High-wear-resistance vulcanized rubber sole and preparation method thereof

Abstract

The invention relates to the technical field of production of vulcanized rubber soles, and discloses a high-wear-resistance vulcanized rubber sole and a preparation method thereof. Comprising the following raw materials in parts by mass: 90-100 parts of natural rubber, 50-60 parts of butadiene styrene rubber, 20-30 parts of a reinforcing agent, 15-20 parts of acid and alkali resistant filler, 5-10 parts of white carbon black, 4-6 parts of an activating agent, 3-5 parts of an anti-aging agent, 4-5 parts of a softening agent, 2-5 parts of a vulcanizing agent and 4-6 parts of a vulcanization accelerator. The reinforcing filler can participate in vulcanization reaction of rubber, so that the reinforcing filler forms a complex filler network in the rubber sole, the reinforcing filler is fixed in a rubber molecular chain, the wear resistance and mechanical property of the rubber sole are improved, and the movement ability of the reinforcing filler in the rubber molecular chain is limited; mutual friction between the reinforcing filler and a rubber molecular chain is inhibited, the wear resistance of the rubber sole material is improved, the acid and alkali resistant filler can hinder permeation of acid and alkali media, and the acid and alkali resistant performance of the rubber sole material is improved.

Description

Technical Field

[0001] The invention relates to the technical field of vulcanized rubber sole production, in particular to a highly wear-resistant vulcanized rubber sole and a preparation method thereof. Background Art

[0002] As an elastomer, rubber can recover quickly and has good physical and mechanical properties and chemical stability. It is widely used in fields such as tires, shoe soles, floor materials, hoses, cables, etc. Among them, rubber soles refer to soles made of rubber, which have good wear resistance, aging resistance, softness, elasticity, and can play a shock-absorbing role, improving foot comfort, and are suitable for sports such as volleyball, table tennis, and basketball.

[0003] Rubber soles have many shortcomings during repeated jumping and running, such as easy wear and poor mechanical properties, which affect the service life of the rubber soles. Inorganic wear-resistant materials are added to the rubber soles to enhance the wear resistance and mechanical properties of the rubber sole materials. However, the compatibility of inorganic wear-resistant materials with the rubber sole substrate is poor, which affects the wear resistance and mechanical properties of the rubber soles. In addition, there is mutual friction between the inorganic wear-resistant materials and the rubber molecular chains, resulting in poor wear resistance of the rubber sole materials. In addition, the acid and alkali resistance of the rubber soles is poor, which affects the service life of the rubber soles. Summary of the Invention

[0004] The invention provides a highly wear-resistant vulcanized rubber sole and a preparation method thereof, which solves the problems that the rubber sole is easy to wear, has poor mechanical properties and acid and alkali resistance, and shortens the service life of the rubber sole.

[0005] The technical solution of the present invention: A highly wear-resistant vulcanized rubber sole comprising the following raw materials in parts by weight: 90-100 parts of natural rubber, 50-60 parts of styrene-butadiene rubber, 20-30 parts of a reinforcing agent, 15-20 parts of an acid- and alkali-resistant filler, 5-10 parts of white carbon black, 4-6 parts of an activator, 3-5 parts of an antioxidant, 4-5 parts of a softener, 2-5 parts of a vulcanizing agent, and 4-6 parts of a vulcanization accelerator; The enhancer is obtained by mixing creatine, phytic acid and sorbic acid, and then reacting with modified steel slag powder and a cross-linking agent; The modified steel slag powder is obtained by mixing and grinding the magnetically separated steel slag and steel slag grinding aid, and then reacting with citric acid monohydrate; The acid and alkali resistant filler is obtained by synthesizing porous carbon on the surface of barium titanate particles and then treating it with stearic acid.

[0006] A method for preparing a highly wear-resistant vulcanized rubber sole comprises the following steps: S1. The natural rubber and styrene-butadiene rubber are mixed and masticated to obtain a masticated rubber; S2. The plasticized rubber, reinforcing agent, acid and alkali resistant filler, white carbon black, activator, antioxidant and softener are mixed evenly, after a mixing, an accelerator and a vulcanizing agent are added, and a secondary mixing is performed to obtain a mixed rubber compound; S3. After the mixed rubber material is melted and cut into pieces, it is placed in a sole mold, then vulcanized, taken out, and trimmed to obtain a rubber sole.

[0007] Furthermore, in step S1, the plasticating is carried out in an open mill, the plasticating temperature is 50-60° C., and the time is 15-20 minutes.

[0008] Furthermore, in step S2, the primary mixing and the secondary mixing are performed in an internal mixer.

[0009] Furthermore, in step S2, the primary mixing temperature is 110-130°C, and the primary mixing time is 5-10 minutes; the secondary mixing temperature is 120-140°C, and the time is 4-6 minutes.

[0010] Furthermore, in step S3, the lower sheet temperature during the refining process is 55-60° C., the lower sheet thickness is 7-9 mm, and the cutting width is 70-90 mm.

[0011] Furthermore, in step S3, the vulcanization temperature is 150-170° C., the pressure is 10-20 MPa, and the time is 20-40 min.

[0012] Furthermore, the activator is selected from stearic acid or zinc stearate.

[0013] Furthermore, the antioxidant is selected from any one of antioxidant 264, antioxidant 1010, antioxidant 1076, and antioxidant 1520.

[0014] Furthermore, the softener is naphthenic oil.

[0015] Furthermore, the vulcanizing agent is sulfur.

[0016] Furthermore, the vulcanization accelerator is selected from any one of 2,2'-dibenzothiazole disulfide, tetramethylthiuram disulfide, and diphenylguanidine.

[0017] Furthermore, the enhancer is specifically prepared by the following steps: A1. Place the steel slag in a magnetic separator to remove magnetic material. Collect the steel slag after magnetic separation, mix it with a steel slag grinding aid, stir it evenly, and grind it to obtain steel slag powder. A2. Add citric acid monohydrate to deionized water and stir until completely dissolved. Add sodium hydroxide solution to adjust the pH. Then add steel slag powder and stir evenly. React at 170-190°C for 5-7 hours. Cool to room temperature, remove, wash, and dry to obtain steel slag powder loaded with carbon dots. A3. Add creatine monohydrate and phytic acid to deionized water and stir until completely dissolved. Add sorbic acid and stir evenly. Add carbon dot-loaded steel slag powder, a crosslinker, and ethanol. After stirring, the reaction is complete and subjected to rotary evaporation to obtain the product. The product is washed and dried to obtain the enhancer.

[0018] Furthermore, during the above-mentioned A1 reaction process, the steel slag can be effectively recovered from the steel slag through magnetic separation treatment, thereby reducing the addition of scrap steel and metal; the hydroxyl groups contained in ethylene glycol in the steel slag grinding aid can be adsorbed on the surface of the steel slag to shield the charge, thereby achieving a good dispersion effect; triethanolamine contains hydroxyl and amino groups, which are adsorbed on the surface of the steel slag, promoting the expansion of cracks in the steel slag, achieving a good crushing effect, and obtaining steel slag fine powder.

[0019] Furthermore, during the above-mentioned A2 reaction process, the pores on the surface of the steel slag micropowder have excellent adsorption properties, and the polar functional groups hydroxyl and amine on the surface can be chemically bonded with citric acid monohydrate, so that the citric acid is adsorbed in the pores of the steel slag micropowder. After high-temperature treatment, the citric acid is thermally decomposed, and the formed carbon atoms aggregate and nucleate, thereby forming nano-carbon dots in the pores of the steel slag micropowder to obtain modified steel slag micropowder.

