An environment-friendly cork-based insole and its preparation process

Abstract

The present invention relates to the technical field of insole, in particular to an environmentally friendly cork-based insole and its preparation process; in order to improve the environmental performance of the insole, the present invention uses cork granules and bio-based polyurethane as raw materials to prepare an environmentally friendly cork-based insole; it can provide good cushioning and shock absorption performance, and absorb the water vapor of foot sweating, so as to keep the feet dry; and the present invention also adds and prepares a hydrophilic antibacterial activated carbon material, introducing a triazine ring and a haloamine structure on the surface of the activated carbon, improving the surface polarity of the activated carbon, increasing the hydrophilicity while enhancing its antibacterial performance, enhancing the antibacterial effect of the insole on fungi and bacteria, and maintaining the wearing comfort of the insole for a long time.

Description

Technical Field

[0001] The present invention relates to the technical field of insoles, and specifically to an environmentally friendly cork-based insole and its preparation process. Background Art

[0002] Insoles are a type of essential daily necessities that affect the foot comfort when people wear shoes. During the wearing process, insoles can provide additional cushioning and support, thereby reducing the foot impact caused by walking and standing, and thus reducing fatigue. Also, the design of insoles can play a role in absorbing moisture and perspiration, thereby helping to absorb the sweat on the feet, maintaining dryness, and thus enhancing foot comfort.

[0003] In existing market products, insoles are usually foam resin insoles and traditional cloth insoles. Traditional cloth insoles have excellent moisture absorption and perspiration functions, but due to the disadvantages of the preparation process, conventional cloth insoles are generally flat structures and cannot provide sufficient support and cushioning for the feet. While foam resin insoles can have more diverse designs in terms of shape and structure, can be more ergonomic, and play a better role in support and cushioning, but foam resin belongs to high molecular resin materials and is not easily degraded in nature, imposing a heavy burden on the natural environment. Therefore, it is necessary to redesign the preparation process of insoles to address the above-mentioned defects of insoles, so as to prepare an environmentally friendly insole. Summary of the Invention

[0004] The purpose of the present invention is to provide an environmentally friendly cork-based insole and its preparation process to solve the problems raised in the above background art.

[0005] To solve the above technical problems, the present invention provides the following technical solution: A preparation process of an environmentally friendly cork-based insole, comprising the following steps:

[0006] S1. Prepare hydrophilic antibacterial activated carbon;

[0007] S11. Mix powdered activated carbon with concentrated sulfuric acid, ultrasonically mix for 15 - 30 min, then add potassium persulfate thereto, raise the temperature to 85 - 90 °C, carry out negative pressure impregnation, react for 5 - 8 h, cool to 4 - 8 °C, add concentrated nitric acid with a volume half of that of the concentrated sulfuric acid thereto, continue to react for 2 - 4 h, centrifuge to separate the precipitate, add the precipitate to deionized water, carry out negative pressure impregnation for 30 - 45 min, centrifuge to separate the precipitate, then disperse the precipitate in absolute ethanol, stir and disperse for 15 - 30 min, add 3-aminopropyltriethoxysilane thereto, carry out vacuum loading for 20 - 40 min, raise the temperature to 45 - 60 °C, stir and react for 2 - 4 h, filter, and vacuum dry the precipitate to constant weight to obtain an aminated activated carbon material;

[0008] S12. Disperse 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine in xylene, heat up to 65 - 75 °C, stir and disperse for 2 - 4 h, then add N,N'-dicyclohexylcarbodiimide, continue to mix for 15 - 45 min, add the amino-functionalized activated carbon material prepared in step S11, carry out ultrasonic oscillation reaction for 4 - 8 h, centrifuge to separate the precipitate, and vacuum dry to constant weight to obtain the carboxyl-functionalized activated carbon material;

[0009] S13. Disperse the carboxyl-functionalized activated carbon material in ultrapure water, carry out ultrasonic oscillation dispersion for 1 - 2 h, then add azlocillin amide, carry out negative pressure impregnation for 0.5 - 1 h, heat up to 55 - 60 °C, carry out ultrasonic oscillation reaction for 2 - 4 h, centrifuge to separate the precipitate, collect the precipitate and disperse it in ultrapure water, stir and mix for 1 - 1.5 h, then add sodium hypochlorite, stir and react for 4 - 8 h, continuously add hydrochloric acid during the reaction to control the pH value of the reaction system to be 7 - 8, after the reaction is completed, filter, wash the precipitate with deionized water until neutral, and then vacuum dry to constant weight to obtain the hydrophilic and antibacterial activated carbon;

