Waterproof breathable shoe and preparation method thereof

Abstract

The invention relates to the field of shoes, in particular to waterproof breathable shoes and a preparation method thereof, and aims to solve the problem that waterproof performance and breathability of existing waterproof breathable shoes cannot be considered at the same time. According to the preparation method, the mixed doubling threads are treated by using the yarn modification liquid to form the waterproof breathable yarns, and the waterproof breathable vamp prepared from the waterproof breathable yarns can form a large number of breathable but waterproof micropores to allow air molecules to freely pass through, so that a good breathable effect in the shoe is realized; the problem that the feet of a wearer are easy to sweat and wet after long-time exercise is avoided, the wearing comfort is improved, and external moisture can be effectively prevented from invading, so that the shoe is comfortable to wear in rainy days or humid environments, and the feet are kept dry and comfortable; moreover, the preparation method is simple in process, easy to operate, low in cost and beneficial to realization of 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 by 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 5: Immerse the mixed yarn in the yarn modification liquid at a mass ratio of 1:20 for 2-3 hours, then take it out and drain it, then place it in a vacuum drying oven, pre-bake it at a temperature of 90-95°C for 3-5 minutes, and then bake it at a temperature of 130-135°C for 1-2 minutes to obtain a waterproof and breathable yarn;

[0012] Step 6: Weaving the waterproof and breathable yarn into a shoe upper to obtain a waterproof and breathable shoe upper;

[0013] Step 7: Sew the waterproof and breathable upper onto the sole to obtain the waterproof and breathable shoes.

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

[0015] Step s1: triphenylamine, N-bromosuccinimide and anhydrous tetrahydrofuran are added to a three-necked flask equipped with a stirrer, a thermometer and an air duct, and nitrogen is introduced for protection. The mixture is stirred for reaction at a temperature of -5-0°C and a stirring rate of 300-400 r / min for 20-30 min, and then the mixture is heated to 50-55°C and stirred for reaction for 2-3 h. After the reaction is completed, the reaction product is cooled to room temperature, and then poured into a saturated sodium thiosulfate solution, and then extracted with dichloromethane for 2-3 times. The extracts are combined and dried with anhydrous magnesium sulfate, and then vacuum filtered. The filtrate is rotary evaporated to remove the solvent, and then recrystallized with the 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 an air duct, introduce nitrogen protection, stir and react for 30-50 minutes at a temperature of 25-30°C and a stirring rate of 300-400r / min, then heat to 130-135°C and continue to stir and react for 3-4 hours, then heat 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, then let it stand for stratification, and rotary evaporate the organic phase to remove the solvent to obtain intermediate 2;

[0017] Step s3: Add intermediate 2 and anhydrous tetrahydrofuran to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube and a reflux condenser, introduce nitrogen protection, stir and react for 1-1.5 hours at a temperature of 25-30°C and a stirring rate of 300-400r / min, then add potassium hydroxide solution and continue to stir and react for 20-30 minutes, then raise the temperature to reflux and continue to stir and react for 15-20 hours, after the reaction is completed, cool the reaction product to room temperature, then adjust the pH to 3-4 with hydrochloric acid solution, then 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 at a temperature of 50-55°C for 3-4 hours to obtain intermediate 3;

[0018] Step s4: Add intermediate 3, perfluorohexylethanol, p-toluenesulfonic acid and anhydrous tetrahydrofuran into a three-necked flask equipped with a stirrer, a thermometer and a gas guide tube, introduce nitrogen protection, stir and react for 20-30 minutes at a temperature of 25-30°C and a stirring rate of 300-400r / min, then heat to 90-95°C and continue stirring and reacting for 6-7 hours. After the reaction is completed, the reaction product is cooled to room temperature, then washed with saturated brine 2-3 times, and then rotary evaporated 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 an air duct, introduce nitrogen protection, stir the reaction at a temperature of 25-30°C and a stirring rate of 300-400r / min for 20-30min, then raise the temperature to 70-75°C and continue stirring the reaction for 3-4h. After the reaction is completed, the reaction product is cooled to room temperature, and then the solvent is removed by rotary evaporation to obtain a yarn modifier.

