Wear-resistant sole rubber as well as preparation method and application thereof

Abstract

The invention relates to the technical field of rubber for shoes, in particular to wear-resistant sole rubber and a preparation method and application thereof.The wear-resistant sole rubber comprises raw rubber and additives, the raw rubber is composed of rare earth butadiene rubber and block type high styrene vinyl solution polymerized styrene-butadiene rubber, the additives comprise a reinforcing filler, a plasticizer, a surface modifier of the reinforcing filler, a peroxide bridging agent, an accelerant of the peroxide bridging agent, an anti-aging agent and an iron ion absorbent, the raw rubber and part of the additives are mixed and then internally mixed to obtain a mixture, then the mixture is subjected to thin-passing after being discharged and then processed into a sample sheet, and the sample sheet is subjected to hot pressing to obtain the high-strength rubber. And spreading the obtained first intermediate, adding a peroxide bridging agent, carrying out triangular bag making and sheet discharging, and vulcanizing the obtained second intermediate in a mold to obtain the wear-resistant sole rubber. The wear resistance of rubber soles with special purpose requirements such as sports shoes and outdoor shoes prepared by the invention is greatly improved, and higher wear resistance requirements can be met.

Description

Technical Field

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

[0002] As people's living standards continue to improve, the demand for comfort and durability in shoes that meet special needs, such as sports shoes and outdoor shoes, is increasing. Therefore, the research and application of wear-resistant sole materials in the footwear field has become increasingly important. Wear-resistant sole materials refer to materials used to make soles that come into direct contact with the ground. Their main characteristic is excellent wear resistance, which can maintain good wear resistance during long-term use, thereby extending the service life of the sole.

[0003] The Chinese patent document with publication number CN117229576A discloses a wear-resistant and anti-skid outsole rubber for shoes and its preparation process, including the following components by mass: 5 parts of natural rubber, 0-20 parts of solution-polymerized styrene-butadiene rubber, 20-45 parts of brominated butyl rubber, 0-20 parts of carboxylated nitrile rubber, 35-60 parts of cis-1,4-butadiene rubber, 42-48 parts of white carbon black, 6 parts of zinc cobaltate, 3-6 parts of coupling agent, and 20.7 parts of processing aid. The invention can improve the anti-skid performance of the outsole rubber of the shoes produced by mixing non-polar natural rubber, cis-1,4-butadiene rubber with polar rubber brominated butyl rubber and carboxylated nitrile rubber. The surface modification process of the outsole rubber of the shoes produced by the present invention and the setting of the components used can promote the improvement of its wear-resistant and anti-skid performance, wherein the DIN wear is all between 100 and 150 mm. 3 Although this technology has improved DIN abrasion and Akron abrasion, the wear resistance still cannot meet the higher wear resistance requirements of sports shoes and outdoor shoes.

[0004] Patent application publication number CN117362769A discloses a matte, high-performance black sole rubber. It comprises 65 parts of No. 2 standard rubber, 35 parts of butadiene rubber, 2.0 parts of sulfur, 2.2 parts of an accelerator, 8.5 parts of a vulcanization activator, 13 parts of a rubber softener, 3.5 parts of an antioxidant, 0.8 parts of a rubber internal release agent, 60 parts of medium- and ultra-wear-resistant carbon black, 0.20 parts of a brightener, 0.4 parts of a leveling agent, and 4 parts of solid coumarone. The vulcanization temperature for the sole is controlled by an intelligent thermal oil boiler, with the control terminal setting settings for "start-up temperature 175°C, exit control temperature 180°C, and shutdown temperature 185°C." The vulcanization time for the sole is 3.5 to 4.5 minutes, equivalent to mold compression vulcanization. This invention improves the formula and preparation method of sole rubber. By screening the vulcanization process of the sole, a sole rubber with high tensile properties, good wear resistance and good wear resistance is obtained. The sole Akron wear volume is 0.22-0.25cm 3 / 1.61km, extending the service life by more than 6 months compared to the original product. The resulting rubber shoes also have a good gloss reduction effect, meeting the user's detailed requirements. Although this process has achieved good tensile properties, Akron's abrasion resistance still needs to be improved, and its wear resistance still cannot meet the higher wear resistance requirements of sports shoes and outdoor shoes.

[0005] Therefore, it is necessary to research a sole rubber with high wear resistance and other good properties to meet the needs of existing customers. Summary of the Invention

[0006] The present invention provides a wear-resistant sole rubber and a preparation method and application thereof, which overcomes the shortcomings of the above-mentioned prior art and can effectively solve the problem that the existing sole rubber has low wear resistance and cannot meet the higher wear resistance requirements of sports shoes, outdoor shoes, etc.

[0007] One of the technical solutions of the present invention is achieved through the following measures: a wear-resistant sole rubber, the raw materials of which include raw rubber and additives, wherein, by weight, every 100 parts of raw rubber are composed of 65 to 75 parts of rare earth cis-1,4-butadiene rubber and 25 to 35 parts of block-type high-styrene medium-vinyl solution-polymerized styrene-butadiene rubber, and the additives added to every 100 parts of raw rubber include 38 to 42 parts of reinforcing fillers, 3 to 7 parts of plasticizers, 1 to 3 parts of surface modifiers for reinforcing fillers, 0.1 to 0.3 parts of peroxide bridging agents, 0.2 to 0.5 parts of accelerators for peroxide bridging agents, 2.0 to 2.5 parts of antioxidants and 0.1 to 0.3 parts of iron ion absorbers.