[0010] S2. Prepare the cork-based bottom layer;

[0011] Mix polytetramethylene ether glycol with the hydrophilic and antibacterial activated carbon, stir and mix for 5 - 12 min, then add cork particles, continue to mix for 1.5 - 2 h, then add cyclopentane blowing agent, continue to mix for 10 - 15 min, add isophorone diisocyanate and propylene glycol, stir and mix for 20 - 30 min, then inject the mixture into a mold, heat up to 80 - 90 °C, and cure for 2 - 4 h to obtain the cork-based bottom layer;

[0012] S3. Cut the non-woven fabric according to the mold, attach the cut non-woven fabric to the upper surface of the cork-based bottom layer to form a non-woven fabric layer, and then let the insole stand at room temperature for 24 - 48 h to obtain the environmentally friendly cork-based insole.

[0013] Further, by weight, in step S11, the mass ratio of the powdered activated carbon, potassium persulfate, and 3-aminopropyltriethoxysilane is 10:(15 - 20):(15 - 30).

[0014] Further, the particle size of the powdered activated carbon is 200 - 500 mesh.

[0015] Further, by weight, in step S12, the mass ratio of 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine, N,N'-dicyclohexylcarbodiimide, and the amino-functionalized activated carbon material is (5 - 20):(0.05 - 0.1):10.

[0016] Further, by weight parts, in step S13, the mass ratio of the carboxylated activated carbon material, azolamide, and sodium hypochlorite is 10:(5 - 10):(5 - 15).

[0017] Further, by weight parts, in step S2, the cork-based bottom layer is composed of 35 - 60 parts of polytetramethylene ether glycol, 10 - 15 parts of hydrophilic antibacterial activated carbon, 50 - 100 parts of cork granules, 0.3 - 0.8 parts of cyclopentane foaming agent, 5 - 9 parts of isophorone diisocyanate, and 2 - 4 parts of propylene glycol.

[0018] Further, in step S2, the particle size of the cork granules is 0.1 - 4 mm.

[0019] Compared with the prior art, the beneficial effects achieved by the present invention are as follows:

[0020] 1. In order to improve the environmental performance of the insole, the present invention uses cork granules and bio-based polyurethane as raw materials to prepare an environmentally friendly cork-based insole; the cork granules used in the present invention are composed of dry soft wood materials, which are light and durable. And compared with hard wood materials, the cork granules have a certain elasticity, which can provide good buffering and shock absorption performance, thus reducing the vibration caused by walking and standing; and the cork granules have a high porosity, which can absorb the water vapor of foot sweating, thus keeping the feet dry; and in the process of preparing polyurethane in the present invention, bio-based polyether polytetramethylene ether glycol is also used as a raw material, which reacts with isocyanate to prepare a polyurethane foam material with degradable performance. After mixing it with cork granules, it is injection-molded into an environmentally friendly insole, thereby reducing the burden on the environment caused by foam resin insoles and improving the environmental friendliness.

[0021] 2. The present invention uses a bio-based polyurethane foaming material to bond the cork granules to obtain a cork-based insole; however, in the usage scenarios faced by the insole of the present invention, problems such as foot sweating, bacterial and fungal infections will be encountered. Therefore, a hydrophilic antibacterial activated carbon material is added during the preparation of the insole.

[0022] The present invention first performs surface amination treatment on activated carbon. After reacting concentrated nitric acid and concentrated sulfuric acid, 3-aminopropyltriethoxysilane is used again to introduce amino groups on the surface of activated carbon. Then, the surface-aminated activated carbon material is reacted with 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine. By using the reaction between carboxyl and amino groups, a triazine ring is introduced on the surface of activated carbon. The triazine ring has certain antibacterial activity, and the high electronegativity of the nitrogen atoms in the triazine ring can interfere with the vital activities of microorganisms, thereby playing an antibacterial role. On this basis, the activated carbon material of the present invention is further mixed with azolamide, and the amino group reacts with the carboxyl group, so that azolamide is grafted on the surface of activated carbon. Sodium hypochlorite is used to chlorinate the excess -NH- groups in azolamide, thereby further preparing a haloamine structure on the surface of activated carbon. The haloamine can interact with the lipids in the cell membrane of microorganisms, increase the permeability of the cell membrane, and then cause the leakage of cell contents, resulting in a bactericidal effect on bacteria. Moreover, the introduction of the haloamine structure can further change the surface polarity of activated carbon and enhance the adsorption of active oxygen to water vapor, so as to achieve the purpose of rapid sweat absorption and perspiration of the insole. Detailed implementation mode