[0020] As a further solution of the present invention: the usage 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 solution 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 usage ratio of the intermediate 1, 3,4-dihydroxybenzoic acid ethyl ester, anhydrous potassium carbonate, toluene and N,N-dimethylformamide in step s2 is 10mmol:30mmol:35-45mmol:35-40mL:50-55mL.

[0023] As a further solution of the present invention: the usage 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 usage ratio of the intermediate 3, perfluorohexylethanol, 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 usage 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 breathable shoe, the waterproof breathable shoe is prepared according to the preparation method of the waterproof breathable shoe.

[0028] Beneficial effects of the present invention:

[0029] The present invention discloses a waterproof and breathable shoe and a preparation method thereof, wherein cotton fiber and nylon fiber are blended to obtain a mixed yarn, a yarn modifier and deionized water are mixed evenly to obtain a yarn modification liquid, the mixed yarn is immersed in the yarn modification liquid, then taken out and drained, and then placed in a vacuum drying oven for baking to obtain a waterproof and breathable yarn, the waterproof and breathable yarn is woven into a shoe upper to obtain a waterproof and breathable shoe upper, and the waterproof and breathable shoe upper is sewn onto a shoe sole to obtain a waterproof and breathable shoe; the preparation method uses a yarn modification liquid to treat the mixed yarn into a shoe upper The waterproof and breathable yarn is made into a waterproof and breathable yarn, and the waterproof and breathable shoe upper prepared with the waterproof and breathable yarn can form a large number of breathable but impermeable micropores, allowing air molecules to pass freely, achieving good ventilation effect in the shoe, avoiding the problem of sweating and dampness of the wearer's feet after long-term exercise, improving wearing comfort, and effectively blocking the invasion of external moisture, so that wearing is comfortable and worry-free on rainy days or in humid environments, keeping the feet dry; moreover, the preparation method is simple in process, easy to operate, and low in cost, which is conducive to large-scale industrial production.

[0030] In the process of preparing waterproof and breathable shoes, a yarn modifier is first prepared. First, triphenylamine and N-bromosuccinimide are reacted, and N-bromosuccinimide is used as a brominating agent to introduce bromine atoms into the benzene ring of triphenylamine to obtain intermediate 1. Then, intermediate 1 and ethyl 3,4-dihydroxybenzoate are reacted, and the bromine atoms on intermediate 1 react with the hydroxyl groups on ethyl 3,4-dihydroxybenzoate, thereby introducing hydroxyl groups and ester groups to obtain intermediate 2. Then, the ester groups on intermediate 2 are hydrolyzed to form carboxyl groups to obtain intermediate 3. Then, intermediate 3 and perfluorohexylethanol are reacted, and the carboxyl groups on intermediate 3 react with the hydroxyl groups on perfluorohexylethanol to introduce a large number of CF bonds to obtain intermediate 4. Afterwards, the intermediate 4 and isophorone diisocyanate are reacted, and the hydroxyl group on the intermediate 4 reacts with the isocyanate group on the isophorone diisocyanate, and the isocyanate group is introduced at the same time to obtain a yarn modifier; the molecular structure of the yarn modifier contains a large number of isocyanate groups, so that in the process of treating the mixed yarn, the isocyanate group reacts with the hydroxyl group on it, and a large number of CF bonds are grafted on the surface of the mixed yarn in the form of chemical bonds, giving it high hydrophobicity and greatly improving its waterproof performance. In addition, the yarn modifier wraps the mixed yarn to form a hydrophobic layer, which makes it difficult for adjacent mixed yarns to adhere to and entangle, ensuring that there are a large number of micropores between the mixed yarns, ensuring that they have excellent air permeability. DETAILED DESCRIPTION

[0031] The following will be combined with 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 part of the embodiments of the present invention, not all of the embodiments. 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.

