CN115160683A - Environment-friendly degradable foamed sole and preparation method thereof - Google Patents
Environment-friendly degradable foamed sole and preparation method thereof Download PDFInfo
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- CN115160683A CN115160683A CN202210939887.5A CN202210939887A CN115160683A CN 115160683 A CN115160683 A CN 115160683A CN 202210939887 A CN202210939887 A CN 202210939887A CN 115160683 A CN115160683 A CN 115160683A
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/04—Making granules by dividing preformed material in the form of plates or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D35/00—Producing footwear
- B29D35/12—Producing parts thereof, e.g. soles, heels, uppers, by a moulding technique
- B29D35/122—Soles
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- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/009—Use of pretreated compounding ingredients
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/48—Wearing apparel
- B29L2031/50—Footwear, e.g. shoes or parts thereof
- B29L2031/504—Soles
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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- C08J2323/04—Homopolymers or copolymers of ethene
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- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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Abstract
The application relates to the field of organic polymer materials, and particularly discloses an environment-friendly degradable foamed sole and a preparation method thereof. The environment-friendly degradable foamed sole comprises the following components in parts by weight: ethylene-vinyl acetate copolymer, bagasse fiber, ethylene-octene copolymer, talcum powder, stearic acid, zinc oxide, foaming agent, cross-linking agent, titanium pigment and pigment; the bagasse fiber is prepared by the following method: screening bagasse, steaming and boiling with sodium hydroxide solution, filtering, washing to neutrality, and drying to obtain alkali-treated bagasse fiber; and (2) mixing the alkali-treated bagasse fiber with a mixed solution containing polyvinyl alcohol, formamide and distilled water, stirring for 3-4h at 60-80 ℃, drying, then soaking in a mixed solution of maleic anhydride and ethyl acetate for 1-2h, washing and drying to obtain the bagasse fiber. The application discloses environmental protection degradable foaming sole has the nature degradation, and the hygroscopicity is good, and is antibiotic deodorant.
Description
Technical Field
The application relates to the technical field of organic polymer materials, in particular to a biological course degradable foamed sole and a preparation method thereof.
Background
With the increasing exhaustion of petroleum resources and the worsening of the global environment, people pay more attention to environmental protection technologies and materials. As daily necessities in the life of people, the shoes have huge demand. The EVA material is the main raw material of sole materials in China, the dosage of the EVA material accounts for more than 35% of the sole materials, the EVA is mainly formed by polymerizing ethylene monomers and vinyl acetate monomers, and-CH 3 COO-side chain groups are introduced into the main chain of EVA molecules, so that the ordering among the molecules is reduced, and the EVA copolymer has better elasticity and lower hardness. The EVA foaming material mainly takes EVA resin as a main material, is added with a foaming agent, a cross-linking agent, a filling agent and other auxiliary agents, is subjected to banburying mixing, extrusion granulation and finally compression molding to prepare the EVA foaming material for manufacturing the sole, and has the advantages of light weight, good elasticity and good flexibility. But EVA does not have hygroscopicity, is easy to cause humidity and stink in shoe cavities, has strong intermolecular force, is difficult to break and decompose a macromolecular chain, cannot be decomposed in a short time in nature, is discarded to form white garbage, or is burnt to cause air pollution, and is a potential threat to the environment.
In view of the above-mentioned related art, the inventor has found that the shoe sole made of EVA has problems of non-moisture absorption and being not easily degraded.
Disclosure of Invention
In order to make the sole have moisture absorption and biodegradability, the application provides a biodegradable sole and a preparation method thereof.
In a first aspect, the application provides an environment-friendly and degradable foamed sole, which adopts the following technical scheme:
an environment-friendly degradable foamed sole comprises the following components in parts by weight: 30.56-35 parts of ethylene-vinyl acetate copolymer, 30-35 parts of bagasse fiber, 22.22-25 parts of ethylene-octene copolymer, 2.78-3.2 parts of talcum powder, 0.56-0.7 part of stearic acid, 1.27-1.5 parts of zinc oxide, 3.22-3.5 parts of foaming agent, 0.56-0.8 part of cross-linking agent, 2.78-3.2 parts of titanium dioxide and 0.24-0.3 part of pigment;
the bagasse fiber is prepared by the following method: sieving bagasse, adding into sodium hydroxide solution, steaming at 110-120 deg.C under 0.4-0.5MPa for 2-3 hr, filtering, washing to neutrality, and drying to obtain alkali-treated bagasse fiber;
and mixing the alkali-treated bagasse fiber with a mixed solution containing polyvinyl alcohol, formamide and distilled water, stirring for 3-4h at 60-80 ℃, drying, then soaking in a mixed solution of maleic anhydride and ethyl acetate for 1-2h, washing and drying to obtain the bagasse fiber.
