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

Abstract

The application discloses an application of waste diatomite white carbon black, a sole material and a preparation method and application thereof. The application of the waste diatomite white carbon black in preparation of the sole material uses the waste diatomite white carbon black as a reinforcing agent. The sole material comprises the following raw materials in parts by weight: natural rubber 100 parts, waste diatomite white carbon black 20-60 parts, a coupling agent 2-6 parts, a vulcanizing agent 1-3 parts, an accelerator 1.5-4 parts and an antioxidant 1-5 parts. The sole material can be used for preparing a sole. The waste diatomite white carbon black is used for preparing the sole material, the prepared sole material has good 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] This invention relates to the field of shoe sole manufacturing technology, and in particular to the application of waste diatomaceous earth silica, shoe sole materials, their preparation methods and applications. Background Technology

[0002] In beer production, diatomaceous earth is widely used to filter beer brew to remove impurities and suspended solids, ensuring the beer's clarity and taste. However, the waste diatomaceous earth after filtration is usually considered waste and cannot be directly recycled, which not only wastes resources but also increases the processing costs for companies.

[0003] In the footwear industry, sole materials are typically made of synthetic rubber, EVA (ethylene-vinyl acetate copolymer), and other synthetic materials. While these materials offer good abrasion resistance and elasticity, their production process is heavily reliant on petroleum resources and can potentially pollute the environment. In recent years, with increasing environmental awareness, soles made from some renewable materials have gradually appeared on the market; however, these materials still have shortcomings in terms of abrasion resistance, cost, and manufacturing processes.

[0004] With rapid socio-economic development, people's demands for footwear products are increasing. Early consumers primarily cared about the sturdiness and durability of shoes. However, with societal progress and improved living standards, consumers have gradually become more concerned with shoe quality and performance; safety and comfort have become the development goals of the entire footwear industry. Data shows that sole materials account for approximately 50% of the total weight of a shoe.

[0005] Therefore, it is necessary to develop a shoe sole material with good wear resistance and an environmentally friendly production process, while making resource utilization of waste diatomaceous earth to reduce production costs and environmental pollution. Summary of the Invention

[0006] The purpose of this invention is to provide an application of waste diatomaceous earth silica, a shoe sole material, and its preparation method and application. This invention uses waste diatomaceous earth silica in the preparation of shoe sole materials, and the resulting shoe sole materials have good wear resistance, tear resistance and slip resistance. Moreover, the production process is environmentally friendly, and 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 the application of waste diatomaceous earth silica in the preparation of shoe sole materials, using the waste diatomaceous earth silica as a reinforcing agent.

[0008] In the aforementioned application of waste diatomaceous earth silica in the preparation of shoe sole materials, waste diatomaceous earth silica is compounded with natural rubber and / or synthetic rubber at a weight ratio of 20-60:100, and then added to the auxiliary materials for preparing shoe sole materials to prepare shoe sole materials.

[0009] In the aforementioned application of waste diatomaceous earth silica in the preparation of shoe sole materials, the ratio of silica to natural rubber and / or synthetic rubber is 30-50:100.

[0010] The aforementioned application of waste diatomaceous earth silica in the preparation of shoe sole materials includes the following steps in the preparation method of the waste diatomaceous earth silica.

[0011] Step A, crushing and screening: crush large particles in the waste diatomaceous earth and pass them through an 80-130 mesh sieve to remove large particle impurities;

[0012] Step B, heat treatment: Place the waste diatomaceous earth after removing large particulate impurities in an oven and heat treat it at 300-360℃ for 40-100 minutes.

[0013] Step C, acid washing: Soak the heat-treated waste diatomaceous earth in an acidic solution with pH < 3.8 at 60-80℃ for 2-3.5 hours, then wash with water;

[0014] Step D, Preparation of water glass solution: The acid-washed waste diatomaceous earth is mixed with a sodium hydroxide or potassium hydroxide solution with a concentration of 2-4.5 mol / L and reacted. The ratio of waste diatomaceous earth to alkaline solution is 100g: 1-1.5L. The reaction is carried out at 80-90℃ for 2-4 hours. The undissolved part is filtered to obtain water glass solution.

