Application of waste diatomite white carbon black, sole material as well as preparation method and application of sole material

Abstract

The invention discloses application of waste diatomite white carbon black, a sole material and a preparation method and application of the sole material. According to the application of the waste diatomite white carbon black in preparation of a sole material, the waste diatomite white carbon black is used as a reinforcing agent. The sole material comprises the following raw materials in parts by weight: 100 parts of natural rubber, 20-60 parts of waste diatomite white carbon black, 2-6 parts of a coupling agent, 1-3 parts of a vulcanizing agent, 1.5-4 parts of an accelerant and 1-5 parts of an anti-aging agent. The sole material can be used for preparing soles. The waste diatomite white carbon black is used for preparing the sole material, the prepared sole material has better wear resistance, tear resistance and wet skid resistance, the production process is environment-friendly, meanwhile, the waste diatomite can be recycled, the production cost is remarkably reduced, and the environmental pollution is reduced.

Description

Technical Field

[0001] The invention relates to the technical field of sole manufacturing, in particular to the application of waste diatomite and white carbon black, a sole material, and a preparation method and application thereof. Background Art

[0002] During beer production, diatomaceous earth is widely used to filter beer mash to remove impurities and suspended matter, ensuring beer clarity and taste. However, the spent diatomaceous earth after filtration is often considered waste and cannot be directly recycled, resulting in a waste of resources and increased processing costs for companies.

[0003] In the footwear industry, soles are typically made of synthetic materials such as synthetic rubber and EVA (ethylene-vinyl acetate copolymer). While these materials offer excellent wear resistance and elasticity, their production relies heavily on petroleum resources and can pollute the environment. In recent years, with growing environmental awareness, soles made from some renewable materials have gradually appeared on the market, but these materials still have drawbacks in terms of wear resistance, cost, and production process.

[0004] With rapid socioeconomic development, people's expectations for footwear are growing. Early consumers primarily focused on whether shoes were sturdy and durable. With social progress and improved living standards, consumers are increasingly concerned with shoe quality and performance. Safety and comfort are the development goals of the entire footwear industry. Data shows that sole materials account for approximately 50% of a shoe's weight.

[0005] Therefore, it is necessary to develop a sole material with good wear resistance and an environmentally friendly production process, and at the same time recycle waste diatomaceous earth to reduce production costs and reduce environmental pollution. Summary of the Invention

[0006] The purpose of the present invention is to provide an application of waste diatomaceous earth and white carbon black, a sole material and its preparation method and application. The present invention uses waste diatomaceous earth and white carbon black to prepare the sole material. The prepared sole material has good wear resistance, tear resistance and wet-slip resistance, and the production process is environmentally friendly. At the same time, the waste diatomaceous earth can be utilized as a resource, significantly reducing production costs and reducing environmental pollution.

[0007] The technical solution of the present invention is to use waste diatomite and white carbon black in the preparation of shoe sole materials, using the waste diatomite and white carbon black as a reinforcing agent.

[0008] The aforementioned waste diatomite silica is used in the preparation of shoe sole materials. The waste diatomite silica is compounded with natural rubber and / or synthetic rubber in a weight ratio of 20-60:100, and auxiliary materials for preparing shoe sole materials are added to prepare the shoe sole materials.

[0009] The application of the aforementioned waste diatomite white carbon black in the preparation of shoe sole material, the ratio of the white carbon black to natural rubber and / or synthetic rubber is 30-50:100.

[0010] The application of the aforementioned waste diatomite white carbon black in the preparation of shoe sole material, the preparation method of the waste diatomite white carbon black comprises the following steps,

[0011] Step A, crushing and screening: crushing the large particles in the waste diatomite and then screening through a 80-130 mesh sieve to remove large particle impurities;

[0012] Step B, heat treatment: placing the waste diatomite after removing large particle impurities in an oven and heat treating at 300-360℃ for 40-100min;

[0013] Step C, acid washing: soaking the waste diatomite after heat treatment in an acid solution with pH<3.8 at 60-80℃ for 2-3.5h and then washing with water;

[0014] Step D, preparation of water glass solution: mixing and reacting the waste diatomite after acid washing with a sodium hydroxide or potassium hydroxide solution with a concentration of 2-4.5mol / L, the ratio of the waste diatomite to the lye being 100g:1-1.5L, and reacting at 80-90℃ for 2-4h, filtering the undissolved part to obtain a water glass solution;

[0015] Step E, precipitation reaction: introducing carbon dioxide gas into the water glass solution for precipitation reaction, the introduced carbon dioxide gas having a volume percentage concentration of 30%-90%, the gas introduction pressure being 0.1-0.2MPa, and the aging time being 2-4h, filtering the filter cake, grinding and drying the filter cake to obtain the waste diatomite white carbon black.