[0008] The following is a further optimization and / or improvement of one of the above-mentioned technical solutions: The above is that the Mooney viscosity of rare earth cis-1,1-butadiene rubber is 41 to 49, the cis-butadiene content is ≥98%, the Mooney viscosity of high styrene vinyl solution butadiene rubber is 40 to 50, the styrene content of block-block high styrene vinyl solution butadiene rubber is 46% to 50%, and the vinyl content is 26% to 30%.

[0009] The reinforcing filler is at least one of carbon black and white carbon black.

[0010] The plasticizer is a carboxylic acid ester compound.

[0011] The surface modifier of the reinforcing filler is an organic silane coupling agent.

[0012] The above-mentioned peroxide bridging agent includes cycloalkane peroxide and benzene organic peroxide.

[0013] The accelerator of the above-mentioned peroxide bridging agent is propane acrylate.

[0014] The above antioxidant is a mixed multifunctional antioxidant.

[0015] The carboxylate compound is at least one of isopropyl cyclohexanecarboxylate, diisononyl 1,2-cyclohexanedicarboxylate and isononyl 1-cyclohexanecarboxylate.

[0016] The organic silane coupling agent is at least one of vinyltriethoxysilane, vinyltrimethoxysilane and vinyltri(β-methoxyethoxy)silane.

[0017] The propane acrylate is at least one of trimethylolpropane trimethacrylate, triethylolpropane triethylacrylate, trimethylolpropane triethylacrylate and triethylolpropane trimethacrylate.

[0018] The above-mentioned mixed multifunctional antioxidant is composed of a thioester peroxidation inhibitor, a light stabilizer and a hindered phenol antioxidant, wherein the light stabilizer is o-hydroxyphenyl triazine, and the hindered phenol antioxidant is one of BHT (i.e., 2,6-di-tert-butyl-p-cresol), antioxidant 1076, and antioxidant 1010.

[0019] In the above peroxide bridging agent, the mass ratio of cycloalkane peroxide to benzene organic peroxide is 1:2.

[0020] In the mixed multifunctional antioxidant, the mass ratio of the thioester peroxidation inhibitor, the light stabilizer and the hindered phenol antioxidant is 1 to 1.5:0.5:0.5.

[0021] The above raw materials include raw rubber and additives, among which, by weight, every 100 parts of raw rubber are composed of 70 parts of rare earth cis-1,4-butadiene rubber and 30 parts of block-type high styrene medium vinyl solution styrene butadiene rubber; and the additives added to every 100 parts of raw rubber include 40 parts of reinforcing filler, 5 parts of plasticizer, 2 parts of organic silane coupling agent, 0.2 parts of peroxide bridging agent, 0.35 parts of peroxide bridging agent promoter, 2.2 parts of antioxidant and 0.2 parts of iron ion absorbent.

[0022] The above was prepared according to the following method: S1, mixing the required amount of raw rubber, reinforcing filler, plasticizer, surface modifier of the reinforcing filler, accelerator of peroxide bridging agent, antioxidant and iron ion absorbent, and then kneading to obtain a mixture; S2, the mixed material is then discharged and thin-passed 3 to 5 times, and then cooled and processed into a sample to obtain a first intermediate; S3, after spreading the first intermediate, adding a required amount of peroxide bridging agent, forming a triangle package, and producing a sheet to obtain a second intermediate; S4, vulcanizing the second intermediate in a mold to obtain a wear-resistant sole rubber.

[0023] In the above step S1, the banburying temperature is 90° C. to 120° C., and the banburying time is 3 min to 5 min.

[0024] In the above step S3, the triangular packages are made in an open mill, the temperature of the open mill is 40° C. to 60° C., and the time for making the triangular packages is 8 minutes to 10 minutes.

[0025] In the above step S3, before the first intermediate is spread, the first intermediate is placed at room temperature for 6 to 12 hours.

[0026] In the above step S4, the vulcanization temperature is 150° C. to 160° C., and the vulcanization time is 4 min to 5 min.

[0027] In the above step S4, before the second intermediate is vulcanized in the mold, the second intermediate is placed at room temperature for 10 to 12 hours.

[0028] The second technical solution of the present invention is achieved by the following measures: a preparation method of wear-resistant sole rubber is carried out according to the following method: S1, mixing the required amount of raw rubber, reinforcing filler, plasticizer, surface modifier of the reinforcing filler, accelerator of peroxide bridging agent, antioxidant and iron ion absorbent, and then kneading to obtain a mixture; S2, the mixed material is then discharged and thin-passed 3 to 5 times, and then cooled and processed into a sample to obtain a first intermediate; S3, after spreading the first intermediate, adding a required amount of peroxide bridging agent, forming a triangle package, and producing a sheet to obtain a second intermediate; S4, vulcanizing the second intermediate in a mold to obtain a wear-resistant sole rubber.

[0029] The following is a further optimization and / or improvement of the second technical solution of the above invention: In the above step S1, the banburying temperature is 90° C. to 120° C., and the banburying time is 3 min to 5 min.

[0030] In the above step S3, the triangular packages are made in an open mill, the temperature of the open mill is 40° C. to 60° C., and the time for making the triangular packages is 8 minutes to 10 minutes.

[0031] In the above step S3, before the first intermediate is spread, the first intermediate is placed at room temperature for 6 to 12 hours.

