ETPA thermoplastic elastomer shoe material and preparation method thereof

Abstract

The invention provides an ETPA thermoplastic elastomer shoe material and a preparation method thereof, the ETPA thermoplastic elastomer shoe material comprises the following raw materials by weight: 100 parts of ETPA thermoplastic elastomer, 50-70 parts of a composite reinforcing agent, 2-3 parts of a cross-linking agent, 1-1.5 parts of an activator, 4-6 parts of magnesium oxide, and 1.5-2.5 parts of zinc stearate; wherein the composite reinforcing agent comprises functional polyester fibers and functional aramid fibers; in the preparation process of the functionalized polyester fiber, the polyester fiber coated with polyurethane on the surface is uniformly mixed with an emulsion containing a polyether amine grafted ETPA thermoplastic elastomer, and then spray drying is performed to obtain the functionalized polyester fiber. According to the invention, the shoe material has good performance, and has advantages in strength, toughness, wear resistance and the like.

Description

Technical Field

[0001] The present invention relates to the field of preparation of thermoplastic elastomer shoe materials, and more specifically, to an ETPA thermoplastic elastomer shoe and a preparation method thereof. Background Art

[0002] Thermoplastic elastomer shoe materials play an important role in the field of shoemaking. They combine the elasticity of rubber and the processing properties of plastics and are widely used in the manufacture of various types of shoes. At present, the shoe material industry is constantly pursuing high performance, lightweight and environmental protection. In terms of material reinforcement, polyester fiber and aramid fiber are often used as reinforcing materials to improve the strength and other properties of shoe materials. At the same time, the use of cross-linking agents and activators helps to improve the cross-linking structure of the material, thereby affecting the physical properties of the shoe material. In terms of preparation technology, steps such as mixing, kneading and hot pressing are common processing methods, and different process parameters will affect the final performance of the shoe material.

[0003] In the process of implementing the embodiments of the present invention, the inventors found that there are at least the following problems or defects in the prior art: the prior art still has limitations in improving the performance of shoe materials, such as the reinforcement effect is not ideal, the compatibility between materials and the comprehensive performance need to be further improved, and the problems such as cannot fully meet the growing demand for shoe materials in terms of high performance, lightweight and environmental protection. Summary of the invention

[0004] The invention provides an ETPA thermoplastic elastomer shoe and a preparation method thereof.

[0005] In a first aspect of the present invention, there is provided an ETPA thermoplastic elastomer shoe, comprising: ETPA thermoplastic elastomer 100 parts, composite reinforcing agent 50-70 parts, cross-linking agent 2-3 parts, activator 1-1.5 parts, magnesium oxide 4-6 parts, zinc stearate 1.5-2.5 parts; The composite reinforcing agent includes: functionalized polyester fiber and functionalized aramid fiber; In the preparation process of the functionalized polyester fiber, the polyester fiber coated with polyurethane on the surface is mixed with an emulsion containing polyetheramine grafted ETPA thermoplastic elastomer, and then spray-dried to obtain the functionalized polyester fiber.

[0006] Furthermore, in the preparation process of the functionalized polyester fiber, the solid content of the emulsion containing the polyetheramine grafted ETPA thermoplastic elastomer is 10-20wt%.

[0007] Furthermore, in the preparation process of the functionalized polyester fiber, the mixed surface area ratio of the polyester fiber coated with polyurethane and the emulsion containing the polyetheramine grafted ETPA thermoplastic elastomer is 1:0.2-0.4.

[0008] Furthermore, the diameter of the functionalized polyester fiber is ≤300 nm.

[0009] Furthermore, in the preparation process of the functionalized aramid fiber, the aramid fiber loaded with nano-titanium dioxide is mixed with an emulsion containing an acrylate-grafted ETPA thermoplastic elastomer, and then spray-dried to obtain the functionalized aramid fiber.

[0010] Furthermore, in the preparation process of the functionalized aramid fiber, the solid content of the emulsion containing the acrylate-grafted ETPA thermoplastic elastomer is 10-20wt%.

[0011] Furthermore, in the preparation process of the functionalized aramid fiber, the mixed surface area ratio of the aramid fiber loaded with nano-titanium dioxide and the emulsion containing the acrylate grafted ETPA thermoplastic elastomer is 1:0.2-0.4.

[0012] Furthermore, the weight ratio of the functionalized polyester fiber to the functionalized aramid fiber is 2-4:1.

[0013] Furthermore, the crosslinking agent is an organic peroxide crosslinking agent, and the activator is barium stearate.

[0014] In a second aspect of the present invention, a method for preparing an ETPA thermoplastic elastomer shoe material is provided, comprising the following steps: First, preheat the ETPA thermoplastic elastomer in an internal mixer at 150-160°C for 5-8 minutes and a rotation speed of 30-40 rpm; Next, magnesium oxide and zinc stearate are added to the internal mixer in batches, with an interval of 1-2 minutes between each addition. After the addition is completed, mixing is continued for 8-12 minutes, while the temperature is increased to 160-170°C and the speed is increased to 40-50rpm; Then, the composite reinforcing agent is added in three times. The first time, one third is added, and kneading is carried out at 170-180°C and a rotation speed of 50-60rpm for 6-8 minutes; the second time, one third is added, and kneading is carried out at 180-190°C and a rotation speed of 60-70rpm for 8-10 minutes; finally, the remaining one third is added, and kneading is carried out at 190-200°C and a rotation speed of 70-80rpm for 10-12 minutes; After that, the crosslinking agent and the activator are mixed and added into the internal mixer twice, and mixed for 5-7 minutes after each addition, with the temperature maintained at 200-210°C and the speed at 70-80rpm; Finally, the mixed material is rolled out into sheets through an open mixing mill, the thickness of the sheets is 2-3 mm, and then the sheets are placed in a mold, hot-pressed at 180-200°C and a pressure of 10-15 MPa, and cooled and demolded to obtain ETPA thermoplastic elastomer shoe materials.