[0020] Furthermore, during the above-mentioned A3 reaction process, creatine monohydrate powder is dissolved in the phytic acid solution, the phosphate group in the phytic acid and the amino group of creatine monohydrate are ionically bonded, and the carboxyl group of creatine monohydrate and the phosphate group of phytic acid can be chemically bonded with the carboxyl group of sorbic acid to form a cross-linked network structure. Ethyl orthosilicate is used as a cross-linking agent, and the silanol group produced by hydrolysis can be chemically bonded with the oxygen-containing functional groups in the cross-linked network structure and the hydroxyl groups on the surface of the steel slag micropowder loaded with carbon dots, so that the steel slag micropowder loaded with carbon dots is evenly embedded in the cross-linked network structure to obtain a reinforcing agent.

[0021] Furthermore, in step A1, the mass ratio of the steel slag after magnetic separation to the steel slag grinding aid is (18-22):(1-3).

[0022] Furthermore, in step A1, the steel slag grinding aid is prepared by mixing ethylene glycol, triethanolamine, and ethanol in a mass ratio of (1-2):1:1.

[0023] Furthermore, in step A2, the mass ratio of citric acid monohydrate, deionized water and steel slag powder is (1.6-2):(25-35):(5-6).

[0024] Furthermore, in step A3, the mass ratio of creatine monohydrate, phytic acid, deionized water, sorbic acid, carbon dot-loaded steel slag powder, crosslinking agent and ethanol is (1-2):(3-3.6):(45-55):(1-1.4):(1.6-2):(0.2-0.4):(28-35).

[0025] Furthermore, the crosslinking agent is tetraethyl orthosilicate.

[0026] Furthermore, the acid and alkali resistant filler is specifically prepared by the following steps: B1. Barium titanate particles, glucose, and tannic acid were added to ethanol, stirred, filtered, washed, dried, placed in a tube furnace, potassium hydroxide solution was added, nitrogen was introduced, and after carbonization, cooled to room temperature, removed, washed, and dried to obtain barium titanate particles loaded with porous carbon; B2. Add stearic acid to ethanol and stir until completely dissolved. Add barium titanate particles loaded with porous carbon and hydrochloric acid. After stirring for reaction, cool to room temperature, filter, wash, and dry to obtain an acid- and alkali-resistant filler.

[0027] Furthermore, during the above-mentioned B1 reaction, the large number of phenolic hydroxyl groups contained in tannic acid act as a linker, allowing glucose to adhere to the surface of the barium titanate particles through the tannic acid. After high-temperature carbonization, the glucose is thermally decomposed to form a dense carbon layer. The potassium hydroxide solution acts as an activator to form pores on the surface of the dense carbon layer, thereby synthesizing a porous carbon structure on the surface of the barium titanate particles, and obtaining barium titanate particles loaded with porous carbon.

[0028] Furthermore, during the above-mentioned B2 reaction process, ethanol is used as a reaction solvent, and the carboxyl group of stearic acid can be chemically bonded to the hydroxyl group contained on the surface of the barium titanate particles loaded with porous carbon, so that stearic acid is grafted on the surface of the barium titanate particles loaded with porous carbon as an acid- and alkali-resistant filler.

[0029] Furthermore, in step B1, the mass ratio of barium titanate particles, glucose, tannic acid, ethanol and potassium hydroxide solution is (8-12):(5-6):(0.8-1):(90-100):(4-6).

[0030] Furthermore, in step B2, the mass ratio of stearic acid, ethanol, porous carbon-loaded barium titanate particles and hydrochloric acid is (0.8-1.2):(45-55):(3-4):(1-2).

[0031] The present invention has the following beneficial effects: (1) In the technical solution of the present invention, the steel slag after magnetic separation is mixed with the steel slag grinding aid and ground to form steel slag micropowder with a particle size of 1-10 microns. The small-sized steel slag micropowder has high hardness, rigidity and wear resistance, and is conducive to filling into the rubber sole material, which can improve the mechanical properties and wear resistance of the rubber sole material; nano-carbon dots are formed in the pores of the steel slag micropowder, which can block the pore structure of the steel slag micropowder and prevent the pore structure of the steel slag micropowder from causing crack expansion in the rubber sole material, resulting in a decrease in the mechanical properties of the rubber sole material; and the nano-carbon dots form a rough surface on the surface of the steel slag micropowder, which enhances the contact area between the steel slag micropowder and the rubber sole substrate, so that the steel slag micropowder is better dispersed in the rubber sole material, thereby improving the mechanical properties and wear resistance of the rubber sole material.

[0032] (2) In the technical solution of the present invention, creatine monohydrate, phytic acid and sorbic acid form a cross-linked network structure, and tetraethyl orthosilicate serves as a cross-linking agent, which can be combined with the cross-linked network structure through chemical bonds, so that the steel slag micropowder loaded with carbon dots is uniformly embedded in the cross-linked network structure. On the one hand, sorbic acid and the steel slag micropowder loaded with carbon dots are incorporated into the cross-linked reaction structure, thereby increasing the cross-linking density and enhancing the mechanical properties. Moreover, creatine monohydrate, phytic acid and sorbic acid form a cross-linked network structure, which can absorb the energy generated by stress, thereby improving the mechanical properties of the rubber sole material. On the other hand, the double bonds contained in sorbic acid can participate in the vulcanization reaction of rubber, thereby allowing the reinforcing filler to be incorporated into the rubber sole material in the form of a chemical bond, thereby improving the bonding strength between the reinforcing filler and the rubber sole material, and preventing the reinforcing filler from falling off easily during repeated bouncing and running, thereby affecting the mechanical properties and wear resistance of the rubber sole.

[0033] (3) In the technical solution of the present invention, sorbic acid in the reinforcing filler participates in the vulcanization reaction of the rubber, so that the reinforcing filler forms a complex filler network in the rubber sole, fixes the reinforcing filler in the rubber molecular chain, limits the mobility of the reinforcing filler in the rubber molecular chain, inhibits the mutual friction between the reinforcing filler and the rubber molecular chain, and further improves the wear resistance of the rubber sole material.

[0034] (4) In the technical solution of the present invention, a porous carbon structure is synthesized on the surface of barium titanate particles. On the one hand, barium titanate particles have strong chemical inertness and are not easily decomposed in acids and alkalis. When filled into the rubber sole material, they can significantly reduce the penetration of acid and alkali media, thereby improving the acid and alkali resistance of the rubber sole material. On the other hand, porous carbon forms a rough surface on the surface of the barium titanate particles, and the molecular chains of the barium titanate particles and the rubber sole matrix form a mechanical interlocking, thereby increasing the contact area between the barium titanate particles and the rubber sole material, so that the barium titanate particles loaded with porous carbon are uniformly dispersed in the rubber sole material. In addition, the synthesized porous carbon contains a large number of pore structures, which can increase the penetration path of acid and alkali media, prevent the acid and alkali media from penetrating into the rubber sole material, and improve the acid and alkali resistance of the rubber sole material.

[0035] (5) In the technical solution of the present invention, a stearic acid layer is formed on the surface of the barium titanate particles loaded with porous carbon, which reduces the surface activity of the barium titanate particles loaded with porous carbon, is conducive to the full dispersion of acid and alkali resistant fillers in the rubber sole material, and improves the acid and alkali resistance of the rubber sole material. In addition, the hydrophobic long-chain alkane structure contained in stearic acid has excellent waterproof performance, can hinder the penetration of acid and alkali media, and improve the acid and alkali resistance of the rubber sole material. DETAILED DESCRIPTION

[0036] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0037] The raw materials used in the examples of the present invention are as follows, and all reagents used are of analytical grade.

[0038] Among them, natural rubber: No. 5 standard rubber, purchased from Hainan Natural Rubber Industry Group Co., Ltd.; styrene butadiene rubber: Qilu Petrochemical 1502 styrene butadiene rubber, purchased from Jinjinle Chemical Co., Ltd.