[0032] Embodiment 1:

[0033] This embodiment is a method for preparing waterproof and breathable shoes, comprising the following steps:

[0034] Step A1: 10 mmol triphenylamine, 30 mmol N-bromosuccinimide and 40 mL anhydrous tetrahydrofuran were added to a three-necked flask equipped with a stirrer, a thermometer and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred at a temperature of -5°C and a stirring rate of 300 r / min for 20 min, and then the temperature was raised to 50°C and the stirring reaction was continued for 2 h. After the reaction was completed, the reaction product was cooled to room temperature and then poured into a saturated sodium thiosulfate solution, and then extracted twice with dichloromethane, the extracts were combined and dried with anhydrous magnesium sulfate, and then vacuum filtered, the filtrate was rotary evaporated to remove the solvent, and then recrystallized with a mixed solution of ethyl acetate and petroleum ether in a volume ratio of 1:5 to obtain intermediate 1;

[0035] Step A2: 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 were added to a three-necked flask equipped with a stirrer, a thermometer and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred for reaction at a temperature of 25° C. and a stirring rate of 300 r / min for 30 min, and then the mixture was heated to 130° C. and continued to stir for reaction for 3 h, and then the mixture was heated to 150° C. and continued to stir for reaction for 2 h. After the reaction was completed, the reaction product was cooled to room temperature, and then poured into ice water, and then allowed to stand for stratification, and the organic phase was rotary evaporated to remove the solvent to obtain intermediate 2;

[0036] Step A3: 10 mmol of intermediate 2 and 20 mL of anhydrous tetrahydrofuran were added to a three-necked flask equipped with a stirrer, a thermometer, a gas duct and a reflux condenser, and nitrogen was introduced for protection. The mixture was stirred at 25° C. and a stirring rate of 300 r / min for 1 h, and then 30 mL of a 10% potassium hydroxide solution was added and the stirring reaction was continued for 20 min. The mixture was then heated to reflux and the stirring reaction was continued for 15 h. After the reaction was completed, the reaction product was cooled to room temperature, and then adjusted to pH 3 with a 25% hydrochloric acid solution, and then allowed to stand to precipitate, and then centrifuged. The precipitate was washed twice with distilled water, and then placed in a vacuum drying oven and dried at 50° C. for 3 h to obtain intermediate 3;

[0037] Step A4: 10 mmol of intermediate 3, 30 mmol of perfluorohexylethanol, 0.01 g of p-toluenesulfonic acid and 80 mL of anhydrous tetrahydrofuran were added to a three-necked flask equipped with a stirrer, a thermometer and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred at 25° C. and a stirring rate of 300 r / min for 20 min, and then the temperature was raised to 90° C. and the stirring reaction was continued for 6 h. After the reaction was completed, the reaction product was cooled to room temperature, and then washed twice with saturated brine, and then the solvent was removed by rotary evaporation to obtain intermediate 4;

[0038] Step A5: 10 mmol of intermediate 4, 30 mmol of isophorone diisocyanate, 0.02 g of dibutyltin dilaurate and 100 mL of anhydrous tetrahydrofuran were added to a three-necked flask equipped with a stirrer, a thermometer and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred at a temperature of 25° C. and a stirring rate of 300 r / min for 20 min, and then the temperature was raised to 70° C. and the stirring reaction was continued for 3 h. After the reaction was completed, the reaction product was cooled to room temperature, and then the solvent was removed by rotary evaporation to obtain a yarn modifier;

[0039] Step A6: Weigh 45 parts of cotton fiber and 10 parts of nylon fiber according to weight and set aside;

[0040] Step A7: blending cotton fiber and nylon fiber to obtain blended yarn;

[0041] Step A8: Weigh 0.5 parts of yarn modifier and 100 parts of deionized water according to weight and set aside;

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

[0043] Step A10: immersing the mixed yarn in the yarn modification liquid at a mass ratio of 1:20 for 2 hours, then taking it out and draining it, and then placing it in a vacuum drying oven, pre-baking it at a temperature of 90° C. for 3 minutes, and then baking it at a temperature of 130° C. for 1 minute to obtain a waterproof and breathable yarn;

[0044] Step A11: Weaving 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 upper onto the sole to obtain the waterproof and breathable shoes.