[0016] In the application of the aforementioned waste diatomite white carbon black in the preparation of shoe sole material, in Step A, the large particles in the waste diatomite are crushed and then screened through a 110 mesh sieve; in Step B, heat treating at 330℃ for 70min; in Step C, soaking the waste diatomite after heat treatment in an acid solution with pH 3.5 at 70℃ for 2.7h and then washing with water to neutral; in Step D, mixing and reacting the waste diatomite after acid washing with a sodium hydroxide or potassium hydroxide solution with a concentration of 3.3mol / L, the ratio of the waste diatomite to the lye being 100g:1.3L, and reacting at 85℃ for 2.6h; in Step E, the introduced carbon dioxide gas having a volume percentage concentration of 60%, the gas introduction pressure being 0.15MPa, and the aging time being 3h.

[0017] The above-mentioned sole material prepared from white carbon black comprises the following raw materials in parts by weight: 100 parts of natural rubber, 20-60 parts of waste diatomaceous earth white carbon black, 2-6 parts of coupling agent, 1-3 parts of vulcanizing agent, 1.5-4 parts of accelerator, and 1-5 parts of antioxidant.

[0018] The above-mentioned sole material includes the following raw materials in parts by weight: 100 parts of natural rubber, 40 parts of waste diatomaceous earth and white carbon black, 4 parts of coupling agent, 2 parts of vulcanizing agent, 3.2 parts of accelerator, and 2.5 parts of antioxidant.

[0019] In the above-mentioned sole material, the coupling agent is bis-[γ-(triethoxysilyl)propyl]tetrasulfide (Si69), bis-[3-(triethoxysilyl)propyl]-disulfide (Si75), γ-aminopropyltriethoxysilane (KH 550), the vulcanizing agent is sulfur, the accelerator is diphenylguanidine (DPG), N-cyclohexyl-2-benzothiazole sulfenamide (CBS), N-tert-butyl-2-benzothiazole sulfenamide (TBBS), and the antioxidant is 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), N,N'-dimethylphenylenediamine (DTPD), N-isopropyl-N'-phenyl-p-phenylenediamine (TMQ), N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD), and 2,6-di-tert-butyl-p-methylphenol (BHT).

[0020] The preparation method of the above-mentioned sole material comprises mixing natural rubber, waste diatomaceous earth and white carbon black, a coupling agent, a vulcanizing agent, an accelerator, and an antioxidant, kneading the mixture evenly in an internal mixer at a temperature of 145-155°C, and then vulcanizing the mixture at 150-190°C for 12-60 minutes to prepare the sole material.

[0021] Application of the aforementioned sole material in the preparation of soles.

[0022] Compared to existing technologies, this invention utilizes waste diatomite and silica to produce a shoe sole material. The resulting sole material exhibits superior wear resistance, tear resistance, and wet-slip resistance. The production process is environmentally friendly and transforms waste diatomite into a high-value-added product, improving economic efficiency. This not only achieves resource utilization of waste, but also significantly reduces production costs and environmental pollution, aligning with the concept of sustainable development. The shoe sole material of this invention, selected and proportioned through extensive experimentation, demonstrates that the resulting sole exhibits 20% greater wear resistance than conventional soles, while also exhibiting excellent tear resistance and wet-slip resistance. DETAILED DESCRIPTION

[0023] The present invention will be further described below with reference to the examples, but they are not intended to limit the present invention.