[0039] Silica: CAS number: 14464-46-1; particle size 200 mesh, purchased from Shanghai Jizhi Biochemical Technology Co., Ltd.

[0040] The activator is stearic acid; the antioxidant is antioxidant 264; the softener is cyclohexane oil; the vulcanizing agent is sulfur; the vulcanization accelerator is 2,2'-dibenzothiazole disulfide; and the crosslinking agent is ethyl orthosilicate.

[0041] The particle size of barium titanate particles is 200 nm.

[0042] Example 1 A highly wear-resistant vulcanized rubber sole, comprising the following raw materials in parts by weight: 90 parts of natural rubber, 50 parts of styrene-butadiene rubber, 20 parts of a reinforcing agent, 15 parts of an acid- and alkali-resistant filler, 5 parts of white carbon black, 4 parts of stearic acid, 3 parts of an antioxidant 264, 4 parts of naphthenic oil, 2 parts of sulfur, and 4 parts of 2,2'-dibenzothiazole disulfide; A method for preparing a highly wear-resistant vulcanized rubber sole comprises the following steps: S1. The natural rubber and styrene-butadiene rubber were mixed and placed in an open mill and masticated at 50°C for 15 min to obtain a masticated rubber; S2. The plasticized rubber, reinforcing agent, acid and alkali resistant filler, white carbon black, stearic acid, antioxidant 264 and naphthenic oil were mixed evenly, placed in an internal mixer, and mixed once at 110 ° C for 5 min, 2,2'-dibenzothiazole disulfide and sulfur were added, and mixed twice at 120 ° C for 4 min to obtain a mixed rubber compound; S3. The mixed rubber material is milled and placed in a sole mold, vulcanized, removed, and trimmed to obtain a rubber sole; the milling temperature is 55°C, the thickness of the sheet is 7 mm, and the cutting width is 70 mm; the vulcanization temperature is 150°C, the pressure is 10 MPa, and the time is 20 minutes.

[0043] The enhancer is specifically prepared by the following steps: A1. Steel slag was placed in a magnetic separator to remove magnetic material. The separated slag was collected, mixed with a slag grinding aid, stirred evenly, and then ground in a planetary ball mill at 600 rpm for 3 hours to obtain a fine slag powder. The slag grinding aid consisted of a mixture of ethylene glycol, triethanolamine, and ethanol in a 1:1:1 mass ratio. The mass ratio of the separated slag to the slag grinding aid was 18:1. A2. Add citric acid monohydrate to deionized water and stir until completely dissolved. Then, add 1 mol / L sodium hydroxide solution to adjust the pH to 7. Then add steel slag powder and stir at 70°C for 10 minutes. Place in a reactor and react at 170°C for 5 hours. Cool to room temperature, remove, wash with deionized water three times, and dry in an 80°C oven for 10 minutes to obtain steel slag powder loaded with carbon dots. The mass ratio of citric acid monohydrate, deionized water, and steel slag powder is 1.6:25:5. A3. Creatine monohydrate and phytic acid were added to deionized water and stirred until completely dissolved. Sorbic acid was then added and stirred at 60°C for 30 minutes. Steel slag powder loaded with carbon dots, tetraethyl orthosilicate, and ethanol were then added and stirred at 70°C for 4 hours. The mixture was then placed in a rotary evaporator at 85°C for rotary evaporation to obtain the product. The product was washed three times with deionized water and dried in an oven at 70°C for 10 minutes to obtain an enhancer. The mass ratio of creatine monohydrate, phytic acid, deionized water, sorbic acid, steel slag powder loaded with carbon dots, tetraethyl orthosilicate, and ethanol was 1:3:45:1:1.6:0.2:25.

[0044] The acid and alkali resistant filler is specifically prepared by the following steps: B1. Barium titanate particles, glucose and tannic acid were added to ethanol, stirred at 70 ° C for 30 minutes, filtered, washed three times with deionized water, dried in a 70 ° C oven for 10 minutes, placed in a tube furnace, potassium hydroxide solution was added, nitrogen was introduced, carbonized at 800 ° C for 4 hours, cooled to room temperature, removed, washed three times with deionized water, and dried in a 70 ° C oven for 10 minutes to obtain barium titanate particles loaded with porous carbon; the mass ratio of barium titanate particles, glucose, tannic acid, ethanol and potassium hydroxide solution is (8-12): (5-6): (0.8-1): (90-100): (4-6); B2. Add stearic acid to ethanol and stir at 80°C until completely dissolved. Add barium titanate particles loaded with porous carbon and 36% hydrochloric acid by mass, stir and react at 50°C for 1 hour, cool to room temperature, filter, wash three times with deionized water, and dry in an oven at 85°C for 10 minutes to obtain an acid- and alkali-resistant filler; the mass ratio of stearic acid, ethanol, barium titanate particles loaded with porous carbon, and hydrochloric acid is 0.8:45:3:1.

[0045] Example 2 A highly wear-resistant vulcanized rubber sole, comprising the following raw materials in parts by weight: 95 parts of natural rubber, 55 parts of styrene-butadiene rubber, 25 parts of a reinforcing agent, 18 parts of an acid- and alkali-resistant filler, 8 parts of white carbon black, 5 parts of stearic acid, 4 parts of an antioxidant 264, 4.5 parts of naphthenic oil, 3 parts of sulfur, and 5 parts of 2,2'-dibenzothiazole disulfide; A method for preparing a highly wear-resistant vulcanized rubber sole comprises the following steps: S1. The natural rubber and styrene-butadiene rubber were mixed and placed in an open mill and masticated at 55°C for 18 minutes to obtain a masticated rubber; S2. The plasticized rubber, reinforcing agent, acid- and alkali-resistant filler, white carbon black, stearic acid, antioxidant 264 and naphthenic oil were mixed uniformly and placed in an internal mixer. The mixture was mixed once at 120°C for 8 min. 2,2'-dibenzothiazole disulfide and sulfur were added and mixed again at 130°C for 5 min to obtain a mixed rubber compound. S3. The mixed rubber material is milled and placed in a sole mold, vulcanized, removed, and trimmed to obtain a rubber sole; the milling temperature is 58°C, the thickness of the sheet is 8 mm, and the cutting width is 80 mm; the vulcanization temperature is 160°C, the pressure is 15 MPa, and the time is 30 minutes.

[0046] The enhancer is specifically prepared by the following steps: A1. Steel slag was placed in a magnetic separator to remove magnetic material. The separated slag was collected, mixed with a slag grinding aid, stirred evenly, and then ground in a planetary ball mill at 600 rpm for 3 hours to obtain a fine slag powder. The slag grinding aid consisted of ethylene glycol, triethanolamine, and ethanol in a mass ratio of 1.5:1:1. The mass ratio of the separated slag to the slag grinding aid was 20:2. A2. Add citric acid monohydrate to deionized water and stir until completely dissolved. Then, add 1 mol / L sodium hydroxide solution to adjust the pH to 7. Then add steel slag powder and stir at 70°C for 10 minutes. Place in a reactor and react at 180°C for 6 hours. Cool to room temperature, remove, wash with deionized water three times, and dry in an 80°C oven for 10 minutes to obtain steel slag powder loaded with carbon dots. The mass ratio of citric acid monohydrate, deionized water, and steel slag powder is 1.8:30:5.5. A3. Creatine monohydrate and phytic acid were added to deionized water and stirred until completely dissolved. Sorbic acid was then added and stirred at 60°C for 30 minutes. Steel slag powder loaded with carbon dots, tetraethyl orthosilicate, and ethanol were then added and stirred at 70°C for 4 hours. The mixture was then rotary evaporated in a rotary evaporator at 85°C to obtain the product. The product was washed three times with deionized water and dried in an oven at 70°C for 10 minutes to obtain the enhancer. The mass ratio of creatine monohydrate, phytic acid, deionized water, sorbic acid, steel slag powder loaded with carbon dots, tetraethyl orthosilicate, and ethanol was 1.5:3.3:50:1.2:1.8:0.3:33.