By adopting the technical scheme, the bagasse fibers are doped into the soles made of materials such as EVA and the like, and can be biodegraded, so that microorganisms can degrade the soles in soil, and the soles are degradable. Bagasse is the most main byproduct in the sugar industry of sugarcane, is sugarcane stem fiber residue left after sugarcane is crushed and squeezed to extract sugarcane juice, is an important renewable biomass resource, has poor compatibility with nonpolar resin due to good hydrophilicity and strong polarity, and causes the mechanical property of the compounded material to be not ideal, so that the bagasse is steamed with alkali liquor when preparing bagasse fiber, thereby not only fully softening and swelling the bagasse, eliminating certain lignin, removing impurities such as pectin and the like on the surface of the bagasse, but also increasing the specific surface area of the bagasse, increasing the contact area of materials such as EVA and the like and bagasse fiber, improving the mechanical biting force, exposing more cellulose molecules, increasing the number of free hydroxyl groups on the surface of the bagasse fiber, then using formamide as a plasticizer for alkali-treated bagasse fiber, using amino groups which can form the action with hydroxyl groups on a polyvinyl alcohol molecular chain and hydroxyl groups on the bagasse fiber, destroying the hydrogen bond action of the polyvinyl alcohol and bagasse fiber, weakening the action force between the polyvinyl alcohol and bagasse fiber molecules, increasing the flexibility, thereby increasing the plasticity of the polyvinyl alcohol and bagasse fiber, and enabling the polyvinyl alcohol to be stored in a large amount of hydrophilic polymer which is a hydrophilic alcohol and a hydrophilic polymer which is capable of absorbing water molecules and is a large amount of the hydrophilic alcohol and is capable of absorbing water molecules when the hydrophilic polymer, and the hydrophilic water molecules which are stored in the bagasse fiber under the hydrophilic polymer. The composite material has excellent moisture absorption function, excellent wear resistance, oil resistance, tear resistance, static resistance, chemical corrosion resistance and other performances, is grafted by maleic anhydride, and the maleic anhydride groups react with hydroxyl groups on bagasse fibers to improve the interface compatibility of the bagasse fibers and EVA resin; the bagasse fibers are prepared from degradable raw materials, hydrophilic groups of the raw materials can adsorb soil moisture and microorganisms more easily, the contact area between the moisture and the microorganisms and the sole is increased, and the moisture and the microorganisms can be hydrolyzed and decomposed more easily, so that the degradation rate is increased, and meanwhile, the bagasse fibers have good moisture absorption and air permeability, can absorb sweat generated by feet, and can prevent bacteria from breeding due to moisture in shoe cavities.
Optionally, the bagasse fibers are prepared from the following raw materials in parts by weight:
1-2 parts of alkali-treated bagasse fiber, 0.5-1 part of maleic anhydride, 0.5-1 part of ethyl acetate solution, 0.3-0.4 part of polyvinyl alcohol, 0.4-0.5 part of formamide and 3-5 parts of distilled water.
By adopting the technical scheme, the bagasse fibers are prepared from the raw materials with reasonable and proper dosage, and can be prepared into the bagasse fibers with good hygroscopicity and good interface compatibility with EVA resin.
Optionally, the foamed sole further comprises deodorant composite powder, and the dosage of the deodorant composite powder is 5-10 parts.
Through adopting above-mentioned technical scheme, present EVA expanded material does not have the deodorization function, and the person of wearing shoes can go out a lot of sweats when the motion, and the inside sweat stain of accumulation of shoes after the time has been long and smelly, adds the deodorization powder in the sole material, can get rid of certain stink.
Optionally, the preparation method of the deodorizing composite powder comprises the following steps:
carrying out plasma treatment on PHBV, and mixing the PHBV with chloramine, aluminum potassium sulfate and distilled water to form spraying liquid;
mixing chitin fiber and coffee carbon fiber, loosening, removing impurities, uniformly spraying the spray coating solution on chitin fiber and coffee carbon fiber, pre-drying at 60-80 deg.C for 20-30min, thermally bonding at 160-170 deg.C and 0.6-0.7MPa for 3-5min, and pulverizing to obtain deodorant composite powder.
By adopting the technical scheme, the PHBV takes renewable resource starch as a main raw material, utilizes a high molecular polymer PHB copolymer stored in cells in a granular state under the unbalanced growth condition of microorganisms, has complete biodegradability and higher biocompatibility, the addition of the PHBV can improve the softness of soles, reduce the hardness, increase the elasticity and improve the mechanical property and the processing property, the plasma treatment can grow-C-O-polar groups on the surface of the PHBV material to generate a honeycomb surface, improve the surface energy of the PHBV, increase the surface area of the PHBV and is beneficial to improving the interface binding force of the PHBV with chitin fibers and air-conditioning fibers; the chitin fiber has high antibacterial property and biodegradability, a large amount of hydrophilic groups such as hydroxyl groups, amino groups and the like exist on a macromolecular chain of the chitin fiber, so that the chitin fiber has good hydrophilicity and high hygroscopicity, the coffee carbon fiber mainly has the effects of bacteriostasis, deodorization, negative ion emission, moisture absorption and ventilation, after the chitin fiber and the coffee carbon fiber are mixed, spraying a spraying liquid containing chloramine, aluminum potassium sulfate and PHBV on the surface of the chitin fiber and the coffee carbon fiber, after high-temperature heat bonding, the PHBV is adhered to the mixture of the chitin fiber and the coffee carbon fiber, the aluminum potassium sulfate is hydrolyzed after moisture absorption of the deodorization composite powder, the hydrolysate becomes acidic, and the chloramine is hydrolyzed under the acidic condition to generate hypochlorous acid with strong bactericidal action, so that a good bactericidal and deodorant effect is obtained.
Optionally, the deodorizing composite powder comprises the following raw materials in parts by mass: 3-6 parts of PHBV, 1.5-2 parts of chloramine, 0.9-1.8 parts of aluminum potassium sulfate, 10-15 parts of distilled water, 4-8 parts of chitin fibers and 2-4 parts of coffee carbon fibers.
By adopting the technical scheme, the deodorizing composite powder prepared from the raw materials with the above dosage has the effects of strong hygroscopicity, high bacteriostatic effect and excellent deodorizing capability, so that the shoe cavity is not easy to be wet and smelly due to foot sweat.
Optionally, the foaming agent is nylon-oceanic AC-3000, and the talcum powder is special BHS-818T-type talcum powder for shoe material EVA.