[0023] 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. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0024] The powdered activated carbon used in the embodiments of the present invention is provided by Henan Yujia Environmental Protection Materials Co., Ltd., and the particle size is 200 mesh; the 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine used is provided by Zhengzhou Alpha Chemical Co., Ltd.; the azolamide used is provided by Shanghai Yuanye Bio-Technology Co., Ltd.; the polytetramethylene ether glycol used is SKECOPROL H2000 from South Korea, and the molecular weight is 1900 - 2100; the cork granules used are provided by Henan Huiyu Water Purification Materials Co., Ltd., and are obtained by self-crushing and sieving.

[0025] Example 1. A preparation process of an environmentally friendly cork-based insole, comprising the following steps:

[0026] S1. Prepare hydrophilic antibacterial activated carbon;

[0027] S11. Weigh 10 parts of powdered activated carbon and mix it with 100 parts of concentrated sulfuric acid by weight. After ultrasonic mixing for 15 min, add 15 parts of potassium persulfate to it, heat up to 85 °C, impregnate under negative pressure, react for 5 h, then cool to 4 °C. Add concentrated nitric acid with a volume half of that of the concentrated sulfuric acid, continue to react for 2 h, then centrifuge to separate the precipitate. Add the precipitate to deionized water, impregnate under negative pressure for 30 min, centrifuge to separate the precipitate again, then disperse the precipitate in absolute ethanol. After stirring and dispersing for 15 min, add 15 parts of 3-aminopropyltriethoxysilane, load under vacuum for 20 min, heat up to 45 °C, stir and react for 2 h, filter, and vacuum dry the precipitate to constant weight to obtain the aminated activated carbon material;

[0028] S12. Weigh 5 parts of 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine and disperse it in xylene by weight. Heat up to 65 °C, stir and disperse for 2 h, then add 0.05 part of N,N'-dicyclohexylcarbodiimide, continue to mix for 15 min, add 10 parts of the aminated activated carbon material prepared in step S11, react by ultrasonic oscillation for 4 h, centrifuge to separate the precipitate, and vacuum dry to constant weight to obtain the carboxylated activated carbon material;

[0029] S13. Weigh 10 parts of the carboxylated activated carbon material and disperse it in ultrapure water by weight. After ultrasonic oscillation and dispersion for 1 h, add 5 parts of azolamide, impregnate under negative pressure for 0.5 h, heat up to 55 °C, react by ultrasonic oscillation for 2 h, centrifuge to separate the precipitate, collect the precipitate and disperse it in ultrapure water, stir and mix for 1 h, then add 5 parts of sodium hypochlorite, stir and react for 4 h. During the reaction, continuously add hydrochloric acid to control the pH value of the reaction system to 7. After the reaction is completed, filter, wash the precipitate with deionized water until it is neutral, and then vacuum dry to constant weight to obtain the hydrophilic and antibacterial activated carbon;

[0030] S2. Prepare the cork-based bottom layer;

[0031] Weigh 35 parts of polytetramethylene ether glycol and mix it with 10 parts of the hydrophilic and antibacterial activated carbon by weight. After stirring and mixing for 5 min, add 50 parts of cork particles, continue to mix for 1.5 h, then add 0.3 part of cyclopentane blowing agent, continue to mix for 10 min, add 8 parts of isophorone diisocyanate and 2 parts of propylene glycol, stir and mix for 20 min, then inject the mixture into a mold, heat up to 85 °C, and cure for 4 h to obtain the cork-based bottom layer;

[0032] S3. Cut the non-woven fabric according to the mold, attach the cut non-woven fabric to the upper surface of the cork-based bottom layer to form a non-woven fabric layer, and then let the insole stand at room temperature for 24 h to obtain the environmentally friendly cork-based insole.

