and entangle, ensuring that there are a large number of micropores between the blended yarns and ensuring excellent air permeability. Detailed implementation manners

[0031] The following will combine the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments in 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.

[0032] Example 1:

[0033] This example is a preparation method of a waterproof and breathable shoe, including the following steps:

[0034] Step A1: Add 10 mmol of triphenylamine, 30 mmol of N-bromosuccinimide, and 40 mL of anhydrous tetrahydrofuran into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Stir and react for 20 min under the conditions of a temperature of -5 °C and a stirring rate of 300 r / min. Then, continue to stir and react for 2 h under the condition of heating to 50 °C. After the reaction is completed, cool the reaction product to room temperature, then pour it into a saturated sodium thiosulfate solution, extract it twice with dichloromethane, combine the extracts and dry them with anhydrous magnesium sulfate, then perform vacuum filtration. Rotate and evaporate the filtrate to remove the solvent, and then recrystallize it with a mixed solution of ethyl acetate and petroleum ether mixed according to a volume ratio of 1:5 to obtain Intermediate 1;

[0035] Step A2: Add 10 mmol of Intermediate 1, 30 mmol of ethyl 3,4-dihydroxybenzoate, 35 mmol of anhydrous potassium carbonate, 35 mL of toluene, and 50 mL of N,N-dimethylformamide into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Stir and react for 30 min under the conditions of a temperature of 25 °C and a stirring rate of 300 r / min. Then, continue to stir and react for 3 h under the condition of heating to 130 °C, and then continue to stir and react for 2 h under the condition of heating to 150 °C. After the reaction is completed, cool the reaction product to room temperature, then pour it into ice water, then let it stand for liquid separation. Rotate and evaporate the organic phase to remove the solvent to obtain Intermediate 2;

[0036] Step A3: Add 10 mmol of Intermediate 2 and 20 mL of anhydrous tetrahydrofuran into a three-necked flask equipped with a stirrer, a thermometer, a gas pipe, and a reflux condenser. Introduce nitrogen for protection. Stir and react for 1 h under the conditions of a temperature of 25 °C and a stirring rate of 300 r / min. Then, add 30 mL of a 10% potassium hydroxide solution and continue to stir and react for 20 min. Then, continue to stir and react for 15 h under the condition of heating to reflux. After the reaction is completed, cool the reaction product to room temperature, then adjust it to pH 3 with a 25% hydrochloric acid solution, then let it stand to precipitate, then centrifuge. Wash the precipitate twice with distilled water, and then place it in a vacuum drying oven and dry it at a temperature of 50 °C for 3 h to obtain Intermediate 3;

[0037] Step A4: Add 10 mmol of Intermediate 3, 30 mmol of perfluorohexyl ethanol, 0.01 g of p-toluenesulfonic acid, and 80 mL of anhydrous tetrahydrofuran into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Stir and react for 20 min under the conditions of a temperature of 25 °C and a stirring rate of 300 r / min. Then, continue to stir and react for 6 h under the condition of heating to 90 °C. After the reaction is completed, cool the reaction product to room temperature, then wash it twice with saturated brine, and then rotate and evaporate to remove the solvent to obtain Intermediate 4;

[0038] Step A5: Add 10 mmol of intermediate 4, 30 mmol of isophorone diisocyanate, 0.02 g of dibutyltin dilaurate, and 100 mL of anhydrous tetrahydrofuran into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Stir and react for 20 min at a temperature of 25°C and a stirring rate of 300 r / min. Then, continue to stir and react for 3 h under the condition of raising the temperature to 70°C. After the reaction is completed, cool the reaction product to room temperature, and then remove the solvent by rotary evaporation to obtain a yarn modifier;

[0039] Step A6: Weigh 45 parts by weight of cotton fiber and 10 parts by weight of nylon fiber for standby;

[0040] Step A7: Blend the cotton fiber and the nylon fiber to obtain a blended yarn;

[0041] Step A8: Weigh 0.5 part by weight of the yarn modifier and 100 parts by weight of deionized water for standby;