[0046] Embodiment 2:

[0047] This embodiment is a method for preparing waterproof and breathable shoes, comprising the following steps:

[0048] Step A1: 10 mmol triphenylamine, 32 mmol N-bromosuccinimide and 45 mL anhydrous tetrahydrofuran were added to a three-necked flask equipped with a stirrer, a thermometer and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred at a temperature of -3°C and a stirring rate of 350 r / min for 25 min, and then the mixture was heated to 52°C and continued to stir for 2.5 h. After the reaction, the reaction product was cooled to room temperature, and then poured into a saturated sodium thiosulfate solution, and then extracted twice with dichloromethane, the extracts were combined and dried over anhydrous magnesium sulfate, and then vacuum filtered, the filtrate was rotary evaporated to remove the solvent, and then recrystallized with a mixed solution of ethyl acetate and petroleum ether in a volume ratio of 1:5 to obtain intermediate 1;

[0049] Step A2: 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 were added to a three-necked flask equipped with a stirrer, a thermometer and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred for reaction at a temperature of 28° C. and a stirring rate of 350 r / min for 40 min, and then the mixture was heated to 132° C. and continued to stir for reaction for 3.5 h, and then the mixture was heated to 152° C. and continued to stir for reaction for 2.5 h. After the reaction was completed, the reaction product was cooled to room temperature, and then poured into ice water, and then allowed to stand for stratification, and the organic phase was rotary evaporated to remove the solvent to obtain intermediate 2;

[0050] Step A3: 10 mmol of intermediate 2 and 22 mL of anhydrous tetrahydrofuran were added to a three-necked flask equipped with a stirrer, a thermometer, a gas guide tube and a reflux condenser, and nitrogen was introduced for protection. The mixture was stirred at a temperature of 28° C. and a stirring rate of 350 r / min for 1.2 h, and then 32 mL of a 12% potassium hydroxide solution was added and the stirring reaction was continued for 25 min. The mixture was then heated to reflux and the stirring reaction was continued for 18 h. After the reaction was completed, the reaction product was cooled to room temperature, and then adjusted to pH 3.5 with a 28% hydrochloric acid solution, and then allowed to stand to precipitate, and then centrifuged. The precipitate was washed twice with distilled water, and then placed in a vacuum drying oven and dried at a temperature of 52° C. for 3.5 h to obtain intermediate 3;

[0051] Step A4: 10 mmol of intermediate 3, 30 mmol of perfluorohexylethanol, 0.02 g of p-toluenesulfonic acid and 90 mL of anhydrous tetrahydrofuran were added to a three-necked flask equipped with a stirrer, a thermometer and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred at 28° C. and a stirring rate of 350 r / min for 25 min, and then the mixture was heated to 92° C. and stirred for 6.5 h. After the reaction, the reaction product was cooled to room temperature, washed twice with saturated brine, and then the solvent was removed by rotary evaporation to obtain intermediate 4;

[0052] Step A5: 10 mmol of intermediate 4, 30 mmol of isophorone diisocyanate, 0.04 g of dibutyltin dilaurate and 110 mL of anhydrous tetrahydrofuran were added to a three-necked flask equipped with a stirrer, a thermometer and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred at a temperature of 28° C. and a stirring rate of 350 r / min for 25 min, and then the temperature was raised to 72° C. and the stirring reaction was continued for 3.5 h. After the reaction was completed, the reaction product was cooled to room temperature, and then the solvent was removed by rotary evaporation to obtain a yarn modifier;

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

[0054] Step A7: blending cotton fiber and nylon fiber to obtain blended yarn;

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

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

[0057] Step A10: immersing the mixed yarn in the yarn modification liquid at a mass ratio of 1:20 for 2.5 hours, then taking it out and draining it, and then placing it in a vacuum drying oven, pre-baking it at a temperature of 92° C. for 4 minutes, and then baking it at a temperature of 132° C. for 1.5 minutes to obtain a waterproof and breathable yarn;

[0058] Step A11: Weaving 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 upper onto the sole to obtain the waterproof and breathable shoes.