[0033] Example 2. A preparation process for an environmentally friendly cork-based insole, comprising the following steps:

[0034] Compared with Example 1, the addition amount of 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine in step S12 was increased in this comparative example;

[0035] S1. Prepare hydrophilic antibacterial activated carbon;

[0036] S11. By weight, mix 10 parts of powdered activated carbon with 100 parts of concentrated sulfuric acid. After ultrasonic mixing for 15 min, add 15 parts of potassium persulfate thereto, heat up to 85°C, impregnate under negative pressure, react for 5 h, cool to 4°C, add concentrated nitric acid with a volume half of that of the concentrated sulfuric acid thereto, continue to react for 2 h, then centrifuge to separate the precipitate. Add the precipitate to deionized water, impregnate under negative pressure for 30 min, centrifuge to separate the precipitate, then disperse the precipitate in absolute ethanol, stir and disperse for 15 min, add 15 parts of 3-aminopropyltriethoxysilane thereto, load under vacuum for 20 min, heat up to 45°C, stir and react for 2 h, filter, and vacuum dry the precipitate to constant weight to obtain an aminated activated carbon material;

[0037] S12. By weight, disperse 20 parts of 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine in xylene, heat up to 65°C, stir and disperse for 2 h, add 0.05 part of N,N'-dicyclohexylcarbodiimide, continue to mix for 15 min, then add 10 parts of the aminated activated carbon material prepared in step S11, carry out ultrasonic oscillation reaction for 4 h, centrifuge to separate the precipitate, vacuum dry to constant weight to obtain a carboxylated activated carbon material;

[0038] S13. By weight, disperse 10 parts of the carboxylated activated carbon material in ultrapure water, carry out ultrasonic oscillation dispersion for 1 h, add 5 parts of azlocillin, impregnate under negative pressure for 0.5 h, heat up to 55°C, carry out ultrasonic oscillation reaction for 2 h, centrifuge to separate the precipitate, collect the precipitate and disperse it in ultrapure water, stir and mix for 1 h, add 5 parts of sodium hypochlorite, stir and react for 4 h. During the reaction, continuously add hydrochloric acid to control the pH value of the reaction system to 7. After the reaction is completed, filter, wash the precipitate with deionized water until neutral, and then vacuum dry to constant weight to obtain hydrophilic antibacterial activated carbon;

[0039] S2. Prepare a cork-based bottom layer;

[0040] By weight, mix 35 parts of polytetramethylene ether glycol with 10 parts of hydrophilic antibacterial activated carbon, stir and mix for 5 min, then add 50 parts of cork granules, continue to mix for 1.5 h, then add 0.3 part of cyclopentane blowing agent, continue to mix for 10 min, add 8 parts of isophorone diisocyanate and 2 parts of propylene glycol, stir and mix for 20 min, then inject the mixture into a mold, heat up to 85°C, and cure for 4 h to obtain a cork-based bottom layer;

[0041] S3. Cut the non-woven fabric according to the mold, attach the cut non-woven fabric to the upper surface of the cork base layer. After forming the non-woven fabric layer, let the insole stand at room temperature for 24 hours to obtain an environmentally friendly cork base insole.

[0042] Example 3. A preparation process of an environmentally friendly cork base insole, comprising the following steps:

[0043] Compared with Example 1, the addition amount of azolamide in step S13 is increased in this example;

[0044] S1. Prepare hydrophilic antibacterial activated carbon;

[0045] S11. By weight, mix 10 parts of powdered activated carbon with 100 parts of concentrated sulfuric acid, ultrasonically mix for 15 minutes, then add 15 parts of potassium persulfate thereto, raise the temperature to 85 °C, impregnate under negative pressure, react for 5 hours, cool to 4 °C, add concentrated nitric acid with a volume half of that of the concentrated sulfuric acid thereto, continue to react for 2 hours, centrifuge to separate the precipitate, add the precipitate to deionized water, impregnate under negative pressure for 30 minutes, centrifuge to separate the precipitate, then disperse the precipitate in absolute ethanol, stir and disperse for 15 minutes, add 15 parts of 3-aminopropyltriethoxysilane thereto, vacuum load for 20 minutes, raise the temperature to 45 °C, stir and react for 2 hours, filter, and vacuum dry the precipitate to constant weight to obtain an aminated activated carbon material;

[0046] S12. By weight, disperse 5 parts of 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine in xylene, raise the temperature to 65 °C, stir and disperse for 2 hours, add 0.05 part of N,N'-dicyclohexylcarbodiimide, continue to mix for 15 minutes, then add 10 parts of the aminated activated carbon material prepared in step S11, ultrasonically oscillate and react for 4 hours, centrifuge to separate the precipitate, vacuum dry to constant weight to obtain a carboxylated activated carbon material;