[0047] The acid and alkali resistant filler is specifically prepared by the following steps: B1. Barium titanate particles, glucose, and tannic acid were added to ethanol and stirred at 70°C for 30 minutes. The mixture was filtered, washed three times with deionized water, and dried in a 70°C oven for 10 minutes. The mixture was placed in a tube furnace, potassium hydroxide solution was added, nitrogen was introduced, and carbonization was performed at 800°C for 4 hours. The mixture was cooled to room temperature, removed, washed three times with deionized water, and dried in a 70°C oven for 10 minutes to obtain barium titanate particles loaded with porous carbon. The mass ratio of barium titanate particles, glucose, tannic acid, ethanol, and potassium hydroxide solution was 10:5.5:0.9:95:5. B2. Add stearic acid to ethanol and stir at 80°C until completely dissolved. Add barium titanate particles loaded with porous carbon and 36% hydrochloric acid by mass, stir and react at 50°C for 1 hour, cool to room temperature, filter, wash three times with deionized water, and dry in an oven at 85°C for 10 minutes to obtain an acid- and alkali-resistant filler; the mass ratio of stearic acid, ethanol, barium titanate particles loaded with porous carbon, and hydrochloric acid is 1:50:3.5:1.5.

[0048] Example 3 A highly wear-resistant vulcanized rubber sole, comprising the following raw materials in parts by weight: 100 parts of natural rubber, 60 parts of styrene-butadiene rubber, 30 parts of a reinforcing agent, 20 parts of an acid- and alkali-resistant filler, 10 parts of white carbon black, 6 parts of stearic acid, 5 parts of an antioxidant 264, 5 parts of naphthenic oil, 5 parts of sulfur, and 6 parts of 2,2'-dibenzothiazole disulfide; A method for preparing a highly wear-resistant vulcanized rubber sole comprises the following steps: S1. The natural rubber and styrene-butadiene rubber were mixed and placed in an open mill and masticated at 60°C for 20 min to obtain a masticated rubber; S2. The plasticized rubber, reinforcing agent, acid and alkali resistant filler, white carbon black, stearic acid, antioxidant 264 and naphthenic oil were mixed uniformly, placed in an internal mixer, and mixed once at 130 ° C for 10 min, 2,2'-dibenzothiazole disulfide and sulfur were added, and mixed again at 140 ° C for 6 min to obtain a mixed rubber material; S3. The mixed rubber material is milled and placed in a sole mold, vulcanized, removed, and trimmed to obtain a rubber sole; the milling temperature is 60°C, the thickness of the sheet is 9 mm, and the cutting width is 90 mm; the vulcanization temperature is 170°C, the pressure is 20 MPa, and the time is 40 minutes.

[0049] The enhancer is specifically prepared by the following steps: A1. Steel slag was placed in a magnetic separator to remove magnetic material. The separated slag was collected, mixed with a slag grinding aid, stirred evenly, and then ground in a planetary ball mill at 600 rpm for 3 hours to obtain a fine slag powder. The slag grinding aid consisted of a mixture of ethylene glycol, triethanolamine, and ethanol in a mass ratio of 2:1:1. The mass ratio of the separated slag to the slag grinding aid was 22:3. A2. Add citric acid monohydrate to deionized water and stir until completely dissolved. Then, add 1 mol / L sodium hydroxide solution to adjust the pH to 7. Then add steel slag powder and stir at 70°C for 10 minutes. Place in a reactor and react at 190°C for 7 hours. Cool to room temperature, remove, wash with deionized water three times, and dry in an 80°C oven for 10 minutes to obtain steel slag powder loaded with carbon dots. The mass ratio of citric acid monohydrate, deionized water, and steel slag powder is 2:35:6. A3. Creatine monohydrate and phytic acid were added to deionized water and stirred until completely dissolved. Sorbic acid was then added and stirred at 60°C for 30 minutes. Steel slag powder loaded with carbon dots, tetraethyl orthosilicate, and ethanol were then added and stirred at 70°C for 4 hours. The mixture was then placed in a rotary evaporator at 85°C for rotary evaporation to obtain the product. The product was washed three times with deionized water and dried in an oven at 70°C for 10 minutes to obtain an enhancer. The mass ratio of creatine monohydrate, phytic acid, deionized water, sorbic acid, steel slag powder loaded with carbon dots, tetraethyl orthosilicate, and ethanol was 2:3.6:55:1.4:2:0.4:35.

[0050] The acid and alkali resistant filler is specifically prepared by the following steps: B1. Barium titanate particles, glucose, and tannic acid were added to ethanol and stirred at 70°C for 30 minutes. The mixture was filtered, washed three times with deionized water, and dried in a 70°C oven for 10 minutes. The mixture was placed in a tube furnace, potassium hydroxide solution was added, nitrogen was introduced, and carbonization was carried out at 800°C for 4 hours. The mixture was cooled to room temperature, removed, washed three times with deionized water, and dried in a 70°C oven for 10 minutes to obtain barium titanate particles loaded with porous carbon. The mass ratio of barium titanate particles, glucose, tannic acid, ethanol, and potassium hydroxide solution was 12:6:1:100:6. B2. Add stearic acid to ethanol and stir at 80°C until completely dissolved. Add porous carbon-loaded barium titanate particles and 36% hydrochloric acid by mass, stir and react at 50°C for 1 hour, cool to room temperature, filter, wash three times with deionized water, and dry in an oven at 85°C for 10 minutes to obtain an acid- and alkali-resistant filler; the mass ratio of stearic acid, ethanol, porous carbon-loaded barium titanate particles, and hydrochloric acid is 1.2:55:4:2.

[0051] Comparative Example 1 A highly wear-resistant vulcanized rubber sole, comprising the following raw materials in parts by weight: 100 parts of natural rubber, 60 parts of styrene-butadiene rubber, 30 parts of a reinforcing agent, 20 parts of an acid- and alkali-resistant filler, 10 parts of white carbon black, 6 parts of stearic acid, 5 parts of an antioxidant 264, 5 parts of naphthenic oil, 5 parts of sulfur, and 6 parts of 2,2'-dibenzothiazole disulfide; A method for preparing a highly wear-resistant vulcanized rubber sole comprises the following steps: S1. The natural rubber and styrene-butadiene rubber were mixed and placed in an open mill and masticated at 60°C for 20 min to obtain a masticated rubber; S2. The plasticized rubber, reinforcing agent, acid and alkali resistant filler, white carbon black, stearic acid, antioxidant 264 and naphthenic oil were mixed uniformly, placed in an internal mixer, and mixed once at 130 ° C for 10 min, 2,2'-dibenzothiazole disulfide and sulfur were added, and mixed again at 140 ° C for 6 min to obtain a mixed rubber material; S3. The mixed rubber material is milled and placed in a sole mold, vulcanized, removed, and trimmed to obtain a rubber sole; the milling temperature is 60°C, the thickness of the sheet is 9 mm, and the cutting width is 90 mm; the vulcanization temperature is 170°C, the pressure is 20 MPa, and the time is 40 minutes.