[0042] Step A9: Mix the yarn modifier and the deionized water evenly to obtain a yarn modification liquid;

[0043] Step A10: Immerse the blended yarn in the yarn modification liquid at a mass ratio of 1:20 for 2 h, then take it out and drain it, and then place it in a vacuum drying oven. Pre-dry it for 3 min at a temperature of 90°C, and then bake it for 1 min at a temperature of 130°C to obtain a waterproof and breathable yarn;

[0044] Step A11: Weave the waterproof and breathable yarn into a shoe upper to obtain a waterproof and breathable shoe upper;

[0045] Step A12: Sew the waterproof and breathable shoe upper onto the sole to obtain a waterproof and breathable shoe.

[0046] Example 2:

[0047] The preparation method of a waterproof and breathable shoe in this example includes the following steps:

[0048] Step A1: Add 10 mmol of triphenylamine, 32 mmol of N-bromosuccinimide, and 45 mL of anhydrous tetrahydrofuran into a three-necked flask equipped with a stirrer, a thermometer, and a gas inlet tube. Protect the reaction system by introducing nitrogen gas. Stir the reaction mixture at -3 °C and a stirring rate of 350 r / min for 25 min. Then, raise the temperature to 52 °C and continue stirring for 2.5 h. After the reaction is completed, cool the reaction product to room temperature, pour it into a saturated sodium thiosulfate solution, extract it twice with dichloromethane, combine the extracts, dry them with anhydrous magnesium sulfate, filter them by vacuum filtration, rotary evaporate the filtrate to remove the solvent, and recrystallize the residue with a mixed solution of ethyl acetate and petroleum ether in a volume ratio of 1:5 to obtain Intermediate 1;

[0049] Step A2: Add 10 mmol of Intermediate 1, 30 mmol of ethyl 3,4-dihydroxybenzoate, 40 mmol of anhydrous potassium carbonate, 38 mL of toluene, and 52 mL of N,N-dimethylformamide into a three-necked flask equipped with a stirrer, a thermometer, and a gas inlet tube. Protect the reaction system by introducing nitrogen gas. Stir the reaction mixture at 28 °C and a stirring rate of 350 r / min for 40 min. Then, raise the temperature to 132 °C and continue stirring for 3.5 h. Subsequently, raise the temperature to 152 °C and continue stirring for 2.5 h. After the reaction is completed, cool the reaction product to room temperature, pour it into ice water, let it stand for liquid separation, rotary evaporate the organic phase to remove the solvent, and obtain Intermediate 2;

[0050] Step A3: Add 10 mmol of Intermediate 2 and 22 mL of anhydrous tetrahydrofuran into a three-necked flask equipped with a stirrer, a thermometer, a gas inlet tube, and a reflux condenser. Protect the reaction system by introducing nitrogen gas. Stir the reaction mixture at 28 °C and a stirring rate of 350 r / min for 1.2 h. Then, add 32 mL of a 12% potassium hydroxide solution and continue stirring for 25 min. Subsequently, raise the temperature to reflux and continue stirring for 18 h. After the reaction is completed, cool the reaction product to room temperature, adjust the pH to 3.5 with a 28% hydrochloric acid solution, let it stand to precipitate, centrifuge it, wash the precipitate twice with distilled water, and then place it in a vacuum drying oven and dry it at 52 °C for 3.5 h to obtain Intermediate 3;

[0051] Step A4: Add 10 mmol of intermediate 3, 30 mmol of perfluorohexyl ethanol, 0.02 g of p-toluenesulfonic acid, and 90 mL of anhydrous tetrahydrofuran into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Stir and react at a temperature of 28 °C and a stirring rate of 350 r / min for 25 min, then raise the temperature to 92 °C and continue to stir and react for 6.5 h. After the reaction is completed, cool the reaction product to room temperature, then wash it twice with saturated brine, and then rotary evaporate to remove the solvent to obtain intermediate 4;