[0047] S13. By weight, disperse 10 parts of the carboxylated activated carbon material in ultrapure water, ultrasonically oscillate and disperse for 1 hour, add 10 parts of azolamide, impregnate under negative pressure for 0.5 hour, raise the temperature to 55 °C, ultrasonically oscillate and react for 2 hours, centrifuge to separate the precipitate, collect the precipitate and disperse it in ultrapure water, stir and mix for 1 hour, then add 5 parts of sodium hypochlorite, stir and react for 4 hours, continuously add hydrochloric acid during the reaction to control the pH value of the reaction system to 7. After the reaction, filter, wash the precipitate with deionized water to neutrality, and then vacuum dry to constant weight to obtain hydrophilic antibacterial activated carbon;

[0048] S2. Prepare the cork base layer;

[0049] By weight, 35 parts of polytetramethylene ether glycol are mixed with 10 parts of hydrophilic antibacterial activated carbon. After stirring and mixing for 5 min, 50 parts of cork granules are added thereto. After continuing to mix for 1.5 h, 0.3 part of cyclopentane foaming agent is added thereto. After continuing to mix for 10 min, 8 parts of isophorone diisocyanate and 2 parts of propylene glycol are added. After stirring and mixing for 20 min, the mixture is injected into a mold, heated to 85 °C, and cured for 4 h to obtain a cork-based bottom layer;

[0050] S3. Cut the non-woven fabric according to the mold, attach the cut non-woven fabric to the upper surface of the cork-based bottom layer. After forming a non-woven fabric layer, the insole is left standing at room temperature for 24 h to obtain an environmentally friendly cork-based insole.

[0051] Example 4. A preparation process of an environmentally friendly cork-based insole, comprising the following steps:

[0052] Compared with Example 1, the addition amount of sodium hypochlorite in step S13 is increased in this example;

[0053] S1. Prepare hydrophilic antibacterial activated carbon;

[0054] S11. By weight, 10 parts of powdered activated carbon are mixed with 100 parts of concentrated sulfuric acid. After ultrasonic mixing for 15 min, 15 parts of potassium persulfate are added thereto. The temperature is raised to 85 °C, and negative pressure impregnation is carried out. After reacting for 5 h, it is cooled to 4 °C. Concentrated nitric acid with a volume of 1 / 2 of the concentrated sulfuric acid is added thereto. After continuing to react for 2 h, the precipitate is separated by centrifugation. The precipitate is added to deionized water, and negative pressure impregnation is carried out for 30 min. After centrifuging and separating the precipitate, the precipitate is dispersed in absolute ethanol. After stirring and dispersing for 15 min, 15 parts of 3-aminopropyltriethoxysilane are added thereto. After vacuum loading for 20 min, the temperature is raised to 45 °C, and stirring reaction is carried out for 2 h. After filtration, the precipitate is vacuum dried to constant weight to obtain an aminated activated carbon material;

[0055] S12. By weight, 5 parts of 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine are dispersed in xylene. The temperature is raised to 65 °C, and stirring and dispersing are carried out for 2 h. Then 0.05 part of N,N'-dicyclohexylcarbodiimide is added, and after continuing to mix for 15 min, 10 parts of the aminated activated carbon material prepared in step S11 are added. After ultrasonic oscillation reaction for 4 h, the precipitate is separated by centrifugation and vacuum dried to constant weight to obtain a carboxylated activated carbon material;

[0056] S13. By weight, disperse 10 parts of carboxylated activated carbon material into ultrapure water. After ultrasonic dispersion for 1 h, add 5 parts of azolamide, impregnate under negative pressure for 0.5 h, then raise the temperature to 55 °C, carry out ultrasonic reaction for 2 h, centrifuge to separate the precipitate, collect the precipitate and disperse it into ultrapure water. After stirring and mixing for 1 h, add 15 parts of sodium hypochlorite, stir and react for 4 h, continuously dropwise add hydrochloric acid during the reaction to control the pH value of the reaction system to 7. After the reaction ends, filter, wash the precipitate with deionized water until neutral, and then vacuum dry to constant weight to obtain hydrophilic antibacterial activated carbon;

[0057] S2. Prepare a cork-based bottom layer;

[0058] By weight, mix 35 parts of polytetramethylene ether glycol with 10 parts of hydrophilic antibacterial activated carbon, stir and mix for 5 min, then add 50 parts of cork particles thereto, continue to mix for 1.5 h, then add 0.3 part of cyclopentane foaming agent thereto, continue to mix for 10 min, add 8 parts of isophorone diisocyanate and 2 parts of propylene glycol, stir and mix for 20 min, then inject the mixture into a mold, raise the temperature to 85 °C, and cure for 4 h to obtain a cork-based bottom layer;

[0059] S3. Cut the non-woven fabric according to the mold, attach the cut non-woven fabric to the upper surface of the cork-based bottom layer to form a non-woven fabric layer, and then let the insole stand at room temperature for 24 h to obtain an environmentally friendly cork-based insole.