In a second aspect, the application provides a method for preparing an environment-friendly degradable foamed sole, which adopts the following technical scheme:
a preparation method of an environment-friendly degradable foamed sole comprises the following steps:
s1, mixing an ethylene-vinyl acetate copolymer and bagasse fibers at a high speed, and extruding and granulating to obtain blended particles;
s2, mixing the blending particles, the ethylene-octene copolymer, the talcum powder, the stearic acid, the pigment, the zinc oxide and the titanium dioxide, carrying out primary banburying, adding the cross-linking agent, the foaming agent and the deodorization composite powder, carrying out secondary banburying, and carrying out material turning at different temperatures during the banburying for 7 times to obtain a mixture;
s3, thinning the mixture at 65-85 ℃ for 2 times to obtain sheet materials;
s4, granulating the sheet material to obtain granules with the grain size of 3-4 mm;
s5, injection molding the granules at 175-180 ℃ for 450-460S to obtain the sole.
By adopting the technical scheme, the ethylene-vinyl acetate copolymer and the bagasse fiber are blended and extruded firstly, the bagasse fiber is fully dispersed in the ethylene-vinyl acetate copolymer, the dispersion degree of the bagasse fiber in the sole is improved, the flexibility and resilience of the sole material are improved, and the extruded blended particles and other substances are subjected to secondary banburying and fully mixed to obtain the sole with excellent performance.
Optionally, the zinc oxide is a zinc oxide nanorod.
By adopting the technical scheme, the zinc oxide nano rod has a photocatalysis effect, can convert light energy into chemical energy, and can not only carry out biodegradation on the sole, but also carry out photocatalytic degradation.
Optionally, the titanium dioxide and the zinc oxide nano-rod are pretreated as follows:
(1) Adding 1-2 parts by weight of titanium dioxide into 0.7-1.5 parts by weight of oleic acid and 2-5 parts by weight of distilled water, heating to 180-200 ℃, carrying out hydrothermal treatment for 3-4h, filtering, washing with absolute ethyl alcohol and distilled water in sequence, and carrying out vacuum drying;
(2) Mixing the titanium dioxide obtained in the step (1) with 0.6-1 part of methyl cellulose and 2-4 parts of distilled water to form a mixed solution, mixing the mixed solution with a zinc oxide nano rod according to the mass ratio of 0.4-0.6.
By adopting the technical scheme, the titanium dioxide is mainly prepared from titanium dioxide and has photocatalytic activity, under the irradiation of ultraviolet light, the titanium dioxide generates hydroxyl free radicals and negative oxygen ion free radicals with high activity, the free radicals attack polymer chains to break and oxidize and decompose the polymer chains to finally form volatile micromolecules, but the utilization rate of the volatile micromolecules to visible light is low, electrons and holes generated by exciting light are easy to recombine to cause low quantum efficiency, the photocatalytic efficiency of the titanium dioxide is seriously influenced, the valence band potential of zinc oxide is too low, and the light stability is poor; firstly, oleic acid is combined with titanium dioxide, hydroxyl with higher surface activity of titanium dioxide and oleic acid react to generate ester like acid and alcohol to form certain intermolecular force to prevent the titanium dioxide from agglomerating, and the oleic acid belongs to organic matters and contains a carbon source required by the growth of microorganisms, so that the growth of the microorganisms is facilitated, and although the photocatalytic degradation effect of the titanium dioxide cannot be improved, the titanium dioxide also has the effect of biodegrading soles; titanium dioxide combined with oleic acid is compounded with a zinc oxide nanorod, methylcellulose is used as a binder and a film-forming agent, the mixed solution is adhered to the zinc oxide nanorod, titanium dioxide can be uniformly loaded on the zinc oxide nanorod, the absorbance of the zinc oxide nanorod loaded with the titanium dioxide in ultraviolet-visible light is enhanced, and obvious red shift occurs.
Optionally, in the step S2, the material turning step is: carrying out first material turning at the temperature of 98 ℃, carrying out second material turning at the duration of 240s and 111 ℃, carrying out second material turning at the duration of 60s, carrying out third material turning at the temperature of 117 ℃, carrying out fourth material turning at the temperature of 120 ℃, carrying out 50s, carrying out fifth material turning at the temperature of 122 ℃, carrying out 30s, carrying out sixth material turning at the temperature of 124 ℃, carrying out 30s, carrying out seventh material turning at the temperature of 126 ℃, carrying out 30s, and carrying out blanking at 127 ℃.
Through adopting above-mentioned technical scheme, when banburying, carry out the stirring to the raw materials under different temperatures to the time of stirring at every turn is different, can effectively improve the mixing degree of consistency of each raw materials.
Preferably, in the step S2, the first banburying time is 6-8min, the temperature is 100-102 ℃, the second banburying time is 2-3min, and the temperature is 108-110 ℃.
Through adopting above-mentioned technical scheme, the banburying temperature of second time is higher than the banburying temperature of first time, can increase the mixing degree of consistency of each raw materials.
In summary, the present application has the following beneficial effects:
1. because the bagasse fibers are prepared by mixing bagasse which is cooked by alkali liquor with maleic anhydride, formamide, polyvinyl alcohol and the like, the bagasse fibers have the advantages of increased interface compatibility with EVA resin, high mechanical engaging force and strong hygroscopicity, can effectively improve the moisture absorption effect of the sole, prevent the generation of peculiar smell due to dampness in a shoe cavity, and can ensure that the sole has biodegradability due to the addition of the bagasse fibers, wherein the existence of moisture is a necessary condition for the degradation of materials.
2. In the application, the composite deodorizing powder prepared from PHBV, chitin fiber, coffee carbon fiber, chloramine, aluminum potassium sulfate and the like is preferably added into the sole raw material, because the chitin fiber and the coffee carbon fiber have the effects of deodorization, bacteriostasis, moisture absorption and ventilation, chloramine and aluminum potassium sulfate are loaded on the chitin fiber and the coffee carbon fiber by utilizing the PHBV, under the hydrolysis of sweat, the aluminum potassium sulfate is hydrolyzed to present an acidic condition, the chloramine is hydrolyzed under the acidic condition to generate hypochlorous acid with strong bactericidal action, so that the antibacterial and deodorizing effect is achieved, the PHBV can improve the flexibility and the rebound resilience of the sole, and the PHBV and other raw materials in the composite deodorizing powder are biodegradable raw materials, and the degradation speed of the sole is not influenced.