[0015] Step E, precipitation reaction: Carbon dioxide gas is introduced into a water glass solution to carry out a precipitation reaction. The carbon dioxide gas has a volume percentage concentration of 30%-90% and an introduction pressure of 0.1-0.2 MPa. The solution is allowed to stand and age for 2-4 hours. The filter cake is then filtered, ground, and dried to obtain waste diatomaceous earth silica.

[0016] In the aforementioned application of waste diatomaceous earth silica in the preparation of shoe sole materials, in step A, large particles of the waste diatomaceous earth are crushed and passed through a 110-mesh sieve; in step B, it is heat-treated at 330℃ for 70 minutes; in step C, the heat-treated waste diatomaceous earth is soaked in an acidic solution with a pH of 3.5 at 70℃ for 2.7 hours, and then 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, and the ratio of waste diatomaceous earth to alkaline solution is 100 g: 1.3 L, and the reaction is carried out at 85℃ for 2.6 hours; in step E, carbon dioxide gas with a volume percentage concentration of 60% is introduced at a pressure of 0.15 MPa, and the aging time is 3 hours.

[0017] The aforementioned shoe sole material prepared from silica includes the following raw materials in parts by weight: 100 parts natural rubber, 20-60 parts waste diatomaceous earth silica, 2-6 parts coupling agent, 1-3 parts vulcanizing agent, 1.5-4 parts accelerator, and 1-5 parts antioxidant.

[0018] The aforementioned sole material includes the following raw materials in parts by weight: 100 parts natural rubber, 40 parts waste diatomaceous earth silica, 4 parts coupling agent, 2 parts vulcanizing agent, 3.2 parts accelerator, and 2.5 parts antioxidant.

[0019] In the aforementioned sole material, the coupling agent is bis-[γ-(triethoxysilyl)propyl]tetrasulfide (Si69), bis-[3-(triethoxysilyl)propyl]disulfide (Si75), or γ-aminopropyltriethoxysilane (KH). One or more of the following (550), wherein the vulcanizing agent is sulfur, the accelerator is one or more of diphenylguanidine (DPG), N-cyclohexyl-2-benzothiazole sulfenamide (CBS), and N-tert-butyl-2-benzothiazole sulfenamide (TBBS), and the antioxidant is one or more of 2,2,4-trimethyl-1,2-dihydroquinoline polymer (RD), N,N'-xylyl-p-phenylenediamine (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 aforementioned method for preparing shoe sole materials involves mixing natural rubber, waste diatomaceous earth silica, coupling agent, vulcanizing agent, accelerator, and antioxidant, then mixing them evenly in a mixer at a temperature of 145-155℃, and finally vulcanizing them at 150-190℃ for 12-60 minutes to produce shoe sole materials.

[0021] The aforementioned sole materials are used in the manufacture of soles.

[0022] Compared with existing technologies, this invention uses waste diatomaceous earth and silica in the preparation of shoe sole materials. The resulting shoe sole materials exhibit better abrasion resistance, tear resistance, and wet slip resistance. Furthermore, the production process is environmentally friendly, transforming waste diatomaceous earth into a high-value-added product, thus 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 materials of this invention were selected and formulated through extensive experiments, resulting in shoe soles with 20% higher abrasion resistance than traditional shoe soles, while also possessing excellent tear resistance and wet slip resistance. Detailed Implementation

[0023] The present invention will be further described below with reference to embodiments, but these embodiments are not intended to limit the scope of the invention.

[0024] Example 1: Waste diatomaceous earth silica

[0025] The method for preparing the waste diatomaceous earth silica includes the following steps:

[0026] Step A, Crushing and Screening: Crush large particles in the waste diatomaceous earth and pass them through a 110-mesh sieve to remove large particle impurities.