[0060] Example 5. A preparation process of an environmentally friendly cork-based insole, comprising the following steps:

[0061] Compared with Example 1, the amount of hydrophilic antibacterial activated carbon added in step S2 is increased in this example;

[0062] S1. Prepare hydrophilic antibacterial activated carbon;

[0063] S11. By weight, mix 10 parts of powdered activated carbon with 100 parts of concentrated sulfuric acid, ultrasonically mix for 15 min, then add 15 parts of potassium persulfate thereto, raise the temperature to 85 °C, impregnate under negative pressure, react for 5 h, then cool to 4 °C, add concentrated nitric acid with a volume half of that of the concentrated sulfuric acid thereto, continue to react for 2 h, centrifuge to separate the precipitate, add the precipitate to deionized water, impregnate under negative pressure for 30 min, then centrifuge to separate the precipitate, disperse the precipitate into absolute ethanol, stir and disperse for 15 min, then add 15 parts of 3-aminopropyltriethoxysilane thereto, vacuum load for 20 min, then raise the temperature to 45 °C, stir and react for 2 h, filter, and vacuum dry the precipitate to constant weight to obtain an amino-functionalized activated carbon material;

[0064] S12. Disperse 5 parts of 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine by weight into xylene, heat up to 65 °C, stir and disperse for 2 h, then add 0.05 part of N,N'-dicyclohexylcarbodiimide. After continuing to mix for 15 min, add 10 parts of the amino-functionalized activated carbon material prepared in step S11. After ultrasonic oscillation reaction for 4 h, centrifuge to separate the precipitate, and vacuum dry to constant weight to obtain the carboxyl-functionalized activated carbon material;

[0065] S13. Disperse 10 parts of the carboxyl-functionalized activated carbon material by weight into ultrapure water, ultrasonically oscillate and disperse for 1 h, then add 5 parts of azoamide. After negative pressure impregnation for 0.5 h, heat up to 55 °C, ultrasonically oscillate and react for 2 h, then centrifuge to separate the precipitate. Collect the precipitate and disperse it into ultrapure water, stir and mix for 1 h, then add 5 parts of sodium hypochlorite, stir and react for 4 h. During the reaction, continuously dropwise add hydrochloric acid to control the pH value of the reaction system to 7. After the reaction is completed, filter, wash the precipitate with deionized water until neutral, and then vacuum dry to constant weight to obtain the hydrophilic and antibacterial activated carbon;

[0066] S2. Prepare the cork-based bottom layer;

[0067] Mix 35 parts of polytetramethylene ether glycol and 15 parts of the hydrophilic and antibacterial activated carbon by weight, stir and mix for 5 min, then add 50 parts of cork granules. After continuing to mix for 1.5 h, add 0.3 part of cyclopentane foaming agent. After continuing to mix for 10 min, add 8 parts of isophorone diisocyanate and 2 parts of propylene glycol. Stir and mix for 20 min, then inject the mixture into a mold, heat up to 85 °C, and cure for 4 h to obtain the cork-based bottom layer;

[0068] S3. Cut the non-woven fabric according to the mold, attach the cut non-woven fabric to the upper surface of the cork-based bottom layer to form a non-woven fabric layer, and then let the insole stand at room temperature for 24 h to obtain the environmentally friendly cork-based insole.

[0069] Comparative Example 1. A preparation process of an environmentally friendly cork-based insole, comprising the following steps:

[0070] Compared with Example 1, this comparative example does not add the preparation of hydrophilic and antibacterial activated carbon;

[0071] S1. Prepare the cork-based bottom layer;

[0072] Mix 35 parts of polytetramethylene ether glycol and 50 parts of cork granules by weight, continue to mix for 1.5 h, then add 0.3 part of cyclopentane foaming agent. After continuing to mix for 10 min, add 8 parts of isophorone diisocyanate and 2 parts of propylene glycol. Stir and mix for 20 min, then inject the mixture into a mold, heat up to 85 °C, and cure for 4 h to obtain the cork-based bottom layer;

[0073] S2. Cut the non-woven fabric according to the mold, attach the cut non-woven fabric to the upper surface of the cork base layer. After forming the non-woven fabric layer, let the insole stand at room temperature for 24 hours to obtain the environmentally friendly cork base insole.