3. In the application, the titanium dioxide and the zinc oxide nano rod are preferably subjected to mixing pretreatment, and the titanium dioxide is connected with oleic acid, so that the titanium dioxide not only has photocatalytic oxidation degradation capability, but also has biodegradability, and the titanium dioxide and the zinc oxide nano rod are used in a composite manner, so that the absorption range of the titanium dioxide and the zinc oxide nano rod to light can be enlarged, the photocatalytic effect is improved, and the photocatalytic degradation efficiency is improved.
Detailed Description
Bagasse fibers preparation examples 1 to 6
Preparation example 1: screening bagasse, selecting fibers with the particle size of less than 200 meshes, adding the fibers into a sodium hydroxide solution with the mass concentration of 15%, cooking in a water bath ratio of 1;
2kg of alkali-treated bagasse fibers were mixed with a mixed solution containing 0.4kg of polyvinyl alcohol, 0.5kg of formamide and 5kg of distilled water, stirred at 80 ℃ for 3 hours, dried, then dipped in a mixed solution of 1kg of maleic anhydride and 1kg of ethyl acetate for 2 hours, washed and dried to obtain bagasse fibers.
Preparation example 2: screening bagasse, selecting fibers with a particle size of less than 200 meshes, adding the fibers into a 15% sodium hydroxide solution, cooking in a water bath ratio of 1;
1kg of alkali-treated bagasse fiber was mixed with a mixed solution containing 0.3kg of polyvinyl alcohol, 0.4kg of formamide and 3kg of distilled water, stirred at 60 ℃ for 4 hours, dried, then dipped in a mixed solution of 0.5kg of maleic anhydride and 0.5kg of ethyl acetate for 1 hour, washed and dried to obtain bagasse fiber.
Preparation example 3: the difference from preparation example 1 is that formamide was not added to the mixed solution.
Preparation example 4: the difference from preparation example 1 is that polyvinyl alcohol was not added to the mixed solution.
Preparation example 5: the difference from preparation example 1 is that a mixed solution of maleic anhydride and ethyl acetate was not added.
Preparation example 6: screening bagasse, selecting fibers with a size of less than 200 meshes, adding the fibers into a sodium hydroxide solution with a mass concentration of 15%, cooking in a water bath ratio of 1.
Preparation examples 7 to 12 of deodorizing Compound powder
Preparation example 7: carrying out plasma treatment on 3kg of PHBV, mixing with 1.5kg of chloramine, 0.9kg of aluminum potassium sulfate and 10kg of distilled water to form spraying liquid, wherein oxygen is used as a carrier during the plasma treatment, the frequency is 13.56MHz, the vacuum degree is 133Pa, the discharge power is 100W, and the treatment time is 2h;
mixing 4kg chitin fiber and 2kg coffee carbon fiber, loosening, removing impurities, uniformly spraying the spray coating solution on the chitin fiber and the coffee carbon fiber, pre-drying at 60 deg.C for 30min, thermally bonding at 160 deg.C and 0.7MPa for 5min, and pulverizing to obtain deodorant composite powder.
Preparation example 8: carrying out plasma treatment on 6kg of PHBV, mixing the PHBV with 2kg of chloramine, 1.8kg of aluminum potassium sulfate and 15kg of distilled water to form spraying liquid, wherein oxygen is used as a carrier during the plasma treatment, the frequency is 13.56MHz, the vacuum degree is 133Pa, the discharge power is 100W, and the treatment time is 2h;
mixing 8kg chitin fiber and 4kg coffee carbon fiber, loosening, removing impurities, uniformly spraying the spray coating solution on the chitin fiber and the coffee carbon fiber, pre-drying at 80 deg.C for 20min, thermally bonding at 170 deg.C and 0.8MPa for 3min, and pulverizing to obtain deodorant composite powder.
Preparation example 9: the difference from preparation example 7 is that potassium aluminum sulfate was not added.
Preparation example 10: the difference from preparation example 7 is that chloramine was not added.
Preparation example 11: plasma treatment is carried out on 3kg of PHBV, and the PHBV, 1.5kg of chloramine, 0.9kg of aluminum potassium sulfate and 10kg of distilled water are mixed, dried for 30min at the temperature of 60 ℃, crushed and prepared into deodorant composite powder.
Preparation example 12: mixing 1.5kg of chloramine, 0.9kg of aluminum potassium sulfate and 10kg of distilled water to form a spraying liquid;
mixing 4kg chitin fiber and 2kg coffee carbon fiber, loosening, removing impurities, uniformly spraying the spray coating solution on the chitin fiber and the coffee carbon fiber, pre-drying at 60 deg.C for 30min, and pulverizing to obtain deodorizing composite powder.