[0015] According to the above embodiments of the present invention, at least the following beneficial effects are achieved: the ETPA thermoplastic elastomer shoe material raw material of the present invention contains a specific composite reinforcing agent, and the synergistic effect of the functionalized polyester fiber and the functionalized aramid fiber can enhance the overall strength and toughness of the shoe material, making it difficult for the shoe material to deform or be damaged when subjected to external forces, and can improve the wear resistance of the shoe material and extend the service life of the shoe material. At the same time, the reasonable raw material ratio and strict process control during the preparation process can make the various components fully mixed and uniform, ensure the stable performance of the shoe material, and maintain good performance under different environmental conditions.

[0016] In terms of preparation methods, adding various raw materials in stages and steps and controlling parameters such as temperature, rotation speed and time can make the raw materials fully react and fuse, thereby further improving the comprehensive performance of the shoe material. The hot pressing step can make the shoe material well formed, ensure its dimensional accuracy and appearance quality, so that it not only performs well in function, but also meets consumer needs in appearance, which helps to improve the competitiveness of shoe materials in the market. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] The above and other objects, features and advantages of the exemplary embodiments of the present invention will become readily understood by reading the detailed description below with reference to the accompanying drawings. In the accompanying drawings, several embodiments of the present invention are shown in an exemplary and non-limiting manner, in which: Figure 1 A schematic flow chart of a method for preparing an ETPA thermoplastic elastomer shoe material provided in one embodiment of the present invention. DETAILED DESCRIPTION

[0018] The principles and spirit of the present invention will be described below with reference to several exemplary embodiments. It should be understood that these embodiments are provided only to enable those skilled in the art to better understand and implement the present invention, and are not intended to limit the scope of the present invention in any way. On the contrary, these embodiments are provided to make the present invention more thorough and complete, and to fully convey the scope of the present invention to those skilled in the art.

[0019] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. All features disclosed in this specification, or steps in all methods or processes disclosed, except for mutually exclusive characteristics and / or steps, can be combined in any way, unless otherwise described, and can be replaced by other equivalent or alternative features with similar purposes, that is, unless otherwise described, each feature is only one embodiment in a series of equivalent or similar features.

[0020] Among them, the organic peroxide crosslinking agent is NOFperhexa 25b-40 produced by NOF; Activator Example 1

[0021] A method for preparing an ETPA thermoplastic elastomer shoe material is prepared from the following raw materials in parts by weight: 100 parts of ETPA thermoplastic elastomer, 65 parts of a composite reinforcing agent, 2.5 parts of a cross-linking agent, 1.25 parts of an activator barium stearate, 5 parts of magnesium oxide, and 2 parts of zinc stearate.

[0022] The preparation method of this embodiment comprises the following steps: S1. Preheat the ETPA thermoplastic elastomer in an internal mixer at 155°C for 6 minutes at a speed of 35 rpm; S2. The magnesium oxide and zinc stearate were added to the internal mixer twice, each time with an interval of 1.5 minutes, and mixing was continued for 10 minutes after the addition was completed, while the temperature was raised to 165 ° C and the speed was increased to 45 rpm; S3. Add the composite reinforcing agent (functionalized polyester fiber and functionalized aramid fiber) in three times. The first time, add one third of the total amount and mix at 175℃ and 55rpm for 7 minutes; the second time, add one third of the total amount and mix at 185℃ and 65rpm for 9 minutes; finally, add the remaining one third and mix at 195℃ and 75rpm for 11 minutes; S4. After the crosslinking agent and activator are pre-mixed, they are added to the internal mixer twice, and mixed for 6 minutes after each addition, the temperature is maintained at 205 ° C and the speed is 75 rpm; S5. The mixed material is rolled out into sheets through an open mill, the thickness of the sheet is 2.5 mm, and then the sheet is placed in a mold, hot-pressed at 190° C. and a pressure of 12.5 MPa, and cooled and demolded to obtain an ETPA thermoplastic elastomer shoe material.

[0023] In this embodiment, the weight ratio of the functionalized polyester fiber to the functionalized aramid fiber in the composite reinforcing agent is 3:1, and the diameter of the functionalized polyester fiber is ≤300 nm, thereby ensuring the excellent performance of the shoe material.

[0024] It should be noted that the functionalized polyester fiber is obtained by mixing the polyester fiber coated with polyurethane on the surface with the emulsion containing polyetheramine grafted ETPA thermoplastic elastomer and spray drying it on the basis of ordinary polyester fiber. The polyurethane coating can bring some special properties to the polyester fiber. The polyurethane has good wear resistance, flexibility and chemical corrosion resistance. In the application of footwear materials, this coating can enable the fiber to maintain good performance in the case of friction, bending and the like during walking, reducing wear and damage. The combination of polyetheramine grafted ETPA emulsion and polyester fiber further enhances the compatibility between the fiber and the ETPA thermoplastic elastomer. Polyetheramine can improve the flexibility and elasticity of the material. At the same time, grafting on ETPA can make ETPA better adhere to the surface of polyester fiber, so that the fiber can better play a reinforcing role in the ETPA matrix and improve the overall mechanical properties of the footwear material.

[0025] Functionalized aramid fiber is obtained by modifying traditional aramid fiber. In this embodiment, aramid fiber loaded with nano-titanium dioxide is mixed with an emulsion containing acrylate grafted ETPA thermoplastic elastomer and spray dried. Nano-titanium dioxide has a variety of excellent properties, such as photocatalytic performance, antibacterial performance, ultraviolet absorption capacity, etc. In the application of shoe materials, its ultraviolet absorption capacity can protect the shoe materials from the damage of ultraviolet rays and delay aging; the antibacterial property helps to reduce the growth of bacteria in the shoes and keep the environment inside the shoes clean. At the same time, nano-titanium dioxide is loaded on the aramid fiber, which can give it new functions without affecting the inherent high strength, high modulus and other properties of the aramid fiber. The acrylate grafted ETPA emulsion is mixed with the aramid fiber loaded with nano-titanium dioxide, which, on the one hand, improves the bonding force between the aramid fiber and the ETPA matrix, and on the other hand, the acrylate can improve the processing performance and flexibility of the material. In this way, when the shoe material is subjected to external force, the aramid fiber can better disperse the stress and enhance the overall strength and toughness of the shoe material.

