A high dynamic anti-skid rubber sole and preparation method thereof

Abstract

The present invention provides a high dynamic anti-skid rubber sole and a preparation method thereof. The present invention selects rare earth cis-butadiene rubber, polar carboxyl nitrile rubber, polar amino-soluble polystyrene-butadiene rubber and saturated polar chlorohydrin rubber as base rubber, and uses active carboxyl silica as a reinforcing agent and polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin as a tackifier, so that the hard density of the finally prepared rubber sole is 1.0-1.1 g / cm 3 , hardness 60±3 A, dynamic anti-slip ≥0.6, DIN wear resistance ≤60 mm 3 , tensile strength>15 MPa, right-angle tear strength≥30 N / mm, yellowing resistance≥Level 4, ozone resistance≥Level 4, which meet the needs of indoor and outdoor wetland sports scenes and improve sports safety.

Description

Technical Field

[0001] The invention belongs to the field of rubber materials, and in particular relates to a high-dynamic anti-skid rubber sole and a preparation method thereof. Background Art

[0002] The anti-slip property of the sole directly affects the comfort and safety of consumers when wearing shoes. Currently, more and more consumers are keen on outdoor off-road sports, but when hiking or climbing on rugged mountain roads, they will inevitably encounter wetlands frequently. If the anti-slip property of the shoes is poor on wet and smooth roads, it is easy for consumers to slip. Therefore, in view of the above sports scenarios, consumers have put forward high anti-slip performance requirements for sports shoe soles, so as to provide sufficient safety protection for more consumers.

[0003] Generally, the material and pattern design of rubber soles have a great impact on the performance of outdoor hiking shoes and cross-country running shoes. The formula of rubber soles contains various types of rubber matrices, and different rubbers have different properties. For example, cis-butyl rubber has good wear resistance, but extremely poor anti-slip performance and poor mechanical properties; natural rubber has good mechanical properties, but average wear resistance and anti-slip performance; styrene-butadiene rubber has good wear resistance and dry anti-slip performance, but poor processability, poor self-adhesion, and average wet anti-slip performance; butyl rubber has good shock absorption, air tightness, and anti-slip performance, but poor wear resistance and poor adhesion; chloroprene rubber has good oil resistance and ozone resistance, but average wear resistance and anti-slip performance. Therefore, the industry often achieves the performance goals of different shoes by matching different rubbers.

[0004] In the prior art, patent CN 113444303 A discloses an anti-slip bio-based rubber sole, which includes the following components in parts by weight: 50 parts of bio-based solution-polymerized styrene-butadiene rubber, 26-34 parts of carboxylated nitrile rubber, 16-24 parts of epoxidized natural rubber, 35-50 parts of white carbon black, 2.1-2.8 parts of silane coupling agent, 1.2-1.5 parts of stearic acid, 1.0-1.3 parts of antioxidant, 1.9-2.5 parts of activator, 4-6 parts of zinc oxide, 1.2-1.5 parts of polyethylene wax, 1.4-1.8 parts of anti-spitting cream agent, 1.3-1.7 parts of tackifying resin, 1.0-1.2 parts of vulcanization accelerator, and 1.1-1.5 parts of insoluble sulfur.

[0005] Patent CN 110577680 A discloses a lightweight anti-skid rubber sole material, including: 15-30 parts of brominated butyl rubber, 15-30 parts of solution-polymerized styrene-butadiene rubber, 15-30 parts of neodymium-based butadiene rubber, 10-30 parts of syndiotactic polybutadiene resin, 5-20 parts of natural rubber, 1-2 parts of tackifying resin, 10-15 parts of fumed silica, 3-5 parts of zinc oxide, 1-3 parts of silica activator, 0.5-2.0 parts of silane coupling agent, 0.5-1.0 parts of stearic acid, 3-4 parts of chemical antioxidant, 0.5-1.0 parts of physical antioxidant, 0.5-1.5 parts of insoluble sulfur, and 1-2 parts of accelerator.

[0006] The above patents CN 113444303 A and CN 110577680 A both focus on the design of the base rubber and use tackifying resins to achieve anti-slip performance. In terms of tackifying resins, any one or more selected from C5 petroleum resin, C9 petroleum resin, terpene resin, C5 resin, C9 resin, phenolic resin or coumarone-indene resin are generally directly selected. However, the above tackifying resins are not modified. Although a certain amount can produce a weak tackifying effect to improve the compatibility of the overall rubber after being added, the above tackifying resins themselves have the disadvantages of low molecular weight, large molecular chain rigidity, high brittleness, poor film-forming properties, and no polar groups compatible with other resins in the molecular structure. Therefore, they have poor compatibility with polar base rubbers, and their low molecular weight has an adverse effect on the wear resistance of the overall rubber. Therefore, the wear resistance of the rubber sole disclosed in patent CN 113444303 A is >150 mm 3 , and the dynamic wet skid resistance is 0.68~0.79; the wear resistance of the rubber sole disclosed in patent CN 110577680 A is >100 mm 3 , while the static dry skid performance is 0.82~1.02, and the static wet skid performance is 0.58~0.72, which makes it difficult to achieve both excellent anti-slip properties and wear resistance.

[0007] Patent CN 102964646 A discloses a method for preparing a dicyclopentadiene petroleum resin modified rubber, comprising the following steps: mixing rubber latex with dicyclopentadiene petroleum resin and a compounding agent in an organic solvent, coagulating, and extruding and drying to obtain a modified raw rubber; kneading the modified raw rubber with stearic acid, zinc oxide, sulfur, a vulcanization accelerator and carbon black, and obtaining a dicyclopentadiene petroleum resin modified rubber after tableting and vulcanization. Generally, various types of rubber raw rubber are in a solid state. This method requires the addition of a large amount of emulsifiers, water and other liquids to convert solid rubber into latex. Not only are the subsequent coagulation and drying processes cumbersome and increase production costs, but also after the rubber latex is formed, the original elasticity and wear resistance of the rubber are lost. In addition, the dicyclopentadiene petroleum resin is only dispersed in the rubber latex through this technical solution, and the polarity is not increased or other functional groups are added, so the performance of the dicyclopentadiene petroleum resin itself is not improved. It can be inferred from this that preparing dicyclopentadiene petroleum resin modified rubber by this method cannot improve the anti-slip and wear resistance of the overall rubber. Summary of the invention

[0008] In view of this, the object of the present invention is to provide a high dynamic anti-skid rubber sole and a preparation method thereof. The rubber sole has excellent wet anti-skid performance and excellent wear resistance.