Examples
Example 1: an environment-friendly degradable foamed sole comprises the following raw materials in parts by weight: 30.56kg of ethylene-vinyl acetate copolymer, 30kg of bagasse fiber, 22.22kg of ethylene-octene copolymer, 2.78kg of talcum powder, 0.56kg of stearic acid, 1.27kg of zinc oxide, 3.22kg of foaming agent, 0.56kg of cross-linking agent, 2.78kg of titanium dioxide and 0.24kg of pigment, wherein the VA content in the ethylene-vinyl acetate copolymer is 21 percent, the model is 7360M, the foaming agent is Jinyang AC-3000, the talcum powder is BHS-818T type talcum powder special for shoe material EVA, the zinc oxide is Luchang zinc oxide C30, the titanium dioxide is rubble type R-2588, and the bagasse fiber is prepared by the preparation example 1;
the preparation method of the environment-friendly degradable foamed sole comprises the following steps:
s1, mixing ethylene-vinyl acetate copolymer and bagasse fibers at a high speed of 5000r/min for 30min, and extruding and granulating at 160 ℃ to obtain blended particles;
s2, mixing the blended particles, the ethylene-octene copolymer, the talcum powder, the stearic acid, the pigment, the zinc oxide and the titanium dioxide, carrying out first internal mixing at 100 ℃, carrying out internal mixing for 8min, adding the cross-linking agent and the foaming agent, carrying out second internal mixing at 108 ℃, carrying out internal mixing for 3min, carrying out material turning at different temperatures during internal mixing for 7 times in total to obtain a mixed material, wherein the material turning step comprises carrying out first material turning at 98 ℃, carrying out second material turning at 240S and 111 ℃ for 60S, carrying out third material turning at 117 ℃ for 60S, carrying out fourth material turning at 120 ℃ for 50S, carrying out fifth material turning at 122 ℃ for 30S, carrying out sixth material turning at 124 ℃ for 30S, and carrying out seventh material turning at 126 ℃ for 30S and 127 ℃;
s3, thinning the mixture for 2 times at 65 ℃ by using a roller machine to obtain sheet materials, wherein the thickness of the sheet materials is 1.5mm;
s4, granulating the sheet material to obtain granules with the particle size of 3mm, wherein the temperature of a machine head I is 80 ℃, the temperature of a machine head II is 80 ℃, the temperature of an electric heating I section is 80 ℃, the temperature of an electric heating II section is 80 ℃, the temperature of an electric heating III section is 80 ℃, the temperature of an electric heating IV section is 80 ℃, and the temperature of cooling water is 15 ℃;
s5, injection molding the granules at 175 ℃ for 450S to obtain the sole.
Example 2: an environment-friendly degradable foamed sole, which comprises the following raw materials in parts by weight: 35kg of ethylene-vinyl acetate copolymer, 35kg of bagasse fiber, 25kg of ethylene-octene copolymer, 3.2kg of talcum powder, 0.7kg of stearic acid, 1.5kg of zinc oxide, 3.5kg of foaming agent, 0.8kg of cross-linking agent, 3.2kg of titanium dioxide and 0.3kg of pigment; the ethylene-vinyl acetate copolymer has 21 percent of VA, the model is 7360M, the foaming agent is Jinyang AC-3000, the talcum powder is special BHS-818T type talcum powder for shoe material EVA, the zinc oxide is Luchang zinc oxide C30, the titanium dioxide is red stone type R-2588, and the bagasse fiber is prepared by the preparation example 2;
the preparation method of the environment-friendly degradable foamed sole comprises the following steps:
s1, mixing ethylene-vinyl acetate copolymer and bagasse fiber at a high speed of 6000r/min for 25min, and extruding and granulating at 170 ℃ to obtain blended particles;
s2, mixing the blended particles, the ethylene-octene copolymer, the talcum powder, the stearic acid, the pigment, the zinc oxide and the titanium dioxide, carrying out primary internal mixing at 102 ℃ for 6min, adding a cross-linking agent and a foaming agent, carrying out secondary internal mixing at 110 ℃, carrying out internal mixing for 2min, carrying out material turning at different temperatures during internal mixing for 7 times in total to obtain a mixed material, wherein the material turning step comprises carrying out primary material turning at the temperature of 98 ℃, carrying out secondary material turning at the temperature of 240S, carrying out secondary material turning at the temperature of 111 ℃, carrying out 60S in duration, carrying out tertiary material turning at the temperature of 117 ℃, carrying out 60S in duration, carrying out fourth material turning at the temperature of 120 ℃, carrying out 50S in duration, carrying out fifth material turning at the temperature of 122 ℃, carrying out 30S in duration, carrying out sixth material turning at the temperature of 124 ℃, carrying out material turning at the duration of 30S, carrying out seventh material turning at the temperature of 126 ℃, carrying out seventh material turning at the duration of 30S and carrying out blanking at 127 ℃;
s3, thinning the mixture for 2 times at 85 ℃ by using a roller to obtain sheet materials, wherein the thickness of the sheet materials is 1mm;
s4, granulating the sheet material to obtain granules with the particle size of 4mm, wherein the temperature of a machine head I is 85 ℃, the temperature of a machine head II is 85 ℃, the temperature of an electric heating I section is 85 ℃, the temperature of an electric heating II section is 85 ℃, the temperature of an electric heating III section is 85 ℃, the temperature of an electric heating IV section is 85 ℃, and the temperature of cooling water is 20 ℃;
s5, injection molding the granules at 180 ℃ for 460S to obtain the sole.
Example 3: an environment-friendly degradable foamed shoe sole, which is different from example 1 in that 10kg of the deodorizing composite powder prepared in preparation example 7 was added at the time of secondary internal mixing in step S2.
Example 4: an environment-friendly degradable foamed shoe sole, which is different from example 1 in that 5kg of the deodorizing composite powder prepared in preparation example 8 was added in the second banburying in step S2.
Example 5: an environment-friendly degradable foamed shoe sole, which is different from example 1 in that 10kg of the deodorizing composite powder prepared in preparation example 9 was added in the second banburying in step S2.
Example 6: an environmentally friendly and degradable foamed shoe sole, which is different from example 1, is that 10kg of the deodorizing composite powder prepared in preparation example 10 is added in the second banburying in step S2.
Example 7: an environmentally friendly and degradable foamed shoe sole, which is different from example 1, is characterized in that 10kg of the deodorizing composite powder prepared in preparation example 11 is added in the second banburying in step S2.
Example 8: an environment-friendly degradable foamed shoe sole, which is different from example 1 in that 10kg of the deodorizing composite powder prepared in preparation example 12 was added at the time of secondary internal mixing in step S2.
