TPE (thermoplastic elastomer) and reclaimed rubber blended high-wear-resistance child insole material and preparation method thereof

Abstract

The invention discloses a TPE and reclaimed rubber blended high-wear-resistance child insole material and a preparation method thereof. The child insole material comprises 60-85 parts of TPE, 10-30 parts of reclaimed rubber, 10-20 parts of a solubilizer, 0.5-1.5 parts of a silane coupling agent, 5-10 parts of a polyester elastomer, 1-5 parts of a wear-resistant aid, 2-8 parts of a plasticizer, 0.1-2 parts of an antibacterial agent and 0.1-1 part of an antioxidant. According to the material, the TPE is compounded with the reclaimed rubber, the polyester elastomer, the wear-resistant additive, the silane coupling agent, the plasticizer, the solubilizer, the antibacterial agent, the antioxidant and other materials, so that the material has the advantages of better wear resistance, better elasticity and the like.

Description

Technical Field

[0001] This invention relates to the field of children's insole technology, and in particular to a high abrasion-resistant children's insole material made from a blend of TPE and recycled rubber, and its preparation method. Background Technology

[0002] Most existing children's insole materials are made of pure TPE or EVA foam, which have good elasticity and comfort, but lack wear resistance and are prone to surface wear and deformation after long-term use.

[0003] Reclaimed rubber, as a product of waste rubber resource utilization, has the characteristics of low cost and good wear resistance, but it has poor compatibility with TPE. Direct blending can easily lead to the deterioration of mechanical properties.

[0004] In the existing technology, compatibilizers are added to the blend of TPE and reclaimed rubber. Although compatibilizers can improve the compatibility between the two, existing blends of TPE and reclaimed rubber still have problems such as poor wear resistance and insufficient elasticity. Summary of the Invention

[0005] In order to overcome the shortcomings of the prior art, one of the objectives of this invention is to provide a high abrasion-resistant children's insole material blended with TPE and recycled rubber, so as to solve the above-mentioned traditional technical problems.

[0006] The second objective of this invention is to provide a method for preparing the above-mentioned high abrasion-resistant children's insole material blended with TPE and recycled rubber.

[0007] One of the objectives of this invention is achieved through the following technical solution: A high-abrasion-resistant children's insole material blended with TPE and recycled rubber, comprising the following components in parts by weight: 60-85 parts TPE, 10-30 parts reclaimed rubber, 10-20 parts solubilizer, 0.5-1.5 parts silane coupling agent, 5-10 parts polyester elastomer, 1-5 parts abrasion resistant agent, 2-8 parts plasticizer, 0.1-2 parts antibacterial agent, and 0.1-1 part antioxidant.

[0008] Furthermore, the TPE has a particle size requirement of 0.5-2 mm; the reclaimed rubber has a particle size requirement of 1-3 mm.

[0009] Furthermore, the solubilizer is maleic anhydride grafted with SEBS, with a grafting rate of 1.4%-2%.

[0010] Furthermore, the silane coupling agent is one or more of KH550 and KH570.

[0011] Furthermore, the polyester elastomer comprises the following components in parts by weight: 20-40 parts of the first reactant, 20-40 parts of the second reactant, and 0.1-1 parts of the catalyst; The first reactant is one or more of 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, and neopentyl glycol; the second reactant is one or more of 3,4-furandicarboxylic acid, 2-methylfuran-3,4-dicarboxylic acid, 2,5-dimethylfuran-3,4-dicarboxylic acid, 2,5-dicarboxylic acid di ...

[0012] Furthermore, the preparation steps of the polyester elastomer are as follows: In a polymerization reactor, the first reactant, the second reactant, and the catalyst are added, and esterification is carried out at 200℃-230℃ for 2-2.5 hours. Then, the vacuum is evacuated to a vacuum degree of less than 80 Pa, and polycondensation is carried out at 240℃-260℃ for 2-3 hours. Finally, the product is pressed into granules to obtain the final product.

[0013] Furthermore, the plasticizer is one or more of paraffin oil and naphthenic oil, and the wear-resistant agent is polyamide short fiber.

[0014] Furthermore, the antibacterial agent is alkyl dimethyl benzyl ammonium chloride and / or dialcyl dimethyl ammonium chloride; the antioxidant is antioxidant 1010 and / or antioxidant 168.

[0015] The second objective of this invention is achieved by the following technical solution: A method for preparing a high abrasion-resistant children's insole material blended with TPE and recycled rubber includes the following steps: S1: In a mixer at a temperature of 120℃-200℃, TPE is mixed with silane coupling agent, polyester elastomer, wear-resistant agent, plasticizer and antibacterial agent for 20 min-30 min to obtain a blend mixture; S2: Irradiate the blend to obtain a crosslinked product; wherein the irradiation dose is 50 kGy - 150 kGy; S3: Using a twin-screw extruder, the above crosslinked material is melt-blended with reclaimed rubber, solubilizer and antioxidant. The melt is then calendered to obtain the final product.