[0060] Embodiment 3:

[0061] This embodiment is a method for preparing waterproof and breathable shoes, comprising the following steps:

[0062] Step A1: 10 mmol of triphenylamine, 35 mmol of N-bromosuccinimide and 50 mL of anhydrous tetrahydrofuran were added to a three-necked flask equipped with a stirrer, a thermometer and a gas duct, and nitrogen was introduced for protection. The mixture was stirred for reaction at a temperature of 0° C. and a stirring rate of 400 r / min for 30 min, and then the mixture was heated to 55° C. and continued to stir for reaction for 3 h. After the reaction, the reaction product was cooled to room temperature, and then poured into a saturated sodium thiosulfate solution, and then extracted with dichloromethane for 3 times. The extracts were combined and dried over anhydrous magnesium sulfate, and then vacuum filtered. The filtrate was rotary evaporated to remove the solvent, and then recrystallized with a mixed solution of ethyl acetate and petroleum ether in a volume ratio of 1:5 to obtain intermediate 1;

[0063] Step A2: 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 were added to a three-necked flask equipped with a stirrer, a thermometer and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred for reaction at a temperature of 30° C. and a stirring rate of 400 r / min for 50 min, and then the mixture was heated to 135° C. and stirred for reaction for 4 h, and then heated to 155° C. and stirred for reaction for 3 h. After the reaction was completed, the reaction product was cooled to room temperature, and then poured into ice water, and then allowed to stand for stratification, and the organic phase was rotary evaporated to remove the solvent to obtain intermediate 2;

[0064] Step A3: 10 mmol of intermediate 2 and 25 mL of anhydrous tetrahydrofuran were added to a three-necked flask equipped with a stirrer, a thermometer, a gas guide tube and a reflux condenser, and nitrogen was introduced for protection. The mixture was stirred at a temperature of 30° C. and a stirring rate of 400 r / min for 1.5 h, and then 35 mL of a 15% potassium hydroxide solution was added and the stirring reaction was continued for 30 min. The mixture was then heated to reflux and the stirring reaction was continued for 20 h. After the reaction was completed, the reaction product was cooled to room temperature, and then adjusted to pH 4 with a 30% hydrochloric acid solution, and then allowed to stand to precipitate, and then centrifuged. The precipitate was washed 3 times with distilled water, and then placed in a vacuum drying oven and dried at a temperature of 55° C. for 4 h to obtain intermediate 3;

[0065] Step A4: 10 mmol of intermediate 3, 30 mmol of perfluorohexylethanol, 0.03 g of p-toluenesulfonic acid and 100 mL of anhydrous tetrahydrofuran were added to a three-necked flask equipped with a stirrer, a thermometer and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred at 30° C. and a stirring rate of 400 r / min for 30 min, and then the temperature was raised to 95° C. and the stirring reaction was continued for 7 h. After the reaction was completed, the reaction product was cooled to room temperature, and then washed with saturated brine 3 times, and then the solvent was removed by rotary evaporation to obtain intermediate 4;

[0066] Step A5: 10 mmol of intermediate 4, 30 mmol of isophorone diisocyanate, 0.06 g of dibutyltin dilaurate and 120 mL of anhydrous tetrahydrofuran were added to a three-necked flask equipped with a stirrer, a thermometer and a gas guide tube, and nitrogen was introduced for protection. The mixture was stirred at a temperature of 30° C. and a stirring rate of 400 r / min for 30 min, and then the temperature was raised to 75° C. and the stirring reaction was continued for 4 h. After the reaction was completed, the reaction product was cooled to room temperature, and then the solvent was removed by rotary evaporation to obtain a yarn modifier;

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

[0068] Step A7: blending cotton fiber and nylon fiber to obtain blended yarn;

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

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

[0071] Step A10: immersing the mixed yarn in the yarn modification liquid at a mass ratio of 1:20 for 3 hours, then taking it out and draining it, and then placing it in a vacuum drying oven, pre-baking it at a temperature of 95° C. for 5 minutes, and then baking it at a temperature of 135° C. for 2 minutes to obtain a waterproof and breathable yarn;

[0072] Step A11: Weaving 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 upper onto the sole to obtain the waterproof and breathable shoes.

