High-non-slip rubber sole and preparation method thereof

Abstract

The invention relates to a preparation method of a high-non-slip rubber sole. Comprising the following steps: S1, uniformly mixing 50-60 parts by weight of modified epoxy resin, 10-20 parts by weight of a polyurethane-acrylate copolymer, 20-30 parts by weight of modified PEG, 3-5 parts by weight of stearic acid, 1-4 parts by weight of zinc oxide, 3-5 parts by weight of zinc stearate and 2-4 parts by weight of zinc oxide; the preparation method comprises the following steps: uniformly mixing 1-3 parts by weight of magnesium oxide and 1-3 parts by weight of an AC foaming agent in an internal mixer at the temperature of 60-70 DEG C, internally mixing for 30-60 minutes, continuously mixing for 15-20 minutes at the temperature of 90-95 DEG C, granulating after open milling, and standing for 20-24 hours at room temperature to obtain a molding master batch; s2, putting the molding master batch into a foaming mold for compression molding, controlling the mold closing pressure to be 15-25MPa, then heating to 180-190 DEG C together with the foaming mold, performing vulcanization treatment for 8-15 minutes, cooling, and performing standing treatment at room temperature for 20-24 hours to obtain the high-non-slip rubber sole. According to the high-non-slip rubber sole and the preparation method thereof, the high-non-slip rubber sole has excellent wet non-slip performance and also has excellent wear resistance.

Description

Technical Field

[0001] This invention relates to the field of footwear, specifically to a high-slip rubber sole and its preparation method. Background Technology

[0002] The traction of shoe soles directly affects the comfort and safety of consumers when wearing shoes. Currently, more and more consumers are enthusiastic about outdoor off-road sports, but when hiking or climbing on rugged mountain trails, they inevitably encounter wet surfaces. On wet, slippery surfaces, if the shoes have poor traction, consumers are prone to slipping and falling. Therefore, considering these sports scenarios, consumers demand high traction performance from athletic shoe soles to provide sufficient safety protection for more consumers.

[0003] Existing athletic shoe materials without any anti-slip treatment typically have a coefficient of friction of less than 0.5, and their anti-slip performance is not within the safety standard range. Summary of the Invention

[0004] In view of this, the purpose of this invention is to provide a high-slip rubber sole and its preparation method, which has excellent wet slip resistance and excellent wear resistance.

[0005] To achieve the above objectives, the present invention provides the following technical solution: A method for preparing a high-slip rubber sole includes the following steps: S1: Mix 50-60 parts by weight of modified epoxy resin, 10-20 parts by weight of polyurethane-acrylate copolymer, 20-30 parts by weight of modified PEG, 3-5 parts by weight of stearic acid, 1-4 parts by weight of zinc oxide, 3-5 parts by weight of zinc stearate, 2-4 parts by weight of zinc oxide, 1-3 parts by weight of magnesium oxide and 1-3 parts by weight of AC foaming agent in an internal mixer at 60-70°C for 30-60 min, and continue mixing at 90-95°C for 15-20 min. After open milling, granulate and let stand at room temperature for 20-24 h to obtain molding masterbatch. S2: Place the molding masterbatch into the foaming mold and press it into shape. The mold closing pressure is 15-25MPa. Then, heat the mold together to 180-190℃ and vulcanize for 8-15 minutes. Cool down and let it stand at room temperature for 20-24 hours to obtain a high-slip rubber shoe sole.

[0006] Preferably, the preparation method of the modified epoxy resin in step S1 is as follows: 2-aminosulfonic acid, epoxy resin and tetrabutylammonium bromide are dissolved in deionized water, the pH of the solution is adjusted to 8, the reaction is carried out at 90-95℃ for 3-4 hours, dicyandiamide and polyurea accelerator SH-A100 are added, and the mixture is stirred for 1-2 hours to obtain the modified epoxy resin.

[0007] Preferably, the weight ratio of 2-aminosulfonic acid, epoxy resin, tetrabutylammonium bromide, deionized water, dicyandiamide and polyurea accelerator SH-A100 is 1:3:2:20:2:1.

[0008] Preferably, the preparation method of modified PEG in step S1 is as follows: S11: Preparation of modified polybenzimidazole; S12: Mix modified polybenzimidazole, modified iron oxide, N-methylpyrrolidone and PEG (Mn:4000), stir the solution until clear, and obtain modified PEG.

[0009] Preferably, the weight ratio of the modified polybenzimidazole, modified iron oxide, N-methylpyrrolidone and PEG is 3:2:4:3.