[0016] Furthermore, the temperature settings of the twin-screw extruder are as follows: Zone 1 130℃-140℃, Zone 2 150℃-160℃, Zone 3 170℃-180℃, and die head 185℃-190℃; the screw speed of the twin-screw extruder is 90 rpm-110 rpm, and the residence time is 3 min-5 min; the calendering temperature is 160℃-170℃, and the pressure is 4 MPa-6 MPa.

[0017] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. The material of the present invention is compounded with TPE and reclaimed rubber, polyester elastomer, wear-resistant additives, silane coupling agents, plasticizers, solubilizers, antibacterial agents and antioxidants, etc., so that the material has the advantages of good wear resistance and good elasticity.

[0018] 2. The material of this invention adopts a "pre-crosslinking followed by blending" process, which enables the TPE matrix to form a stable crosslinked network before the introduction of reclaimed rubber, significantly improving the material's resistance to deformation and dynamic abrasion resistance; the polyester elastomer, as a rigid reinforcing phase, works synergistically with the crosslinked TPE to improve the material's thermal stability and resilience; the solubilizer effectively improves the interfacial bonding between the reclaimed rubber and the crosslinked TPE in the later stage of blending, avoiding phase separation; the silane coupling agent reacts with the hydroxyl groups on the surface of TPE and polyester elastomer in the pre-crosslinking stage, enhancing intermolecular bonding and improving the overall mechanical properties. Detailed Implementation

[0019] To address the problems of poor abrasion resistance, poor deformation resistance, and insufficient elasticity in existing TPE and reclaimed rubber blends, this invention provides a high abrasion-resistant children's insole material made from a blend of TPE and reclaimed rubber, which exhibits better abrasion resistance and elasticity.

[0020] Specifically, this TPE and recycled rubber blended high abrasion-resistant children's insole material comprises the following components in parts by weight: 60-85 parts TPE, 10-30 parts reclaimed rubber, 10-20 parts solubilizer, 0.5-1.5 parts silane coupling agent, 5-10 parts polyester elastomer, 1-5 parts abrasion resistant agent, 2-8 parts plasticizer, 0.1-2 parts antibacterial agent, and 0.1-1 part antioxidant.

[0021] The preparation steps for this children's insole material include the following steps: In a mixer at a temperature of 120℃-200℃, 60-85 parts of TPE, 0.5-1.5 parts of silane coupling agent, 5-10 parts of polyester elastomer, 1-5 parts of abrasion resistant agent, 2-8 parts of plasticizer and 0.1-2 parts of antibacterial agent are mixed for 20 min-30 min to obtain a blend. The blend was irradiated with an electron beam (EB) or gamma rays to induce the formation of a carbon-carbon cross-linked network between the molecular chains, resulting in a cross-linked product; the irradiation dose was 50 kGy - 150 kGy. Using a twin-screw extruder, the above-mentioned crosslinked material is melt-blended with 10-30 parts of reclaimed rubber, 10-20 parts of solubilizer, and 0.1-1 parts of antioxidant. The melt is then calendered to obtain the final product. The twin-screw extruder temperatures are set as follows: Zone 1 130℃-140℃, Zone 2 150℃-160℃, Zone 3 170℃-180℃, and die head 185℃-190℃; the screw speed is 90 rpm-110 rpm, and the residence time is 3 min-5 min; the calendering temperature is 160℃-170℃, and the pressure is 4 MPa-6 MPa. The molded insole material is obtained by naturally cooling to room temperature. After demolding, the edges can be trimmed.

[0022] In the above invention, a "pre-crosslinking followed by blending" process is adopted, which enables the TPE matrix to form a stable crosslinked network before the introduction of reclaimed rubber, significantly improving the material's resistance to deformation and dynamic wear resistance; the polyester elastomer, as a rigid reinforcing phase, works synergistically with the crosslinked TPE to improve the material's thermal stability and resilience; the solubilizer effectively improves the interfacial bonding between the reclaimed rubber and the crosslinked TPE in the later stage of blending, avoiding phase separation; the silane coupling agent reacts with the hydroxyl groups on the surface of TPE and polyester elastomer in the pre-crosslinking stage, enhancing intermolecular bonding and improving the overall mechanical properties.

[0023] In this embodiment, TPE (thermoplastic elastomer) is a material that combines the elasticity of rubber and the processability of plastic, with a particle size requirement of 0.5-2mm, and was purchased from Shenzhen Suyuan Industrial Co., Ltd.