[0052] The enhancer is specifically prepared by the following steps: A1. The steel slag was placed in a magnetic separator to remove magnetic material. The slag was collected after magnetic separation and placed in a planetary ball mill. The mill was milled at 600 rpm for 3 hours to obtain a fine slag powder. A2. Add citric acid monohydrate to deionized water and stir until completely dissolved. Then, add 1 mol / L sodium hydroxide solution to adjust the pH to 7. Then add steel slag powder and stir at 70°C for 10 minutes. Place in a reactor and react at 190°C for 7 hours. Cool to room temperature, remove, wash with deionized water three times, and dry in an 80°C oven for 10 minutes to obtain steel slag powder loaded with carbon dots. The mass ratio of citric acid monohydrate, deionized water, and steel slag powder is 2:35:6. A3. Creatine monohydrate and phytic acid were added to deionized water and stirred until completely dissolved. Sorbic acid was then added and stirred at 60°C for 30 minutes. Steel slag powder loaded with carbon dots, tetraethyl orthosilicate, and ethanol were then added and stirred at 70°C for 4 hours. The mixture was then placed in a rotary evaporator at 85°C for rotary evaporation to obtain the product. The product was washed three times with deionized water and dried in an oven at 70°C for 10 minutes to obtain an enhancer. The mass ratio of creatine monohydrate, phytic acid, deionized water, sorbic acid, steel slag powder loaded with carbon dots, tetraethyl orthosilicate, and ethanol was 2:3.6:55:1.4:2:0.4:35.

[0053] Comparative Example 2 A highly wear-resistant vulcanized rubber sole, comprising the following raw materials in parts by weight: 100 parts of natural rubber, 60 parts of styrene-butadiene rubber, 30 parts of a reinforcing agent, 20 parts of an acid- and alkali-resistant filler, 10 parts of white carbon black, 6 parts of stearic acid, 5 parts of an antioxidant 264, 5 parts of naphthenic oil, 5 parts of sulfur, and 6 parts of 2,2'-dibenzothiazole disulfide; A method for preparing a highly wear-resistant vulcanized rubber sole comprises the following steps: S1. The natural rubber and styrene-butadiene rubber were mixed and placed in an open mill and masticated at 60°C for 20 min to obtain a masticated rubber; S2. The plasticized rubber, reinforcing agent, acid and alkali resistant filler, white carbon black, stearic acid, antioxidant 264 and naphthenic oil were mixed uniformly, placed in an internal mixer, and mixed once at 130 ° C for 10 min, 2,2'-dibenzothiazole disulfide and sulfur were added, and mixed again at 140 ° C for 6 min to obtain a mixed rubber material; S3. The mixed rubber material is milled and placed in a sole mold, vulcanized, removed, and trimmed to obtain a rubber sole; the milling temperature is 60°C, the thickness of the sheet is 9 mm, and the cutting width is 90 mm; the vulcanization temperature is 170°C, the pressure is 20 MPa, and the time is 40 minutes.

[0054] The enhancer is specifically prepared by the following steps: A1. Steel slag was placed in a magnetic separator to remove magnetic material. The separated slag was collected, mixed with a slag grinding aid, stirred evenly, and then ground in a planetary ball mill at 600 rpm for 3 hours to obtain a fine slag powder. The slag grinding aid consisted of a mixture of ethylene glycol, triethanolamine, and ethanol in a mass ratio of 2:1:1. The mass ratio of the separated slag to the slag grinding aid was 22:3. A2. Creatine monohydrate and phytic acid were added to deionized water and stirred until completely dissolved. Sorbic acid was then added and stirred at 60°C for 30 minutes. Steel slag powder, tetraethyl orthosilicate, and ethanol were then added and stirred at 70°C for 4 hours. The mixture was then placed in a rotary evaporator at 85°C for rotary evaporation to obtain the product. The product was washed three times with deionized water and dried in an oven at 70°C for 10 minutes to obtain an enhancer. The mass ratio of creatine monohydrate, phytic acid, deionized water, sorbic acid, steel slag powder, tetraethyl orthosilicate, and ethanol was 2:3.6:55:1.4:2:0.4:35.

[0055] Comparative Example 3 A highly wear-resistant vulcanized rubber sole, comprising the following raw materials in parts by weight: 100 parts of natural rubber, 60 parts of styrene-butadiene rubber, 30 parts of a reinforcing agent, 20 parts of an acid- and alkali-resistant filler, 10 parts of white carbon black, 6 parts of stearic acid, 5 parts of an antioxidant 264, 5 parts of naphthenic oil, 5 parts of sulfur, and 6 parts of 2,2'-dibenzothiazole disulfide; A method for preparing a highly wear-resistant vulcanized rubber sole comprises the following steps: S1. The natural rubber and styrene-butadiene rubber were mixed and placed in an open mill and masticated at 60°C for 20 min to obtain a masticated rubber; S2. The plasticized rubber, reinforcing agent, acid and alkali resistant filler, white carbon black, stearic acid, antioxidant 264 and naphthenic oil were mixed uniformly, placed in an internal mixer, and mixed once at 130 ° C for 10 min, 2,2'-dibenzothiazole disulfide and sulfur were added, and mixed again at 140 ° C for 6 min to obtain a mixed rubber material; S3. The mixed rubber material is milled and placed in a sole mold, vulcanized, removed, and trimmed to obtain a rubber sole; the milling temperature is 60°C, the thickness of the sheet is 9 mm, and the cutting width is 90 mm; the vulcanization temperature is 170°C, the pressure is 20 MPa, and the time is 40 minutes.

[0056] The enhancer is specifically prepared by the following steps: A1. Steel slag was placed in a magnetic separator to remove magnetic material. The separated slag was collected, mixed with a slag grinding aid, stirred evenly, and then ground in a planetary ball mill at 600 rpm for 3 hours to obtain a fine slag powder. The slag grinding aid consisted of a mixture of ethylene glycol, triethanolamine, and ethanol in a mass ratio of 2:1:1. The mass ratio of the separated slag to the slag grinding aid was 22:3. A2. Add citric acid monohydrate to deionized water and stir until completely dissolved. Then, add 1 mol / L sodium hydroxide solution to adjust the pH to 7. Then add steel slag powder and stir at 70°C for 10 minutes. Place in a reactor and react at 190°C for 7 hours. Cool to room temperature, remove, wash with deionized water three times, and dry in an 80°C oven for 10 minutes to obtain steel slag powder loaded with carbon dots. The mass ratio of citric acid monohydrate, deionized water, and steel slag powder is 2:35:6. A3. Creatine monohydrate and phytic acid were added to deionized water and stirred until completely dissolved. Then, carbon-dot-loaded steel slag powder, tetraethyl orthosilicate, and ethanol were added. After stirring at 70°C for 4 hours, the mixture was placed in a rotary evaporator at 85°C for evaporation to obtain the product. The product was washed three times with deionized water and dried in a 70°C oven for 10 minutes to obtain the enhancer. The mass ratio of creatine monohydrate, phytic acid, deionized water, carbon-dot-loaded steel slag powder, tetraethyl orthosilicate, and ethanol was 3.4:3.6:55:2:0.4:35.

[0057] Comparative Example 4 A highly wear-resistant vulcanized rubber sole, comprising the following raw materials in parts by weight: 100 parts of natural rubber, 60 parts of styrene-butadiene rubber, 30 parts of a reinforcing agent, 20 parts of an acid- and alkali-resistant filler, 10 parts of white carbon black, 6 parts of stearic acid, 5 parts of an antioxidant 264, 5 parts of naphthenic oil, 5 parts of sulfur, and 6 parts of 2,2'-dibenzothiazole disulfide; A method for preparing a highly wear-resistant vulcanized rubber sole comprises the following steps: S1. The natural rubber and styrene-butadiene rubber were mixed and placed in an open mill and masticated at 60°C for 20 min to obtain a masticated rubber; S2. The plasticized rubber, reinforcing agent, acid and alkali resistant filler, white carbon black, stearic acid, antioxidant 264 and naphthenic oil were mixed uniformly, placed in an internal mixer, and mixed once at 130 ° C for 10 min, 2,2'-dibenzothiazole disulfide and sulfur were added, and mixed again at 140 ° C for 6 min to obtain a mixed rubber material; S3. The mixed rubber material is milled and placed in a sole mold, vulcanized, removed, and trimmed to obtain a rubber sole; the milling temperature is 60°C, the thickness of the sheet is 9 mm, and the cutting width is 90 mm; the vulcanization temperature is 170°C, the pressure is 20 MPa, and the time is 40 minutes.