[0027] Step B, heat treatment: Place the waste diatomaceous earth with large particulate impurities removed into an oven and heat treat it at 330℃ for 70 minutes;

[0028] Step C, acid washing: The heat-treated waste diatomaceous earth is soaked in a hydrochloric acid solution with a pH of 3.5 at 70°C for 2.7 hours, and then washed with water until neutral.

[0029] Step D, Preparation of water glass solution: Acid-washed waste diatomaceous earth is mixed with a 3.3 mol / L sodium hydroxide solution and reacted. The ratio of waste diatomaceous earth to alkali solution is 100 g: 1.3 L. The reaction is carried out at 85 °C for 2.6 h. The undissolved part is filtered to obtain water glass solution.

[0030] Step E, precipitation reaction: Carbon dioxide gas is introduced into a water glass solution to carry out a precipitation reaction. The carbon dioxide gas has a volume percentage concentration of 60% and an introduction pressure of 0.15 MPa. The solution is allowed to stand and age for 3 hours. The filter cake is then filtered, ground, and dried to obtain waste diatomaceous earth silica.

[0031] Example 2: Shoe Sole Material

[0032] The raw materials for the shoe sole are: 100 parts natural rubber, 20 parts waste diatomaceous earth and silica, 2 parts coupling agent Si75, 1 part sulfur, 1.5 parts accelerator TBBS, and 1 part antioxidant TMQ.

[0033] The natural rubber, waste diatomaceous earth silica, coupling agent, vulcanizing agent, accelerator, and antioxidant are mixed and then mixed evenly in a mixer at a temperature of about 150°C. The mixture is then vulcanized at 150°C for 60 minutes to produce the shoe sole material.

[0034] Example 3: Shoe Sole Material

[0035] The raw materials for the shoe sole are: 100 parts natural rubber, 60 parts waste diatomaceous earth and silica, 3 parts coupling agent KH550, 3 parts coupling agent Si69, 3 parts sulfur, 1 part accelerator CBS, 1.2 parts accelerator TBBS, and 1.5 parts antioxidant DTPD.

[0036] The natural rubber, waste diatomaceous earth silica, coupling agent, vulcanizing agent, accelerator, and antioxidant are mixed and then mixed evenly in a mixer at a temperature of about 155°C. The mixture is then vulcanized at 190°C for 12 minutes to produce shoe sole material.

[0037] Example 4: Shoe Sole Material

[0038] The raw materials for the shoe sole are: 100 parts natural rubber, 40 parts waste diatomaceous earth and silica, 4 parts coupling agent Si75, 2 parts sulfur, 2 parts accelerator DPG, 1.2 parts accelerator CBS, 1 part antioxidant RD, and 1.5 parts antioxidant 6PPD.

[0039] The natural rubber, waste diatomaceous earth silica, coupling agent, vulcanizing agent, accelerator, and antioxidant are mixed and then mixed evenly in a mixer at 150°C. The mixture is then vulcanized at 170°C for 20 minutes to produce the shoe sole material.

[0040] The waste diatomaceous earth silica used in Examples 2-4 was prepared from Example 1.

[0041] Example 5: Application of shoe sole materials

[0042] The environmentally friendly sole materials from Examples 2-4 were used to prepare athletic shoe soles using conventional processes.

[0043] Experimental Examples: Samples of the shoe sole materials prepared in Examples 2-4 were taken and tested. 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 samples were tested. The results are shown in Table 1.

[0044] Table 1. Test Results of Shoe Sole Material Performance

[0045]

[0046] Test results show that the sole material prepared by the present invention has good abrasion resistance, tear resistance and wet slip resistance. Its abrasion resistance is 20% higher than that of traditional soles (such as Huntsman TPU, which is prepared by the same process as the sole material in Example 4).

[0047] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the appended claims.