[0024] Reclaimed rubber, also known as recycled rubber, is a rubber material with plasticity and elasticity obtained by using waste rubber products (such as tires, hoses, shoe soles, etc.) as raw materials and processing them through physical and chemical processes such as desulfurization, crushing, and refining. The particle size requirement is 1-3mm. It was purchased from Shandong Dingfang Rubber Co., Ltd. and is butyl reclaimed rubber.

[0025] The solubilizer is maleic anhydride grafted SEBS, purchased from Dongguan Yucheng Plastic Chemical Co., Ltd., G7720-1001, with a grafting rate of 1.4%-2%. The silane coupling agent is one or more of KH550 and KH570, purchased from Hubei Chengfeng Chemical.

[0026] Polyester elastomers comprise the following components in parts by weight: 20-40 parts of the first reactant, 20-40 parts of the second reactant, and 0.1-1 parts of the catalyst.

[0027] The preparation steps of polyester elastomer are as follows: In a polymerization reactor, the first reactant, the second reactant, and the catalyst are added, and esterification is carried out at 200℃-230℃ for 2-2.5 hours. Then, the vacuum is evacuated to a vacuum degree of less than 80 Pa, and polycondensation is carried out at 240℃-260℃ for 2-3 hours. Finally, the product is pressed into granules to obtain the final product. The first reactant is one or more of 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, and neopentyl glycol; the second reactant is one or more of 3,4-furandicarboxylic acid, 2-methylfuran-3,4-dicarboxylic acid, 2,5-dimethylfuran-3,4-dicarboxylic acid, 2,5-dicarboxyloylfuran-3,4-dicarboxylic acid, 2-phenylfuran-3,4-dicarboxylic acid, 2-(4-methoxyphenyl)-3,4-furandicarboxylic acid, 2,5-diphenylfuran-3,4-dicarboxylic acid, and [2,2'-bifuran]-5,5'-dicarboxylic acid; and the catalyst is antimony trioxide. The particle size of the polyester elastomer is required to be 1-5 mm.

[0028] The plasticizers, one or more of paraffin oil and naphthenic oil, were purchased from Guangzhou Housheng New Materials Co., Ltd. The wear-resistant additives, polyamide staple fibers with a monofilament diameter of 8-15 μm, were purchased from Hengtian Zhongxian Textile Chemical Wuxi Co., Ltd. The antibacterial agents, alkyl dimethyl benzyl ammonium chloride and / or dialcyl dimethyl ammonium chloride, were purchased from Wuhan Rongcan Biotechnology Co., Ltd. The antioxidants, antioxidant 1010 and / or antioxidant 168, were purchased from Kandis Chemical (Hubei) Co., Ltd.

[0029] The present invention will now be further described in conjunction with specific embodiments. It should be noted that, without conflict, the various embodiments or technical features described below can be arbitrarily combined to form new embodiments. In the following embodiments, the materials are all components in parts by weight.

[0030] Example 1: A children's insole material includes the following steps: In a mixer at 180°C, 70 parts of TPE, 1 part of silane coupling agent, 8 parts of polyester elastomer, 2 parts of abrasion resistant agent, 2 parts of plasticizer and 0.3 parts of antibacterial agent are mixed for 30 minutes to obtain a blend. The blend was irradiated with gamma rays to induce the formation of a carbon-carbon cross-linked network between the molecular chains, resulting in a cross-linked product; the irradiation dose was 50 kGy. Using a twin-screw extruder, the above-mentioned crosslinked compound was melt-blended with 20 parts of reclaimed rubber, 15 parts of solubilizer, and 0.1 parts of antioxidant. The melt was then calendered. The twin-screw extruder temperatures were set as follows: Zone 1 135℃, Zone 2 155℃, Zone 3 175℃, and die head 185℃; the screw speed was 100 rpm, and the residence time was 4 min; the calender temperature was 165℃, and the pressure was 5 MPa. The molded insole material is obtained by naturally cooling to room temperature. After demolding, the edges can be trimmed.

[0031] The TPE particle size was 0.5-2mm, purchased from Shenzhen Suyuan Industrial Co., Ltd.; the reclaimed rubber particle size was 1-3mm, purchased from Shandong Dingfang Rubber Co., Ltd.; the solubilizer was maleic anhydride-grafted SEBS, purchased from Dongguan Yucheng Plastic Chemical Co., Ltd., G7720-1001, with a grafting rate of 1.4%-2%; the silane coupling agent was KH550, purchased from Hubei Chengfeng Chemical; the plasticizer was paraffin oil, purchased from Guangzhou Housheng New Materials Co., Ltd.; the wear-resistant additive was polyamide short fiber, with a single filament diameter of 8-15μm, purchased from Hengtian Zhongxian Textile Chemical Wuxi Co., Ltd.; the antibacterial agent was alkyl dimethyl benzyl ammonium chloride, purchased from Wuhan Rongcan Biotechnology Co., Ltd.; and the antioxidant was antioxidant 1010, purchased from Kandis Chemical (Hubei) Co., Ltd.