[0009] To achieve this object, the present invention adopts the following technical solutions:

[0010] In a first aspect, the present invention provides a high dynamic anti-skid rubber sole, which comprises, by weight: 40-60 parts of rare earth cis-1,4-butadiene rubber, 10-20 parts of carboxyl nitrile rubber, 5-20 parts of amino-soluble polystyrene-butadiene rubber, 5-20 parts of chlorohydrin rubber, 30-40 parts of active carboxyl white carbon black, 5-10 parts of polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin, 4-8 parts of softening oil, 2.0-3.0 parts of zinc oxide, 1.5-2.5 parts of polyethylene glycol, 0.5-1.0 parts of stearic acid, 0.4-0.8 parts of antioxidant, 0.4-0.8 parts of antioxidant, 2.0-3.0 parts of microcrystalline wax, 0.5-2 parts of acid absorber, 2.0-3.0 parts of cross-linking agent, and 1.5-2.5 parts of accelerator.

[0011] Preferably, the content of cis-1,4-butadiene in the rare earth butadiene rubber is ≥97 wt %, and the Mooney viscosity of the rare earth butadiene rubber is 60±5 (ML1+4@100° C.).

[0012] Preferably, the amino content of the amino-solution-polymerized styrene-butadiene rubber is 0.5-4 wt %, the styrene content is 18-35 wt %, and the Mooney viscosity is 47±5 (ML1+4@100° C.).

[0013] Preferably, the Mooney viscosity of the epichlorohydrin rubber is 58±5 (ML1+4@100°C).

[0014] Preferably, the carboxylated nitrile rubber is obtained by copolymerization of butadiene, acrylonitrile and an organic acid.

[0015] Preferably, the organic acid is selected from acrylic acid and / or methacrylic acid.

[0016] Preferably, the carboxyl content of the carboxyl nitrile rubber is 1.5-5 wt %, and the acrylonitrile content is 25-35 wt %.

[0017] Preferably, the Mooney viscosity of the carboxylated nitrile rubber is 45±5 (ML1+4@100°C).

[0018] Preferably, the polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin is obtained by modifying alicyclic dicyclopentadiene hydrogenated petroleum resin with methacrylic acid and α-methylstyrene.

[0019] Preferably, the polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin has a methacrylic acid content of 10-15 wt%, and an α-methylstyrene content of 8-12 wt%; the polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin has a softening point of 100-106°C, a Gardner color of 1.1-2.2, and an average molecular weight of 460-720.

[0020] Preferably, the active carboxyl silica is methacrylic acid-modified silica.

[0021] Preferably, the softening oil comprises paraffin oil and / or naphthenic oil.

[0022] Preferably, the antioxidant includes an amine antioxidant and / or a phenolic antioxidant.

[0023] Preferably, the antioxidant comprises a phosphite antioxidant and / or a phenol antioxidant.

[0024] Preferably, the microcrystalline wax comprises C25~C30 microcrystalline wax.

[0025] Preferably, the acid scavenger is selected from magnesium oxide.

[0026] Preferably, the cross-linking agent is selected from sulfur.

[0027] Preferably, the accelerator includes any one or more of a sulfenamide accelerator, a thiazole accelerator, a thiuram accelerator, a guanidine accelerator, a thiourea accelerator or a dithiocarbamate accelerator.

[0028] Preferably, the antioxidant is selected from styrenated phenol.

[0029] Preferably, the antioxidant is selected from butylated hydroxytoluene.

[0030] Preferably, the specific surface area of ​​the zinc oxide is 25±5 m 2 / g, the purity of the zinc oxide is ≥95%.

[0031] Preferably, the average relative molecular mass of the polyethylene glycol is 3600-4200.

[0032] Preferably, the total sulfur content of the sulfur is ≥70 wt%, and the oil-extending content of the sulfur is 19-21%.

[0033] Preferably, the accelerator includes accelerator DM, accelerator D and accelerator TS.

[0034] Preferably, the high dynamic anti-slip rubber sole comprises, by weight: 40-60 parts of rare earth cis-1,4-butadiene rubber, 10-20 parts of carboxyl nitrile rubber, 5-20 parts of amino-soluble polystyrene-butadiene rubber, 5-20 parts of chlorohydrin rubber, 30-40 parts of active carboxyl white carbon black, 5-10 parts of polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin, 4-8 parts of softening oil, 2.0-3.0 parts of zinc oxide, 1.5-2.5 parts of polyethylene glycol, 0.5-1.0 parts of stearic acid, 0.4-0.8 parts of antioxidant, 0.4-0.8 parts of antioxidant, 2.0-3.0 parts of microcrystalline wax, 0.5-2 parts of magnesium oxide, 2.0-3.0 parts of sulfur, 1-2 parts of accelerator DM, 0.5-1.0 parts of accelerator D, and 0.05-0.1 parts of accelerator TS.

[0035] In a second aspect, the present invention provides a method for preparing the above-mentioned high dynamic anti-slip rubber sole, comprising the following steps:

[0036] S1: Mix rare earth cis-1,1-butadiene rubber, carboxyl nitrile rubber, amino-soluble styrene-butadiene rubber, chlorohydrin rubber and polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin, and discharge the rubber at 100-110°C to produce sheets;

[0037] S2: after uniformly mixing the mixed components obtained in step S1 with other components except the accelerator and sulfur, further mixing the mixed components with the accelerator and sulfur to produce tablets;

[0038] S3: Cut the obtained mixed sheet and vulcanize it in a sole mold to obtain a high dynamic anti-skid rubber sole.

[0039] Preferably, the vulcanization temperature is 150-180° C.; and the vulcanization time is 220-260 s.