[0052] Step A5: Add 10 mmol of intermediate 4, 30 mmol of isophorone diisocyanate, 0.04 g of dibutyltin dilaurate, and 110 mL of anhydrous tetrahydrofuran into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Stir and react at a temperature of 28 °C and a stirring rate of 350 r / min for 25 min, then raise the temperature to 72 °C and continue to stir and react for 3.5 h. After the reaction is completed, cool the reaction product to room temperature, and then rotary evaporate to remove the solvent to obtain the yarn modifier;

[0053] Step A6: Weigh 50 parts of cotton fiber and 12 parts of nylon fiber by weight, and set aside;

[0054] Step A7: Blend the cotton fiber and nylon fiber to obtain a blended yarn;

[0055] Step A8: Weigh 1.5 parts of the yarn modifier and 100 parts of deionized water by weight, and set aside;

[0056] Step A9: Mix the yarn modifier and deionized water evenly to obtain a yarn modification liquid;

[0057] Step A10: Immerse the blended yarn in the yarn modification liquid at a mass ratio of 1:20 for 2.5 h, then take it out and drain, and then place it in a vacuum drying oven. Pre-dry it at a temperature of 92 °C for 4 min, and then bake it at a temperature of 132 °C for 1.5 min to obtain the waterproof and breathable yarn;

[0058] Step A11: Weave the waterproof and breathable yarn into a shoe upper to obtain a waterproof and breathable shoe upper;

[0059] Step A12: Sew the waterproof and breathable shoe upper onto the sole to obtain a waterproof and breathable shoe.

[0060] Example 3:

[0061] This example is a preparation method of a waterproof and breathable shoe, including the following steps:

[0062] Step A1: Add 10 mmol of triphenylamine, 35 mmol of N-bromosuccinimide, and 50 mL of anhydrous tetrahydrofuran into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Stir and react for 30 min under the conditions of a temperature of 0 °C and a stirring rate of 400 r / min. Then, raise the temperature to 55 °C and continue to stir and react for 3 h. After the reaction is completed, cool the reaction product to room temperature, then pour it into a saturated sodium thiosulfate solution, extract it 3 times with dichloromethane, combine the extracts and dry them with anhydrous magnesium sulfate, then perform vacuum filtration. Rotate evaporate the filtrate to remove the solvent, and then recrystallize it with a mixed solution of ethyl acetate and petroleum ether in a volume ratio of 1:5 to obtain Intermediate 1;

[0063] Step A2: Add 10 mmol of Intermediate 1, 30 mmol of ethyl 3,4-dihydroxybenzoate, 45 mmol of anhydrous potassium carbonate, 40 mL of toluene, and 55 mL of N,N-dimethylformamide into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Stir and react for 50 min under the conditions of a temperature of 30 °C and a stirring rate of 400 r / min. Then, raise the temperature to 135 °C and continue to stir and react for 4 h. Then, raise the temperature to 155 °C and continue to stir and react for 3 h. After the reaction is completed, cool the reaction product to room temperature, then pour it into ice water, then let it stand for liquid separation. Rotate evaporate the organic phase to remove the solvent to obtain Intermediate 2;

[0064] Step A3: Add 10 mmol of Intermediate 2 and 25 mL of anhydrous tetrahydrofuran into a three-necked flask equipped with a stirrer, a thermometer, a gas pipe, and a reflux condenser. Introduce nitrogen for protection. Stir and react for 1.5 h under the conditions of a temperature of 30 °C and a stirring rate of 400 r / min. Then, add 35 mL of a 15% potassium hydroxide solution and continue to stir and react for 30 min. Then, raise the temperature to reflux and continue to stir and react for 20 h. After the reaction is completed, cool the reaction product to room temperature, then adjust it to pH 4 with a 30% hydrochloric acid solution, then let it stand to precipitate, then centrifuge. Wash the precipitate 3 times with distilled water, and then place it in a vacuum drying oven and dry it at a temperature of 55 °C for 4 h to obtain Intermediate 3;