[0032] The preparation steps of polyester elastomer are as follows: In a polymerization reactor, 30 parts of the first reactant, 30 parts of the second reactant, and 1 part of the catalyst were added. Esterification was carried out at 200℃ for 2 hours, followed by vacuuming to a vacuum degree of less than 80 Pa, and polycondensation was carried out at 260℃ for 3 hours. The resulting product was then pressed into particles of 1-5 mm. The first reactant was trimethylolpropane, purchased from Jinan Century Tongda Chemical Co., Ltd.; the second reactant was 2,5-dicarboxylic acid 2,5-diformylfuran-3,4-dicarboxylic acid, purchased from Shandong Suitai Biotechnology Co., Ltd.; and the catalyst was antimony trioxide.

[0033] Example 2: A children's insole material includes the following steps: In a mixer at 180°C, 70 parts of TPE, 1 part of silane coupling agent, 8 parts of polyester elastomer, 2 parts of abrasion resistant agent, 2 parts of plasticizer and 0.3 parts of antibacterial agent are mixed for 30 minutes to obtain a blend. The blend was irradiated with gamma rays to induce the formation of a carbon-carbon cross-linked network between the molecular chains, resulting in a cross-linked product; the irradiation dose was 100 kGy. Using a twin-screw extruder, the above-mentioned crosslinked compound was melt-blended with 20 parts of reclaimed rubber, 15 parts of solubilizer, and 0.1 parts of antioxidant. The melt was then calendered. The twin-screw extruder temperatures were set as follows: Zone 1 135℃, Zone 2 155℃, Zone 3 175℃, and die head 185℃; the screw speed was 100 rpm, and the residence time was 4 min; the calender temperature was 165℃, and the pressure was 5 MPa. The molded insole material is obtained by naturally cooling to room temperature. After demolding, the edges can be trimmed.

[0034] The TPE particle size was 0.5-2mm, purchased from Shenzhen Suyuan Industrial Co., Ltd.; the reclaimed rubber particle size was 1-3mm, purchased from Shandong Dingfang Rubber Co., Ltd.; the solubilizer was maleic anhydride-grafted SEBS, purchased from Dongguan Yucheng Plastic Chemical Co., Ltd., G7720-1001, with a grafting rate of 1.4%-2%; the silane coupling agent was KH550, purchased from Hubei Chengfeng Chemical; the plasticizer was paraffin oil, purchased from Guangzhou Housheng New Materials Co., Ltd.; the wear-resistant additive was polyamide short fiber, with a single filament diameter of 8-15μm, purchased from Hengtian Zhongxian Textile Chemical Wuxi Co., Ltd.; the antibacterial agent was alkyl dimethyl benzyl ammonium chloride, purchased from Wuhan Rongcan Biotechnology Co., Ltd.; and the antioxidant was antioxidant 1010, purchased from Kandis Chemical (Hubei) Co., Ltd.

[0035] The preparation steps of polyester elastomer are as follows: In a polymerization reactor, 30 parts of the first reactant, 30 parts of the second reactant, and 1 part of the catalyst were added. Esterification was carried out at 200℃ for 2 hours, followed by vacuuming to a vacuum degree of less than 80 Pa, and polycondensation was carried out at 260℃ for 3 hours. The resulting product was then pressed into particles of 1-5 mm. The first reactant was trimethylolpropane, purchased from Jinan Century Tongda Chemical Co., Ltd.; the second reactant was 2,5-dicarboxylic acid 2,5-diformylfuran-3,4-dicarboxylic acid, purchased from Shandong Suitai Biotechnology Co., Ltd.; and the catalyst was antimony trioxide.

[0036] Example 3: A children's insole material includes the following steps: In a mixer at 180°C, 70 parts of TPE, 1 part of silane coupling agent, 8 parts of polyester elastomer, 2 parts of abrasion resistant agent, 2 parts of plasticizer and 0.3 parts of antibacterial agent are mixed for 30 minutes to obtain a blend. The blend was irradiated with gamma rays to induce the formation of a carbon-carbon cross-linked network between molecular chains, resulting in a cross-linked product; the irradiation dose was 150 kGy. Using a twin-screw extruder, the above-mentioned crosslinked compound was melt-blended with 20 parts of reclaimed rubber, 15 parts of solubilizer, and 0.1 parts of antioxidant. The melt was then calendered. The twin-screw extruder temperatures were set as follows: Zone 1 135℃, Zone 2 155℃, Zone 3 175℃, and die head 185℃; the screw speed was 100 rpm, and the residence time was 4 min; the calender temperature was 165℃, and the pressure was 5 MPa. The molded insole material is obtained by naturally cooling to room temperature. After demolding, the edges can be trimmed.