[0032] In the above step S4, the vulcanization temperature is 150° C. to 160° C., and the vulcanization time is 4 min to 5 min.

[0033] In the above step S4, before the second intermediate is vulcanized in the mold, the second intermediate is placed at room temperature for 10 to 12 hours.

[0034] The third technical solution of the present invention is achieved through the following measures: application of a wear-resistant sole rubber in making the soles of sports shoes and outdoor shoes.

[0035] The wear resistance of the rubber soles for special purposes such as sports shoes and outdoor shoes prepared by the present invention is greatly improved, and higher wear resistance requirements can be met. DETAILED DESCRIPTION

[0036] The present invention is not limited to the following embodiments, and specific implementation methods can be determined based on the technical solutions of the present invention and actual conditions. Unless otherwise specified, the various chemical reagents and chemicals mentioned in the present invention are all chemical reagents and chemicals commonly known in the prior art. Normal temperature and room temperature in the present invention generally refer to temperatures between 15°C and 25°C, and are generally defined as 25°C.

[0037] The present invention will be further described below in conjunction with the embodiments: Example 1: The wear-resistant sole rubber, the raw materials include raw rubber and additives, wherein, by weight, every 100 parts of raw rubber are composed of 65 to 75 parts (for example, 68 parts, 70 parts or 72 parts) of rare earth cis-1,4-butadiene rubber and 25 to 35 parts (for example, 28 parts, 30 parts or 32 parts) of block-type high styrene medium vinyl solution styrene butadiene rubber, and every 100 parts of raw rubber are added with additives including 38 to 42 parts (for example, 39 parts, 40 parts or 41 parts) of reinforcing filler, 3 to 7 parts (for example, 4 parts, 5 parts or 6 parts) of plasticizer, 1 to 3 The present invention also comprises the following components: 1.5 parts (for example, 1.5 parts, 2 parts or 2.5 parts) of a surface modifier for a reinforcing filler, 0.1 to 0.3 parts (for example, 0.15 parts, 0.20 parts or 0.25 parts) of a peroxide bridging agent, 0.2 to 0.5 parts (for example, 0.3 parts, 0.4 parts or 0.45 parts) of an accelerator for the peroxide bridging agent, 2.0 to 2.5 parts (for example, 2.1 parts, 2.2 parts, 2.3 parts or 2.4 parts) of an antioxidant and 0.1 to 0.3 parts (for example, 0.15 parts, 0.20 parts or 0.25 parts) of an iron ion absorbent.

[0038] In the present invention, the Mooney viscosity of the rare earth butadiene rubber is 41 to 49 (i.e., 45±4), and the cis-butadiene content is ≥98%. For example, the rare earth butadiene rubber can be NdBR9101N produced by Dushanzi Petrochemical Company; the styrene content of the block-type high styrene medium vinyl solution styrene butadiene rubber is 46% to 50% (i.e., 48±2%), the vinyl content is 26% to 30% (i.e., 28±2%), and the Mooney viscosity is 40 to 50 (i.e., 45±5). For example, the block-type high styrene medium vinyl solution styrene butadiene rubber is SSBR4630 produced by Xinjiang Dushanzi Petrochemical Company.

[0039] The rare earth cis-1,4-butadiene rubber in the raw materials used in the wear-resistant sole rubber of the present invention plays a major role in the wear resistance of the sole. The block-type high-styrene vinyl solution-polymerized styrene-butadiene rubber not only better controls the shape and size of the sole, making it less prone to deformation, but also improves the wear resistance of the sole. Under the synergistic effect of other additives, the wear resistance of the rubber sole suitable for special use requirements such as sports shoes and outdoor shoes prepared using the preparation method provided by the present invention is greatly improved, which can meet higher wear resistance requirements.

[0040] In the present invention, rare earth cis-1,4-butadiene rubber (RBR) has the best wear resistance and is used as the main component of raw rubber to provide wear resistance for the sole rubber. However, using only rare earth cis-1,4-butadiene rubber as the raw rubber component of the sole rubber can easily lead to reduced processing performance of the sole rubber, uneven thickness, and rough surface of the produced sole rubber sheet.

[0041] Conventional solution-polymerized styrene-butadiene rubber (SBR) offers excellent wear resistance, along with excellent roller operability and calenderability, making it ideal for improving the processing properties of rubber for shoe soles. Furthermore, SBR can adjust the hardness of the sole, increasing its flexural resistance and making it less susceptible to cracking and breakage. It also ensures dimensional stability, preventing deformation and dimensional deviation.

[0042] In the present invention, vinyl solution-polymerized styrene butadiene rubber (SBR) in block-type high styrene is used as an auxiliary raw rubber component. The SBR of this partial block has both retained a certain degree of block characteristics in molecular structure and is not completely equivalent to typical styrene butadiene block copolymer SBS, that is, conventional SBR. There is an ordered arrangement of some polystyrene segments and polybutadiene segments in its molecule, but this arrangement is not a completely regular block structure. The structure of this partial block makes the rubber material have certain particularity in performance, for example, significantly improves in terms of mechanical properties, elasticity and resilience. The vinyl solution-polymerized styrene butadiene rubber in the block-type high styrene has both certain strength and hardness, and can maintain good flexibility and elasticity, and can better adapt to different use environments and requirements. In addition, the vinyl solution-polymerized styrene butadiene rubber in the block-type high styrene has excellent wear resistance, and in applications such as soles and tires that need to withstand friction and wear, the service life of the product can be effectively extended. In addition, some block-type high-styrene medium-vinyl solution-polymerized styrene-butadiene rubber may have similar moldability to a certain extent and can adapt to different production process requirements, such as injection molding, extrusion, etc.; it also has a certain wear resistance, which enables it to resist daily wear in applications such as soles and extend the service life of the product.