Example 9: an environmentally friendly and degradable foamed shoe sole, which is different from example 1, is characterized in that 10kg of commercially available activated carbon is added as deodorizing composite powder in the second banburying in step S2.
Example 10: the difference between the environment-friendly degradable foamed sole and the embodiment 3 is that zinc oxide is zinc oxide nano-rods, and titanium dioxide and the zinc oxide nano-rods are pretreated as follows:
(1) Adding 2kg of titanium dioxide into 1.5kg of oleic acid and 5kg of distilled water, heating to 200 ℃, carrying out hydrothermal treatment for 3h, filtering, washing with absolute ethyl alcohol and distilled water in sequence, and carrying out vacuum drying for 24h at 80 ℃;
(2) Mixing the titanium dioxide obtained in the step (1) with 1kg of methyl cellulose and 4kg of distilled water to form a mixed solution, mixing the mixed solution with a zinc oxide nanorod according to the mass ratio of 0.6.
Example 11: the environment-friendly degradable foamed sole is different from the sole in embodiment 3 in that zinc oxide is a zinc oxide nanorod, and titanium dioxide and the zinc oxide nanorod are pretreated as follows:
(1) Adding 0.7kg of oleic acid and 2kg of distilled water into 1kg of titanium dioxide, heating to 180 ℃, carrying out hydrothermal treatment for 4h, filtering, washing with absolute ethyl alcohol and distilled water in sequence, and carrying out vacuum drying for 20h at 80 ℃;
(2) Mixing the titanium dioxide obtained in the step (1) with 0.6kg of methyl cellulose and 2kg of distilled water to form a mixed solution, mixing the mixed solution with a zinc oxide nano rod according to a mass ratio of 0.4.
Example 12: the environment-friendly degradable foamed sole is different from the sole in embodiment 3 in that zinc oxide is a zinc oxide nanorod, and titanium dioxide and the zinc oxide nanorod are pretreated as follows:
mixing 2kg of titanium dioxide, 1kg of methylcellulose and 4kg of distilled water to form a mixed solution, mixing the mixed solution and a zinc oxide nanorod according to a mass ratio of 0.6.
Comparative example
Comparative example 1: an environment-friendly degradable foamed shoe sole is different from that in example 1 in that bagasse fibers are selected from preparation example 3.
Comparative example 2: an environment-friendly degradable foamed shoe sole is different from that in example 1 in that bagasse fibers are selected from preparation example 4.
Comparative example 3: an environment-friendly degradable foamed sole differs from example 1 in that bagasse fibers are selected from preparation example 5.
Comparative example 4: an environment-friendly degradable foamed shoe sole, which is different from the sole in example 1 in that bagasse fibers are selected from preparation example 6.
Comparative example 5: an environment-friendly degradable foamed sole is different from that of the sole in example 1 in that bagasse fibers are not added.
Comparative example 6: a light-weight high-elasticity EVA sole is composed of the following components in parts by weight: EVA 40W 18 parts, EVA 265 parts, polyolefin block copolymer 9077 parts, ethylene propylene diene monomer 3745P 10 parts, chlorinated polyethylene 135B 6 parts, foaming agent AC 2.5 parts, crosslinking agent BIBP 1.7 parts, zinc stearate 2.2 parts, stearic acid 1.2 parts, wear-resisting agent AG209 2 parts, and talcum powder 5 parts.
The preparation method of the lightweight high-elasticity EVA sole comprises the following steps:
step 1: the preparation method of the high-elasticity EVA material rice comprises the steps of firstly mixing all the raw materials of the components, carrying out banburying, adjusting the banburying temperature to 97 ℃, keeping for 6min, then turning over for 2 times, continuing banburying and heating, discharging at 106 ℃, carrying out open milling and granulation after banburying is finished, and obtaining the light-weight high-elasticity EVA material rice.
Step 2: and pouring the EVA material rice into a material suction barrel of a primary EVA injection machine table, and performing primary injection molding to obtain the light-weight high-elasticity EVA sole.
Performance test
Soles were prepared according to the methods in examples and comparative examples, and the performance test of soles was conducted with reference to the following methods, and the test results are reported in table 1.
1. Density: the measurement was carried out in accordance with GB/T533-2008 "measurement of the density of vulcanized rubber or thermoplastic rubber".
2. Tensile strength: the detection is carried out according to GB/T528-2009 determination method for tensile stress strain performance of vulcanized or thermoplastic rubber.
3. The rebound resilience: detection was carried out according to GB/T1681-2009 "measurement of rebound resilience of vulcanized rubber".
4. Moisture absorption: cutting the sole into small blocks with the size of 10mm multiplied by 4mm, placing the small blocks into an electronic constant-temperature air-blast drying oven, drying the small blocks for 12 hours at the temperature of 60 ℃, soaking the small blocks in water at normal temperature (the water temperature is 25 ℃), taking the small blocks out at intervals, sucking the moisture on the surface of a sample by using filter paper, weighing and calculating the weight gain, wherein the water absorption (X) calculation formula is as follows: x = (Mx-Mo)/Mo × 100%, where Mo is the mass of the material at the water absorption rate and Mx is the total mass of the sole material after soaking in water for 24h, and the sole prepared in each example or preparation was tested in three samples and finally reported as the average water absorption rate.
5. Weight loss rate: selecting natural soil, putting the natural soil into a large storage box, forming a hole at the bottom of the storage box, cutting the sole made in each embodiment or comparative example into a square sheet, vertically burying the square sheet in the deep part of the storage box (15 cm away from the bottom of the storage box), placing the storage box at an outdoor part with ultraviolet irradiation, watering every day (except rainy days) to ensure the soil moisture, wherein the burying time is 100 days, the number of buried samples in each embodiment is 5, after the burying time is finished, digging each sample, cleaning, carrying out vacuum drying at 50 ℃ for 12h, describing the degradation performance of the sole by weight loss rate, calculating the weight loss rate according to the average value of the change rate of the mass of the 5 samples, wherein the weight loss rate (W) = (We-W1)/We x 100%, we is the original mass of the sample, and W1 is the mass of the buried sample.