[0040] Compared with the prior art, the present invention has the following beneficial effects:

[0041] First, the innovation of the rubber sole formula: the present invention uses rare earth cis-1,4-butadiene rubber, polar carboxyl nitrile rubber, polar amino-soluble polystyrene-butadiene rubber, and saturated polar chlorohydrin rubber as base rubber, and then combines polar active carboxyl silica as a reinforcing agent and polar aromatic hydrocarbon-modified alicyclic hydrogenated petroleum resin as a tackifier to prepare a rubber sole that is resistant to wet and slippery conditions, wear-resistant, and resistant to ozone yellowing and has good mechanical properties. Among them, rare earth cis-1,1-butadiene rubber contributes to excellent wear resistance, and polar groups such as carboxyl of carboxylated nitrile rubber, amino of amino-soluble polystyrene-butadiene rubber, and chloromethyl of chlorohydrin rubber in polar rubber can react with carboxyl groups in active carboxyl silica and polar aromatic hydrocarbon-modified alicyclic hydrogenated petroleum resin to form strong chemical bonds and covalent bonds. In addition, polar rubber has excellent compatibility with polar reinforcing agent and polar petroleum resin, which improves the reinforcement effect and improves the wet anti-slip property, wear resistance, ozone resistance and physical and mechanical properties of rubber soles as a whole.

[0042] Second, the innovation of the selection of tackifier materials: Compared with the traditional rubber tackification technology, the present invention uses polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin with excellent adhesion and polarity to replace the existing C5 petroleum resin, C9 petroleum resin or cyclopentadiene petroleum resin for the first time. Under the condition of the same addition amount, the wear resistance / wet slip / tensile strength / tear strength of the rubber sole are greatly improved. Therefore, the present invention not only improves the dynamic wet slip performance through the design of the base rubber, but also creatively selects a new tackifier to help improve the performance, which is creative in the industry;

[0043] Third, the advancement of technology: Compared with the existing anti-skid rubber technology, the present invention mainly uses polar rubber containing carboxyl, amino, and chloromethyl. After cross-linking and chemical reaction, the rubber has more hydrophilic amide bonds and chlorinated acyl segments in its molecular structure, as well as some unreacted hydrophilic groups such as carboxyl and amino groups. Therefore, the rubber sole after blending, vulcanization and cross-linking is hydrophilic as a whole. When in contact with water, these hydrophilic polar groups can form a weak covalent force with water, increase the contact area and bonding force between water and the rubber sole, thereby enhancing the grip on wet and slippery grounds, further improving the wet anti-skid performance of the rubber sole, and making great progress in the technical level.

[0044] According to the test, the hardness density of the rubber sole finally prepared according to the formula of the present invention is 1.0-1.1 g / cm 3 , hardness 60±3 A, dynamic anti-slip ≥0.6, DIN wear resistance ≤60 mm 3, tensile strength>15 MPa, right-angle tear strength≥30 N / mm, yellowing resistance≥4, ozone resistance≥4. It can be seen that the rubber sole provided by the present invention has excellent wet anti-slip performance and excellent wear resistance, which meets the needs of indoor and outdoor wetland sports scenes and improves sports safety. DETAILED DESCRIPTION

[0045] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments 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 creative work are within the scope of protection of the present invention.

[0046] Based on the requirements of consumers for the anti-skid performance of outdoor shoes in the prior art, the present invention provides a high-dynamic anti-skid rubber sole, which comprises, by weight: 40-60 parts of rare earth cis-1,4-butadiene rubber, 10-20 parts of carboxyl nitrile rubber, 5-20 parts of amino-soluble polystyrene-butadiene rubber, 5-20 parts of chlorohydrin rubber, 30-40 parts of active carboxyl white carbon black, 5-10 parts of polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin, 4-8 parts of softening oil, 2.0-3.0 parts of zinc oxide, 1.5-2.5 parts of polyethylene glycol, 0.5-1.0 parts of stearic acid, 0.4-0.8 parts of antioxidant, 0.4-0.8 parts of antioxidant, 2.0-3.0 parts of microcrystalline wax, 0.5-2 parts of acid absorber, 2.0-3.0 parts of cross-linking agent and 1.5-2.5 parts of accelerator.

[0047] As a preferred technical solution, the high dynamic anti-skid rubber sole includes, by weight: 40-60 parts of rare earth cis-1,4-butadiene rubber, 10-20 parts of carboxyl nitrile rubber, 5-20 parts of amino-soluble polystyrene-butadiene rubber, 5-20 parts of chlorohydrin rubber, 30-40 parts of active carboxyl white carbon black, 5-10 parts of polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin, 4-8 parts of softening oil, 2.0-3.0 parts of zinc oxide, 1.5-2.5 parts of polyethylene glycol, 0.5-1.0 parts of stearic acid, 0.4-0.8 parts of antioxidant, 0.4-0.8 parts of antioxidant, 2.0-3.0 parts of microcrystalline wax, 0.5-2 parts of magnesium oxide, 2.0-3.0 parts of sulfur, 1-2 parts of accelerator DM, 0.5-1.0 parts of accelerator D, and 0.05-0.1 parts of accelerator TS.

[0048] In the present invention, the rare earth cis-1,4-butadiene rubber, also known as neodymium-based cis-1,4-butadiene rubber, is a type of cis-1,4-butadiene rubber polymerized by a catalytic system with rare earth metal neodymium as the main body. Its ultra-high cis-structure content makes the molecular chain have a highly stereoregular structure, and is superior to traditional titanium, cobalt, and nickel-based cis-1,4-butadiene rubber in terms of tear strength, heat generation, hysteresis loss, and abrasion. The rare earth cis-1,4-butadiene rubber selected in the present invention not only maintains the excellent wear resistance of cis-1,4-butadiene rubber, but also does not affect the anti-slip property of the rubber sole. In some embodiments of the present invention, the rare earth cis-1,4-butadiene rubber is a product including a cis-1,4-butadiene content ≥97 wt% and a Mooney viscosity of 60±5 (ML1+4@100°C).

[0049] In the present invention, the carboxylated nitrile rubber is formed by ternary copolymerization of butadiene, acrylonitrile and organic acid (acrylic acid, methacrylic acid, etc.). Due to the introduction of polar carboxyl groups, the polarity of the rubber matrix is ​​increased, and it has good anti-slip properties, adhesion and aging resistance, improves the wear resistance and tear strength of ordinary nitrile rubber, and increases the rubber strength. In some embodiments of the present invention, the carboxylated nitrile rubber is a product including a carboxyl content of 1.5~5 wt%, preferably 2.0~4 wt%; an acrylonitrile content of 25~35 wt%, preferably 30~35 wt%; and a Mooney viscosity of 45±5 (ML1+4@100°C).