[0010] Preferably, the preparation method of modified polybenzimidazole in step S11 is as follows: 1,6-dibromohexane, N-methylpiperidine and ethyl acetate solution are uniformly mixed, reacted at 50-60℃ for 36-48h, and cooled to room temperature to obtain the precursor; Under a nitrogen atmosphere, polybenzimidazole, dimethyl sulfoxide, and sodium hydride were added to the above precursor solution, and the reaction was continued at 70-80℃ for 36-48 h. After washing, filtration, and drying, modified polybenzimidazole was obtained.

[0011] Preferably, the weight ratio of the 1,6-dibromohexane, N-methylpiperidine, and ethyl acetate solution is 1:1:3; The weight ratio of polybenzimidazole, dimethyl sulfoxide, sodium hydride, and precursor solution is 1:3:1:1.

[0012] Preferably, the preparation method of modified iron oxide in step S12 is as follows: nano iron oxide, silane coupling agent and ethanol solution with a volume fraction of 25% are dispersed for 20-24 hours, stirred at 40-50℃ for 1-2 hours, stirred at 60-70℃ for 1-2 hours, graphene is added, cooled to room temperature, filtered, and dried to obtain modified iron oxide.

[0013] Preferably, the weight ratio of the nano-iron oxide, silane coupling agent, ethanol solution and graphene is 1:1:3:1.

[0014] A high-slip rubber sole is prepared by the above-mentioned preparation method, and the surface of the sole is also provided with anti-slip patterns.

[0015] The active hydrogen on the dicyandiamide of this invention can react with the epoxy groups of the epoxy resin to form strong chemical bonds and covalent bonds, thereby constituting a cross-linked network structure with high strength and adhesion. Furthermore, sulfonic acid groups are grafted onto the epoxy resin, which have a strong adsorption effect on the component particles, enhancing the interfacial adhesion between other components and the epoxy resin, improving the internal density of the components, forming a uniform and stable component structure, increasing the surface roughness of the material, increasing the effective contact area with the ground, and improving the anti-slip performance and friction of the material.

[0016] This invention modifies iron(III) oxide and incorporates a graphene network structure, giving it an extremely high specific surface area and excellent adsorption performance. The abundant active sites and covalent interactions improve the aggregation of components. The smaller nanostructures can fill within the PEG macromolecules, providing reinforcement and increasing the system density. Simultaneously, the modified PEG long-chain structure intertwines with the modified epoxy resin to form a cross-linked structure with a larger specific surface area and roughness. Furthermore, utilizing the microscopic guidance and isotropic structure of the modified iron(III) oxide, stress is dispersed through the cross-linked network structure, preventing localized stress concentration and reducing the wear volume of the sole material. The blended, vulcanized, and cross-linked rubber sole exhibits overall hydrophilicity. When in contact with water, these hydrophilic groups, such as sulfonic acid groups and modified PEG, can form weak covalent forces with water, increasing the contact area and bonding force with the sole, thereby enhancing grip and improving the overall wet slip resistance of the rubber sole. Attached Figure Description

[0017] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0018] Figure 1 This is a schematic diagram of the overall structure of a rubber shoe sole. Detailed Implementation

[0019] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. In addition, it should be specifically noted that the raw materials and equipment of the present invention are all commercially available and will not be listed one by one. Among them, the raw materials of the present invention are all commercially available and well known to those skilled in the art, and will not be described in detail.

[0020] Example 1: A method for preparing a high-slip rubber sole includes the following steps: S1: Mix 50 parts by weight of modified epoxy resin, 10 parts by weight of polyurethane-acrylate copolymer, 20 parts by weight of modified PEG, 3 parts by weight of stearic acid, 1 part by weight of zinc oxide, 3 parts by weight of zinc stearate, 2 parts by weight of zinc oxide, 1 part by weight of magnesium oxide and 1 part by weight of AC foaming agent in a mixer at 60°C for 30 min, and continue mixing at 90°C for 15 min. After open milling, granulate and let stand at room temperature for 20 h to obtain molding masterbatch. S2: Place the molding masterbatch into the foaming mold and press it into shape. The mold closing pressure is 15MPa. Then, heat the mold together to 180℃ and vulcanize for 8 minutes. Cool down and let it stand at room temperature for 20 hours to obtain a high anti-slip rubber shoe sole.

[0021] The preparation method of the modified epoxy resin in step S1 is as follows: 2-aminosulfonic acid, epoxy resin and tetrabutylammonium bromide are dissolved in deionized water, the pH of the solution is adjusted to 8, and the reaction is carried out at 90℃ for 3 hours. Dicyandiamide and polyurea accelerator SH-A100 are added. The weight ratio of 2-aminosulfonic acid, epoxy resin, tetrabutylammonium bromide, deionized water, dicyandiamide and polyurea accelerator SH-A100 is 1:3:2:20:2:1. The mixture is stirred for 1 hour to obtain the modified epoxy resin.