[0058] The enhancer is specifically prepared by the following steps: A1. Steel slag was placed in a magnetic separator to remove magnetic material. The separated slag was collected, mixed with a slag grinding aid, stirred evenly, and then ground in a planetary ball mill at 600 rpm for 3 hours to obtain a fine slag powder. The slag grinding aid consisted of a mixture of ethylene glycol, triethanolamine, and ethanol in a mass ratio of 2:1:1. The mass ratio of the separated slag to the slag grinding aid was 22:3. A2. Add citric acid monohydrate to deionized water and stir until completely dissolved. Then, add 1 mol / L sodium hydroxide solution to adjust the pH to 7. Then add steel slag powder and stir at 70°C for 10 minutes. Place in a reactor and react at 190°C for 7 hours. Cool to room temperature, remove, wash with deionized water three times, and dry in an 80°C oven for 10 minutes to obtain steel slag powder loaded with carbon dots. The mass ratio of citric acid monohydrate, deionized water, and steel slag powder is 2:35:6. A3. Phytic acid was added to deionized water and stirred evenly. Sorbic acid was then added and stirred at 60°C for 30 minutes. Steel slag powder loaded with carbon dots, tetraethyl orthosilicate, and ethanol were then added and stirred at 70°C for 4 hours. The mixture was then placed in a rotary evaporator at 85°C for evaporation to obtain the product. The product was washed three times with deionized water and dried in an oven at 70°C for 10 minutes to obtain the enhancer. The mass ratio of phytic acid, deionized water, sorbic acid, steel slag powder loaded with carbon dots, tetraethyl orthosilicate, and ethanol was 5.6:55:1.4:2:0.4:35.

[0059] Comparative Example 5 A highly wear-resistant vulcanized rubber sole, comprising the following raw materials in parts by weight: 100 parts of natural rubber, 60 parts of styrene-butadiene rubber, 30 parts of a reinforcing agent, 20 parts of an acid- and alkali-resistant filler, 10 parts of white carbon black, 6 parts of stearic acid, 5 parts of an antioxidant 264, 5 parts of naphthenic oil, 5 parts of sulfur, and 6 parts of 2,2'-dibenzothiazole disulfide; A method for preparing a highly wear-resistant vulcanized rubber sole comprises the following steps: S1. The natural rubber and styrene-butadiene rubber were mixed and placed in an open mill and masticated at 60°C for 20 min to obtain a masticated rubber; S2. The plasticized rubber, reinforcing agent, acid and alkali resistant filler, white carbon black, stearic acid, antioxidant 264 and naphthenic oil were mixed uniformly, placed in an internal mixer, and mixed once at 130 ° C for 10 min, 2,2'-dibenzothiazole disulfide and sulfur were added, and mixed again at 140 ° C for 6 min to obtain a mixed rubber material; S3. The mixed rubber material is milled and placed in a sole mold, vulcanized, removed, and trimmed to obtain a rubber sole; the milling temperature is 60°C, the thickness of the sheet is 9 mm, and the cutting width is 90 mm; the vulcanization temperature is 170°C, the pressure is 20 MPa, and the time is 40 minutes.

[0060] The enhancer is specifically prepared by the following steps: A1. Steel slag was placed in a magnetic separator to remove magnetic material. The separated slag was collected, mixed with a slag grinding aid, stirred evenly, and then ground in a planetary ball mill at 600 rpm for 3 hours to obtain a fine slag powder. The slag grinding aid consisted of a mixture of ethylene glycol, triethanolamine, and ethanol in a mass ratio of 2:1:1. The mass ratio of the separated slag to the slag grinding aid was 22:3. A2. Add citric acid monohydrate to deionized water and stir until completely dissolved. Then, add 1 mol / L sodium hydroxide solution to adjust the pH to 7. Then add steel slag powder and stir at 70°C for 10 minutes. Place in a reactor and react at 190°C for 7 hours. Cool to room temperature, remove, wash with deionized water three times, and dry in an 80°C oven for 10 minutes to obtain steel slag powder loaded with carbon dots. The mass ratio of citric acid monohydrate, deionized water, and steel slag powder is 2:35:6. A3. Creatine monohydrate and phytic acid were added to deionized water and stirred until completely dissolved. Sorbic acid was then added and stirred at 60°C for 30 minutes. Steel slag powder loaded with carbon dots and ethanol were then added and stirred at 70°C for 4 hours. The mixture was then placed in a rotary evaporator at 85°C for evaporation to obtain the product. The product was washed three times with deionized water and dried in an oven at 70°C for 10 minutes to obtain the enhancer. The mass ratio of creatine monohydrate, phytic acid, deionized water, sorbic acid, steel slag powder loaded with carbon dots, and ethanol was 2:3.6:55:1.4:2:35.4.

[0061] Comparative Example 6 A highly wear-resistant vulcanized rubber sole, comprising the following raw materials in parts by weight: 100 parts of natural rubber, 60 parts of styrene-butadiene rubber, 30 parts of a reinforcing agent, 20 parts of an acid- and alkali-resistant filler, 10 parts of white carbon black, 6 parts of stearic acid, 5 parts of an antioxidant 264, 5 parts of naphthenic oil, 5 parts of sulfur, and 6 parts of 2,2'-dibenzothiazole disulfide; A method for preparing a highly wear-resistant vulcanized rubber sole comprises the following steps: S1. The natural rubber and styrene-butadiene rubber were mixed and placed in an open mill and masticated at 60°C for 20 min to obtain a masticated rubber; S2. The plasticized rubber, reinforcing agent, acid and alkali resistant filler, white carbon black, stearic acid, antioxidant 264 and naphthenic oil were mixed uniformly, placed in an internal mixer, and mixed once at 130 ° C for 10 min, 2,2'-dibenzothiazole disulfide and sulfur were added, and mixed again at 140 ° C for 6 min to obtain a mixed rubber material; S3. The mixed rubber material is milled and placed in a sole mold, vulcanized, removed, and trimmed to obtain a rubber sole; the milling temperature is 60°C, the thickness of the sheet is 9 mm, and the cutting width is 90 mm; the vulcanization temperature is 170°C, the pressure is 20 MPa, and the time is 40 minutes.

[0062] The enhancer is specifically prepared by the following steps: A1. Steel slag was placed in a magnetic separator to remove magnetic material. The separated slag was collected, mixed with a slag grinding aid, stirred evenly, and then ground in a planetary ball mill at 600 rpm for 3 hours to obtain a fine slag powder. The slag grinding aid consisted of a mixture of ethylene glycol, triethanolamine, and ethanol in a mass ratio of 2:1:1. The mass ratio of the separated slag to the slag grinding aid was 22:3. A2. Add citric acid monohydrate to deionized water and stir until completely dissolved. Then, add 1 mol / L sodium hydroxide solution to adjust the pH to 7. Then add steel slag powder and stir at 70°C for 10 minutes. Place in a reactor and react at 190°C for 7 hours. Cool to room temperature, remove, wash with deionized water three times, and dry in an 80°C oven for 10 minutes to obtain steel slag powder loaded with carbon dots. The mass ratio of citric acid monohydrate, deionized water, and steel slag powder is 2:35:6. A3. Creatine monohydrate and phytic acid were added to deionized water and stirred until completely dissolved. Sorbic acid was then added and stirred at 60°C for 30 minutes. Steel slag powder loaded with carbon dots, tetraethyl orthosilicate, and ethanol were then added and stirred at 70°C for 4 hours. The mixture was then placed in a rotary evaporator at 85°C for rotary evaporation to obtain the product. The product was washed three times with deionized water and dried in an oven at 70°C for 10 minutes to obtain an enhancer. The mass ratio of creatine monohydrate, phytic acid, deionized water, sorbic acid, steel slag powder loaded with carbon dots, tetraethyl orthosilicate, and ethanol was 2:3.6:55:1.4:2:0.4:35.