[0050] It should be noted that solution-polymerized styrene-butadiene rubber is non-polar and has poor compatibility with polar white carbon black as a polar reinforcing agent. By modifying the solution-polymerized styrene-butadiene rubber with amino groups, the polarity of the solution-polymerized styrene-butadiene rubber is improved, and the compatibility is better when blended with polar rubber and polar reinforcing agents, so as to better exert its own performance. Therefore, the present invention preferably uses amino solution-polymerized styrene-butadiene rubber, which is obtained by functionalizing the end groups on the matrix of solution-polymerized styrene-butadiene rubber. In some embodiments of the present invention, the amino solution-polymerized styrene-butadiene rubber is provided by the China Petrochemical Research Institute, specifically a product including an amino content of 0.5~4 wt%, preferably 1.0~3 wt%; a styrene content of 18%~35 wt%, preferably 30%~35 wt%; and a Mooney viscosity of 47±5 (ML1+4@100℃).

[0051] In the present invention, the epichlorohydrin rubber is a polyether elastomer prepared by ring-opening polymerization under the action of a catalyst using an epoxy compound (any one or more of epichlorohydrin, ethylene oxide or propylene oxide) as a monomer. Due to its high molecular weight, the epichlorohydrin rubber has an ether bond -O- as the main chain, a highly saturated structure, and a large chloromethyl polar side chain. Therefore, it has the common properties of saturated rubber and polar rubber, and has good compatibility with polar rubber and polar reinforcing agent. In some embodiments of the present invention, the epichlorohydrin rubber is a product with a Mooney viscosity of 58±5 (ML1+4@100℃).

[0052] The invention introduces the above-mentioned four base rubbers of rare earth cis-1,4-butadiene rubber, carboxyl nitrile rubber, amino-solution-polymerized styrene-butadiene rubber and epichlorohydrin rubber for organic coordination. The rare earth cis-1,4-butadiene rubber has the characteristics of extreme wear resistance, high strength and wet-slip resistance, and its performance is better than that of conventional nickel-based cis-1,4-butadiene rubber, and can improve the wear resistance of the overall formula without affecting the anti-slip property of the rubber sole. The carboxyl nitrile rubber has good anti-slip property, adhesion and aging resistance due to the introduction of strongly polar carboxyl groups in the molecular structure, and the polarity of the rubber matrix is ​​increased. The wear resistance and tear strength are also better than those of ordinary nitrile rubber. The amino-solution-polymerized styrene-butadiene rubber has improved polarity of solution-polymerized styrene-butadiene rubber by introducing polar amino groups in the molecular structure, and can have better compatibility with polar white carbon black and other polar rubbers, so that the wet-slip resistance is better. The main chain of epichlorohydrin rubber is mainly ether bonds, the structure is highly saturated, and it has a huge chloromethyl polar side chain, so it has the common properties of saturated rubber and polar rubber, and has excellent ozone resistance, shock absorption, air tightness and anti-slip property.

[0053] In the present invention, the active carboxyl silica is used as a polar reinforcing agent, preferably methacrylic acid modified silica. The present invention improves the polarity of silica by using methacrylic acid modified silica, so that it has better compatibility with polar carboxyl nitrile rubber, amino-soluble polystyrene-butadiene rubber, epichlorohydrin rubber, etc. in the matrix rubber, and the carboxyl group contained in methacrylic acid can form a strong amide bond chemical bond with the amino group of amino-soluble polystyrene-butadiene rubber, and can form a chloride chemical bond with the chloromethyl group of epichlorohydrin rubber, so that the reinforcement effect is more excellent, which not only improves the wear resistance, tensile strength and tear strength of the rubber sole, but also helps to improve the anti-slip property of the rubber and reduce the rolling resistance of the rubber. In some embodiments of the present invention, the methacrylic acid modified silica includes a methacrylic acid content of 2 to 4 wt%, preferably 2.5 to 3.5 wt%, and a specific surface area of ​​160 m 2 / g, preferably >170 m 2 / g of product.

[0054] It should be noted that in the art, although the introduction of petroleum resin in the production process of rubber soles can produce a weak viscosity-increasing effect to improve the compatibility and uniformity of the overall rubber, the petroleum resin itself has the disadvantages of low molecular weight, large molecular chain rigidity, large brittleness, poor film-forming property, and no polar groups in the molecular structure that are compatible with other resins, so it has poor compatibility with polar matrix rubber. At the same time, its own low molecular weight has an adverse effect on the wear resistance of the overall rubber. Therefore, from the perspective of chemical modification of petroleum resin, the present invention preferably adopts polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin as an additive, and specifically preferably alicyclic dicyclopentadiene hydrogenated petroleum resin modified by methacrylic acid and α-methylstyrene. On the one hand, α-methylstyrene can increase the molecular weight of alicyclic dicyclopentadiene petroleum resin, and by aromatizing alicyclic petroleum resin, the problems of deep hue, poor adhesion, poor thermal stability, etc. of alicyclic dicyclopentadiene petroleum resin can be improved, and finally a modified petroleum resin with stronger adhesion and better physical and mechanical properties can be obtained. On the other hand, the present invention introduces a polar functional group carboxyl group into the rubber so that it has a certain polarity, so as to achieve the purpose of improving adhesion, stability and weather resistance. At the same time, the polar carboxyl group can form a strong amide bond chemical bond with the amino group of the amino-soluble polystyrene-butadiene rubber, form a chlorinated acyl chemical bond with the chloromethyl group of the epichlorohydrin rubber, and form a strong covalent bond with the carboxyl group in the active carboxyl white carbon black, thereby improving the overall rubber wet anti-slip performance while maintaining excellent wear resistance.

[0055] In some embodiments of the present invention, the polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin preferably comprises a methacrylic acid content of 10-15 wt%, preferably 11-13 wt%; and an α-methylstyrene content of 8-12 wt%, preferably 9-11 wt%. In some embodiments of the present invention, the polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin has a softening point of 100-106°C, preferably 102-104°C; a Gardner color of 1.1-2.2, preferably 1.3-2.0; and an average molecular weight of 460-720, preferably 500-600.

[0056] In the present invention, the softening oil includes paraffin oil and / or naphthenic oil, preferably paraffin oil.

[0057] In the invention, the zinc oxide is used as a vulcanization activator to promote the increase of the crosslinking density of the rubber and improve various physical and mechanical properties. In some embodiments of the present invention, a specific surface area of ​​25 ± 5 m 2 / g, zinc oxide product with purity ≥95 wt%.