[0022] The specific method for preparing modified PEG in step S1 is as follows: S11: Preparation of modified polybenzimidazole: 1,6-dibromohexane, N-methylpiperidine and ethyl acetate solution were uniformly mixed in a weight ratio of 1:1:3, reacted at 50°C for 36 h, and cooled to room temperature to obtain the precursor; Under a nitrogen atmosphere, polybenzimidazole, dimethyl sulfoxide and sodium hydride were added to the above precursor solution in a weight ratio of 1:3:1:1. The reaction was continued at 70°C for 36 h. After washing, filtration and drying, modified polybenzimidazole was obtained. S12: Modified polybenzimidazole, modified iron oxide, N-methylpyrrolidone and PEG (Mn:4000) are mixed in a weight ratio of 3:2:4:3 and the solution is stirred until transparent to obtain modified PEG.

[0023] The specific preparation method of modified iron oxide is as follows: nano-iron oxide, silane coupling agent and ethanol solution with a volume fraction of 25% are dispersed for 20h, stirred at 40℃ for 1h, stirred at 60℃ for 1h, graphene is added, and the weight ratio of nano-iron oxide, silane coupling agent, ethanol solution and graphene is 1:1:3:1. The mixture is cooled to room temperature, filtered, and dried to obtain modified iron oxide.

[0024] A high-slip rubber sole is prepared by the above-mentioned preparation method, and the surface of the sole is also provided with anti-slip patterns.

[0025] Example 2: A method for preparing a high-slip rubber sole includes the following steps: S1: 55 parts by weight of modified epoxy resin, 15 parts by weight of polyurethane-acrylate copolymer, 25 parts by weight of modified PEG, 4 parts by weight of stearic acid, 3 parts by weight of zinc oxide, 4 parts by weight of zinc stearate, 3 parts by weight of zinc oxide, 2 parts by weight of magnesium oxide and 2 parts by weight of AC foaming agent are mixed evenly in an internal mixer at 65°C for 45 min, and then mixed at 92°C for 18 min. After open milling, the mixture is granulated and allowed to stand at room temperature for 22 h to obtain molding masterbatch. S2: Place the molding masterbatch into the foaming mold and press it into shape. The mold closing pressure is 20MPa. Then, heat the mold together to 185℃ and vulcanize for 10 minutes. Cool down and let it stand at room temperature for 22 hours to obtain a high anti-slip rubber shoe sole.

[0026] The preparation method of the modified epoxy resin in step S1 is as follows: 2-aminosulfonic acid, epoxy resin and tetrabutylammonium bromide are dissolved in deionized water, the pH of the solution is adjusted to 8, and the reaction is carried out at 92℃ for 3.5h. Dicyandiamide and polyurea accelerator SH-A100 are added. The weight ratio of 2-aminosulfonic acid, epoxy resin, tetrabutylammonium bromide, deionized water, dicyandiamide and polyurea accelerator SH-A100 is 1:3:2:20:2:1. The mixture is stirred for 1.5h to obtain the modified epoxy resin.

[0027] The specific method for preparing modified PEG in step S1 is as follows: S11: Preparation of modified polybenzimidazole: 1,6-dibromohexane, N-methylpiperidine and ethyl acetate solution were uniformly mixed in a weight ratio of 1:1:3, reacted at 55℃ for 40h, and cooled to room temperature to obtain the precursor; Under a nitrogen atmosphere, polybenzimidazole, dimethyl sulfoxide and sodium hydride were added to the above precursor solution in a weight ratio of 1:3:1:1. The reaction was continued at 75°C for 40 h. After washing, filtration and drying, modified polybenzimidazole was obtained. S12: Modified polybenzimidazole, modified iron oxide, N-methylpyrrolidone and PEG (Mn:4000) are mixed in a weight ratio of 3:2:4:3 and the solution is stirred until transparent to obtain modified PEG.

[0028] The specific preparation method of modified iron oxide is as follows: nano-iron oxide, silane coupling agent and ethanol solution with a volume fraction of 25% are dispersed for 22 hours, stirred at 45℃ for 1.5 hours, stirred at 65℃ for another 1.5 hours, graphene is added, and the weight ratio of nano-iron oxide, silane coupling agent, ethanol solution and graphene is 1:1:3:1. The mixture is cooled to room temperature, filtered, and dried to obtain modified iron oxide.

[0029] A high-slip rubber sole is prepared by the above-mentioned preparation method, and the surface of the sole is also provided with anti-slip patterns.