[0074] Comparative Example 2. A preparation process for an environmentally friendly cork base insole, comprising the following steps:

[0075] Compared with Example 1, this comparative example performs step S13 treatment;

[0076] S1. Prepare hydrophilic antibacterial activated carbon;

[0077] S11. By weight, mix 10 parts of powdered activated carbon with 100 parts of concentrated sulfuric acid, ultrasonically mix for 15 minutes, then add 15 parts of potassium persulfate, heat up to 85 °C, impregnate under negative pressure, react for 5 hours, cool to 4 °C, add concentrated nitric acid with half the volume of concentrated sulfuric acid, continue to react for 2 hours, centrifuge to separate the precipitate, add the precipitate to deionized water, impregnate under negative pressure for 30 minutes, centrifuge to separate the precipitate, then disperse the precipitate in absolute ethanol, stir and disperse for 15 minutes, add 15 parts of 3-aminopropyltriethoxysilane, vacuum load for 20 minutes, heat up to 45 °C, stir and react for 2 hours, filter, and vacuum dry the precipitate to constant weight to obtain the amino-functionalized activated carbon material;

[0078] S12. By weight, disperse 5 parts of 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine in xylene, heat up to 65 °C, stir and disperse for 2 hours, add 0.05 part of N,N'-dicyclohexylcarbodiimide, continue to mix for 15 minutes, then add 10 parts of the amino-functionalized activated carbon material prepared in step S11, ultrasonically oscillate and react for 4 hours, centrifuge to separate the precipitate, and vacuum dry to constant weight to obtain hydrophilic antibacterial activated carbon;

[0079] S2. Prepare the cork base layer;

[0080] By weight, mix 35 parts of polytetramethylene ether glycol with 10 parts of hydrophilic antibacterial activated carbon, stir and mix for 5 minutes, then add 50 parts of cork granules, continue to mix for 1.5 hours, then add 0.3 part of cyclopentane blowing agent, continue to mix for 10 minutes, add 8 parts of isophorone diisocyanate and 2 parts of propylene glycol, stir and mix for 20 minutes, then inject the mixture into the mold, heat up to 85 °C, and cure for 4 hours to obtain the cork base layer;

[0081] S3. Cut the non-woven fabric according to the mold, attach the cut non-woven fabric to the upper surface of the cork base layer. After forming the non-woven fabric layer, let the insole stand at room temperature for 24 hours to obtain the environmentally friendly cork base insole.

[0082] Detection:

[0083] Degradation performance detection: After removing the non-woven fabric layer from the environmentally friendly cork-based insole prepared in Examples 1-5 and Comparative Examples 1-2, the degradation efficiency was detected according to GB / T 19277. The detection was carried out 3 times, and the average value of the detection results was taken;

[0084] Water absorption detection: After removing the non-woven fabric layer from the environmentally friendly cork-based insole prepared in Examples 1-5 and Comparative Examples 1-2, specimens with dimensions of 5*20*20 were prepared. After drying them in an 80°C drying oven for 24 h, they were placed in a beaker filled with deionized water. After standing for 4 h, they were taken out, the free water on the surface was wiped off, and the water absorption rate was calculated;

[0085] Antibacterial property detection: Using Staphylococcus aureus, a Staphylococcus aureus culture solution with a concentration of 1.00*10 7 CFU / mL was prepared. The cork-based layer after removing the non-woven fabric layer from the environmentally friendly cork-based insole prepared in Examples 1-5 and Comparative Examples 1-2 was inoculated with the bacterial solution at an inoculation amount of 0.2 ml / cm 3 . Then it was sealed in a plastic bag and cultured in an environment of 37°C for 24 h. After eluting with normal saline, the number of Staphylococcus aureus in the eluate was observed, and the antibacterial rate was calculated. The detection results are shown in the following table;

[0086] Degradation efficiency (%) Water absorbency (%) Antibacterial rate (%) Example 1 96.32 417 97.4 Example 2 96.15 424 97.6 Example 3 96.08 429 97.8 Example 4 96.11 436 97.7 Example 5 96.04 451 98.2 Comparative example 1 90.34 362 62.1 Comparative example 2 96.83 398 87.2