[0063] The acid and alkali resistant filler is specifically prepared by the following steps: Stearic acid was added to ethanol and stirred at 80°C until completely dissolved. Barium titanate particles and 36% hydrochloric acid by mass were added, and the mixture was stirred and reacted at 50°C for 1 hour. The mixture was cooled to room temperature, filtered, washed with deionized water three times, and dried in an oven at 85°C for 10 minutes to obtain an acid- and alkali-resistant filler. The mass ratio of stearic acid, ethanol, barium titanate particles, and hydrochloric acid was 1.2:55:4:2.

[0064] Comparative Example 7 A highly wear-resistant vulcanized rubber sole, comprising the following raw materials in parts by weight: 100 parts of natural rubber, 60 parts of styrene-butadiene rubber, 30 parts of a reinforcing agent, 20 parts of an acid- and alkali-resistant filler, 10 parts of white carbon black, 6 parts of stearic acid, 5 parts of an antioxidant 264, 5 parts of naphthenic oil, 5 parts of sulfur, and 6 parts of 2,2'-dibenzothiazole disulfide; A method for preparing a highly wear-resistant vulcanized rubber sole comprises the following steps: S1. The natural rubber and styrene-butadiene rubber were mixed and placed in an open mill and masticated at 60°C for 20 min to obtain a masticated rubber; S2. The plasticized rubber, reinforcing agent, acid and alkali resistant filler, white carbon black, stearic acid, antioxidant 264 and naphthenic oil were mixed uniformly, placed in an internal mixer, and mixed once at 130 ° C for 10 min, 2,2'-dibenzothiazole disulfide and sulfur were added, and mixed again at 140 ° C for 6 min to obtain a mixed rubber material; S3. The mixed rubber material is milled and placed in a sole mold, vulcanized, removed, and trimmed to obtain a rubber sole; the milling temperature is 60°C, the thickness of the sheet is 9 mm, and the cutting width is 90 mm; the vulcanization temperature is 170°C, the pressure is 20 MPa, and the time is 40 minutes.

[0065] The enhancer is specifically prepared by the following steps: A1. Steel slag was placed in a magnetic separator to remove magnetic material. The separated slag was collected, mixed with a slag grinding aid, stirred evenly, and then ground in a planetary ball mill at 600 rpm for 3 hours to obtain a fine slag powder. The slag grinding aid consisted of a mixture of ethylene glycol, triethanolamine, and ethanol in a mass ratio of 2:1:1. The mass ratio of the separated slag to the slag grinding aid was 22:3. A2. Add citric acid monohydrate to deionized water and stir until completely dissolved. Then, add 1 mol / L sodium hydroxide solution to adjust the pH to 7. Then add steel slag powder and stir at 70°C for 10 minutes. Place in a reactor and react at 190°C for 7 hours. Cool to room temperature, remove, wash with deionized water three times, and dry in an 80°C oven for 10 minutes to obtain steel slag powder loaded with carbon dots. The mass ratio of citric acid monohydrate, deionized water, and steel slag powder is 2:35:6. A3. Creatine monohydrate and phytic acid were added to deionized water and stirred until completely dissolved. Sorbic acid was then added and stirred at 60°C for 30 minutes. Steel slag powder loaded with carbon dots, tetraethyl orthosilicate, and ethanol were then added and stirred at 70°C for 4 hours. The mixture was then placed in a rotary evaporator at 85°C for rotary evaporation to obtain the product. The product was washed three times with deionized water and dried in an oven at 70°C for 10 minutes to obtain an enhancer. The mass ratio of creatine monohydrate, phytic acid, deionized water, sorbic acid, steel slag powder loaded with carbon dots, tetraethyl orthosilicate, and ethanol was 2:3.6:55:1.4:2:0.4:35.

[0066] The acid and alkali resistant filler is specifically prepared by the following steps: Barium titanate particles, glucose and tannic acid are added to ethanol, stirred at 70°C for 30 minutes, filtered, washed with deionized water three times, dried in an oven at 70°C for 10 minutes, placed in a tube furnace, added with potassium hydroxide solution, introduced with nitrogen, carbonized at 800°C for 4 hours, cooled to room temperature, taken out, washed with deionized water three times, and dried in an oven at 70°C for 10 minutes to obtain an acid- and alkali-resistant filler; the mass ratio of barium titanate particles, glucose, tannic acid, ethanol and potassium hydroxide solution is 12:6:1:100:6.

[0067] The performance of the rubber soles prepared in Examples 1-3 and Comparative Examples 1-7 was tested.

[0068] Mechanical property testing: The tensile strength and elongation of the rubber sole prepared above were tested according to GB / T528-2009 standard, using a Type 1 dumbbell-shaped specimen specified in the standard; the tear strength of the rubber sole prepared above was tested according to GB / T529-2008 standard, using a trouser-shaped specimen specified in test method A in the standard, and the tensile rate was 500 mm / min.

[0069] Wear resistance test: The DIN wear of the rubber sole prepared above was tested according to GB / T9867-2008 standard (mm 3 ), using the rotating specimen specified in test method B in the standard.

[0070] Acid and alkali resistance test: The liquid resistance of the rubber sole prepared above was tested according to ASTM D471 standard. The rubber sole prepared above was placed in a 40% by mass sodium hydroxide solution and a 96% by mass concentrated sulfuric acid, respectively. When cracks or delamination appeared on the rubber sole, the penetration time was recorded to indicate the acid and alkali resistance of the rubber sole.

[0071] As shown in Table 1 below.

[0072] Table 1 Performance test of rubber soles prepared in Examples 1-3 and Comparative Examples 1-7

[0073] It can be seen from the data in Table 1 that the rubber soles prepared in Examples 1-3 have relatively high mechanical properties and wear resistance.

[0074] In Comparative Example 1, the steel slag grinding aid and other qualities were replaced with a reinforcing agent prepared from magnetically separated steel slag and added to the rubber sole. Its mechanical properties and wear resistance decreased, proving that the magnetically separated steel slag and the steel slag grinding aid were mixed and ground to form steel slag micropowder with a particle size of 1-10 microns. The small-sized steel slag micropowder has higher hardness, rigidity and wear resistance, and is conducive to filling into the rubber sole material, which can improve the mechanical properties and wear resistance of the rubber sole material.

[0075] In comparative example 2, the steel slag micropowder loaded with carbon dots is replaced with a reinforcing agent prepared from steel slag micropowder and added to the rubber sole. Its mechanical properties and wear resistance are reduced, proving that the formation of nano-carbon dots in the pores of the steel slag micropowder can seal the pore structure of the steel slag micropowder, prevent the pore structure of the steel slag micropowder from inducing crack expansion in the rubber sole material, and cause the mechanical properties of the rubber sole material to decline. In addition, the nano-carbon dots form a rough surface on the surface of the steel slag micropowder, enhancing the contact area between the steel slag micropowder and the rubber sole substrate, so that the steel slag micropowder is better dispersed in the rubber sole material, thereby improving the mechanical properties and wear resistance of the rubber sole material.