[0026] Experimental data: Synthesis method: Follow the above steps S1 to S5.

[0027] Reaction conditions: preheating temperature 155°C, mixing temperature 165°C to 205°C, mixing speed 35rpm to 75rpm, hot pressing temperature 190°C, pressure 12.5MPa.

[0028] Yield: The theoretical yield is 100%, and the actual yield is 97%.

[0029] Performance test: Through the tensile test, the ETPA thermoplastic elastomer shoe material has a tensile strength of 20MPa and an elongation at break of 500%, and has good elasticity and durability.

[0030] Uses and effects: The ETPA thermoplastic elastomer shoe material prepared in this embodiment is suitable for manufacturing sports shoes, casual shoes, etc. Experiments show that the shoe material prepared using this embodiment has excellent wear resistance, tear resistance and comfort, and is suitable for long-term wearing.

[0031] It should be noted that in Examples 2-9 of the present application, the preparation process and parameters of the composite reinforcing agent are mainly adjusted, as follows: Example 2 A method for preparing an ETPA thermoplastic elastomer shoe material is prepared from the following raw materials in parts by weight: 100 parts of ETPA thermoplastic elastomer, 65 parts of a composite reinforcing agent, 2.5 parts of a cross-linking agent, 1.25 parts of an activator barium stearate, 5 parts of magnesium oxide, and 2 parts of zinc stearate.

[0032] The preparation method of this embodiment comprises the following steps: S1. Preheat the ETPA thermoplastic elastomer in an internal mixer at 155°C for 6 minutes at a speed of 35 rpm; S2. The magnesium oxide and zinc stearate were added to the internal mixer twice, each time with an interval of 1.5 minutes, and mixing was continued for 10 minutes after the addition was completed, while the temperature was raised to 165 ° C and the speed was increased to 45 rpm; S3. In the preparation process of the functionalized polyester fiber, the solid content of the emulsion containing the polyetheramine grafted ETPA thermoplastic elastomer is 15 wt %; S4. Add the composite reinforcing agent (functionalized polyester fiber and functionalized aramid fiber) in three times. The first time, add one third of the total amount and mix at 175°C and 55 rpm for 7 minutes; the second time, add one third of the total amount and mix at 185°C and 65 rpm for 9 minutes; finally, add the remaining one third and mix at 195°C and 75 rpm for 11 minutes; S5. After the crosslinking agent and activator are pre-mixed, they are added to the internal mixer twice, and mixed for 6 minutes after each addition, the temperature is maintained at 205 ° C and the speed is 75 rpm; S6. The mixed material is rolled out into sheets with a thickness of 2.5 mm through an open mixing mill. The sheets are then placed in a mold and hot-pressed at 190° C. and a pressure of 12.5 MPa. The sheets are cooled and demolded to obtain ETPA thermoplastic elastomer shoe materials.

[0033] In this embodiment, during the preparation of the functionalized polyester fiber in the composite reinforcing agent, the solid content of the emulsion containing the polyetheramine grafted ETPA thermoplastic elastomer is 15 wt %, which ensures the excellent performance of the functionalized polyester fiber.

[0034] Experimental data: Synthesis method: Follow the above steps S1 to S6.

[0035] Reaction conditions: preheating temperature 155°C, mixing temperature 165°C to 205°C, mixing speed 35rpm to 75rpm, hot pressing temperature 190°C, pressure 12.5MPa.

[0036] Yield: The theoretical yield is 100%, and the actual yield is 97%.

[0037] Performance test: Through the tensile test, the ETPA thermoplastic elastomer shoe material has a tensile strength of 22MPa and an elongation at break of 550%, and has good elasticity and durability.

[0038] Uses and effects: The ETPA thermoplastic elastomer shoe material prepared in this embodiment is suitable for manufacturing sports shoes, casual shoes, etc. Experiments show that the shoe material prepared using this embodiment has excellent wear resistance, tear resistance and comfort, and is suitable for long-term wearing.

[0039] Example 3 A method for preparing an ETPA thermoplastic elastomer shoe material is prepared from the following raw materials in parts by weight: 100 parts of ETPA thermoplastic elastomer, 65 parts of a composite reinforcing agent, 2.5 parts of a cross-linking agent, 1.25 parts of an activator barium stearate, 5 parts of magnesium oxide, and 2 parts of zinc stearate.

[0040] The preparation method of this embodiment comprises the following steps: S1. Preheat the ETPA thermoplastic elastomer in an internal mixer at 155°C for 6 minutes at a speed of 35 rpm; S2. The magnesium oxide and zinc stearate were added to the internal mixer twice, each time with an interval of 1.5 minutes, and mixing was continued for 10 minutes after the addition was completed, while the temperature was raised to 165 ° C and the speed was increased to 45 rpm; S3. In the preparation process of the functionalized polyester fiber, the surface area ratio of the polyester fiber coated with polyurethane and the emulsion containing the polyetheramine grafted ETPA thermoplastic elastomer is 1:0.3; S4. Add the composite reinforcing agent (functionalized polyester fiber and functionalized aramid fiber) in three times. The first time, add one third of the total amount and mix at 175°C and 55 rpm for 7 minutes; the second time, add one third of the total amount and mix at 185°C and 65 rpm for 9 minutes; finally, add the remaining one third and mix at 195°C and 75 rpm for 11 minutes; S5. After the crosslinking agent and activator are pre-mixed, they are added to the internal mixer twice, and mixed for 6 minutes after each addition, the temperature is maintained at 205 ° C and the speed is 75 rpm; S6. The mixed material is rolled out into sheets with a thickness of 2.5 mm through an open mixing mill. The sheets are then placed in a mold and hot-pressed at 190° C. and a pressure of 12.5 MPa. The sheets are cooled and demolded to obtain ETPA thermoplastic elastomer shoe materials.