[0024] Example 1 waste diatomite white carbon black

[0025] The preparation method of the waste diatomite white carbon black comprises the following steps,

[0026] Step A, crushing and screening: the large particles in the waste diatomite are crushed and then passed through a 110-mesh screen to remove large-particle impurities;

[0027] Step B, heat treatment: the waste diatomite from which the large-particle impurities have been removed is placed in an oven and heat treated at 330°C for 70 min;

[0028] Step C, acid washing: the waste diatomite after heat treatment is soaked in a hydrochloric acid solution with a pH of 3.5 at 70°C for 2.7 h and washed with water until neutral;

[0029] Step D, preparation of water glass solution: the waste diatomite after acid washing is mixed with a sodium hydroxide solution with a concentration of 3.3 mol / L, the ratio of the waste diatomite to the lye being 100 g:1.3 L, and the mixture is reacted at 85°C for 2.6 h, and the undissolved part is filtered to obtain a water glass solution;

[0030] Step E, precipitation reaction: carbon dioxide gas is introduced into the water glass solution to perform a precipitation reaction, the carbon dioxide gas being introduced at a volume percentage concentration of 60%, the gas pressure being 0.15 MPa, and the aging time being 3 h, and the filter cake is obtained by filtration, ground and dried to obtain the waste diatomite white carbon black.

[0031] Example 2 shoe sole material

[0032] The raw materials of the shoe sole material are 100 parts of natural rubber, 20 parts of waste diatomite white carbon black, 7.5 parts of coupling agent Si75, 1 part of sulfur, 1.5 parts of accelerator TBBS, and 1 part of antioxidant TMQ.

[0033] The natural rubber, waste diatomite white carbon black, coupling agent, vulcanizing agent, accelerator, and antioxidant are mixed and uniformly mixed in an internal mixer at a temperature of about 150°C, and then vulcanized at 150°C for 60 min to produce the shoe sole material.

[0034] Example 3 shoe sole material

[0035] The raw materials of the shoe sole material are 100 parts of natural rubber, 60 parts of waste diatomite white carbon black, 3 parts of coupling agent KH550, 6.9 parts of coupling agent Si69, 3 parts of sulfur, 1 part of accelerator CBS, 1.2 parts of accelerator TBBS, and 1.5 parts of antioxidant DTPD.

[0036] The natural rubber, waste diatomite white carbon black, coupling agent, vulcanizing agent, accelerator, and antioxidant are mixed and uniformly mixed in an internal mixer at a temperature of about 155°C, and then vulcanized at 190°C for 12 min to produce the shoe sole material.

[0037] Example 4 shoe sole material

[0038] The raw materials of the shoe sole material are 100 parts of natural rubber, 40 parts of waste diatomite white carbon black, 7.5 parts of coupling agent Si754, 2 parts of sulfur, 2 parts of accelerator DPG, 1.2 parts of accelerator CBS, 1 part of antioxidant RD, and 1.5 parts of antioxidant 6PPD.

[0039] After the natural rubber, waste diatomite white carbon black, coupling agent, vulcanizing agent, accelerator, and antioxidant are mixed, they are uniformly mixed in a mixer at a temperature of 150°C, and then vulcanized at 170°C for 20 minutes to produce the shoe sole material.

[0040] The waste diatomite white carbon black used in Examples 2-4 is prepared according to Example 1.

[0041] Example 5 application of the shoe sole material

[0042] The environmentally friendly shoe sole material in Examples 2-4 is used to prepare the shoe sole of sports shoes according to a conventional process.

[0043] In the experimental example, the shoe sole material prepared in Examples 2-4 is sampled and detected, and the hardness (Shore hardness tester), density (weighing method), M300 modulus (tensile test), tensile strength (GB / T528-2009), elongation at break (GB / T528-2009), DIN abrasion (GB / T9867-2008), slip resistance coefficient (dry) (HG / T2729-2012), slip resistance coefficient (wet) (HG / T2729-2012), room temperature resilience (GB / T6670-2008), and hydrolysis resistance (constant temperature and humidity hydrolysis resistance tester) of the test sample are tested, and the results are shown in Table 1.

[0044] Table 1 shoe sole material performance test results

[0045]

[0046] The test results show that the shoe sole material prepared by the present application has good wear resistance, tear resistance, and wet skid resistance, and the wear resistance is improved by 20% compared with traditional shoe soles (such as Huntsman TPU, and the shoe sole material prepared in Example 4 is prepared by the same process).

[0047] Of course, the present application can have other various embodiments, and those skilled in the art can make various corresponding changes and modifications according to the present application without departing from the spirit and essence of the present application, but these corresponding changes and modifications should all belong to the protection scope of the claims attached to the present application.

Claims

1. The application of waste diatomite and white carbon black in the preparation of shoe sole materials is characterized by: The waste diatomite and white carbon black are used as a reinforcing agent.

2. The use of waste diatomite silica in the preparation of shoe sole materials according to claim 1, characterized in that: Waste diatomite white carbon black and natural rubber and / or synthetic rubber in a weight ratio of 20-60: 100 is compounded, and auxiliary materials for preparing sole materials are added to prepare sole materials.