[0043] The invention adopts rare earth cis-1,4-butadiene rubber and segmented high-styrene medium-vinyl solution-polymerized styrene-butadiene rubber as raw rubber components of the sole rubber, utilizes the excellent processing performance and molding performance of the segmented high-styrene medium-vinyl solution-polymerized styrene-butadiene rubber, and compensates for the disadvantage of poor processing and molding of the rare earth cis-1,4-butadiene rubber, thereby obtaining the sole rubber with excellent wear resistance, good processing performance and good moldability, capable of maintaining a good sole appearance during long-term use, and extending the service life of the sole.

[0044] Furthermore, from a chemical perspective, the backbone of rare earth cis-1,4-polybutadiene is a cis-1,4-polybutadiene structure, while the backbone of block-type high-styrene medium-vinyl solution polystyrene butadiene rubber is primarily composed of butadiene and styrene units. The similarities between the two main chains allow them to be mixed to a certain extent, thus improving the overall performance of the resulting shoe sole rubber.

[0045] In addition, the block-type high styrene medium vinyl solution polymerized styrene butadiene rubber is easy to prepare and has a low production cost. The present invention uses rare earth polybutadiene rubber and block-type high styrene medium vinyl solution polymerized styrene butadiene rubber as the raw rubber components of the sole rubber, which is conducive to reducing the production cost of the sole rubber.

[0046] Example 2: As an optimization of the above example, the Mooney viscosity of the rare earth cis-1,1-butadiene rubber is 41 to 49, the cis-butadiene content is ≥98%, the Mooney viscosity of the block-type high styrene vinyl solution-polymerized styrene-butadiene rubber is 40 to 50, the styrene content of the block-type high styrene vinyl solution-polymerized styrene-butadiene rubber is 46% to 50%, and the vinyl content is 26% to 30%.

[0047] Example 3: As an optimization of the above example, the reinforcing filler is at least one of carbon black and white carbon black.

[0048] Example 4: As an optimization of the above example, the plasticizer is a carboxylic acid ester compound.

[0049] Example 5: As an optimization of the above example, the surface modifier of the reinforcing filler is an organic silane coupling agent.

[0050] Example 6: As an optimization of the above example, the peroxide bridging agent includes cycloalkane peroxides and benzene organic peroxides.

[0051] Example 7: As an optimization of the above example, the accelerator of the peroxide bridging agent is propane acrylate.

[0052] Example 8: As an optimization of the above example, the antioxidant is a mixed multifunctional antioxidant.

[0053] Example 9: As an optimization of the above example, the carboxylate compound is at least one of isopropyl cyclohexanecarboxylate, diisononyl 1,2-cyclohexanedicarboxylate and isononyl 1-cyclohexanecarboxylate.

[0054] Example 10: As an optimization of the above example, the organic silane coupling agent is at least one of vinyltriethoxysilane, vinyltrimethoxysilane and vinyltri(β-methoxyethoxy)silane.

[0055] Example 11: As an optimization of the above example, the propane acrylate is at least one of trimethylolpropane trimethacrylate, triethylolpropane triethyl acrylate, trimethylolpropane triethyl acrylate and triethylolpropane trimethacrylate.

[0056] Example 12: As an optimization of the above example, a mixed multifunctional antioxidant is composed of a thioester peroxidation inhibitor, a light stabilizer and a hindered phenol antioxidant, wherein the light stabilizer is o-hydroxyphenyltriazine, and the hindered phenol antioxidant is one of BHT, antioxidant 1076, and antioxidant 1010.

[0057] Example 13: As an optimization of the above example, in the peroxide bridging agent, the mass ratio of cycloalkane peroxide to benzene organic peroxide is 1:2.

[0058] Among the present invention, synergy between two kinds of peroxides makes the performances such as intensity, wear resistance, heat resistance of rubber for soles improve greatly.Particularly, under heat or radiation, two kinds of peroxides all can decompose and produce free radicals, and these free radicals can cause the cross-linking reaction between the rubber molecule chain.Under the joint action of the two, can accelerate the carrying out of cross-linking reaction, make sole reach ideal vulcanization state faster.Both synergy can also optimize crosslinking density, make sole both have enough intensity but also keep good elasticity.But the addition of cycloalkane peroxide and benzene organic peroxide needs strict control, too much or too little all can affect vulcanization effect.

[0059] Example 14: As an optimization of the above example, in the mixed multifunctional antioxidant, the mass ratio of the thioester peroxidation inhibitor, the light stabilizer and the hindered phenol antioxidant is 1 to 1.5:0.5:0.5 (for example, 1.1:0.5:0.5, 1.2:0.5:0.5, 1.3:0.5:0.5, 1.4:0.5:0.5 or 1.45:0.5:0.5).