[0037] The TPE particle size was 0.5-2mm, purchased from Shenzhen Suyuan Industrial Co., Ltd.; the reclaimed rubber particle size was 1-3mm, purchased from Shandong Dingfang Rubber Co., Ltd.; the solubilizer was maleic anhydride-grafted SEBS, purchased from Dongguan Yucheng Plastic Chemical Co., Ltd., G7720-1001, with a grafting rate of 1.4%-2%; the silane coupling agent was KH550, purchased from Hubei Chengfeng Chemical; the plasticizer was paraffin oil, purchased from Guangzhou Housheng New Materials Co., Ltd.; the wear-resistant additive was polyamide short fiber, with a single filament diameter of 8-15μm, purchased from Hengtian Zhongxian Textile Chemical Wuxi Co., Ltd.; the antibacterial agent was alkyl dimethyl benzyl ammonium chloride, purchased from Wuhan Rongcan Biotechnology Co., Ltd.; and the antioxidant was antioxidant 1010, purchased from Kandis Chemical (Hubei) Co., Ltd.

[0038] The preparation steps of polyester elastomer are as follows: In a polymerization reactor, 30 parts of the first reactant, 30 parts of the second reactant, and 1 part of the catalyst were added. Esterification was carried out at 200℃ for 2 hours, followed by vacuuming to a vacuum degree of less than 80 Pa, and polycondensation was carried out at 260℃ for 3 hours. The resulting product was then pressed into particles of 1-5 mm. The first reactant was trimethylolpropane, purchased from Jinan Century Tongda Chemical Co., Ltd.; the second reactant was 2,5-dicarboxylic acid 2,5-diformylfuran-3,4-dicarboxylic acid, purchased from Shandong Suitai Biotechnology Co., Ltd.; and the catalyst was antimony trioxide.

[0039] Comparative Example 1 A children's insole material includes the following steps: In a mixer at 180°C, 70 parts of TPE, 1 part of silane coupling agent, 2 parts of wear-resistant agent, 2 parts of plasticizer and 0.3 parts of antibacterial agent are mixed for 30 minutes to obtain a blend. The blend was irradiated with gamma rays to induce the formation of a carbon-carbon cross-linked network between the molecular chains, resulting in a cross-linked product; the irradiation dose was 50 kGy. Using a twin-screw extruder, the above-mentioned crosslinked compound was melt-blended with 20 parts of reclaimed rubber, 15 parts of solubilizer, and 0.1 parts of antioxidant. The melt was then calendered. The twin-screw extruder temperatures were set as follows: Zone 1 135℃, Zone 2 155℃, Zone 3 175℃, and die head 185℃; the screw speed was 100 rpm, and the residence time was 4 min; the calender temperature was 165℃, and the pressure was 5 MPa. The molded insole material is obtained by naturally cooling to room temperature. After demolding, the edges can be trimmed.

[0040] The TPE particle size was 0.5-2mm, purchased from Shenzhen Suyuan Industrial Co., Ltd.; the reclaimed rubber particle size was 1-3mm, purchased from Shandong Dingfang Rubber Co., Ltd.; the solubilizer was maleic anhydride-grafted SEBS, purchased from Dongguan Yucheng Plastic Chemical Co., Ltd., G7720-1001, with a grafting rate of 1.4%-2%; the silane coupling agent was KH550, purchased from Hubei Chengfeng Chemical; the plasticizer was paraffin oil, purchased from Guangzhou Housheng New Materials Co., Ltd.; the wear-resistant additive was polyamide short fiber, with a single filament diameter of 8-15μm, purchased from Hengtian Zhongxian Textile Chemical Wuxi Co., Ltd.; the antibacterial agent was alkyl dimethyl benzyl ammonium chloride, purchased from Wuhan Rongcan Biotechnology Co., Ltd.; and the antioxidant was antioxidant 1010, purchased from Kandis Chemical (Hubei) Co., Ltd.

[0041] Comparative Example 2 A children's insole material includes the following steps: In a mixer at 180°C, 70 parts of TPE, 1 part of silane coupling agent, 8 parts of polyester elastomer, 2 parts of plasticizer and 0.3 parts of antibacterial agent were mixed for 30 minutes to obtain a blend. The blend was irradiated with gamma rays to induce the formation of a carbon-carbon cross-linked network between the molecular chains, resulting in a cross-linked product; the irradiation dose was 50 kGy. Using a twin-screw extruder, the above-mentioned crosslinked compound was melt-blended with 20 parts of reclaimed rubber, 15 parts of solubilizer, and 0.1 parts of antioxidant. The melt was then calendered. The twin-screw extruder temperatures were set as follows: Zone 1 135℃, Zone 2 155℃, Zone 3 175℃, and die head 185℃; the screw speed was 100 rpm, and the residence time was 4 min; the calender temperature was 165℃, and the pressure was 5 MPa. The molded insole material is obtained by naturally cooling to room temperature. After demolding, the edges can be trimmed.

