Lightweight high-elasticity long carbon chain nylon carbon plate material and preparation method and application thereof

Abstract

This invention discloses a lightweight, highly elastic long-chain nylon carbon plate material and its preparation method. The material comprises 5-10% toughening agent, 10-20% carbon fiber, 5-10% compatibilizer, 3-8% nylon microfoam masterbatch, 0.5-3% carbon fiber surface treatment agent, 0.2-1% antioxidant, 0.2-0.7% lubricant, 1-3% colorant, and the balance PA612 medium-viscosity resin. This invention achieves lightweighting through a microfoaming process, reducing the density to 1.01-1.07 g / cm³, a weight reduction of over 20% compared to traditional thermosetting carbon plates. Through the compounding of toughening agent and compatibilizer, the flexural modulus reaches 6000-8000 MPa, and the notched impact strength reaches 12-20 KJ / m², exhibiting both high elasticity and bending resistance, making it suitable for high-end sports shoe carbon plates.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to a lightweight, highly elastic long-chain carbon nylon carbon plate material, its preparation method, and its application. Background Technology

[0002] High-performance racing shoes typically incorporate carbon plates with a special mechanical structure embedded in the midsole. These plates are used for energy recovery and mechanical remodeling during intense exercise, significantly improving biomechanical efficiency during running. Early generations of athletic shoes primarily used thermosetting carbon fiber composites for their carbon plates. However, these thermosetting materials exhibit excessive rigidity and stiffness, resulting in insufficient cushioning and joint protection for the ankle and foot during high-frequency running. Long-term use can lead to cumulative health damage for athletes. Furthermore, thermosetting carbon fiber itself has limited resistance to bending fatigue, making it prone to brittle fracture under severe deformation or complex stress conditions, ultimately causing overall failure of the carbon plate.

[0003] To overcome the inherent defects of thermosetting materials, researchers have begun to explore the use of thermoplastic resins with higher toughness (such as nylon resin) to modify carbon fibers and construct novel carbon plates. Among these, long-chain nylon resins (such as PA612 resin) exhibit high application potential in sports equipment due to their low water absorption, low density, high impact strength, and excellent wear and chemical corrosion resistance. However, long-chain nylon resins, due to the large number of methylene groups in their molecular chains, exhibit significant non-polar or weakly polar characteristics, while untreated short-chopped carbon fibers have a high surface polarity, resulting in extremely poor interfacial compatibility between the two.

[0004] In existing conventional modification methods, if only the two are physically blended, the high-rigidity carbon fiber cannot form a good interfacial wetting and stress transfer effect in the weakly polar long-chain carbon nylon matrix. This not only fails to bring out the perfect combination advantages of flexibility and rigidity, but also leads to serious phase separation defects. After molding, the composite material has persistently high hardness, and its elongation at break and flexibility are significantly deteriorated. Once subjected to stress and deformation, microcracks are very likely to initiate and rapidly propagate from the loose resin-fiber interface, causing the carbon plate to be prone to early fracture under actual bending stress.

[0005] In addition, conventional nylon resins (such as PA6 and PA66) have a high equilibrium water absorption rate (PA6 about 3% and PA66 about 2.7%), which leads to a significant decrease in their mechanical properties in a humid environment and affects the long-term stability of carbon fiber plate materials.

[0006] With the extreme pursuit of lightweight structural components in modern high-end sports shoes, how to further reduce weight while ensuring the bending stiffness and support strength of carbon plate materials, and at the same time ensure that the materials maintain stable mechanical properties under high-frequency dynamic use environments, is one of the core technical problems that have not yet been solved in the field of thermoplastic modified engineering plastics. Summary of the Invention

[0007] Based on this, the purpose of this invention is to provide a lightweight, highly elastic long-chain carbon nylon carbon plate material, its preparation method, and its application, so as to solve the problems mentioned in the background art.

[0008] To achieve the above objectives, the present invention provides the following technical solution: In a first aspect, this invention discloses a lightweight, highly elastic long-chain carbon nylon carbon plate material, which is prepared from the following components in the following mass percentages, wherein the sum of the mass percentages of each component is 100%: Toughening agent 5-10%, Carbon fiber 10-20%, Compatibilizer 5-10%, Nylon microfoaming masterbatch 3-8%, Carbon fiber surface treatment agent 0.5-3%, Antioxidant 0.2-1%, Lubricant 0.2-0.7%, Colorant 1-3%, The remainder is long-chain nylon resin; The long-chain nylon resin is PA612 medium viscosity resin with a relative viscosity of 2.3-2.5.

[0009] As a further aspect of the present invention: the toughening agent is at least one of POE, LDPE, EPDM and SEBS; the compatibilizer is a grafted compatibilizer.

[0010] As a further aspect of the present invention: the carbon fiber is at least one of SYT45, T700, HF-30 and T700DPA.