[0030] Example 3: A method for preparing a high-slip rubber sole includes the following steps: S1: 60 parts by weight of modified epoxy resin, 20 parts by weight of polyurethane-acrylate copolymer, 30 parts by weight of modified PEG, 5 parts by weight of stearic acid, 4 parts by weight of zinc oxide, 5 parts by weight of zinc stearate, 4 parts by weight of zinc oxide, 3 parts by weight of magnesium oxide and 3 parts by weight of AC foaming agent are mixed evenly in an internal mixer at 70°C for 60 min, and then mixed at 95°C for 20 min. After open milling, the mixture is granulated and allowed to stand at room temperature for 24 h to obtain molding masterbatch. S2: Place the molding masterbatch into the foaming mold and press it into shape. The mold closing pressure is 25MPa. Then, heat the mold together to 190℃ and vulcanize for 15 minutes. Cool down and let it stand at room temperature for 24 hours to obtain a high anti-slip rubber shoe sole.

[0031] The preparation method of the modified epoxy resin in step S1 is as follows: 2-aminosulfonic acid, epoxy resin and tetrabutylammonium bromide are dissolved in deionized water, the pH of the solution is adjusted to 8, and the reaction is carried out at 95°C for 4 hours. Dicyandiamide and polyurea accelerator SH-A100 are added. The weight ratio of 2-aminosulfonic acid, epoxy resin, tetrabutylammonium bromide, deionized water, dicyandiamide and polyurea accelerator SH-A100 is 1:3:2:20:2:1. The mixture is stirred for 2 hours to obtain the modified epoxy resin.

[0032] The specific method for preparing modified PEG in step S1 is as follows: S11: Preparation of modified polybenzimidazole: 1,6-dibromohexane, N-methylpiperidine and ethyl acetate solution were uniformly mixed in a weight ratio of 1:1:3, reacted at 60℃ for 48h, and cooled to room temperature to obtain the precursor; Under a nitrogen atmosphere, polybenzimidazole, dimethyl sulfoxide and sodium hydride were added to the above precursor solution in a weight ratio of 1:3:1:1. The reaction was continued at 80°C for 48 h. After washing, filtration and drying, modified polybenzimidazole was obtained. S12: Modified polybenzimidazole, modified iron oxide, N-methylpyrrolidone and PEG (Mn:4000) are mixed in a weight ratio of 3:2:4:3 and the solution is stirred until transparent to obtain modified PEG.

[0033] The specific preparation method of modified iron oxide is as follows: nano-iron oxide, silane coupling agent and ethanol solution with a volume fraction of 25% are stirred at 50℃ for 2 hours for 24 hours, and then stirred at 70℃ for 2 hours. Graphene is added. The weight ratio of nano-iron oxide, silane coupling agent, ethanol solution and graphene is 1:1:3:1. The mixture is cooled to room temperature, filtered and dried to obtain modified iron oxide.

[0034] A high-slip rubber sole is prepared by the above-mentioned preparation method, and the surface of the sole is also provided with anti-slip patterns.

[0035] Comparative Example 1: The preparation method of Comparative Example 1 is basically the same as that of Example 1, except that the epoxy resin and PEG are not modified. Specifically: A method for preparing a high-slip rubber sole includes the following steps: S1: Mix 50 parts by weight of epoxy resin, 10 parts by weight of polyurethane-acrylate copolymer, 20 parts by weight of PEG, 3 parts by weight of stearic acid, 1 part by weight of zinc oxide, 3 parts by weight of zinc stearate, 2 parts by weight of zinc oxide, 1 part by weight of magnesium oxide and 1 part by weight of AC foaming agent in a mixer at 60°C for 30 min, and continue mixing at 90°C for 15 min. After open milling, granulate and let stand at room temperature for 20 h to obtain molding masterbatch. S2: Place the molding masterbatch into the foaming mold and press it into shape. The mold closing pressure is 15MPa. Then, heat the mold together to 180℃ and vulcanize for 8 minutes. Cool down and let it stand at room temperature for 20 hours to obtain a high anti-slip rubber shoe sole.

[0036] A high-slip rubber sole is prepared by the above-described method, and the sole surface is further provided with anti-slip patterns. The following tests were conducted on the anti-slip effect and abrasion resistance of the soles obtained in Examples 1-3, the commercially available soles from Wangdu County Jiaoshang Shoes Co., Ltd., and the soles obtained in Comparative Example 1.

[0037] Anti-slip coefficient: Tested according to the methods specified in GB / T3903.6-2017 and SATRA TM144:2021.

[0038] Abrasion resistance: Tested according to the method specified in national standard GB / T 9867-2008.