[0042] The TPE particles, with a particle size of 0.5-2mm, were purchased from Shenzhen Suyuan Industrial Co., Ltd.; the reclaimed rubber particles, with a particle size requirement of 1-3mm, were purchased from Shandong Dingfang Rubber Co., Ltd.; the solubilizer, maleic anhydride-grafted SEBS, was purchased from Dongguan Yucheng Plastic Chemical Co., Ltd., G7720-1001, with a grafting rate of 1.4%-2%; the silane coupling agent, KH550, was purchased from Hubei Chengfeng Chemical; the plasticizer, paraffin oil, was purchased from Guangzhou Housheng New Materials Co., Ltd.; the antibacterial agent, alkyl dimethyl benzyl ammonium chloride, was purchased from Wuhan Rongcan Biotechnology Co., Ltd.; and the antioxidant, antioxidant 1010, was purchased from Kandis Chemical (Hubei) Co., Ltd.

[0043] The preparation steps of polyester elastomer are as follows: In a polymerization reactor, 30 parts of the first reactant, 30 parts of the second reactant, and 1 part of the catalyst were added. Esterification was carried out at 200℃ for 2 hours, followed by vacuuming to a vacuum degree of less than 80 Pa, and polycondensation was carried out at 260℃ for 3 hours. The resulting product was then pressed into particles of 1-5 mm. The first reactant was trimethylolpropane, purchased from Jinan Century Tongda Chemical Co., Ltd.; the second reactant was 2,5-dicarboxylic acid 2,5-diformylfuran-3,4-dicarboxylic acid, purchased from Shandong Suitai Biotechnology Co., Ltd.; and the catalyst was antimony trioxide.

[0044] Comparative Example 3 A children's insole material includes the following steps: In a mixer at 180°C, 70 parts of TPE, 1 part of silane coupling agent, 8 parts of polyester elastomer, 2 parts of abrasion resistant agent, 2 parts of plasticizer and 0.3 parts of antibacterial agent are mixed for 30 minutes to obtain a blend. The blend was irradiated with gamma rays to induce the formation of a carbon-carbon cross-linked network between the molecular chains, resulting in a cross-linked product; the irradiation dose was 30 kGy. Using a twin-screw extruder, the above-mentioned crosslinked compound was melt-blended with 20 parts of reclaimed rubber, 15 parts of solubilizer, and 0.1 parts of antioxidant. The melt was then calendered. The twin-screw extruder temperatures were set as follows: Zone 1 135℃, Zone 2 155℃, Zone 3 175℃, and die head 185℃; the screw speed was 100 rpm, and the residence time was 4 min; the calender temperature was 165℃, and the pressure was 5 MPa. The molded insole material is obtained by naturally cooling to room temperature. After demolding, the edges can be trimmed.

[0045] The TPE particle size was 0.5-2mm, purchased from Shenzhen Suyuan Industrial Co., Ltd.; the reclaimed rubber particle size was 1-3mm, purchased from Shandong Dingfang Rubber Co., Ltd.; the solubilizer was maleic anhydride-grafted SEBS, purchased from Dongguan Yucheng Plastic Chemical Co., Ltd., G7720-1001, with a grafting rate of 1.4%-2%; the silane coupling agent was KH550, purchased from Hubei Chengfeng Chemical; the plasticizer was paraffin oil, purchased from Guangzhou Housheng New Materials Co., Ltd.; the wear-resistant additive was polyamide short fiber, with a single filament diameter of 8-15μm, purchased from Hengtian Zhongxian Textile Chemical Wuxi Co., Ltd.; the antibacterial agent was alkyl dimethyl benzyl ammonium chloride, purchased from Wuhan Rongcan Biotechnology Co., Ltd.; and the antioxidant was antioxidant 1010, purchased from Kandis Chemical (Hubei) Co., Ltd.

[0046] The preparation steps of polyester elastomer are as follows: In a polymerization reactor, 30 parts of the first reactant, 30 parts of the second reactant, and 1 part of the catalyst were added. Esterification was carried out at 200℃ for 2 hours, followed by vacuuming to a vacuum degree of less than 80 Pa, and polycondensation was carried out at 260℃ for 3 hours. The resulting product was then pressed into particles of 1-5 mm. The first reactant was trimethylolpropane, purchased from Jinan Century Tongda Chemical Co., Ltd.; the second reactant was 2,5-dicarboxylic acid 2,5-diformylfuran-3,4-dicarboxylic acid, purchased from Shandong Suitai Biotechnology Co., Ltd.; and the catalyst was antimony trioxide.