[0041] In this embodiment, during the preparation of the functionalized polyester fiber in the composite reinforcing agent, the mixed surface area ratio of the polyester fiber coated with polyurethane and the emulsion containing the polyetheramine grafted ETPA thermoplastic elastomer is 1:0.3, ensuring the uniform distribution and reinforcing effect of the functionalized polyester fiber.

[0042] Experimental data: Synthesis method: Follow the above steps S1 to S6.

[0043] Reaction conditions: preheating temperature 155°C, mixing temperature 165°C to 205°C, mixing speed 35rpm to 75rpm, hot pressing temperature 190°C, pressure 12.5MPa.

[0044] Yield: The theoretical yield is 100%, and the actual yield is 97%.

[0045] Performance test: Through the tensile test, the ETPA thermoplastic elastomer shoe material has a tensile strength of 22MPa and an elongation at break of 550%, and has good elasticity and durability.

[0046] Uses and effects: The ETPA thermoplastic elastomer shoe material prepared in this embodiment is suitable for manufacturing sports shoes, casual shoes, etc. Experiments show that the shoe material prepared using this embodiment has excellent wear resistance, tear resistance and comfort, and is suitable for long-term wearing.

[0047] Example 4 A method for preparing an ETPA thermoplastic elastomer shoe material is prepared from the following raw materials in parts by weight: 100 parts of ETPA thermoplastic elastomer, 65 parts of a composite reinforcing agent, 2.5 parts of a cross-linking agent, 1.25 parts of an activator barium stearate, 5 parts of magnesium oxide, and 2 parts of zinc stearate.

[0048] The preparation method of this embodiment comprises the following steps: S1. Preheat the ETPA thermoplastic elastomer in an internal mixer at 155°C for 6 minutes at a speed of 35 rpm; S2. The magnesium oxide and zinc stearate were added to the internal mixer twice, each time with an interval of 1.5 minutes, and mixing was continued for 10 minutes after the addition was completed, while the temperature was raised to 165 ° C and the speed was increased to 45 rpm; S3. During the preparation of the functionalized polyester fiber, the diameter of the functionalized polyester fiber is ensured to be ≤300 nm; S4. Add the composite reinforcing agent (functionalized polyester fiber and functionalized aramid fiber) in three times. The first time, add one third of the total amount and mix at 175°C and 55 rpm for 7 minutes; the second time, add one third of the total amount and mix at 185°C and 65 rpm for 9 minutes; finally, add the remaining one third and mix at 195°C and 75 rpm for 11 minutes; S5. After the crosslinking agent and activator are pre-mixed, they are added to the internal mixer twice, and mixed for 6 minutes after each addition, the temperature is maintained at 205 ° C and the speed is 75 rpm; S6. The mixed material is rolled out into sheets with a thickness of 2.5 mm through an open mixing mill. The sheets are then placed in a mold and hot-pressed at 190° C. and a pressure of 12.5 MPa. The sheets are cooled and demolded to obtain ETPA thermoplastic elastomer shoe materials.

[0049] In this embodiment, the preparation process of the functionalized polyester fiber is precisely controlled to ensure that the diameter of the functionalized polyester fiber is ≤300 nm, thereby improving the overall performance of the shoe material.

[0050] Experimental data: Synthesis method: Follow the above steps S1 to S6.

[0051] Reaction conditions: preheating temperature 155°C, mixing temperature 165°C to 205°C, mixing speed 35rpm to 75rpm, hot pressing temperature 190°C, pressure 12.5MPa.

[0052] Yield: The theoretical yield is 100%, and the actual yield is 97%.

[0053] Performance test: Through the tensile test, the ETPA thermoplastic elastomer shoe material has a tensile strength of 22MPa and an elongation at break of 550%, and has good elasticity and durability.

[0054] Uses and effects: The ETPA thermoplastic elastomer shoe material prepared in this embodiment is suitable for manufacturing sports shoes, casual shoes, etc. Experiments show that the shoe material prepared using this embodiment has excellent wear resistance, tear resistance and comfort, and is suitable for long-term wearing.

[0055] Example 5 A method for preparing an ETPA thermoplastic elastomer shoe material is prepared from the following raw materials in parts by weight: 100 parts of ETPA thermoplastic elastomer, 70 parts of a composite reinforcing agent, 3 parts of a cross-linking agent, 1.5 parts of an activator barium stearate, 6 parts of magnesium oxide, and 2.5 parts of zinc stearate.

[0056] The preparation method of this embodiment comprises the following steps: S1. Preheat the ETPA thermoplastic elastomer in an internal mixer at 150°C for 5 minutes at a speed of 30 rpm; S2. The magnesium oxide and zinc stearate were added to the internal mixer in batches, each addition was 1 minute apart, and mixing was continued for 8 minutes after the addition was completed, while the temperature was raised to 160 ° C and the speed was increased to 40 rpm; S3. In the preparation process of functionalized aramid fiber, the aramid fiber loaded with nano-titanium dioxide is mixed with an emulsion containing an acrylate-grafted ETPA thermoplastic elastomer, and then spray-dried to obtain a functionalized aramid fiber; S4. Add the composite reinforcing agent (functionalized polyester fiber and functionalized aramid fiber) in three times. The first time, add one third of the total amount, and mix at 170°C and 50 rpm for 6 minutes; the second time, add one third of the total amount, and mix at 180°C and 60 rpm for 8 minutes; finally, add the remaining one third, and mix at 190°C and 70 rpm for 10 minutes; S5. After mixing the crosslinking agent and the activator, the mixture was added to the internal mixer twice, and the mixture was mixed for 5 minutes after each addition, the temperature was maintained at 200 ° C and the speed was 70 rpm; S6. The mixed material is rolled out into sheets with a thickness of 3 mm through an open mill, and then the sheet is placed in a mold, hot-pressed at 185° C. and a pressure of 15 MPa, and cooled and demolded to obtain an ETPA thermoplastic elastomer shoe material.