3. The use of waste diatomite silica in the preparation of shoe sole materials according to claim 2, characterized in that: The ratio of the white carbon black to the natural rubber and / or synthetic rubber is 30-50:

100.

4. The use of waste diatomite silica in the preparation of shoe sole materials according to claim 3, characterized in that: The method for preparing waste diatomite white carbon black comprises the following steps: Step A, crushing and screening: crushing large particles in the waste diatomaceous earth and passing them through an 80-130 mesh sieve to remove large particles of impurities; Step B, heat treatment: placing the waste diatomaceous earth after removing large particle impurities in an oven and heat treating it at 300-360° C. for 40-100 minutes; Step C, acid washing: soaking the heat-treated waste diatomaceous earth in an acidic solution with a pH value of less than 3.8 at 60-80° C. for 2-3.5 hours, and then washing with water; Step D, preparing a water glass solution: mixing the acid-washed waste diatomaceous earth with a sodium hydroxide or potassium hydroxide solution having a concentration of 2-4.5 mol / L, wherein the ratio of the waste diatomaceous earth to the alkali solution is 100 g: 1-1.5 L, reacting at 80-90° C. for 2-4 hours, and filtering the undissolved portion to obtain a water glass solution; Step E, precipitation reaction: carbon dioxide gas is introduced into the water glass solution for precipitation reaction, the carbon dioxide gas is introduced at a volume percentage concentration of 30%-90%, the gas pressure is 0.1-0.2 MPa, and the solution is allowed to stand for aging for 2-4 hours. The filter cake is filtered and ground and dried to obtain waste diatomaceous earth and white carbon black.

5. The use of waste diatomite silica in the preparation of shoe sole materials according to claim 3 or 4, characterized in that: In step A, large particles in the waste diatomaceous earth are crushed and then passed through a 110-mesh sieve; in step B, heat treatment is performed at 330° C. for 70 min; in step C, the heat-treated waste diatomaceous earth is soaked in an acidic solution with a pH of 3.5 at 70° C. for 2.7 h and washed with water until neutral; in step D, the acid-washed waste diatomaceous earth is mixed with a sodium hydroxide or potassium hydroxide solution with a concentration of 3.3 mol / L, the waste diatomaceous earth and the alkali solution are mixed in a ratio of 100 g:1.3 L, and the reaction is carried out at 85° C. for 2.6 h; in step E, the carbon dioxide is introduced with a volume percentage concentration of 60% carbon dioxide gas at an introduction pressure of 0.15 MPa, and the aging time is 3 h.

6. Sole material, characterized by: The method comprises the following raw materials in parts by weight: 100 parts of natural rubber, 20-60 parts of waste diatomaceous earth and white carbon black, 2-6 parts of coupling agent, 1-3 parts of vulcanizing agent, 1.5-4 parts of accelerator and 1-5 parts of antioxidant.

7. The sole material according to claim 6, characterized in that: The method comprises the following raw materials in parts by weight: 100 parts of natural rubber, 40 parts of waste diatomaceous earth and white carbon black, 4 parts of coupling agent, 2 parts of vulcanizing agent, 3.2 parts of accelerator and 2.5 parts of antioxidant.

8. The sole material according to claim 6, characterized in that: The coupling agent is one or more of bis-[γ-(triethoxysilyl)propyl]tetrasulfide, bis-[3-(triethoxysilyl)propyl]-disulfide, and γ-aminopropyltriethoxysilane; the vulcanizing agent is sulfur; the accelerator is one or more of diphenylguanidine, N-cyclohexyl-2-benzothiazolesulfonamide, and N-tert-butyl-2-benzothiazolesulfonamide; and the antioxidant is one or more of 2,2,4-trimethyl-1,2-dihydroquinoline polymer, N,N'-dimethylphenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, and 2,6-di-tert-butyl-p-methylphenol.

9. The method for preparing the sole material according to any one of claims 6 to 8, characterized in that: The natural rubber, waste diatomaceous earth white carbon black, coupling agent, vulcanizing agent, accelerator and antioxidant are mixed and kneaded evenly in an internal mixer at a temperature of 145-155 DEG C, and then vulcanized at 150-190 DEG C for 12-60 minutes to prepare the sole material.

10. Use of the sole material according to any one of claims 6 to 8 in preparing soles.

Images