[0047] Comparative Example 4 A children's insole material includes the following steps: In a mixer at 180°C, 70 parts of TPE, 1 part of silane coupling agent, 8 parts of polyester elastomer, 2 parts of abrasion resistant agent, 2 parts of plasticizer and 0.3 parts of antibacterial agent are mixed for 30 minutes to obtain a blend. The blend was irradiated with gamma rays to induce the formation of a carbon-carbon cross-linked network between molecular chains, resulting in a cross-linked product; the irradiation dose was 180 kGy. Using a twin-screw extruder, the above-mentioned crosslinked compound was melt-blended with 20 parts of reclaimed rubber, 15 parts of solubilizer, and 0.1 parts of antioxidant. The melt was then calendered. The twin-screw extruder temperatures were set as follows: Zone 1 135℃, Zone 2 155℃, Zone 3 175℃, and die head 185℃; the screw speed was 100 rpm, and the residence time was 4 min; the calender temperature was 165℃, and the pressure was 5 MPa. The molded insole material is obtained by naturally cooling to room temperature. After demolding, the edges can be trimmed.

[0048] The TPE particle size was 0.5-2mm, purchased from Shenzhen Suyuan Industrial Co., Ltd.; the reclaimed rubber particle size was 1-3mm, purchased from Shandong Dingfang Rubber Co., Ltd.; the solubilizer was maleic anhydride-grafted SEBS, purchased from Dongguan Yucheng Plastic Chemical Co., Ltd., G7720-1001, with a grafting rate of 1.4%-2%; the silane coupling agent was KH550, purchased from Hubei Chengfeng Chemical; the plasticizer was paraffin oil, purchased from Guangzhou Housheng New Materials Co., Ltd.; the wear-resistant additive was polyamide short fiber, with a single filament diameter of 8-15μm, purchased from Hengtian Zhongxian Textile Chemical Wuxi Co., Ltd.; the antibacterial agent was alkyl dimethyl benzyl ammonium chloride, purchased from Wuhan Rongcan Biotechnology Co., Ltd.; and the antioxidant was antioxidant 1010, purchased from Kandis Chemical (Hubei) Co., Ltd.

[0049] The preparation steps of polyester elastomer are as follows: In a polymerization reactor, 30 parts of the first reactant, 30 parts of the second reactant, and 1 part of the catalyst were added. Esterification was carried out at 200℃ for 2 hours, followed by vacuuming to a vacuum degree of less than 80 Pa, and polycondensation was carried out at 260℃ for 3 hours. The resulting product was then pressed into particles of 1-5 mm. The first reactant was trimethylolpropane, purchased from Jinan Century Tongda Chemical Co., Ltd.; the second reactant was 2,5-dicarboxylic acid 2,5-diformylfuran-3,4-dicarboxylic acid, purchased from Shandong Suitai Biotechnology Co., Ltd.; and the catalyst was antimony trioxide.

[0050] Performance testing 1. Safety Testing: Refer to GB 30585-2024 "Technical Specifications for Children's Shoes Safety" Critical limits: Total phthalates (DEHP+DBP+BBP+DIBP) ≤ 0.1%, hexavalent chromium ≤ 3 mg / kg, formaldehyde ≤ 75 mg / kg (not for direct skin contact). If the test results meet the above critical limits, the safety of the material is acceptable; otherwise, the safety of the material is not acceptable.

[0051] 2. Elongation at break: Refer to GB / T528-2009 The elongation at break at 120℃ was determined by preparing the sample into a dumbbell shape with a length of 10 mm and a thickness of 1 mm. The test was conducted using a tensile testing machine at a tensile speed of 200 mm / min.

[0052] 3. Rebound rate: Refer to GB / T6670-2008 The sample was prepared with dimensions of 100 mm in length, 100 mm in width, and 50 mm in height. After standing for 72 hours, the sample was placed horizontally on the rebound hammer. The height from the bottom of the steel ball to the sample surface was adjusted to 460 mm. A 16.3 g steel ball was released, and the maximum rebound height was recorded as an integer. The ball should not hit the wall during the fall or rebound. Three valid rebound values ​​were obtained within 1 minute. Three sets of measurements were taken, and the average value was recorded.

[0053] 4. Air permeability: Refer to GB / T5453-1997 The sample is clamped on the sample frustum, and air is passed through the sample to bring the pressure close to 50 Pa. After 1 minute, the airflow rate is recorded. The calculation formula is: air permeability R = qv / A × 100%; Where qv is the average gas flow rate (dm³) 3 / min), A is the experimental area (cm²) 2 ).

[0054] 5. Wear resistance The wear was measured using a multifunctional material friction behavior tester. The wear material was GCr15 with a diameter of 5 mm, the load was 400 g, the time was 40 min, and the rotation speed was 250 r / min. The wear amount was calculated.