[0065] Step A4: Add 10 mmol of intermediate 3, 30 mmol of perfluorohexyl ethanol, 0.03 g of p-toluenesulfonic acid, and 100 mL of anhydrous tetrahydrofuran into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Stir and react for 30 min at a temperature of 30 °C and a stirring rate of 400 r / min. Then, raise the temperature to 95 °C and continue stirring and reacting for 7 h. After the reaction is completed, cool the reaction product to room temperature, wash it 3 times with saturated brine, and then remove the solvent by rotary evaporation to obtain intermediate 4;

[0066] Step A5: Add 10 mmol of intermediate 4, 30 mmol of isophorone diisocyanate, 0.06 g of dibutyltin dilaurate, and 120 mL of anhydrous tetrahydrofuran into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Stir and react for 30 min at a temperature of 30 °C and a stirring rate of 400 r / min. Then, raise the temperature to 75 °C and continue stirring and reacting for 4 h. After the reaction is completed, cool the reaction product to room temperature, and then remove the solvent by rotary evaporation to obtain the yarn modifier;

[0067] Step A6: Weigh 55 parts of cotton fiber and 15 parts of nylon fiber by weight, and set aside;

[0068] Step A7: Blend the cotton fiber and nylon fiber to obtain a blended yarn;

[0069] Step A8: Weigh 2.5 parts of the yarn modifier and 100 parts of deionized water by weight, and set aside;

[0070] Step A9: Mix the yarn modifier and deionized water evenly to obtain a yarn modification liquid;

[0071] Step A10: Immerse the blended yarn in the yarn modification liquid at a mass ratio of 1:20 for 3 h, then take it out and drain it. Then, place it in a vacuum drying oven and pre-bake it at a temperature of 95 °C for 5 min, and then bake it at a temperature of 135 °C for 2 min to obtain a waterproof and breathable yarn;

[0072] Step A11: Weave the waterproof and breathable yarn into a shoe upper to obtain a waterproof and breathable shoe upper;

[0073] Step A12: Sew the waterproof and breathable shoe upper onto the sole to obtain a waterproof and breathable shoe.

[0074] Comparative Example 1:

[0075] This comparative example is a preparation method of a waterproof and breathable shoe, including the following steps:

[0076] Step A1: Weigh 55 parts of cotton fiber and 15 parts of nylon fiber by weight, and set aside;

[0077] Step A2: Blending cotton fibers and nylon fibers to obtain a blended yarn;

[0078] Step A3: Weaving the blended yarn into a shoe upper to obtain a waterproof and breathable shoe upper;

[0079] Step A4: Sewing the waterproof and breathable shoe upper onto a sole to obtain a waterproof and breathable shoe.

[0080] Comparative Example 2:

[0081] This comparative example is a preparation method of a waterproof and breathable shoe, including the following steps:

[0082] Step A1: Weigh 55 parts of cotton fibers and 15 parts of nylon fibers by weight, and set aside;

[0083] Step A2: Blending cotton fibers and nylon fibers to obtain a blended yarn;

[0084] Step A3: Weigh 2.5 parts of isophorone diisocyanate and 100 parts of deionized water by weight, and set aside;

[0085] Step A4: Mix isophorone diisocyanate and deionized water evenly to obtain a yarn modification liquid;

[0086] Step A5: Immerse the blended yarn in the yarn modification liquid at a mass ratio of 1:20 for 3 h, then take it out and drain it, and then place it in a vacuum drying oven. Pre-bake it at a temperature of 95 °C for 5 min, and then bake it at a temperature of 135 °C for 2 min to obtain a waterproof and breathable yarn;

[0087] Step A6: Weave the waterproof and breathable yarn into a shoe upper to obtain a waterproof and breathable shoe upper;

[0088] Step A7: Sew the waterproof and breathable shoe upper onto a sole to obtain a waterproof and breathable shoe.