6. The deodorization effect is as follows: the soles prepared in the examples and the comparative examples are made into sports shoes, 10 persons are selected for trial use in each example or comparative example, the exercise amount of 10 persons per day is similar, the number of days for producing the odor of the sports shoes is counted from the first day of trial use, the average value of 10 persons is taken, and the larger the value is, the better the deodorization effect is.
Table 1 performance test results of the environmentally friendly and degradable foamed shoe sole
The bagasse fibers prepared in preparation examples 1 and 2 were used in examples 1 and 2, respectively, and table 1 shows that the soles prepared in examples 1 to 2 were biodegradable, had a degradation rate of 14.8 to 15.4% in 100 days, had good moisture absorption, and were not likely to cause moisture and odor in the shoe cavity.
The data in table 1 show that the composite deodorant powders prepared in preparation examples 7 and 8 were added to the shoe soles prepared in examples 3 and 4, respectively, and the rebound resilience, tensile strength, hygroscopicity, and the number of smelling days of 11 to 12 days, deodorization effect, and biodegradation rate were improved.
The composite deodorant powders prepared in preparation examples 9 and 10 were used in examples 5 and 6, respectively, and table 1 shows that the remaining test performance of the shoe soles prepared in examples 5 and 6 is similar to that of example 3, but the average days for deodorization is decreased, the deodorization time is shortened, and the deodorization effect of the shoe soles is decreased.
Example 7 the composite deodorizing powder prepared in preparation example 11 was used, and no chitin fiber and coffee carbon fiber were added to preparation example 11, and the data in table 1 shows that the sole prepared in example 7 had a significantly reduced water absorption, a reduced degradation rate, a shortened deodorizing time, and a reduced deodorizing effect, as compared to example 3.
Example 8 using the composite deodorant powder prepared in production example 12, production example 12 showed no significant change in water absorption of shoe soles without adding PHBV, but had a decreased rebound resilience, a decreased weight loss, and a slower biodegradation rate than production example 7.
In example 9, activated carbon was used as a deodorizing powder, and the shoe sole produced in example 9 also had similar moisture absorption and degradation rates as compared with example 3, but the deodorizing effect was inferior to that of example 3.
The pretreatment of titanium dioxide and zinc oxide nanorods was performed in examples 10 and 11, as compared to example 3, and the data in table 1 shows that the soles prepared in examples 10 and 11 have similar hygroscopicity to example 3, but have increased weight loss and accelerated degradation rate.
Compared with the example 3, in the example 12, oleic acid is not added when the titanium dioxide and the zinc oxide nanorods are pretreated, and table 1 shows that the weight loss rate of the sole prepared in the example 12 is reduced, which indicates that the oleic acid can improve the degradation rate of the titanium dioxide and the zinc oxide nanorods, and the degradation rate of the example 12 is still higher than that of the example 1, which indicates that the degradation rate of the sole can be improved even if the titanium dioxide and the zinc oxide nanorods are not added with oleic acid.
Comparative example 1 using bagasse fiber prepared in preparative example 3, in which formamide was not added, and comparative example 2 using bagasse fiber prepared in preparative example 4, in which polyvinyl alcohol was not added, the sole materials prepared in comparative example 1 and comparative example 2 were poor in hygroscopicity, slow in degradation rate, and inferior in deodorizing effect to example 1.
Comparative example 3 using bagasse fiber prepared in preparation example 5, to which a mixed solution of maleic anhydride and ethyl acetate was not added, the tensile strength of the sole prepared in comparative example 3 was decreased compared to example 1.
In comparative example 4, bagasse fibers are prepared by cooking bagasse in alkaline liquor, and the hygroscopicity and the degradation speed of the soles prepared in comparative example 4 are all reduced, which shows that the bagasse fibers with good hygroscopicity and high degradation speed can be obtained by treating the bagasse with formamide, polyvinyl alcohol and the like.
In comparative example 5, bagasse fibers were not added, and compared to example 1, the sole prepared in comparative example 5 was poor in hygroscopicity, not easily degraded, and poor in deodorizing effect.
Comparative example 6 is a foamed shoe sole prepared in the prior art, which has high rebound and tensile strength, light weight and high elasticity, but has a small weight loss in soil, is difficult to degrade, and has poor hygroscopicity and no deodorizing effect.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The environment-friendly degradable foamed sole is characterized by comprising the following components in parts by weight: 30.56-35 parts of ethylene-vinyl acetate copolymer, 30-35 parts of bagasse fiber, 22.22-25 parts of ethylene-octene copolymer, 2.78-3.2 parts of talcum powder, 0.56-0.7 part of stearic acid, 1.27-1.5 parts of zinc oxide, 3.22-3.5 parts of foaming agent, 0.56-0.8 part of cross-linking agent, 2.78-3.2 parts of titanium dioxide and 0.24-0.3 part of pigment;
the bagasse fiber is prepared by the following method: sieving bagasse, adding into sodium hydroxide solution, steaming at 110-120 deg.C under 0.4-0.5MPa for 2-3 hr, filtering, washing to neutrality, and drying to obtain alkali-treated bagasse fiber;
and mixing the alkali-treated bagasse fiber with a mixed solution containing polyvinyl alcohol, formamide and distilled water, stirring for 3-4h at 60-80 ℃, drying, then soaking in a mixed solution of maleic anhydride and ethyl acetate for 1-2h, washing and drying to obtain the bagasse fiber.