[0055] 6. Antibacterial properties: The antibacterial effect was evaluated according to GB / T20944.3-2008 "Evaluation of antibacterial properties of textiles - Part 3: Shaking method"; Escherichia coli was selected as the bacterial species for antibacterial performance testing. The inhibition rate Y = (Wt-Qt) / Wt×100%, where Y is the inhibition rate (%), Wt is the average viable bacterial concentration of the control sample (CFU / ml), and Qt is the average viable bacterial concentration of the insole. After 200 standard washes, the antibacterial properties of the insole were determined to be the antibacterial durability.

[0056] 7. The test results are shown in Table 1.

[0057] Table 1

[0058] The above embodiments are merely preferred embodiments of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-substantial changes and substitutions made by those skilled in the art based on the present invention shall fall within the scope of protection claimed by the present invention.

Claims

1. A high-wear-resistant children's insole material blended with TPE and recycled rubber, characterized in that, The components include the following parts by weight: 60-85 parts TPE, 10-30 parts reclaimed rubber, 10-20 parts solubilizer, 0.5-1.5 parts silane coupling agent, 5-10 parts polyester elastomer, 1-5 parts abrasion resistant agent, 2-8 parts plasticizer, 0.1-2 parts antibacterial agent, and 0.1-1 part antioxidant.

2. The high abrasion-resistant children's insole material blended with TPE and recycled rubber according to claim 1, characterized in that, The TPE particle size requirement is 0.5-2mm; the reclaimed rubber particle size requirement is 1-3mm.

3. The high abrasion-resistant children's insole material blended with TPE and recycled rubber according to claim 1, characterized in that, The solubilizer is maleic anhydride grafted with SEBS, with a grafting rate of 1.4%-2%.

4. The high abrasion-resistant children's insole material blended with TPE and recycled rubber according to claim 1, characterized in that, The silane coupling agent is one or more of KH550 and KH570.

5. The high abrasion-resistant children's insole material blended with TPE and recycled rubber according to claim 1, characterized in that, The polyester elastomer comprises the following components in parts by weight: 20-40 parts of the first reactant, 20-40 parts of the second reactant, and 0.1-1 parts of the catalyst; The first reactant is one or more of 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, and neopentyl glycol; the second reactant is one or more of 3,4-furandicarboxylic acid, 2-methylfuran-3,4-dicarboxylic acid, 2,5-dimethylfuran-3,4-dicarboxylic acid, 2,5-dicarboxylic acid di ...

6. The high abrasion-resistant children's insole material blended with TPE and recycled rubber according to claim 5, characterized in that, The preparation steps of the polyester elastomer are as follows: In a polymerization reactor, the first reactant, the second reactant, and the catalyst are added, and esterification is carried out at 200℃-230℃ for 2-2.5 hours. Then, the vacuum is evacuated to a vacuum degree of less than 80 Pa, and polycondensation is carried out at 240℃-260℃ for 2-3 hours. Finally, the product is pressed into granules to obtain the final product.

7. The high abrasion-resistant children's insole material blended with TPE and recycled rubber according to claim 1, characterized in that, The plasticizer is one or more of paraffin oil and naphthenic oil, and the wear-resistant additive is polyamide short fiber.

8. The high abrasion-resistant children's insole material blended with TPE and recycled rubber according to claim 1, characterized in that, The antibacterial agent is alkyl dimethyl benzyl ammonium chloride and / or dialcyl dimethyl ammonium chloride; the antioxidant is antioxidant 1010 and / or antioxidant 168.

9. A method for preparing a high abrasion-resistant children's insole material blended with TPE and reclaimed rubber as described in any one of claims 1-8, characterized in that, Includes the following steps: S1: In a mixer at a temperature of 120℃-200℃, TPE is mixed with silane coupling agent, polyester elastomer, wear-resistant agent, plasticizer and antibacterial agent for 20 min-30 min to obtain a blend mixture; S2: Irradiate the blend to obtain a crosslinked product; wherein the irradiation dose is 50 kGy - 150 kGy; S3: Using a twin-screw extruder, the above crosslinked material is melt-blended with reclaimed rubber, solubilizer and antioxidant. The melt is then calendered to obtain the final product.

10. The method for preparing the TPE and recycled rubber blended high abrasion-resistant children's insole material according to claim 9, characterized in that, The temperature settings of the twin-screw extruder are: Zone 1 130℃-140℃, Zone 2 150℃-160℃, Zone 3 170℃-180℃, and die head 185℃-190℃; the screw speed of the twin-screw extruder is 90 rpm-110 rpm, and the residence time is 3 min-5 min; the calender temperature is 160℃-170℃, and the pressure is 4 MPa-6 MPa.

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