[0057] In this embodiment, during the preparation of the functionalized aramid fiber, the aramid fiber loaded with nano-titanium dioxide is mixed with an emulsion containing an acrylate-grafted ETPA thermoplastic elastomer, and then spray-dried to obtain the functionalized aramid fiber, thereby ensuring the reinforcing effect of the shoe material.

[0058] Experimental data: Synthesis method: Follow the above steps S1 to S6.

[0059] Reaction conditions: preheating temperature 150°C, mixing temperature 160°C to 200°C, mixing speed 30rpm to 70rpm, hot pressing temperature 185°C, pressure 15MPa.

[0060] Yield: The theoretical yield is 100%, and the actual yield is 97%.

[0061] Performance test: Through the tensile test, the ETPA thermoplastic elastomer shoe material has a tensile strength of 23MPa and an elongation at break of 600%, and has good elasticity and durability.

[0062] Uses and effects: The ETPA thermoplastic elastomer shoe material prepared in this embodiment is suitable for manufacturing sports shoes, casual shoes, etc. Experiments show that the shoe material prepared using this embodiment has excellent wear resistance, tear resistance and comfort, and is suitable for long-term wearing.

[0063] Example 6 A method for preparing an ETPA thermoplastic elastomer shoe material is prepared from the following raw materials in parts by weight: 100 parts of ETPA thermoplastic elastomer, 70 parts of a composite reinforcing agent, 3 parts of a cross-linking agent, 1.5 parts of an activator barium stearate, 6 parts of magnesium oxide, and 2.5 parts of zinc stearate.

[0064] The preparation method of this embodiment comprises the following steps: S1. Preheat the ETPA thermoplastic elastomer in an internal mixer at 150°C for 5 minutes at a speed of 30 rpm; S2. The magnesium oxide and zinc stearate were added to the internal mixer in batches, each addition was 1 minute apart, and mixing was continued for 8 minutes after the addition was completed, while the temperature was raised to 160 ° C and the speed was increased to 40 rpm; S3. In the preparation process of the functionalized aramid fiber, the solid content of the emulsion containing the acrylate-grafted ETPA thermoplastic elastomer is 15 wt %; S4. Add the composite reinforcing agent (functionalized polyester fiber and functionalized aramid fiber) in three times. The first time, add one third of the total amount, and mix at 170°C and 50 rpm for 6 minutes; the second time, add one third of the total amount, and mix at 180°C and 60 rpm for 8 minutes; finally, add the remaining one third, and mix at 190°C and 70 rpm for 10 minutes; S5. After mixing the crosslinking agent and the activator, the mixture was added to the internal mixer twice, and the mixture was mixed for 5 minutes after each addition, the temperature was maintained at 200 ° C and the speed was 70 rpm; S6. The mixed material is rolled out into sheets with a thickness of 3 mm through an open mill, and then the sheet is placed in a mold, hot-pressed at 185° C. and a pressure of 15 MPa, and cooled and demolded to obtain an ETPA thermoplastic elastomer shoe material.

[0065] In this embodiment, during the preparation of the functionalized aramid fiber, the solid content of the emulsion containing the acrylate-grafted ETPA thermoplastic elastomer is 15 wt %. This specific solid content helps to improve the performance of the functionalized aramid fiber.

[0066] Experimental data: Synthesis method: Follow the above steps S1 to S6.

[0067] Reaction conditions: preheating temperature 150°C, mixing temperature 160°C to 200°C, mixing speed 30rpm to 70rpm, hot pressing temperature 185°C, pressure 15MPa.

[0068] Yield: The theoretical yield is 100%, and the actual yield is 97%.

[0069] Performance test: Through the tensile test, the ETPA thermoplastic elastomer shoe material has a tensile strength of 23MPa and an elongation at break of 600%, and has good elasticity and durability.

[0070] Uses and effects: The ETPA thermoplastic elastomer shoe material prepared in this embodiment is suitable for manufacturing sports shoes, casual shoes, etc. Experiments show that the shoe material prepared using this embodiment has excellent wear resistance, tear resistance and comfort, and is suitable for long-term wearing.

[0071] Example 7 A method for preparing an ETPA thermoplastic elastomer shoe material is prepared from the following raw materials in parts by weight: 100 parts of ETPA thermoplastic elastomer, 68 parts of a composite reinforcing agent, 2.8 parts of a cross-linking agent, 1.3 parts of an activator barium stearate, 5.5 parts of magnesium oxide, and 2.2 parts of zinc stearate.

[0072] The preparation method of this embodiment comprises the following steps: S1. The ETPA thermoplastic elastomer was preheated in an internal mixer at 155°C for 7 minutes at a speed of 37 rpm; S2. The magnesium oxide and zinc stearate were added to the internal mixer twice, each time with an interval of 1.5 minutes, and mixing was continued for 9 minutes after the addition was completed, while the temperature was raised to 165 ° C and the speed was increased to 45 rpm; S3. In the preparation process of functionalized aramid fiber, the mixed surface area ratio of the aramid fiber loaded with nano-titanium dioxide and the emulsion containing acrylate-grafted ETPA thermoplastic elastomer is 1:0.3; S4. Add the composite reinforcing agent (functionalized polyester fiber and functionalized aramid fiber) in three times. The first time, add one third of the total amount and mix at 175°C and 55 rpm for 7 minutes; the second time, add one third of the total amount and mix at 185°C and 65 rpm for 9 minutes; finally, add the remaining one third and mix at 195°C and 75 rpm for 11 minutes; S5. After mixing the crosslinking agent and the activator, the mixture was added to the internal mixer twice, and the mixing was performed for 6 minutes after each addition, the temperature was maintained at 205 ° C and the speed was 75 rpm; S6. The mixed material is rolled out into sheets through an open mill, the thickness of the sheet is 2.8 mm, and then the sheet is placed in a mold, hot-pressed at 190° C. and a pressure of 13 MPa, and cooled and demolded to obtain ETPA thermoplastic elastomer shoe material.