[0074] Comparative Example 1:

[0075] This comparative example is a method for preparing waterproof and breathable shoes, comprising the following steps:

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

[0077] Step A2: blending cotton fiber and nylon fiber to obtain blended yarn;

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

[0079] Step A4: Sew the waterproof and breathable upper onto the sole to obtain the waterproof and breathable shoes.

[0080] Comparative Example 2:

[0081] This comparative example is a method for preparing waterproof and breathable shoes, comprising the following steps:

[0082] Step A1: Weigh 55 parts of cotton fiber and 15 parts of nylon fiber according to weight and set aside;

[0083] Step A2: blending cotton fiber and nylon fiber to obtain blended yarn;

[0084] Step A3: weigh 2.5 parts of isophorone diisocyanate and 100 parts of deionized water according to weight and set aside;

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

[0086] Step A5: immersing the mixed yarn in the yarn modification liquid at a mass ratio of 1:20 for 3 hours, then taking it out and draining it, and then placing it in a vacuum drying oven, pre-baking it at a temperature of 95° C. for 5 minutes, and then baking it at a temperature of 135° C. for 2 minutes to obtain a waterproof and breathable yarn;

[0087] Step A6: Weaving 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 upper onto the sole to obtain the waterproof and breathable shoes.

[0089] The performance of the waterproof and breathable uppers of the waterproof and breathable shoes of Examples 1-3 and Comparative Examples 1-2 was tested, and the test method was as follows:

[0090] The static water contact angle of the waterproof and breathable shoe upper is directly tested by using an OCA15EC contact angle meter to obtain a first contact angle, and then the waterproof and breathable shoe upper is washed 100 times using an SW-12JG washing color fastness tester according to the method of GB / T3921-2008 "Textiles - Tests for Color Fastness - Color Fastness to Soaping", and then the static water contact angle of the waterproof and breathable shoe upper is tested by using an OCA15EC contact angle meter to obtain a 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, based on the comparison between Examples 1-3 and Comparative Examples 1-2, it can be seen that the waterproof and breathable shoes of the present application have excellent waterproof performance and long-lasting and durable waterproof performance.

[0094] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0095] The above contents are merely examples and explanations of the present invention. Those skilled in the art 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 invention or exceed the scope defined in this application, they shall all fall within the protection scope of the present invention.

Claims

1. A method for preparing waterproof and breathable shoes, characterized in that: The following steps are involved: Step 1: Weigh 45-55 parts of cotton fiber and 10-15 parts of nylon fiber by weight and set aside; Step 2: blending cotton fiber and nylon fiber to obtain blended yarn; Step 3: Weigh 0.5-2.5 parts of yarn modifier and 100 parts of deionized water according to weight, and set aside; Step 4: Evenly mix the yarn modifier and deionized water to obtain a yarn modification liquid; Step 5: Immerse the mixed yarn in the yarn modification liquid at a mass ratio of 1:20 for 2-3 hours, then take it out and drain it, then place it in a vacuum drying oven, pre-bake it at a temperature of 90-95°C for 3-5 minutes, and then bake it at a temperature of 130-135°C for 1-2 minutes to obtain a waterproof and breathable yarn; Step 6: Weaving the waterproof and breathable yarn into a shoe upper to obtain a waterproof and breathable shoe upper; Step 7: Sew the waterproof and breathable upper onto the sole to obtain the waterproof and breathable shoes.