[0060] Example 15: As an optimization of the above example, the raw materials include raw rubber and additives, wherein, by weight, every 100 parts of raw rubber are composed of 70 parts of rare earth cis-1,4-butadiene rubber and 30 parts of segmented high styrene medium vinyl solution styrene butadiene rubber, and the additives added to every 100 parts of raw rubber include 40 parts of reinforcing filler, 5 parts of plasticizer, 2 parts of organosilane coupling agent, 0.2 parts of peroxide bridging agent, 0.35 parts of peroxide bridging agent promoter, 2.2 parts of antioxidant and 0.2 parts of iron ion absorbent.

[0061] In the present invention, the peroxide bridging agent decomposes at a certain temperature to produce free radicals. These free radicals can attack the main chain of the polymer material, triggering a crosslinking reaction. Through the crosslinking reaction, the polymer material is transformed from a linear structure to a three-dimensional network structure, thereby significantly improving the physical and chemical properties of the material. For example, after being treated with the peroxide bridging agent, the strength, wear resistance, heat resistance and other properties of the rubber material are greatly improved. The accelerator of the peroxide bridging agent can significantly accelerate the decomposition rate of the peroxide bridging agent, thereby accelerating the bridging reaction. This allows effective crosslinking to be achieved at a lower temperature or in a shorter time, thereby improving production efficiency.

[0062] However, the amount of peroxide bridging agent added will affect the compatibility and reactivity of reinforcing fillers, plasticizers, antioxidants, and rubber substrates, as follows: Reinforcing fillers such as carbon black and white carbon black can affect the crosslinking density and physical and mechanical properties of vulcanized rubber; the amount of peroxide bridging agent added will affect the dispersibility of the reinforcing filler in the rubber and the bonding strength with the rubber substrate.

[0063] Plasticizers such as oils and resins can improve the processing properties of rubber and the flexibility of the vulcanized rubber; however, excessive amounts of plasticizers may reduce the crosslink density and physical and mechanical properties of the vulcanized rubber. Therefore, when adding peroxide bridging agents, it is necessary to consider the impact of the type and amount of plasticizer on the vulcanization effect.

[0064] Antioxidants can slow the aging process of rubber and improve the durability of vulcanized rubber. However, some antioxidants may react with peroxide bridging agents, affecting the vulcanization process. Therefore, when selecting an antioxidant, its compatibility and reactivity with peroxide bridging agents should be considered.

[0065] The compatibility and reactivity of peroxide bridging agents with the rubber substrate directly impact vulcanization results. Different rubber types have varying sensitivities to peroxide bridging agents. Therefore, it's important to select the appropriate peroxide bridging agent type and dosage based on the rubber type.

[0066] During use, the soles of shoes may be exposed to various environmental factors, such as air, moisture, and pollutants. Among them, iron ions are a common pollutant, which can catalyze oxidation reactions and cause discoloration of the sole material.

[0067] In the present invention, an iron ion absorbent is used to combine with iron ions to form a stable complex, thereby preventing the occurrence of iron ion-catalyzed oxidation reactions and maintaining the color stability of the sole. However, the addition of an iron ion absorbent may have a certain impact on the physical properties of the rubber. For example, some iron ion absorbents may increase the hardness of the rubber or reduce its elasticity.

[0068] Example 16: As an optimization of the above example, the following method was used to prepare: S1, mixing the required amount of raw rubber, reinforcing filler, plasticizer, surface modifier of the reinforcing filler, accelerator of peroxide bridging agent, antioxidant and iron ion absorbent, and then kneading to obtain a mixture; S2, the mixed material is then discharged and thin-passed 3 to 5 times, and then cooled and processed into a sample to obtain a first intermediate; S3, after spreading the first intermediate, adding a required amount of peroxide bridging agent, forming a triangle package, and producing a sheet to obtain a second intermediate; S4, vulcanizing the second intermediate in a mold to obtain a wear-resistant sole rubber.

[0069] Example 17: As an optimization of the above example, in step S1, the banburying temperature is 90°C to 120°C (for example, 95°C, 100°C, 105°C, 110°C or 115°C), and the banburying time is 3 min to 5 min.

[0070] Example 18: As an optimization of the above example, in step S3, the triangular packages are made in an open mill, the temperature of the open mill is 40°C to 60°C (for example, 45°C, 50°C or 55°C), and the time for making the triangular packages is 8 minutes to 10 minutes.

[0071] Example 19: As an optimization of the above example, in step S3, before the first intermediate is spread, the first intermediate is placed at room temperature for 6 to 12 hours.

[0072] Example 20: As an optimization of the above example, in step S4, the vulcanization temperature is 150°C to 160°C (for example, 152°C, 155°C or 158°C), and the vulcanization time is 4 min to 5 min.

[0073] Example 21: As an optimization of the above example, in step S4, before the second intermediate is vulcanized in the mold, the second intermediate is placed at room temperature for 10 to 12 hours.

[0074] Example 22: The preparation method of the wear-resistant sole rubber is carried out according to the following method: S1, mixing the required amount of raw rubber, reinforcing filler, plasticizer, surface modifier of the reinforcing filler, accelerator of peroxide bridging agent, antioxidant and iron ion absorbent, and then kneading to obtain a mixture; S2, the mixed material is then discharged and thin-passed 3 to 5 times, and then cooled and processed into a sample to obtain a first intermediate; S3, after spreading the first intermediate, adding a required amount of peroxide bridging agent, forming a triangle package, and producing a sheet to obtain a second intermediate; S4, vulcanizing the second intermediate in a mold to obtain a wear-resistant sole rubber.