[0039] Table 1: Test data of Examples 1-3, commercially available shoe soles, and the shoe sole of Comparative Example 1 As can be seen from the table above, the soles of Examples 1-3 have better anti-slip performance than Comparative Example 1 and commercially available soles (simultaneously meeting the requirements of dynamic wet anti-slip coefficient ≥0.40 and ice surface anti-slip coefficient ≥0.30), and also have excellent wear resistance.

[0040] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily 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 invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing a high-slip rubber shoe sole, characterized in that, Includes the following steps: S1: Mix 50-60 parts by weight of modified epoxy resin, 10-20 parts by weight of polyurethane-acrylate copolymer, 20-30 parts by weight of modified PEG, 3-5 parts by weight of stearic acid, 1-4 parts by weight of zinc oxide, 3-5 parts by weight of zinc stearate, 2-4 parts by weight of zinc oxide, 1-3 parts by weight of magnesium oxide and 1-3 parts by weight of AC foaming agent in an internal mixer at 60-70°C for 30-60 min, and continue mixing at 90-95°C for 15-20 min. After open milling, granulate and let stand at room temperature for 20-24 h to obtain molding masterbatch. S2: Place the molding masterbatch into the foaming mold and press it into shape. The mold closing pressure is 15-25MPa. Then, heat the mold together to 180-190℃ and vulcanize for 8-15 minutes. Cool down and let it stand at room temperature for 20-24 hours to obtain a high-slip rubber shoe sole.

2. The method for preparing a high-slip rubber sole as described in claim 1, characterized in that: The specific preparation method of the modified epoxy resin in step S1 is as follows: 2-aminosulfonic acid, epoxy resin and tetrabutylammonium bromide are dissolved in deionized water, the pH of the solution is adjusted to 8, the reaction is carried out at 90-95℃ for 3-4 hours, dicyandiamide and polyurea accelerator SH-A100 are added, and the mixture is stirred for 1-2 hours to obtain the modified epoxy resin.

3. The method for preparing a high-slip rubber sole as described in claim 2, characterized in that: The weight ratio of 2-aminosulfonic acid, epoxy resin, tetrabutylammonium bromide, deionized water, dicyandiamide, and polyurea accelerator SH-A100 is 1:3:2:20:2:

1.

4. The method for preparing a high-slip rubber sole as described in claim 1, characterized in that: The specific method for preparing modified PEG in step S1 is as follows: S11: Preparation of modified polybenzimidazole; S12: Mix modified polybenzimidazole, modified iron oxide, N-methylpyrrolidone and PEG (Mn:4000), stir the solution until clear, and obtain modified PEG.

5. The method for preparing a high-slip rubber sole as described in claim 4, characterized in that: The weight ratio of the modified polybenzimidazole, modified iron oxide, N-methylpyrrolidone and PEG is 3:2:4:

3.

6. The method for preparing a high-slip rubber sole as described in claim 4, characterized in that: The specific preparation method of modified polybenzimidazole in step S11 is as follows: 1,6-dibromohexane, N-methylpiperidine and ethyl acetate solution are uniformly mixed, reacted at 50-60℃ for 36-48h, and cooled to room temperature to obtain the precursor; Under a nitrogen atmosphere, polybenzimidazole, dimethyl sulfoxide, and sodium hydride were added to the above precursor solution, and the reaction was continued at 70-80℃ for 36-48 h. After washing, filtration, and drying, modified polybenzimidazole was obtained.

7. The method for preparing a high-slip rubber sole as described in claim 6, characterized in that: The weight ratio of the 1,6-dibromohexane, N-methylpiperidine, and ethyl acetate solution is 1:1:

3. The weight ratio of polybenzimidazole, dimethyl sulfoxide, sodium hydride, and precursor solution is 1:3:1:

1.

8. The method for preparing a high-slip rubber sole as described in claim 4, characterized in that: The specific preparation method of modified iron oxide in step S12 is as follows: nano iron oxide, silane coupling agent and ethanol solution with a volume fraction of 25% are dispersed for 20-24 hours, stirred at 40-50℃ for 1-2 hours, stirred at 60-70℃ for 1-2 hours, graphene is added, cooled to room temperature, filtered, and dried to obtain modified iron oxide.

9. The method for preparing a high-slip rubber sole as described in claim 8, characterized in that: The weight ratio of the nano-iron oxide, silane coupling agent, ethanol solution and graphene is 1:1:3:

1.

10. A high-slip rubber sole, characterized in that, The sole is prepared by the preparation method described in claim 1, and the surface of the sole is further provided with anti-slip patterns.

Images