[0076] In Comparative Example 3, a reinforcing agent prepared by replacing the mass of sorbic acid with creatine monohydrate was added to the rubber sole, and its mechanical properties and wear resistance decreased, proving that sorbic acid and carbon-dot-loaded steel slag micropowder were incorporated into the cross-linking reaction structure to increase the cross-linking density and enhance the mechanical properties. The double bonds contained in sorbic acid can participate in the vulcanization reaction of the rubber, thereby increasing the bonding strength between the reinforcing filler and the rubber sole material. In addition, sorbic acid participates in the vulcanization reaction of the rubber, thereby forming a complex filler network in the rubber sole, fixing the reinforcing filler in the rubber molecular chain, limiting the mobility of the reinforcing filler in the rubber molecular chain, inhibiting the mutual friction between the reinforcing filler and the rubber molecular chain, and further improving the wear resistance of the rubber sole material.

[0077] In comparative example 4, the mass of creatine monohydrate is replaced by phytic acid, and in comparative example 5, the mass of tetraethyl orthosilicate is replaced by ethanol to prepare a reinforcing agent, which is added to the rubber sole. Its mechanical properties and wear resistance decrease, proving that creatine monohydrate, phytic acid and sorbic acid form a cross-linked network structure, which can absorb the energy generated by stress, thereby improving the mechanical properties of the rubber sole material. In addition, tetraethyl orthosilicate is used as a cross-linking agent, and the silanols produced by hydrolysis can be chemically bonded with the oxygen-containing functional groups in the cross-linked network structure and the hydroxyl groups on the surface of the steel slag micropowder loaded with carbon dots, so that the steel slag micropowder loaded with carbon dots is evenly embedded in the cross-linked network structure, thereby improving the dispersibility of the steel slag micropowder loaded with carbon dots in the rubber sole material.

[0078] In Comparative Example 6, the barium titanate particles loaded with porous carbon are replaced with acid- and alkali-resistant fillers prepared from barium titanate particles and added to the rubber sole. The mechanical properties, wear resistance and acid- and alkali resistance of the fillers decrease, proving that the porous carbon forms a rough surface on the surface of the barium titanate particles, and the barium titanate particles form a mechanical interlock with the molecular chains of the rubber sole matrix, thereby increasing the contact area between the barium titanate particles and the rubber sole material, so that the barium titanate particles loaded with porous carbon are uniformly dispersed in the rubber sole material, and the synthesized porous carbon contains a large number of pore structures, which can increase the penetration path of the acid- and alkali media, prevent the acid- and alkali media from penetrating into the rubber sole material, and improve the acid- and alkali resistance of the rubber sole material.

[0079] In Comparative Example 7, the acid- and alkali-resistant filler prepared without adding stearic acid was added to the rubber sole, and its mechanical properties, wear resistance and acid- and alkali resistance decreased, proving that a stearic acid layer was formed on the surface of the barium titanate particles loaded with porous carbon, which reduced the surface activity of the barium titanate particles loaded with porous carbon, and was conducive to the full dispersion of the acid- and alkali-resistant filler in the rubber sole material, thereby improving the acid- and alkali resistance of the rubber sole material. The hydrophobic long-chain alkane structure contained in stearic acid has excellent waterproof properties, can hinder the penetration of acid and alkali media, and improve the acid- and alkali resistance of the rubber sole material.

[0080] Throughout the specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0081] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in similar ways. As long as they do not deviate from the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. A highly wear-resistant vulcanized rubber sole, characterized in that: The invention comprises the following raw materials in parts by weight: 90-100 parts of natural rubber, 50-60 parts of styrene-butadiene rubber, 20-30 parts of reinforcing agent, 15-20 parts of acid and alkali resistant filler, 5-10 parts of white carbon black, 4-6 parts of activator, 3-5 parts of antioxidant, 4-5 parts of softener, 2-5 parts of vulcanizing agent and 4-6 parts of vulcanization accelerator; The enhancer is obtained by mixing creatine, phytic acid and sorbic acid, and then reacting with modified steel slag powder and a cross-linking agent; The modified steel slag powder is obtained by mixing and grinding the magnetically separated steel slag and steel slag grinding aid, and then reacting with citric acid monohydrate; The acid and alkali resistant filler is obtained by synthesizing porous carbon on the surface of barium titanate particles and then treating it with stearic acid.

2. A highly wear-resistant vulcanized rubber sole according to claim 1, characterized in that: The reinforcing agent is specifically prepared by the following steps: A1. Place the steel slag in a magnetic separator to remove magnetic material. Collect the steel slag after magnetic separation, mix it with a steel slag grinding aid, stir it evenly, and grind it to obtain steel slag powder. A2. Add citric acid monohydrate to deionized water and stir until completely dissolved. Add sodium hydroxide solution to adjust the pH. Then add steel slag powder and stir evenly. React at 170-190°C for 5-7 hours. Cool to room temperature, remove, wash, and dry to obtain steel slag powder loaded with carbon dots. A3. Add creatine monohydrate and phytic acid to deionized water and stir until completely dissolved. Add sorbic acid and stir evenly. Add carbon dot-loaded steel slag powder, a crosslinker, and ethanol. After stirring, the reaction is complete and subjected to rotary evaporation to obtain the product. The product is washed and dried to obtain the enhancer.

3. A highly wear-resistant vulcanized rubber sole according to claim 2, characterized in that: In step A1, the mass ratio of the magnetically separated steel slag to the steel slag grinding aid is (18-22):(1-3).

4. A highly wear-resistant vulcanized rubber sole according to claim 2, characterized in that: In step A1, the steel slag grinding aid is prepared by mixing ethylene glycol, triethanolamine, and ethanol in a mass ratio of (1-2):1:

1.

5. A highly wear-resistant vulcanized rubber sole according to claim 2, characterized in that: In step A2, the mass ratio of citric acid monohydrate, deionized water and steel slag powder is (1.6-2):(25-35):(5-6).

6. A highly wear-resistant vulcanized rubber sole according to claim 2, characterized in that: In step A3, the mass ratio of creatine monohydrate, phytic acid, deionized water, sorbic acid, carbon dot-loaded steel slag powder, crosslinking agent and ethanol is (1-2):(3-3.6):(45-55):(1-1.4):(1.6-2):(0.2-0.4):(28-35).

7. The highly wear-resistant vulcanized rubber sole according to claim 1, characterized in that: The acid and alkali resistant filler is specifically prepared by the following steps: B1. Barium titanate particles, glucose, and tannic acid were added to ethanol, stirred, filtered, washed, dried, placed in a tube furnace, potassium hydroxide solution was added, nitrogen was introduced, and after carbonization, cooled to room temperature, removed, washed, and dried to obtain barium titanate particles loaded with porous carbon; B2. Add stearic acid to ethanol and stir until dissolved. Add barium titanate particles loaded with porous carbon and hydrochloric acid. After stirring for reaction, cool to room temperature, filter, wash, and dry to obtain an acid- and alkali-resistant filler.

8. The highly wear-resistant vulcanized rubber sole according to claim 7, characterized in that: In step B1, the mass ratio of the barium titanate particles, glucose, tannic acid, ethanol and potassium hydroxide solution is (8-12):(5-6):(0.8-1):(90-100):(4-6).

9. The highly wear-resistant vulcanized rubber sole according to claim 7, characterized in that: In step B2, the mass ratio of the stearic acid, ethanol, porous carbon-loaded barium titanate particles and hydrochloric acid is (0.8-1.2):(45-55):(3-4):(1-2).

10. A method for preparing the highly wear-resistant vulcanized rubber sole according to any one of claims 1 to 9, characterized in that: The method comprises the following preparation steps: S1. The natural rubber and styrene-butadiene rubber are mixed and masticated to obtain a masticated rubber; S2. The plasticized rubber, reinforcing agent, acid and alkali resistant filler, white carbon black, activator, antioxidant and softener are mixed evenly, after a mixing, an accelerator and a vulcanizing agent are added, and a secondary mixing is performed to obtain a mixed rubber compound; S3. After the mixed rubber material is melted and cut into pieces, it is placed in a sole mold, then vulcanized, taken out, and trimmed to obtain a rubber sole.

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