[0075] Example 23: Application of the wear-resistant sole rubber in the manufacture of soles of sports shoes and outdoor shoes, especially in the manufacture of soles of sports shoes and outdoor shoes requiring high wear resistance.

[0076] Example 24: The preparation method of the wear-resistant sole rubber is carried out according to the following method: S1, mixing 100 parts of raw rubber (including 65 parts of rare earth polybutadiene rubber (NdBR) and 35 parts of solution polystyrene butadiene rubber (SSBR)), 40 parts of reinforcing filler (white carbon black), 5 parts of plasticizer (isopropyl cyclohexanecarboxylate), 2 parts of surface modifier of reinforcing filler (organic silane coupling agent), 0.35 parts of accelerator of peroxide bridging agent (propane acrylate), 2.2 parts of antioxidant (1.2 parts of thioester peroxidation inhibitor, 0.5 parts of light stabilizer (o-hydroxyphenyl triazine), 0.5 parts of hindered phenol antioxidant (BHT), and 0.2 parts of iron ion absorber (polyethyleneimine)) in an internal mixer, and performing internal mixing for 3 minutes according to the set program. The internal mixing temperature is controlled at 100°C by adjusting the internal mixer speed. After the internal mixing is completed, a mixture is obtained; S2, after the mixture is discharged to an open mill, it is thin-passed three times on the open mill, and then rapidly cooled, and processed into samples of a certain length according to a specified thickness to obtain a first intermediate, wherein the Mooney viscosity of NdBR is 41 to 49 (i.e., 45±4), and the cis-butadiene content is ≥98%; the SSBR is a block-type high styrene medium vinyl solution styrene butadiene rubber, in which the styrene content is 48±2%, the vinyl content is 28±2%, and the Mooney viscosity is 45±5; S3, the first intermediate is placed at room temperature for 6 to 12 hours, then spread on an open mill, 0.2 parts of a peroxide bridging agent (composed of a cycloalkane peroxide (1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane) and a benzene organic peroxide (diisopropylbenzene peroxide) in a mass ratio of 1:2) is added, the temperature of the open mill is controlled at 40° C., and triangle packing is performed on the open mill for 8 minutes to completely disperse the peroxide bridging agent in the blank, and sheeting is performed to obtain a second intermediate; S4, placing the second intermediate at room temperature for 10 to 12 hours, and then vulcanizing it in a mold at a vulcanization temperature of 154° C. and a vulcanization time of 4 minutes to obtain a wear-resistant sole rubber.

[0077] Example 25: The preparation method of the wear-resistant sole rubber is different from that of Example 23 in that: in step S1, 100 parts of raw rubber used for mixing in the internal mixer include 70 parts of NdBR and 30 parts of SSBR, and the rest of the process is the same.

[0078] Example 26: The preparation method of the wear-resistant sole rubber is different from that of Example 23 in that: in step S1, 100 parts of raw rubber used for mixing in the internal mixer include 75 parts of NdBR and 25 parts of SSBR, and the rest of the process is the same.

[0079] Comparative Example 1: This comparative example provides a method for preparing wear-resistant sole rubber, which is different from Example 25 in that 60 parts of NdBR and 40 parts of SSBR are used in 100 parts of raw rubber during mixing in an internal mixer.

[0080] Comparative Example 2: This comparative example provides a method for preparing wear-resistant sole rubber, which differs from Example 25 in that 80 parts of NdBR and 20 parts of SSBR are used in 100 parts of raw rubber during mixing in an internal mixer.

[0081] Comparative Example 3: This comparative example provides a method for preparing wear-resistant sole rubber, which is different from Example 25 in that the amount of white carbon black is 30 parts.

[0082] Comparative Example 4: This comparative example provides a method for preparing wear-resistant sole rubber, which is different from Example 25 in that the accelerator of the peroxide bridging agent (propane acrylate) is 0.15 parts.

[0083] Comparative Example 5: This comparative example provides a method for preparing wear-resistant sole rubber, which is different from Example 25 in that the accelerator of the peroxide bridging agent (propane acrylate) is 0.6 parts.

[0084] Comparative Example 6: This comparative example provides a method for preparing wear-resistant sole rubber, which is different from Example 25 in that the peroxide bridging agent is 0.05 parts.

[0085] Comparative Example 7: This comparative example provides a method for preparing wear-resistant sole rubber, which is different from Example 25 in that the peroxide bridging agent is 0.5 parts.

[0086] The wear-resistant sole rubbers prepared in Examples 24 to 26 and Comparative Examples 1 to 7 were subjected to relevant performance tests. The physical and mechanical properties of the wear-resistant sole rubbers obtained are shown in Table 1.

[0087] As can be seen from Table 1, from Example 24 to Example 26, as the amount of rare earth butadiene rubber (NdBR) added increases, the wear (Akron abrasion and DIN) of the prepared wear-resistant sole rubber decreases, but the mechanical properties (tear strength) decrease, and the hardness decreases. This will lead to an increase in the compression deformation rate of the sole, a deterioration in the appearance of the shoe, and a shortened service life; conversely, as the amount of rare earth butadiene rubber added decreases, the wear increases.

[0088] Compared with Example 25, in Comparative Example 1, the raw material NdBR of the sole rubber is reduced and the SSBR is increased. The wear of the prepared wear-resistant sole rubber is significantly increased, and the mechanical properties are improved, that is, the elongation at break is reduced and the tear strength is increased. Therefore, the lower NdBR is not conducive to improving the wear resistance of the sole rubber. Although the higher SSBR can improve the mechanical properties of the sole rubber, it cannot take into account the wear resistance of the sole rubber.