[0089] Test the performance of the waterproof and breathable shoe uppers of Examples 1-3 and Comparative Examples 1-2. The test method is as follows:

[0090] Use an OCA15EC type contact angle measuring instrument to directly test the static water contact angle of the waterproof and breathable shoe upper to obtain the first contact angle. Then, according to the method of GB / T3921-2008 "Textiles - Tests for colour fastness - Colour fastness to soaping", use an SW-12JG type colour fastness to washing tester to wash the waterproof and breathable shoe upper 100 times, and then use an OCA15EC type contact angle measuring instrument to test the static water contact angle of the waterproof and breathable shoe upper to obtain the second contact angle;

[0091] The test results are shown in the following table:

[0092] Sample Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 First contact angle, ° 147.5 151.3 156.6 71.9 119.2 Second contact angle, ° 138.1 144.9 150.2 66.7 91.4

[0093] Referring to the data in the above table, by comparing Examples 1-3 with Comparative Examples 1-2, it can be seen that the waterproof breathable shoes of the present application have excellent waterproof performance and long-lasting waterproof performance.

[0094] In the description of this specification, the descriptions referring to terms such as "one embodiment", "example", "specific example", etc. mean that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0095] The above content is only an example and illustration 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 invention or exceed the scope defined by this application, they should all fall within the protection scope of the present invention.

Claims

1. A preparation method of a waterproof and breathable shoe, characterized in that, It includes the following steps: Step 1: Weigh 45 - 55 parts by weight of cotton fiber and 10 - 15 parts by weight of nylon fiber for standby; Step 2: Blended the cotton fiber and nylon fiber to obtain a blended yarn; Step 3: Weigh 0.5 - 2.5 parts by weight of yarn modifier and 100 parts by weight of deionized water for standby; Step 4: Mix the yarn modifier and deionized water evenly to obtain a yarn modification liquid; Step 5: Immerse the blended yarn in the yarn modification liquid at a mass ratio of 1:20 for 2 - 3 h, then take it out and drain, and then place it in a vacuum drying oven. Pre - bake it at a temperature of 90 - 95 °C for 3 - 5 min, and then bake it at a temperature of 130 - 135 °C for 1 - 2 min to obtain a waterproof and breathable yarn; Step 6: Weave the waterproof and breathable yarn into a shoe upper to obtain a waterproof and breathable shoe upper; Step 7: Sew the waterproof and breathable shoe upper onto the sole to obtain a waterproof and breathable shoe; The yarn modifier is prepared by the following steps: Step s1: Add triphenylamine, N - bromosuccinimide, and anhydrous tetrahydrofuran into a three - necked flask equipped with a stirrer, a thermometer, and a gas pipe. Protect it by introducing nitrogen. Stir and react at a temperature of - 5 - 0 °C and a stirring rate of 300 - 400 r / min for 20 - 30 min, then raise the temperature to 50 - 55 °C and continue to stir and react for 2 - 3 h. After the reaction is completed, cool the reaction product to room temperature, then pour it into a saturated sodium thiosulfate solution, then extract it with dichloromethane for 2 - 3 times, combine the extraction liquid and dry it with anhydrous magnesium sulfate, then vacuum filter. Rotate - evaporate the filtrate to remove the solvent, and then recrystallize it with a mixed solution to obtain intermediate 1; Step s2: Add intermediate 1, ethyl 3,4 - dihydroxybenzoate, anhydrous potassium carbonate, toluene, and N,N - dimethylformamide into a three - necked flask equipped with a stirrer, a thermometer, and a gas pipe. Protect it by introducing nitrogen. Stir and react at a temperature of 25 - 30 °C and a stirring rate of 300 - 400 r / min for 30 - 50 min, then raise the temperature to 130 - 135 °C and continue to stir and react for 3 - 4 h, then raise the temperature to 150 - 155 °C and continue to stir and react for 2 - 3 h. After the reaction is completed, cool the reaction product to room temperature, then pour it into ice water, then let it stand for layering. Rotate - evaporate the organic phase to remove the solvent to obtain intermediate 2; Step s3: Add intermediate 2 and anhydrous tetrahydrofuran into a three-necked flask equipped with a stirrer, a thermometer, a gas pipe, and a reflux condenser. Introduce nitrogen for protection. Stir and react for 1 - 1.5 h under the conditions of a temperature of 25 - 30 °C and a stirring rate of 300 - 400 r / min. Then add potassium hydroxide solution and continue to stir and react for 20 - 30 min. Then raise the temperature to reflux and continue to stir and react for 15 - 20 h. After the reaction is completed, cool the reaction product to room temperature. Then adjust the pH to 3 - 4 with hydrochloric acid solution. Then let it stand to precipitate. Then centrifuge. Wash the precipitate with distilled water 2 - 3 times. Then place it in a vacuum drying oven and dry it for 3 - 4 h under the condition of a temperature of 50 - 55 °C to obtain intermediate 3; Step s4: Add intermediate 3, perfluorohexyl ethanol, p-toluenesulfonic acid, and anhydrous tetrahydrofuran into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Stir and react for 20 - 30 min under the conditions of a temperature of 25 - 30 °C and a stirring rate of 300 - 400 r / min. Then raise the temperature to 90 - 95 °C and continue to stir and react for 6 - 7 h. After the reaction is completed, cool the reaction product to room temperature. Then wash it with saturated brine 2 - 3 times. Then rotary evaporate to remove the solvent to obtain intermediate 4; Step s5: Add intermediate 4, isophorone diisocyanate, dibutyltin dilaurate, and anhydrous tetrahydrofuran into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Stir and react for 20 - 30 min under the conditions of a temperature of 25 - 30 °C and a stirring rate of 300 - 400 r / min. Then raise the temperature to 70 - 75 °C and continue to stir and react for 3 - 4 h. After the reaction is completed, cool the reaction product to room temperature. Then rotary evaporate to remove the solvent to obtain the yarn modifier.