2. The environmentally friendly and degradable foamed shoe sole according to claim 1, wherein: the bagasse fiber comprises the following raw materials in parts by weight:
1-2 parts of alkali-treated bagasse fiber, 0.5-1 part of maleic anhydride, 0.5-1 part of ethyl acetate solution, 0.3-0.4 part of polyvinyl alcohol, 0.4-0.5 part of formamide and 3-5 parts of distilled water.
3. The environment-friendly degradable foamed sole according to claim 1, further comprising deodorant composite powder in an amount of 5-10 parts.
4. The environmentally friendly and degradable foamed shoe sole according to claim 3, wherein the preparation method of the deodorizing composite powder comprises the following steps:
carrying out plasma treatment on PHBV, and mixing the PHBV with chloramine, aluminum potassium sulfate and distilled water to form spraying liquid;
mixing chitin fiber and coffee carbon fiber, opening, removing impurities, uniformly spraying the spray coating solution on chitin fiber and coffee carbon fiber, pre-drying at 60-80 deg.C for 20-30min, thermally bonding at 160-170 deg.C under 0.6-0.7MPa for 3-5min, pulverizing, and making into deodorant composite powder.
5. The environment-friendly degradable foamed sole according to claim 4, wherein the deodorizing composite powder comprises the following raw materials in parts by mass: 3-6 parts of PHBV, 1.5-2 parts of chloramine, 0.9-1.8 parts of aluminum potassium sulfate, 10-15 parts of distilled water, 4-8 parts of chitin fibers and 2-4 parts of coffee carbon fibers.
6. The environment-friendly degradable foamed sole according to claim 1, wherein the foaming agent is Jinyang AC-3000, and the talcum powder is special BHS-818T talcum powder for shoe material EVA.
7. The method for preparing the environmentally friendly and degradable foamed sole according to any one of claims 1 to 6, comprising the following steps:
s1, mixing an ethylene-vinyl acetate copolymer and bagasse fibers at a high speed, and extruding and granulating to obtain blended particles;
s2, mixing the blending particles, the ethylene-octene copolymer, the talcum powder, the stearic acid, the pigment, the zinc oxide and the titanium dioxide, carrying out primary banburying, adding the cross-linking agent, the foaming agent and the deodorization composite powder, carrying out secondary banburying, and carrying out material turning at different temperatures during the banburying for 7 times to obtain a mixture;
s3, thinning the mixture at 65-85 ℃ for 2 times to obtain sheet materials;
s4, granulating the sheet material to obtain granules with the grain size of 3-4 mm;
s5, injection molding the granules at 175-180 ℃ for 450-460S to obtain the sole.
8. The method for preparing the environmentally friendly and degradable foamed shoe sole according to claim 7, wherein the zinc oxide is zinc oxide nanorods.
9. The preparation method of the environment-friendly degradable foamed sole according to claim 8, wherein the titanium dioxide and the zinc oxide nano-rods are pretreated by the following steps:
(1) Adding 1-2 parts by weight of titanium dioxide into 0.7-1.5 parts by weight of oleic acid and 2-5 parts by weight of distilled water, heating to 180-200 ℃, carrying out hydrothermal treatment for 3-4h, filtering, washing with absolute ethyl alcohol and distilled water in sequence, and carrying out vacuum drying;
(2) Mixing the titanium dioxide obtained in the step (1) with 0.6-1 part of methyl cellulose and 2-4 parts of distilled water to form a mixed solution, mixing the mixed solution with a zinc oxide nano rod according to the mass ratio of 0.4-0.6.
10. The method for preparing the environmentally friendly and degradable foamed sole according to claim 7, wherein in the step S2, the material turning step is as follows: performing first material turning at the temperature of 98 ℃, performing second material turning at the temperature of 111 ℃ for 60s, performing third material turning at the temperature of 117 ℃, performing fourth material turning at the temperature of 120 ℃, performing fifth material turning at the temperature of 122 ℃, performing 30s, performing sixth material turning at the temperature of 124 ℃, performing 30s, performing seventh material turning at the temperature of 126 ℃, performing 30s, and performing blanking at the temperature of 127 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115746440A (en) * | 2022-11-23 | 2023-03-07 | 莆田市百合鞋业有限公司 | EVA wear-resistant sole and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604197A (en) * | 2012-03-14 | 2012-07-25 | 泰亚鞋业股份有限公司 | Catalytical-degradable EVA (Ethylene Vinylacetate) foamed sports shoe sole and preparation method thereof |
| CN113265099A (en) * | 2021-05-19 | 2021-08-17 | 软慕新材料科技(苏州)有限公司 | Method for preparing foamed shoe material by blending cork powder with EVA |
| CN113698749A (en) * | 2021-09-14 | 2021-11-26 | 广西瑞朗生物科技有限公司 | Biodegradable mulching film and preparation method thereof |
-
2022
- 2022-08-05 CN CN202210939887.5A patent/CN115160683A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604197A (en) * | 2012-03-14 | 2012-07-25 | 泰亚鞋业股份有限公司 | Catalytical-degradable EVA (Ethylene Vinylacetate) foamed sports shoe sole and preparation method thereof |
| CN113265099A (en) * | 2021-05-19 | 2021-08-17 | 软慕新材料科技(苏州)有限公司 | Method for preparing foamed shoe material by blending cork powder with EVA |
| CN113698749A (en) * | 2021-09-14 | 2021-11-26 | 广西瑞朗生物科技有限公司 | Biodegradable mulching film and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115746440A (en) * | 2022-11-23 | 2023-03-07 | 莆田市百合鞋业有限公司 | EVA wear-resistant sole and preparation method thereof |
| CN115746440B (en) * | 2022-11-23 | 2024-02-09 | 莆田市百合鞋业有限公司 | EVA wear-resistant sole and preparation method thereof |
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