[0073] In this embodiment, during the preparation of the functionalized aramid fiber, the mixed surface area ratio of the nano-titanium dioxide loaded aramid fiber and the emulsion containing the acrylate grafted ETPA thermoplastic elastomer is 1:0.3. This specific ratio helps to improve the dispersibility and reinforcement effect of the functionalized aramid fiber.

[0074] Experimental data: Synthesis method: Follow the above steps S1 to S6.

[0075] Reaction conditions: preheating temperature 155°C, mixing temperature 165°C to 205°C, mixing speed 37rpm to 75rpm, hot pressing temperature 190°C, pressure 13MPa.

[0076] Yield: The theoretical yield is 100%, and the actual yield is 97.5%.

[0077] Performance test: Through the tensile test, the ETPA thermoplastic elastomer shoe material has a tensile strength of 22.5MPa and an elongation at break of 580%, and has good elasticity and durability.

[0078] Uses and effects: The ETPA thermoplastic elastomer shoe material prepared in this embodiment is suitable for manufacturing sports shoes, casual shoes, etc. Experiments show that the shoe material prepared using this embodiment has excellent wear resistance, tear resistance and comfort, and is suitable for long-term wearing.

[0079] Example 8 A method for preparing an ETPA thermoplastic elastomer shoe material is prepared from the following raw materials in parts by weight: 100 parts of ETPA thermoplastic elastomer, 62 parts of a composite reinforcing agent, 2.2 parts of a cross-linking agent, 1.4 parts of an activator barium stearate, 5.8 parts of magnesium oxide, and 2.3 parts of zinc stearate.

[0080] The preparation method of this embodiment comprises the following steps: S1. The ETPA thermoplastic elastomer was preheated in an internal mixer at 152°C for 6.5 minutes at a speed of 33 rpm; S2. The magnesium oxide and zinc stearate were added to the internal mixer twice, each time with an interval of 1.25 minutes, and mixing was continued for 9.5 minutes after the addition was completed, while the temperature was raised to 163 ° C and the speed was increased to 43 rpm; S3. In the preparation process of functionalized aramid fiber, the mixed surface area ratio of the aramid fiber loaded with nano-titanium dioxide and the emulsion containing acrylate-grafted ETPA thermoplastic elastomer is 1:0.25; S4. Add the composite reinforcing agent (functionalized polyester fiber and functionalized aramid fiber) in three times. The first time, add one third of the total amount and mix at 173°C and 53 rpm for 6.5 minutes; the second time, add one third of the total amount and mix at 183°C and 63 rpm for 8.5 minutes; finally, add the remaining one third and mix at 193°C and 73 rpm for 10.5 minutes; S5. After mixing the crosslinking agent and the activator, they were added to the internal mixer twice, and mixed for 5.5 minutes after each addition, the temperature was maintained at 203 ° C and the speed was 75 rpm; S6. The mixed material is rolled out into sheets through an open mill, the thickness of the sheet is 2.9 mm, and then the sheet is placed in a mold, hot-pressed at 188° C. and a pressure of 14 MPa, and cooled and demolded to obtain an ETPA thermoplastic elastomer shoe material.

[0081] In this embodiment, the weight ratio of the functionalized polyester fiber to the functionalized aramid fiber in the composite reinforcing agent is 3.5:1. This specific ratio helps to optimize the mechanical properties and durability of the shoe material.

[0082] Experimental data: Synthesis method: Follow the above steps S1 to S6.

[0083] Reaction conditions: preheating temperature 152°C, mixing temperature 163°C to 203°C, mixing speed 33rpm to 75rpm, hot pressing temperature 188°C, pressure 14MPa.

[0084] Yield: The theoretical yield is 100%, and the actual yield is 97.8%.

[0085] Performance test: Through the tensile test, the ETPA thermoplastic elastomer shoe material has a tensile strength of 23MPa and an elongation at break of 620%, and has good elasticity and durability.

[0086] Uses and effects: The ETPA thermoplastic elastomer shoe material prepared in this embodiment is suitable for manufacturing sports shoes, casual shoes, etc. Experiments show that the shoe material prepared using this embodiment has excellent wear resistance, tear resistance and comfort, and is suitable for long-term wearing.

[0087] Example 9 A method for preparing an ETPA thermoplastic elastomer shoe material is prepared from the following raw materials in parts by weight: 100 parts of ETPA thermoplastic elastomer, 65 parts of a composite reinforcing agent, 2.5 parts of a cross-linking agent, 1.25 parts of an activator barium stearate, 5 parts of magnesium oxide, and 2 parts of zinc stearate.

[0088] The preparation method of this embodiment comprises the following steps: S1. Preheat the ETPA thermoplastic elastomer in an internal mixer at 155°C for 6 minutes at a speed of 35 rpm; S2. The magnesium oxide and zinc stearate were added to the internal mixer twice, each time with an interval of 1.5 minutes, and mixing was continued for 10 minutes after the addition was completed, while the temperature was raised to 165 ° C and the speed was increased to 45 rpm; S3. Add the composite reinforcing agent (functionalized polyester fiber and functionalized aramid fiber) in three times. The first time, add one third of the total amount and mix at 175℃ and 55rpm for 7 minutes; the second time, add one third of the total amount and mix at 185℃ and 65rpm for 9 minutes; finally, add the remaining one third and mix at 195℃ and 75rpm for 11 minutes; S4. In this embodiment, the crosslinking agent is dibenzoyl peroxide (an organic peroxide crosslinking agent), and the activator is barium stearate; after the crosslinking agent and the activator are mixed, they are added to the internal mixer twice, and the mixing is performed for 6 minutes after each addition, and the temperature is maintained at 205 ° C and the speed is 75 rpm; S5. The mixed material is rolled out into sheets through an open mill, the thickness of the sheet is 2.5 mm, and then the sheet is placed in a mold, hot-pressed at 190° C. and a pressure of 13 MPa, and cooled and demolded to obtain an ETPA thermoplastic elastomer shoe material.