Claims

1. The application of waste diatomaceous earth silica in the preparation of shoe sole materials, characterized in that: Using the aforementioned waste diatomaceous earth silica as a reinforcing agent; mixing the waste diatomaceous earth silica with natural rubber and / or synthetic rubber at a weight ratio of 20-60: A compound of 100 is added to the auxiliary materials for preparing shoe sole materials to prepare shoe sole materials; the preparation method of the waste diatomaceous earth silica includes the following steps. Step A, crushing and screening: crush large particles in the waste diatomaceous earth and pass them through an 80-130 mesh sieve to remove large particle impurities; Step B, heat treatment: Place the waste diatomaceous earth after removing large particulate impurities in an oven and heat treat it at 300-360℃ for 40-100 minutes. Step C, acid washing: Soak the heat-treated waste diatomaceous earth in an acidic solution with pH < 3.8 at 60-80℃ for 2-3.5 hours and then wash it with water. Step D, Preparation of water glass solution: The acid-washed waste diatomaceous earth is mixed with a sodium hydroxide or potassium hydroxide solution with a concentration of 2-4.5 mol / L and reacted. The ratio of waste diatomaceous earth to alkaline solution is 100g: 1-1.5L. The reaction is carried out at 80-90℃ for 2-4 hours. The undissolved part is filtered to obtain water glass solution. Step E, Precipitation reaction: Carbon dioxide gas is bubbled into a water glass solution to carry out a precipitation reaction, wherein the volume percentage concentration of the bubbly carbon dioxide is... Carbon dioxide gas is introduced at a pressure of 0.1-0.2 MPa and allowed to stand for aging for 2-4 hours. The filter cake is then filtered, ground, and dried to obtain waste diatomaceous earth silica.

2. The application of waste diatomaceous earth silica according to claim 1 in the preparation of shoe sole materials, characterized in that: The ratio of the silica to natural rubber and / or synthetic rubber is 30-50:

100.

3. The application of waste diatomaceous earth silica according to claim 1 or 2 in the preparation of shoe sole materials, characterized in that: In step A, large particles of the waste diatomaceous earth are crushed and passed through a 110-mesh sieve; in step B, the waste diatomaceous earth is heat-treated at 330℃ for 70 minutes; in step C, the heat-treated waste diatomaceous earth is soaked in an acidic solution with a pH of 3.5 at 70℃ for 2.7 hours, and then 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, and the ratio of waste diatomaceous earth to alkaline solution is 100 g: 1.3 L, and the reaction is carried out at 85℃ for 2.6 hours; in step E, carbon dioxide gas with a volume percentage concentration of 60% is introduced at a pressure of 0.15 MPa, and the aging time is 3 hours.

4. The sole material, characterized in that: The raw materials include the following parts by weight: 100 parts natural rubber, waste diatomaceous earth, and silica. Part, coupling agent Parts, vulcanizing agent 1 part, 1.5-4 parts accelerator, anti-aging agent share.

5. The sole material according to claim 4, characterized in that: The raw materials include the following parts by weight: 100 parts natural rubber, 40 parts waste diatomaceous earth silica, 4 parts coupling agent, 2 parts vulcanizing agent, 3.2 parts accelerator, and 2.5 parts antioxidant.

6. The sole material according to claim 4, 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-benzothiazole sulfenamide, and N-tert-butyl-2-benzothiazole hypoflavinamide; and the antioxidant is one or more of 2,2,4-trimethyl-1,2-dihydroquinoline polymer, N,N'-xylyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, and 2,6-di-tert-butyl-p-methylphenol.

7. The method for preparing the sole material according to any one of claims 4-6, characterized in that: Natural rubber, waste diatomaceous earth silica, coupling agent, vulcanizing agent, accelerator, and antioxidant are mixed and then processed in an internal mixer. Mix evenly at the specified temperature, then... Vulcanization is carried out for 12-60 minutes to produce shoe sole material.

8. The use of the sole material according to any one of claims 4-6 in the manufacture of soles.

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