[0058] In the invention, the polyethylene glycol is used as an activating dispersant, which is beneficial to increase the vulcanization rate and the extrusion speed of the rubber. In some embodiments of the present invention, it is preferred to use a polyethylene glycol product with an average relative molecular mass of 3600-4200, preferably 3800-4000.

[0059] In the invention, the stearic acid acts as a lubricant and an anti-sticking agent, which helps to reduce friction during processing.

[0060] The antioxidant includes an amine antioxidant and / or a phenolic antioxidant. The present invention has no particular restrictions on the sources of the amine antioxidant and the phenolic antioxidant, and they can be general commercial products. In some embodiments of the present invention, the antioxidant is preferably a phenolic antioxidant, more preferably styrenated phenol.

[0061] In the present invention, the antioxidant includes a phosphite antioxidant and / or a phenolic antioxidant. The present invention has no particular restrictions on the sources of the phosphite antioxidant and the phenolic antioxidant, and they can be general commercial products. In some embodiments of the present invention, the antioxidant is preferably a phenolic antioxidant, more preferably butylated hydroxytoluene.

[0062] In the present invention, the microcrystalline wax is preferably used as a lubricant to prevent sticking, and the microcrystalline wax preferably includes C25-C30 microcrystalline wax.

[0063] In the present invention, the acid absorber is preferably selected from magnesium oxide, which is used to neutralize HCl released during the vulcanization of epichlorohydrin rubber, promote vulcanization, and prevent sticking and corrosion of molds.

[0064] In the present invention, the crosslinking agent is preferably selected from sulfur. In some embodiments of the present invention, the sulfur includes a total insoluble elemental sulfur content of ≥70 wt%, preferably ≥75 wt%; and an oil-extended content of 19-21 wt%, preferably 19.5-20 wt%.

[0065] In the present invention, the accelerator includes any one or more of sulfonamide accelerators, thiazole accelerators, thiuram accelerators, guanidine accelerators, thiourea accelerators or dithiocarbamate accelerators. In some embodiments of the present invention, it is preferred to select a combination of accelerator DM (2,2'-dibenzothiazole disulfide), accelerator D (diphenylguanidine) and accelerator TS (tetramethylthiuram monosulfide). Among them, accelerator DM has good vulcanization characteristics, can significantly improve the performance of vulcanized rubber, and has good anti-scorch performance; accelerator D, as an acidic accelerator, has high vulcanization activity and can give rubber good aging resistance and fatigue resistance; accelerator TS is often used to shorten the vulcanization time and improve production efficiency. The present invention uses the above three accelerators in combination, which can complement each other's advantages, shorten the vulcanization time, reduce the amount of sulfur used, lower the vulcanization temperature, and improve the scorch performance of the rubber material, so that the rubber material is not prone to premature vulcanization during the processing process, making the vulcanization process more stable, and the performance of the vulcanized rubber is more excellent. In addition, the production efficiency can be improved and the cost can be reduced.

[0066] In summary, the present invention is a base rubber with rare earth cis-1,4-butadiene rubber, carboxylated nitrile rubber, amino-soluble polystyrene-butadiene rubber, and chlorohydrin rubber, and is combined with active carboxylated white carbon black and polar aromatic hydrocarbon-modified alicyclic hydrogenated petroleum resin, wherein the rare earth cis-1,4-butadiene rubber contributes excellent wear resistance, and polar groups such as the carboxyl group of carboxylated nitrile rubber, the amino group of amino-soluble polystyrene-butadiene rubber, and the chloromethyl group of chlorohydrin rubber in the polar rubber can react with the carboxyl group in the active carboxylated white carbon black and the polar aromatic hydrocarbon-modified alicyclic hydrogenated petroleum resin to form a strong chemical bond and covalent bond. Moreover, the polar rubber has excellent compatibility with the active carboxylated white carbon black as a polar reinforcing agent and the polar aromatic hydrocarbon-modified alicyclic hydrogenated petroleum resin as a tackifier, which greatly improves the reinforcement effect, and improves the wet anti-slip property, wear resistance, ozone resistance and physical and mechanical properties of the rubber sole as a whole. Furthermore, the present invention adopts polar rubber containing carboxyl, amine and chloromethyl. After crosslinking and chemical reaction, the rubber has more hydrophilic amide bonds and chlorinated acyl segments in its molecular structure, as well as some unreacted hydrophilic groups such as carboxyl and amine. Therefore, the rubber sole after blending, vulcanization and crosslinking is hydrophilic as a whole. When in contact with water, these hydrophilic polar groups can form a weak covalent force with water, increase the contact area and bonding force between water and the rubber sole, thereby enhancing the grip on slippery grounds to improve the wet anti-skid performance of the rubber sole. Therefore, the present invention is designed according to the above formula, and finally prepares a hard density of 1.0~1.1 g / cm 3 , hardness 60±3 A, dynamic anti-slip ≥ 0.6 (in the prior art, the dynamic anti-slip of general rubber soles is between 0.25 and 0.35), DIN wear resistance ≤ 60 mm 3, rubber soles with excellent performance such as tensile strength>15 MPa, right-angle tear strength≥30 N / mm, yellowing resistance≥level 4, ozone resistance≥level 4, etc.

[0067] In summary, the rubber sole provided by the present invention has excellent wet anti-slip performance while maintaining excellent wear resistance, meeting the needs of indoor and outdoor wetland sports scenes and improving sports safety.

[0068] The present invention also provides a method for preparing the above-mentioned high dynamic anti-slip rubber sole, comprising the following steps:

[0069] S1: Mix rare earth cis-1,1-butadiene rubber, carboxyl nitrile rubber, amino-soluble styrene-butadiene rubber, chlorohydrin rubber and polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin, and discharge the rubber at 100-110°C to produce sheets;

[0070] S2: after uniformly mixing the mixed components obtained in step S1 with other components except the accelerator and sulfur, further mixing the mixed components with the accelerator and sulfur to produce tablets;

[0071] S3: Cut the obtained mixed sheet and vulcanize it in a sole mold to obtain a high dynamic anti-skid rubber sole.

[0072] In the present invention, the vulcanization temperature is 150-180° C., preferably 155-175° C.; the vulcanization time is 220-260 s, preferably 225-245 s.