[0089] In this embodiment, the selection of specific cross-linking agents and activators helps to improve the cross-linking efficiency of the shoe material and the performance of the final product.

[0090] Experimental data: Synthesis method: Follow the above steps S1 to S5.

[0091] Reaction conditions: preheating temperature 155°C, mixing temperature 165°C to 205°C, mixing speed 35rpm to 75rpm, hot pressing temperature 190°C, pressure 13MPa.

[0092] Yield: The theoretical yield is 100%, and the actual yield is 97.5%.

[0093] Performance test: Through the tensile test, the ETPA thermoplastic elastomer shoe material has a tensile strength of 23MPa and an elongation at break of 600%, and has good elasticity and durability.

[0094] Uses and effects: The ETPA thermoplastic elastomer shoe material prepared in this embodiment is suitable for manufacturing sports shoes, casual shoes, etc. Experiments show that the shoe material prepared using this embodiment has excellent wear resistance, tear resistance and comfort, and is suitable for long-term wearing.

[0095] Example 10 A method for preparing an ETPA thermoplastic elastomer shoe material is prepared from the following raw materials in parts by weight: 100 parts of ETPA thermoplastic elastomer, 65 parts of a composite reinforcing agent, 2.5 parts of a cross-linking agent, 1.25 parts of an activator barium stearate, 5 parts of magnesium oxide, and 2 parts of zinc stearate.

[0096] like Figure 1 The preparation method of this embodiment comprises the following steps: First, the ETPA thermoplastic elastomer was preheated in an internal mixer at 155 °C for 6 min and a rotation speed of 35 rpm; Next, magnesium oxide and zinc stearate were added to the internal mixer in batches, with an interval of 1 minute between each addition. After the addition was completed, mixing was continued for 10 minutes, while the temperature was increased to 165°C and the speed was increased to 45 rpm. Then, the composite reinforcing agent was added in three times; one third was added in the first time, and mixed at 175°C and 55 rpm for 7 minutes; one third was added in the second time, and mixed at 185°C and 65 rpm for 9 minutes; and the remaining one third was added in the last time, and mixed at 195°C and 75 rpm for 11 minutes; After that, the crosslinking agent and the activator were mixed and added into the internal mixer twice, and the mixing was performed for 6 minutes after each addition, with the temperature maintained at 205°C and the rotation speed at 75 rpm; Finally, the mixed material is rolled out into sheets through an open mixing mill, the thickness of the sheets is 2-3 mm, and then the sheets are placed in a mold, hot-pressed at 190°C and a pressure of 12 MPa, and cooled and demolded to obtain ETPA thermoplastic elastomer shoe materials.

[0097] In some embodiments, specifically, S1. Preheat the ETPA thermoplastic elastomer in an internal mixer at 155°C for 6 minutes at a speed of 35 rpm; S2. The magnesium oxide and zinc stearate were added to the internal mixer twice, each time with an interval of 1.5 minutes, and mixing was continued for 10 minutes after the addition was completed, while the temperature was raised to 165 ° C and the speed was increased to 45 rpm; S3. Add the composite reinforcing agent (functionalized polyester fiber and functionalized aramid fiber) in three times. The first time, add one third of the total amount and mix at 175℃ and 55rpm for 7 minutes; the second time, add one third of the total amount and mix at 185℃ and 65rpm for 9 minutes; finally, add the remaining one third and mix at 195℃ and 75rpm for 11 minutes; S4. After mixing the crosslinking agent and the activator, they were added to the internal mixer twice, and mixed for 6 minutes after each addition, the temperature was maintained at 205 ° C and the speed was 75 rpm; S5. The mixed material is rolled out into sheets through an open mill, the thickness of the sheet is 2.5 mm, and then the sheet is placed in a mold, hot-pressed at 190° C. and a pressure of 13 MPa, and cooled and demolded to obtain an ETPA thermoplastic elastomer shoe material.

[0098] Experimental data: Synthesis method: Follow the above steps S1 to S5.

[0099] Reaction conditions: preheating temperature 155°C, mixing temperature 165°C to 205°C, mixing speed 35rpm to 75rpm, hot pressing temperature 190°C, pressure 13MPa.

[0100] Yield: The theoretical yield is 100%, and the actual yield is 97.5%.

[0101] Performance test: Through the tensile test, the ETPA thermoplastic elastomer shoe material has a tensile strength of 23MPa and an elongation at break of 600%, and has good elasticity and durability.

[0102] Uses and effects: The ETPA thermoplastic elastomer shoe material prepared in this embodiment is suitable for manufacturing sports shoes, casual shoes, etc. Experiments show that the shoe material prepared using this embodiment has excellent wear resistance, tear resistance and comfort, and is suitable for long-term wearing.

[0103] Comparative Example 1 This comparative example is a traditional thermoplastic elastomer shoe material, which is made from the following raw materials in parts by weight: 100 parts of conventional thermoplastic elastomer, 30 parts of calcium carbonate, 20 parts of talc, 1.5 parts of zinc stearate; The preparation method of the above-mentioned shoe material comprises the following steps: (a) preheating a conventional thermoplastic elastomer in an internal mixer at 160° C. for 10 minutes at a rotation speed of 40 rpm; (b) adding calcium carbonate and talc into an internal mixer twice, with an interval of 2 minutes between each addition, and continuing to mix for 15 minutes after the addition is completed, while increasing the temperature to 170° C. and the speed to 50 rpm; (c) Zinc stearate was added to an internal mixer, and after mixing for 5 minutes, sheets were produced through an open mixer, and the thickness of the sheets was 3 mm. The sheets were then placed in a mold, hot-pressed at 180° C. and a pressure of 12 MPa, and cooled and demolded to obtain a shoe material.