[0089] Compared to Example 25, in Comparative Example 2, the raw material NdBR of the sole rubber was increased while the SSBR was decreased. The resulting wear-resistant sole rubber exhibited significantly increased wear, but significantly decreased mechanical properties. Therefore, excessively high NdBR and low SSBR levels are detrimental to achieving a balanced balance between the wear resistance and mechanical properties of the sole rubber. Furthermore, during the extrusion and molding processes, the rubber compound with a high NdBR dosage may experience problems such as large die swell and unstable molded dimensions. This is because the molecular structure and high dosage of NdBR increase the elastic modulus of the rubber compound, leading to a greater elastic recovery during the extrusion and molding process. This makes it difficult to control the size and shape of the extrudate, impacting the production efficiency and appearance quality of the product.

[0090] Compared with Example 25, the amount of reinforcing filler (silica gel) added in Comparative Example 3 was reduced by 10 parts, and the Akron abrasion of the prepared sole rubber was significantly increased and the mechanical properties (tear strength) were significantly reduced. Therefore, a smaller amount of silica gel is not conducive to improving the wear resistance and mechanical properties of the sole rubber.

[0091] Comparison of Comparative Example 4 with Example 2 shows that when the amount of peroxide bridging agent accelerator is insufficient, the tensile strength and wear resistance after vulcanization decrease. This is because the sparse cross-linked network structure makes the vulcanized rubber more susceptible to deformation and damage when subjected to external forces.

[0092] Comparison of Comparative Example 5 with Example 25 shows that excessive addition of the peroxide bridging agent accelerator can improve the hardness and wear resistance of the vulcanized rubber, but excessive crosslinking density can also reduce the flexibility of the vulcanized rubber and decrease its tensile strength. This is because excessive crosslinking density limits the mobility of the molecular chains, making the vulcanized rubber more susceptible to brittle fracture when subjected to external forces.

[0093] From the comparison of Comparative Examples 6 and 7 with Example 25, it can be seen that when the amount of peroxide bridging agent added is insufficient, the insufficient degree of vulcanization will lead to a decrease in the tensile strength of the rubber and a decrease in the wear resistance; when the amount of peroxide used is too much, it will lead to excessive cross-linking, making the vulcanized rubber hard and brittle, and at the same time reduce its chemical stability such as aging resistance and heat resistance.

[0094] Therefore, it can be seen that the appropriate combination of NdBR and SSBR is beneficial for improving the wear resistance of the sole rubber while also improving its mechanical properties. Using an appropriate amount of reinforcing filler can help improve the wear resistance and mechanical properties of the sole rubber. Furthermore, the appropriate addition of peroxide bridging agents and peroxide bridging agent accelerators can help improve the performance of the vulcanized rubber used in wear-resistant rubber soles.

[0095] The rubber sole prepared according to the wear-resistant sole rubber of the present invention has a breaking elongation of 490% to 590%, a breaking strength of 12.0 MPa to 15.0 MPa, and a specific gravity of 1.05 g / cm 3 to 1.10g / cm 3 , Akron wear is 0.08cm 3 to 0.10cm 3 DIN wear is 60mm 3 Up to 70mm 3 It can be seen that the wear-resistant rubber sole prepared by using the wear-resistant sole rubber of the present invention has greatly improved wear resistance.

[0096] In summary, the wear-resistant sole rubber of the present invention has greatly improved wear resistance of rubber soles for special purposes such as sports shoes and outdoor shoes, and can meet higher wear resistance requirements.

[0097] The above technical features constitute the embodiments of the present invention, which have strong adaptability and implementation effect. Non-essential technical features can be added or removed according to actual needs to meet the requirements of different situations.

Claims

1. A wear-resistant sole rubber, characterized in that The raw materials include raw rubber and additives, wherein, by weight, every 100 parts of raw rubber are composed of 65 to 75 parts of rare earth cis-1,4-butadiene rubber and 25 to 35 parts of segmented high styrene medium vinyl solution styrene butadiene rubber; and the additives added to every 100 parts of raw rubber include 38 to 42 parts of reinforcing fillers, 3 to 7 parts of plasticizers, 1 to 3 parts of surface modifiers for reinforcing fillers, 0.1 to 0.3 parts of peroxide bridging agents, 0.2 to 0.5 parts of promoters for peroxide bridging agents, 2.0 to 2.5 parts of antioxidants and 0.1 to 0.3 parts of iron ion absorbers.

2. The wear-resistant sole rubber according to claim 1, characterized in that The Mooney viscosity of rare earth cis-1,4-butadiene rubber is 41 to 49, and the cis-butadiene content is ≥98%. The Mooney viscosity of block-type high styrene medium vinyl solution styrene butadiene rubber is 40 to 50, and the styrene content of block-type high styrene medium vinyl solution styrene butadiene rubber is 46% to 50%, and the vinyl content is 26% to 30%.

3. The wear-resistant sole rubber according to claim 1 or 2, characterized in that The reinforcing filler is at least one of carbon black and white carbon black; or / and, the plasticizer is a carboxylate compound; or / and, the surface modifier of the reinforcing filler is an organic silane coupling agent; or / and, the peroxide bridging agent includes cycloalkane peroxides and benzene organic peroxides; or / and, the accelerator of the peroxide bridging agent is propane acrylate; Or / and, the antioxidant is a mixed multifunctional antioxidant.