[0073] In the present invention, the reason for adding the accelerator and sulfur last is to ensure that the rubber molecules have been fully mixed to avoid agglomeration, thereby ensuring the uniformity and effectiveness of the vulcanization effect.

[0074] In some embodiments of the present invention, the method for preparing the high dynamic anti-slip rubber sole comprises the following steps:

[0075] Mixing 1: Pour rare earth cis-1,1-butadiene rubber, carboxyl nitrile rubber, amino-soluble styrene-butadiene rubber, chlorohydrin rubber and polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin into an internal mixer, start the internal mixer, mix for 8-10 minutes to fully mix the base rubber and polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin, and pour out the mixed rubber when the temperature of the internal mixer rises to 100-110°C;

[0076] Sheeting 1: Put the mixed rubber into an open mixer, roll it continuously for 5-10 times, and produce a sheet with a thickness of 1-2 cm. Leave it for 5-10 hours for later use.

[0077] Mixing 2: Pour the mixed rubber material after 5-10 hours of storage into the internal mixer again, and pour other additives except the accelerator and crosslinking agent sulfur into the internal mixer, mix for 8-10 minutes, and pour out the mixed rubber material when the temperature of the internal mixer rises to 100-110℃;

[0078] Sheeting 2: Pour the mixed rubber into an open mill, tumble it 5-8 times continuously, add accelerator and cross-linking agent sulfur, and form a sheet with a thickness of 0.5-0.8 cm;

[0079] Vulcanization: Cut a 0.5-0.8 cm thick sheet into the size required by the mold, put it into the sole mold, and vulcanize it at 160°C using a flat vulcanizer for 220-260 s. Take out the vulcanized rubber sole.

[0080] The preparation method provided by the present invention is simple and convenient, and is easy to realize industrial or industrial production.

[0081] To further illustrate the present invention, the following examples are used to provide a detailed description. Among the experimental raw materials used in the following examples of the present invention, rare earth cis-1,4-butadiene rubber: CB22, Lanxess, Germany, cis-1,4-butadiene content is 97 wt%, Mooney viscosity is 63 (ML1+4@100℃); carboxylated nitrile rubber, X146, Lanxess, Germany, carboxyl content is 2 wt%, acrylonitrile content is 32.5 wt%, Mooney viscosity is 45 (ML1+4@100℃); amino-solubilized styrene-butadiene rubber is provided by China Petrochemical Research Institute, amino content is 2 wt%, styrene content is 30 wt%, Mooney viscosity is 48 (ML1+4@100℃); chlorohydrin rubber: C55, Japan Dasou Company, Mooney viscosity is 55 (ML1+4@100℃); active carboxyl white carbon black: HB152, Hubei Huifu Nanomaterials Co., Ltd.; polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin: T-REZ HB103, ENEOS, Japan, methacrylic acid content is 12wt%, α-methylstyrene content is 10wt%; average molecular weight is 580; softening oil: paraffin oil 150N, Shandong Zhuyou Lubrication Technology Co., Ltd.; zinc oxide: ZnO 997, Taixiang Company; polyethylene glycol: PEG 4000, Hai'an Petrochemical Plant, Jiangsu Province; stearic acid: Dukuda Company, Indonesia; antioxidant BHT: Zhengzhou Dexin Chemical Industry Co., Ltd.; antioxidant: SP-GR: Guangdong Duba New Materials Technology Co., Ltd.; microcrystalline wax: RW-159, Lianyungang Ruiba Chemical Co., Ltd.; accelerator DM: Weilin New Materials Technology Co., Ltd.; accelerator D: Weilin New Materials Technology Co., Ltd.; accelerator TS: Weilin New Materials Technology Co., Ltd.; sulfur: S-80, Dongguan Owen New Materials Co., Ltd.

[0082] Embodiments 1 to 12

[0083] The present embodiments 1 to 12 provide rubber soles of different formulations, and their specific formulations are shown in Table 1 and Table 2:

[0084] Table 1

[0085]

[0086] Table 2

[0087]

[0088] The specific preparation method is as follows:

[0089] (1) Mixing 1: Pour the base rubber (rare earth cis-1,1-butadiene rubber, carboxyl nitrile rubber, amino-soluble styrene-butadiene rubber, chlorohydrin rubber) and polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin into an internal mixer, start the internal mixer, and mix for 9 minutes to fully mix the rubber and petroleum resin. When the temperature of the internal mixer rises to 105°C, pour out the mixed rubber.

[0090] (2) Sheeting 1: Place the mixed rubber material into an open mixing mill, tumble it seven times continuously, and form it into a sheet with a thickness of 1 cm. Leave it for eight hours for later use.

[0091] (3) Mixing 2: After standing for 8 hours, pour the mixed rubber into the internal mixer again, and pour other additives (including: active carboxyl silica, softening oil, zinc oxide, polyethylene glycol, stearic acid, antioxidant, antioxidant, microcrystalline wax, magnesium oxide) except the accelerator and crosslinking agent sulfur into the internal mixer. Mix for 8 minutes. When the temperature of the internal mixer rises to 105°C, pour out the mixed rubber.

[0092] (4) Sheeting 2: Pour the mixed rubber into an open mixing mill, tumble it seven times continuously, add accelerator and cross-linking agent sulfur, and roll it into a 0.5 cm thick sheet.

[0093] (5) Vulcanization: Cut a 0.5 cm thick sheet into the size required by the mold, put it into the sole mold, and vulcanize it for 240 seconds at 160°C using a flat vulcanizer. Take out the vulcanized rubber sole.

[0094] Comparative Examples 1 to 10

[0095] Comparative Examples 1 to 10 provide rubber soles with different formulations, and their specific formulations are shown in Table 3 and Table 4:

[0096] Table 3

[0097]

[0098] Table 4

[0099]

[0100] The specific preparation method is shown in Examples 1 to 12.