2. The method for preparing waterproof and breathable shoes according to claim 1, characterized in that: The yarn modifier is prepared by the following steps: Step s1: triphenylamine, N-bromosuccinimide and anhydrous tetrahydrofuran are added to a three-necked flask equipped with a stirrer, a thermometer and an air duct, and nitrogen is introduced for protection. The mixture is stirred for reaction at a temperature of -5-0°C and a stirring rate of 300-400 r / min for 20-30 min, and then the mixture is heated to 50-55°C and stirred for reaction for 2-3 h. After the reaction is completed, the reaction product is cooled to room temperature, and then poured into a saturated sodium thiosulfate solution, and then extracted with dichloromethane for 2-3 times. The extracts are combined and dried with anhydrous magnesium sulfate, and then vacuum filtered. The filtrate is rotary evaporated to remove the solvent, and then recrystallized with the 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 an air duct, introduce nitrogen protection, stir and react for 30-50 minutes at a temperature of 25-30°C and a stirring rate of 300-400r / min, then heat to 130-135°C and continue to stir and react for 3-4 hours, then heat 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, then let it stand for stratification, and rotary evaporate the organic phase to remove the solvent to obtain intermediate 2; Step s3: Add intermediate 2 and anhydrous tetrahydrofuran to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube and a reflux condenser, introduce nitrogen protection, stir and react for 1-1.5 hours at a temperature of 25-30°C and a stirring rate of 300-400r / min, then add potassium hydroxide solution and continue to stir and react for 20-30 minutes, then raise the temperature to reflux and continue to stir and react for 15-20 hours, after the reaction is completed, cool the reaction product to room temperature, then adjust the pH to 3-4 with hydrochloric acid solution, then 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 at a temperature of 50-55°C for 3-4 hours to obtain intermediate 3; Step s4: Add intermediate 3, perfluorohexylethanol, p-toluenesulfonic acid and anhydrous tetrahydrofuran into a three-necked flask equipped with a stirrer, a thermometer and a gas guide tube, introduce nitrogen protection, stir and react for 20-30 minutes at a temperature of 25-30°C and a stirring rate of 300-400r / min, then heat to 90-95°C and continue stirring and reacting for 6-7 hours. After the reaction is completed, the reaction product is cooled to room temperature, then washed with saturated brine 2-3 times, and then rotary evaporated 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 an air duct, introduce nitrogen protection, stir the reaction at a temperature of 25-30°C and a stirring rate of 300-400r / min for 20-30min, then raise the temperature to 70-75°C and continue stirring the reaction for 3-4h. After the reaction is completed, the reaction product is cooled to room temperature, and then the solvent is removed by rotary evaporation to obtain a yarn modifier.

3. The method for preparing waterproof and breathable shoes according to claim 2, characterized in that: The usage ratio of the triphenylamine, N-bromosuccinimide and anhydrous tetrahydrofuran in step s1 is 10 mmol: 30-35 mmol: 40-50 mL.

4. The method for preparing waterproof and breathable shoes according to claim 2, 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.

5. The method for preparing waterproof and breathable shoes according to claim 2, characterized in that: The usage ratio of the intermediate 1, 3,4-dihydroxybenzoic acid ethyl ester, anhydrous potassium carbonate, toluene and N,N-dimethylformamide in step s2 is 10mmol:30mmol:35-45mmol:35-40mL:50-55mL.

6. The method for preparing waterproof and breathable shoes according to claim 2, characterized in that: The usage ratio of the intermediate 2, anhydrous tetrahydrofuran and potassium hydroxide solution in step s3 is 10 mmol: 20-25 mL: 30-35 mL.

7. The method for preparing waterproof and breathable shoes according to claim 2, 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%.

8. The method for preparing waterproof and breathable shoes according to claim 2, characterized in that: The usage ratio of the intermediate 3, perfluorohexylethanol, p-toluenesulfonic acid and anhydrous tetrahydrofuran in step s4 is 10 mmol: 30 mmol: 0.01-0.03 g: 80-100 mL.

9. The method for preparing waterproof and breathable shoes according to claim 2, characterized in that: The usage 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.

10. A waterproof and breathable shoe, characterized in that: The waterproof and breathable shoes are prepared according to the method for preparing waterproof and breathable shoes according to any one of claims 1 to 9.