[0087] Finally, it should be noted that the above are only the preferred embodiments of the present invention and are not used to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements for some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A preparation process for an environmentally friendly cork-based insole, characterized in that, It includes the following steps: S1. Prepare hydrophilic antibacterial activated carbon; S11. Mix powdered activated carbon with concentrated sulfuric acid, ultrasonically mix for 15 - 30 min, then add potassium persulfate, heat up to 85 - 90 °C, impregnate under negative pressure, react for 5 - 8 h, cool to 4 - 8 °C, add concentrated nitric acid with a volume half of that of the concentrated sulfuric acid, continue to react for 2 - 4 h, centrifuge to separate the precipitate, add the precipitate to deionized water, impregnate under negative pressure for 30 - 45 min, centrifuge to separate the precipitate again, disperse the precipitate in absolute ethanol, stir and disperse for 15 - 30 min, then add 3 - aminopropyltriethoxysilane, vacuum load for 20 - 40 min, heat up to 45 - 60 °C, stir and react for 2 - 4 h, filter, vacuum dry the precipitate to constant weight to obtain the aminated activated carbon material; S12. Disperse 2,4,6 - tris(4 - carboxyphenyl)-1,3,5 - triazine in xylene, heat up to 65 - 75 °C, stir and disperse for 2 - 4 h, add N,N’ - dicyclohexylcarbodiimide, continue to mix for 15 - 45 min, then add the aminated activated carbon material prepared in step S11, ultrasonically oscillate and react for 4 - 8 h, centrifuge to separate the precipitate, vacuum dry to constant weight to obtain the carboxylated activated carbon material; S13. Disperse the carboxylated activated carbon material in ultrapure water, ultrasonically oscillate and disperse for 1 - 2 h, add azlocillin, impregnate under negative pressure for 0.5 - 1 h, heat up to 55 - 60 °C, ultrasonically oscillate and react for 2 - 4 h, centrifuge to separate the precipitate, collect the precipitate and disperse it in ultrapure water, stir and mix for 1 - 1.5 h, then add sodium hypochlorite, stir and react for 4 - 8 h, continuously dropwise add hydrochloric acid during the reaction to control the pH value of the reaction system to 7 - 8, after the reaction is completed, filter, wash the precipitate with deionized water until neutral, and then vacuum dry to constant weight to obtain hydrophilic antibacterial activated carbon; S2. Prepare a cork - based bottom layer; Mix polytetramethylene ether glycol with hydrophilic antibacterial activated carbon, stir and mix for 5 - 12 min, then add cork granules, continue to mix for 1.5 - 2 h, then add cyclopentane foaming agent, continue to mix for 10 - 15 min, add isophorone diisocyanate and propylene glycol, stir and mix for 20 - 30 min, then inject the mixture into a mold, heat up to 80 - 90 °C, and cure for 2 - 4 h to obtain the cork - based bottom layer; S3. Cut the non - woven fabric according to the mold, attach the cut non - woven fabric to the upper surface of the cork - based bottom layer to form a non - woven fabric layer, and then let the insole stand at room temperature for 24 - 48 h to obtain an environmentally friendly cork - based insole; By mass, in step S2, the cork - based bottom layer is composed of 35 - 60 parts of polytetramethylene ether glycol, 10 - 15 parts of hydrophilic antibacterial activated carbon, 50 - 100 parts of cork granules, 0.3 - 0.8 parts of cyclopentane foaming agent, 5 - 9 parts of isophorone diisocyanate, and 2 - 4 parts of propylene glycol.

2. The preparation process of an environmentally friendly cork-based insole according to claim 1, characterized in that: By weight, in step S11, the mass ratio of the powdered activated carbon, potassium persulfate, and 3 - aminopropyltriethoxysilane is 10:(15 - 20):(15 - 30).

3. The preparation process of an environmentally friendly cork-based insole according to claim 1, characterized in that: The particle size of the powdered activated carbon is 200 - 500 mesh.

4. The preparation process of an environmentally friendly cork-based insole according to claim 1, characterized in that: By weight, in step S12, the mass ratio of 2,4,6 - tris(4 - carboxyphenyl)-1,3,5 - triazine, N,N'-dicyclohexylcarbodiimide, and the aminated activated carbon material is (5 - 20):(0.05 - 0.1):

10.

5. The preparation process of an environmentally friendly cork-based insole according to claim 1, characterized in that: By weight, in step S13, the mass ratio of the carboxylated activated carbon material, azolamide, and sodium hypochlorite is 10:(5 - 10):(5 - 15).

6. The preparation process of an environmentally friendly cork-based insole according to claim 1, characterized in that: In step S2, the particle size of the cork granules is 0.1 - 4 mm.

7. An environmentally friendly cork-based insole prepared by the preparation process according to any one of claims 1 - 6.