[0101] Performance Testing

[0102] The performance tests were performed on the rubber soles obtained in Examples 1 to 12 and Comparative Examples 1 to 10, wherein the test methods and results of Examples 1 to 12 are shown in Table 5, and the test methods and results of Comparative Examples 1 to 10 are shown in Table 6:

[0103] Table 5

[0104]

[0105] Table 6

[0106]

[0107] The conclusion is as follows:

[0108] (1) From the comparison data of Examples 1 to 6 and Comparative Examples 6 to 7, it can be seen that when the addition amount of the polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin is 4 to 10 parts, the DIN wear resistance and dynamic wet skid resistance of the rubber sole are improved with the increase of the addition amount of the polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin. When the addition amount is 5 parts, the improvement effect is more obvious than when the addition amount is 4 parts. However, as the addition amount increases to 8 to 10 parts, the improvement of the wear resistance and anti-skid performance slows down. When the addition amount reaches 12 parts, DIN wear resistance and dynamic wet slip are lower than when the addition amount is 10 parts. This is mainly because: the polar carboxyl group in the polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin can form a strong amide bond chemical bond with the amino group of the amino-soluble polystyrene butadiene rubber, form a chlorinated acyl chemical bond with the chloromethyl group of the chlorohydrin rubber, and form a strong covalent bond with the carboxyl group in the active carboxyl white carbon black, which is beneficial to improve the wet anti-slip performance and wear resistance. However, when the addition amount exceeds 10 parts, the excess polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin no longer produces a chemical bond in the system, but is free in the rubber matrix. As a small molecule, the mechanical properties of this part of the petroleum resin are weak, resulting in a decrease in the anti-slip, wear resistance, stretching, tearing and other properties of the rubber sole. Therefore, the addition amount of polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin is preferably 5-10 parts.

[0109] (2) From the comparative data of Examples 4, 7 to 12, it can be seen that when the addition amount of polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin is fixed at 8 parts, 40 to 60 parts of rare earth cis-1, 10 to 20 parts of carboxyl nitrile rubber, 5 to 20 parts of amino-solubility polystyrene-butadiene rubber, 5 to 20 parts of chlorohydrin rubber, and 30 to 40 parts of active carboxyl silica, a density of 1.0 to 1.1 g / cm 3, hardness 60±3 A, dynamic anti-slip ≥0.6, DIN wear resistance ≤60 mm 3 , tensile strength>15 MPa, right-angle tear strength≥30 N / mm, yellowing resistance≥4, ozone resistance≥4 and other excellent rubber soles. Among them, as the amount of rare earth cis-1,1-butadiene rubber added increases, the wear resistance of the rubber sole becomes better; the greater the amount of carboxyl nitrile rubber or amino-solubility polystyrene butadiene rubber added, the more conducive it is to improving the wet anti-slip and tear strength of the rubber sole; the greater the amount of chlorohydrin rubber added, the better the ozone resistance and yellowing resistance, and the stronger the tensile strength and tear strength.

[0110] (3) From the comparison data of Comparative Example 1 and Example 4, it can be seen that when the rare earth cis-1,1-butadiene rubber in the formula is replaced by nickel-based cis-1,1-butadiene rubber, the wear resistance and dynamic wet skid resistance are significantly reduced. This is mainly because the rare earth cis-1,1-butadiene rubber has a higher cis-structure content than ordinary cis-1,1-butadiene rubber, which makes the molecular chain have a highly stereoregular structure, and is superior to the traditional nickel-based cis-1,1-butadiene rubber in terms of wear resistance and tear strength, and does not affect the anti-slip performance of the rubber sole. Therefore, the present invention uses rare earth cis-1,1-butadiene rubber to create the ultimate wear resistance.

[0111] (4) From the comparison data of Comparative Example 2 and Example 4, it can be seen that when the carboxyl nitrile rubber in the formula is replaced by nitrile rubber, the dynamic wet skid performance decreases significantly, and the wear resistance, tensile strength, tear strength, etc. decrease slightly. This is mainly because compared with ordinary nitrile rubber, carboxyl nitrile rubber has introduced polar carboxyl groups, which increases the polarity of the rubber matrix and has better anti-slip properties. At the same time, it also has higher wear resistance and tear strength than ordinary nitrile rubber. Therefore, the present invention selects carboxyl nitrile rubber to improve the wet anti-slip performance.

[0112] (5) From the comparison data of Comparative Example 3 and Example 4, it can be seen that when the amino-solution polymerized styrene-butadiene rubber in the formula is replaced by styrene-butadiene rubber, the dynamic wet skid performance decreases significantly, and the wear resistance, tensile strength, tear strength, etc. decrease slightly. This is mainly because the solution polymerized styrene-butadiene rubber is non-polar and has poor compatibility with polar white carbon black. By modifying the solution polymerized styrene-butadiene rubber with amino groups, the polarity of the solution polymerized styrene-butadiene rubber is improved. When blended with white carbon black, it is found that the dispersion of the reinforcing agent can be effectively improved, thereby better improving the anti-skid, wear resistance and other mechanical properties. Therefore, the present invention uses amino-solution polymerized styrene-butadiene rubber to improve the wet anti-skid performance.

[0113] (6) From the comparison data of Comparative Example 4 and Example 4, it can be seen that when the epichlorohydrin rubber in the formula is removed, the ozone resistance and yellowing resistance performance deteriorate sharply. This is mainly because the epichlorohydrin rubber main chain is an ether bond -O- as the main chain, the structure is highly saturated, and it has a large chloromethyl polar side chain. Therefore, it has the common properties of saturated rubber and polar rubber, and has better yellowing resistance and ozone resistance than rare earth cis-1,1-butadiene rubber, carboxyl nitrile rubber and amino-solubility polystyrene butadiene rubber. Therefore, the present invention selects epichlorohydrin rubber with good wear resistance and anti-slip properties to improve the yellowing resistance and ozone resistance of the formula.

[0114] (7) From the comparison data of Comparative Example 5 and Example 4, it can be seen that when the active carboxyl silica in the formula is replaced with ordinary silica, the wear resistance, wet skid resistance, tensile strength, tear strength, etc. are greatly reduced. This is because the silica modified by methacrylic acid has better compatibility with polar carboxyl nitrile rubber, amino-soluble polystyrene-butadiene rubber, epichlorohydrin rubber, etc., and the carboxyl group of methacrylic acid forms a strong amide bond chemical bond with the amino group of amino-soluble polystyrene-butadiene rubber, and forms a chlorinated acyl chemical bond with the chloromethyl group of epichlorohydrin rubber. Compared with ordinary silica, its reinforcement effect is better, which not only improves the wear resistance, tensile strength, and tear strength of the rubber sole, but also helps to improve the wet skid resistance of the rubber. Therefore, the patent of the present invention selects active carboxyl silica as a reinforcing agent.