2. The preparation method of a waterproof and breathable shoe according to claim 1, characterized in that, The dosage ratio of the triphenylamine, N-bromosuccinimide, and anhydrous tetrahydrofuran in step s1 is 10 mmol : 30 - 35 mmol : 40 - 50 mL.

3. The preparation method of a waterproof and breathable shoe according to claim 1, characterized in that, The mixed solution in step s1 is a mixture of ethyl acetate and petroleum ether in a volume ratio of 1 :

5.

4. The preparation method of a waterproof and breathable shoe according to claim 1, characterized in that, The dosage ratio of the intermediate 1, ethyl 3,4-dihydroxybenzoate, anhydrous potassium carbonate, toluene, and N,N-dimethylformamide in step s2 is 10 mmol : 30 mmol : 35 - 45 mmol : 35 - 40 mL : 50 - 55 mL.

5. The preparation method of a waterproof and breathable shoe according to claim 1, characterized in that, The dosage ratio of the intermediate 2, anhydrous tetrahydrofuran, and potassium hydroxide solution in step s3 is 10 mmol : 20 - 25 mL : 30 - 35 mL.

6. The preparation method of a waterproof and breathable shoe according to claim 1, characterized in that, The mass fraction of the potassium hydroxide solution in step s3 is 10 - 15%; the mass fraction of the hydrochloric acid solution is 25 - 30%.

7. The preparation method of a waterproof and breathable shoe according to claim 1, characterized in that, The dosage ratio of the intermediate 3, perfluorohexyl ethanol, p-toluenesulfonic acid, and anhydrous tetrahydrofuran in step s4 is 10 mmol : 30 mmol : 0.01 - 0.03 g : 80 - 100 mL.

8. The preparation method of a waterproof and breathable shoe according to claim 1, characterized in that, The dosage ratio of the intermediate 4, isophorone diisocyanate, dibutyltin dilaurate, and anhydrous tetrahydrofuran in step s5 is 10 mmol: 30 mmol: 0.02 - 0.06 g: 100 - 120 mL.

9. A waterproof and breathable shoe, characterized in that, The waterproof and breathable shoes are prepared according to the preparation method of the waterproof and breathable shoes according to any one of claims 1 - 8.