[0104] Comparative Example 2 This comparative example is a traditional thermoplastic elastomer shoe material, which is made from the following raw materials in parts by weight: 100 parts of conventional thermoplastic elastomer, 25 parts of silicate, 2 parts of calcium stearate; The preparation method of the above-mentioned shoe material comprises the following steps: (a) preheating a conventional thermoplastic elastomer in an internal mixer at 165° C. for 8 minutes at a rotation speed of 38 rpm; (b) adding silicate to an internal mixer and mixing for 10 minutes, then adding calcium stearate to the internal mixer and mixing for 5 minutes while increasing the temperature to 175° C. and the speed to 48 rpm; (c) The sheet is produced through an open mill, and the sheet thickness is 3 mm. The sheet is then placed in a mold, hot-pressed at 185° C. and a pressure of 13 MPa, and cooled and demolded to obtain a shoe material.

[0105] Experimental example The ETPA thermoplastic elastomer shoe materials prepared in Example 9 and Comparative Examples 1 to 2 were obtained respectively; The performance tests of the shoe materials were carried out, including tensile strength, elongation at break, abrasion resistance and tear resistance; the test results are shown in the following table:

[0106] It can be seen from the above table: The ETPA thermoplastic elastomer shoe material prepared by the technical solution of the present application has higher tensile strength and elongation at break, as well as better wear resistance and tear resistance, compared with Comparative Examples 1 and 2, showing better comprehensive performance.

[0107] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein by equivalents. These modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention, and they should all be included in the scope of the claims and specification of the present invention.

[0108] The above descriptions are only some preferred embodiments of the present invention and an explanation of the technical principles used. Those skilled in the art should understand that the scope of the invention involved in the embodiments of the present invention is not limited to the technical solutions formed by a specific combination of the above technical features, but should also cover other technical solutions formed by any combination of the above technical features or their equivalent features without departing from the above inventive concept. For example, the above features are replaced with (but not limited to) technical features with similar functions disclosed in the embodiments of the present invention.

Claims

1. An ETPA thermoplastic elastomer shoe material, characterized in that: The raw materials include by weight: ETPA thermoplastic elastomer 100 parts, composite reinforcing agent 50-70 parts, cross-linking agent 2-3 parts, activator 1-1.5 parts, magnesium oxide 4-6 parts, zinc stearate 1.5-2.5 parts; The composite reinforcing agent includes: functionalized polyester fiber and functionalized aramid fiber; In the preparation process of the functionalized polyester fiber, the polyester fiber coated with polyurethane on the surface is mixed with an emulsion containing polyetheramine grafted ETPA thermoplastic elastomer, and then spray-dried to obtain the functionalized polyester fiber.

2. The ETPA thermoplastic elastomer shoe material according to claim 1, characterized in that: In the preparation process of the functionalized polyester fiber, the solid content of the emulsion containing the polyetheramine grafted ETPA thermoplastic elastomer is 10-20wt%.

3. The ETPA thermoplastic elastomer shoe material according to claim 1, characterized in that: In the preparation process of the functionalized polyester fiber, the mixed surface area ratio of the polyester fiber coated with polyurethane and the emulsion containing the polyetheramine grafted ETPA thermoplastic elastomer is 1:0.2-0.

4.

4. The ETPA thermoplastic elastomer shoe material according to claim 1, characterized in that: The diameter of the functionalized polyester fiber is ≤300nm.

5. The ETPA thermoplastic elastomer shoe material according to claim 1, characterized in that: In the preparation process of the functionalized aramid fiber, the aramid fiber loaded with nano-titanium dioxide is mixed with an emulsion containing an acrylate-grafted ETPA thermoplastic elastomer, and then spray-dried to obtain the functionalized aramid fiber.

6. The ETPA thermoplastic elastomer shoe material according to claim 5, characterized in that: In the preparation process of the functionalized aramid fiber, the solid content of the emulsion containing the acrylate grafted ETPA thermoplastic elastomer is 10-20wt%.

7. The ETPA thermoplastic elastomer shoe material according to claim 5, characterized in that: In the preparation process of functionalized aramid fibers, the mixed surface area ratio of the nano-titanium dioxide loaded aramid fibers and the latex containing acrylate grafted ETPA thermoplastic elastomer is 1:0.2 - 0.

4.

8. The ETPA thermoplastic elastomer shoe material according to claim 1, characterized in that: The weight ratio of the functionalized polyester fiber to the functionalized aramid fiber is 2-4:

1.

9. The ETPA thermoplastic elastomer shoe material according to claim 1, characterized in that: The crosslinking agent is an organic peroxide crosslinking agent, and the activator is barium stearate.

10. A method for preparing the ETPA thermoplastic elastomer shoe material according to any one of claims 1 to 9, characterized in that: The steps include: First, preheat the ETPA thermoplastic elastomer in an internal mixer at 150-160°C for 5-8 minutes and a rotation speed of 30-40 rpm; Next, magnesium oxide and zinc stearate are added to the internal mixer in batches, with an interval of 1-2 minutes between each addition. After the addition is completed, mixing is continued for 8-12 minutes, while the temperature is increased to 160-170°C and the speed is increased to 40-50rpm; Then, the composite reinforcing agent is added in three times; one third is added in the first time, and mixed at 170-180°C and a rotation speed of 50-60rpm for 6-8 minutes; one third is added in the second time, and mixed at 180-190°C and a rotation speed of 60-70rpm for 8-10 minutes; and the remaining one third is added in the last time, and mixed at 190-200°C and a rotation speed of 70-80rpm for 10-12 minutes; After that, the crosslinking agent and the activator are mixed and added into the internal mixer twice, and mixed for 5-7 minutes after each addition, with the temperature maintained at 200-210°C and the speed at 70-80rpm; Finally, the mixed material is rolled out into sheets through an open mixing mill, the thickness of the sheets is 2-3 mm, and then the sheets are placed in a mold, hot-pressed at 180-200°C and a pressure of 10-15 MPa, and cooled and demolded to obtain ETPA thermoplastic elastomer shoe materials.

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