[0115] (8) From the comparison data of Comparative Examples 8 to 10 and Example 4, it can be seen that when the polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin in the formula is replaced with unmodified C5 petroleum resin, C9 petroleum resin or cyclopentadiene petroleum resin, the wear resistance, wet skid resistance, tensile strength, tear strength, etc. are greatly reduced under the same addition amount. The results show that after the polar modification and aromatic modification of the alicyclic dicyclopentadiene hydrogenated petroleum resin, it has stronger adhesion and polarity. The adhesion is conducive to improving the wet skid resistance, and the polarity is conducive to chemical reaction with the polar rubber and polar reinforcing agent in the formula, thereby improving the overall rubber wet skid resistance while maintaining excellent wear resistance.

[0116] Therefore, the present invention selects polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin to improve the wet anti-skid performance of rubber soles.

[0117] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A high dynamic anti-slip rubber sole, characterized in that: The invention comprises, by weight: 40-60 parts of rare earth cis-butadiene rubber, 10-20 parts of carboxylated nitrile rubber, 5-20 parts of amino-soluble polystyrene-butadiene rubber, 5-20 parts of chlorohydrin rubber, 30-40 parts of active carboxylated white carbon black, 5-10 parts of polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin, 4-8 parts of softening oil, 2.0-3.0 parts of zinc oxide, 1.5-2.5 parts of polyethylene glycol, 0.5-1.0 parts of stearic acid, 0.4-0.8 parts of antioxidant, 0.4-0.8 parts of antioxidant, 2.0-3.0 parts of microcrystalline wax, 0.5-2 parts of acid absorbent, 2.0-3.0 parts of cross-linking agent and 1.5-2.5 parts of accelerator. The polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin is obtained by modifying alicyclic dicyclopentadiene hydrogenated petroleum resin with methacrylic acid and alpha-methylstyrene.

2. The high dynamic anti-slip rubber sole according to claim 1, characterized in that: The cis-1,4-butadiene content in the rare earth butadiene rubber is ≥97 wt %, and the ML1+4@100°C Mooney viscosity of the rare earth butadiene rubber is 60±5; The amino solution polystyrene butadiene rubber has an amino content of 0.5-4 wt %, a styrene content of 18-35 wt %, and a Mooney viscosity of ML1+4@100°C of 47±5; The ML1+4@100°C Mooney viscosity of the epichlorohydrin rubber is 58±5.

3. The high dynamic anti-slip rubber sole according to claim 1 or 2, characterized in that: The carboxylated nitrile rubber is obtained by copolymerization of butadiene, acrylonitrile and organic acid; The organic acid is selected from acrylic acid and / or methacrylic acid.

4. The high dynamic anti-slip rubber sole according to claim 3, characterized in that: The carboxyl content of the carboxyl nitrile rubber is 1.5-5 wt %, and the acrylonitrile content is 25-35 wt %; The ML1+4@100°C Mooney viscosity of the carboxylated nitrile rubber is 45±5.

5. The high dynamic anti-slip rubber sole according to claim 1, characterized in that: The polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin has a methacrylic acid content of 10-15 wt%, and an α-methylstyrene content of 8-12 wt%; the polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin has a softening point of 100-106° C., a Gardner chromaticity of 1.1-2.2, and an average molecular weight of 460-720.

6. The high dynamic anti-slip rubber sole according to claim 1, characterized in that: The active carboxyl silica is methacrylic acid-modified silica; The softening oil includes paraffin oil and / or naphthenic oil; The antioxidant includes an amine antioxidant and / or a phenolic antioxidant; The antioxidant includes a phosphite antioxidant and / or a phenol antioxidant; The microcrystalline wax includes C25-C30 microcrystalline wax; The acid absorber is selected from magnesium oxide; The cross-linking agent is selected from sulfur; The accelerator includes any one or more of sulfenamide accelerators, thiazole accelerators, thiuram accelerators, guanidine accelerators, thiourea accelerators or dithiocarbamate accelerators.

7. The high dynamic anti-slip rubber sole according to claim 6, characterized in that: The antioxidant is selected from styrenated phenol; The antioxidant is selected from butylated hydroxytoluene; The specific surface area of ​​the zinc oxide is 25±5 m 2 / g, the purity of the zinc oxide is ≥95%; The average relative molecular mass of the polyethylene glycol is 3600-4200; The total sulfur content of the sulfur is ≥70 wt%, and the oil-extending content of the sulfur is 19-21%; The accelerators include accelerator DM, accelerator D and accelerator TS.

8. A high dynamic non-slip rubber sole, characterized in that: The invention comprises, by weight: 40-60 parts of rare earth cis-butadiene rubber, 10-20 parts of carboxyl nitrile rubber, 5-20 parts of amino-soluble polystyrene-butadiene rubber, 5-20 parts of chlorohydrin rubber, 30-40 parts of active carboxyl white carbon black, 5-10 parts of polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin, 4-8 parts of softening oil, 2.0-3.0 parts of zinc oxide, 1.5-2.5 parts of polyethylene glycol, 0.5-1.0 parts of stearic acid, 0.4-0.8 parts of antioxidant, 0.4-0.8 parts of antioxidant, 2.0-3.0 parts of microcrystalline wax, 0.5-2 parts of magnesium oxide, 2.0-3.0 parts of sulfur, 1-2 parts of accelerator DM, 0.5-1.0 parts of accelerator D and 0.05-0.1 parts of accelerator TS. The polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin is obtained by modifying alicyclic dicyclopentadiene hydrogenated petroleum resin with methacrylic acid and alpha-methylstyrene.

9. A method for preparing a high dynamic anti-slip rubber sole according to any one of claims 1 to 8, characterized in that: The following steps are involved: S1: Mix rare earth cis-1,1-butadiene rubber, carboxyl nitrile rubber, amino-soluble styrene-butadiene rubber, chlorohydrin rubber and polar aromatic hydrocarbon modified alicyclic hydrogenated petroleum resin, and discharge the rubber at 100-110°C to produce sheets; S2: after uniformly mixing the mixed components obtained in step S1 with other components except the accelerator and sulfur, further mixing the mixed components with the accelerator and sulfur to produce tablets; S3: Cut the obtained mixed sheet and vulcanize it in a sole mold to obtain a high dynamic anti-skid rubber sole.

10. The preparation method according to claim 9, characterized in that: The vulcanization temperature is 150-180° C.; the vulcanization time is 220-260 s.

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