4. The wear-resistant sole rubber according to claim 3, characterized in that The carboxylate compound is at least one of isopropyl cyclohexanecarboxylate, diisononyl 1,2-cyclohexanedicarboxylate, and isononyl 1-cyclohexanecarboxylate; or / and, the organosilane coupling agent is at least one of vinyltriethoxysilane, vinyltrimethoxysilane and vinyltri(β-methoxyethoxy)silane; or / and, the propane acrylate is at least one of trimethylolpropane trimethacrylate, triethylolpropane triethyl acrylate, trimethylolpropane triethyl acrylate and triethylolpropane trimethacrylate; Or / and, the mixed multifunctional antioxidant is composed of a thiol ester peroxidation inhibitor, a light stabilizer and a hindered phenol antioxidant, wherein the light stabilizer is o-hydroxyphenyl triazine, and the hindered phenol antioxidant is one of BHT, antioxidant 1076, and antioxidant 1010.

5. The wear-resistant sole rubber according to claim 4, characterized in that In the peroxide bridging agent, the mass ratio of cycloalkane peroxide to benzene organic peroxide is 1:2; Or / and, in the mixed multifunctional antioxidant, the mass ratio of the thioester peroxidation inhibitor, the light stabilizer and the hindered phenol antioxidant is 1 to 1.5:0.5:0.

5.

6. The wear-resistant sole rubber according to claim 5, characterized in that The raw materials include raw rubber and additives, wherein, by weight, every 100 parts of raw rubber are composed of 70 parts of rare earth cis-1,4-butadiene rubber and 30 parts of block-type high styrene medium vinyl solution styrene butadiene rubber; and the additives added to every 100 parts of raw rubber include 40 parts of reinforcing filler, 5 parts of plasticizer, 2 parts of organic silane coupling agent, 0.2 parts of peroxide bridging agent, 0.35 parts of peroxide bridging agent promoter, 2.2 parts of antioxidant and 0.2 parts of iron ion absorbent.

7. The wear-resistant sole rubber according to claim 4, 5 or 6, characterized in that Prepared according to the following method: S1, mixing the required amount of raw rubber, reinforcing filler, plasticizer, surface modifier of the reinforcing filler, accelerator of peroxide bridging agent, antioxidant and iron ion absorbent, and then kneading to obtain a mixture; S2, the mixed material is then discharged and thin-passed 3 to 5 times, and then processed into a sample after cooling to obtain a first intermediate; S3, after spreading the first intermediate, adding a required amount of peroxide bridging agent, forming a triangle package, and producing a sheet to obtain a second intermediate; S4, vulcanizing the second intermediate in a mold to obtain a wear-resistant sole rubber.

8. The wear-resistant sole rubber according to claim 7, characterized in that In step S1 , the banburying temperature is 90° C. to 120° C., and the banburying time is 3 min to 5 min.

9. The wear-resistant sole rubber according to claim 8, characterized in that In step S3, the triangle packages are made in an open mill, the temperature of the open mill is 40° C. to 60° C., and the time for making the triangle packages is 8 minutes to 10 minutes.

10. The wear-resistant sole rubber according to claim 8 or 9, characterized in that In step S3, before spreading the first intermediate, the first intermediate is placed at room temperature for 6 to 12 hours.

11. The wear-resistant sole rubber according to claim 8 or 9, characterized in that In step S4, the vulcanization temperature is 150° C. to 160° C., and the vulcanization time is 4 min to 5 min.

12. The wear-resistant sole rubber according to claim 10, characterized in that In step S4, before the second intermediate is vulcanized in the mold, the second intermediate is placed at room temperature for 10 to 12 hours.

13. A method for preparing the wear-resistant sole rubber according to any one of claims 1 to 6, characterized in that Proceed as follows: S1, mixing the required amount of raw rubber, reinforcing filler, plasticizer, surface modifier of the reinforcing filler, accelerator of peroxide bridging agent, antioxidant and iron ion absorbent, and then kneading to obtain a mixture; S2, the mixed material is then discharged and thin-passed 3 to 5 times, and then processed into a sample after cooling to obtain a first intermediate; S3, after spreading the first intermediate, adding a required amount of peroxide bridging agent, forming a triangle package, and producing a sheet to obtain a second intermediate; S4, vulcanizing the second intermediate in a mold to obtain a wear-resistant sole rubber.

14. The method for preparing the wear-resistant sole rubber according to claim 13, characterized in that In step S1, the banburying temperature is 90° C. to 120° C., and the banburying time is 3 min to 5 min; Or / and, in step S3, the triangular packages are formed in an open mill, the temperature of the open mill is 40° C. to 60° C., and the time for forming the triangular packages is 8 min to 10 min; Or / and, in step S3, before spreading the first intermediate, the first intermediate is placed at room temperature for 6 to 12 hours; or / and, in step S4, the vulcanization temperature is 150° C. to 160° C., and the vulcanization time is 4 min to 5 min; Or / and, in step S4, before the second intermediate is vulcanized in the mold, the second intermediate is placed at room temperature for 10 to 12 hours.

15. Use of the wear-resistant sole rubber according to any one of claims 1 to 12 in making soles of sports shoes and outdoor shoes.

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