[0011] As a further aspect of the present invention: the carbon fiber surface treatment agent is at least one of Hydrosize 200, HY-512 and WLX-PA.

[0012] As a further aspect of the present invention: the colorant is at least one of aniline black masterbatch and nylon carrier aniline black masterbatch; the nylon microfoamed masterbatch includes at least one of A1030GSF, HT233 and MB300.

[0013] As a further aspect of the present invention: the flexural modulus of the material is 6000-8000MPa, the notched impact strength of a simply supported beam is 12-20KJ / m², and the density is 1.01-1.07g / cm³.

[0014] As a further aspect of the present invention, the lubricant is at least one of PETS, OP wax, silicone, silicone oil and erucamide.

[0015] As a further aspect of the present invention: the antioxidant includes a primary antioxidant and a secondary antioxidant, wherein the primary antioxidant is at least one of antioxidant 245, antioxidant 1010, and antioxidant 1098, and the secondary antioxidant is at least one of antioxidant 168, antioxidant 9228, and antioxidant 626.

[0016] Secondly, this invention discloses a method for preparing the aforementioned lightweight, highly elastic long-chain carbon nylon carbon plate material, comprising the following steps: Step 1: Weighing Materials: Dry the resin in PA612, and then weigh each raw material. Step 2, Mixing: Add the PA612 adhesive resin, toughening agent, compatibilizer, nylon microfoaming masterbatch, black masterbatch, and carbon fiber surface treatment agent to a high-speed mixer and mix. Then add lubricant and antioxidant and continue mixing to obtain the mixture. Step 3, Melt Extrusion: The mixture is added to the main feed port of the twin-screw extruder, and carbon fibers are added from the side feed port for melt extrusion. Step 4, Extrusion and Pelletizing: The extruded material is cooled, dried, pelletized, sieved, homogenized, and packaged to obtain the lightweight, highly elastic long-chain nylon carbon sheet material.

[0017] As a further aspect of the present invention: the drying temperature in step one is 80±5℃ and the drying time is 4±0.5 hours.

[0018] As a further aspect of the present invention: the mixing time in step two is 3-8 minutes; As a further aspect of the present invention: the temperature of the twin-screw extruder in step three is set as follows: 60-70℃ in the first zone, 210-250℃ in the second to tenth zones and the die head, the screw speed is 400-600 rpm, and the feeding speed is 25-40 rpm.

[0019] Thirdly, this invention discloses the application of the aforementioned lightweight, highly elastic long-chain carbon nylon carbon plate material in the preparation of carbon plates for sports shoes.

[0020] Compared with the prior art, the present invention has the following beneficial effects: (1) Significant weight reduction: This invention employs a physical foaming process, introducing 3-8% nylon micro-foamed masterbatch into a long-chain nylon (PA612) and carbon fiber system. This process creates a uniform microporous structure inside the molded carbon plate, achieving a weight reduction of over 20% compared to the density of traditional thermosetting carbon plate materials (above 1.35 g / cm³) while meeting the rigidity requirements of athletic shoe soles.

[0021] (2) Improved dynamic resilience and fatigue resistance: Addressing the problem of excessive rigidity and brittle fracture during high-frequency bending of traditional thermosetting carbon sheets, this invention uses thermoplastic PA612 as the base material and incorporates 5-10% elastomer toughening agent. This formulation system maintains structural support while improving the material's flexibility and elongation at break (the elongation at break in the examples reached 2.4-3.5%), effectively enhancing the dynamic bending adaptability of the carbon sheet.

[0022] (3) Optimization of interfacial compatibility and mechanical strength: This invention introduces a special carbon fiber surface treatment agent and 5-10% grafted compatibilizer to improve the compatibility between weakly polar long-chain nylon and carbon fiber. Tests show that the composite material has a flexural modulus of 6000-8000 MPa and a notched impact strength of 12-20 KJ / m², meeting the mechanical requirements for flexural stiffness in sports shoes. Detailed Implementation

[0023] The technical solutions of this disclosure will be clearly and completely described below with reference to specific embodiments. However, those skilled in the art will understand that the embodiments described below are some embodiments of this disclosure, but not all embodiments, and are only used to illustrate this disclosure, and should not be regarded as limiting the scope of this disclosure. Based on the embodiments in this disclosure, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of this disclosure.

[0024] The specific information of the raw materials used in the following examples and comparative examples is as follows: The lubricant is PETS, manufactured by Italian company FAG, and its brand name is AP. The main antioxidant is antioxidant 1098, manufactured by BASF. The auxiliary antioxidant is antioxidant 168, manufactured by BASF. The toughening agent is EPDM, manufactured by Dow Chemical, and its brand name is 3745P. The compatibilizer is manufactured by Koton and its brand name is KT-8. The carbon fiber is manufactured by Zhongfu Shenying and its grade is SYT45. Nylon microfoamed masterbatch, manufactured by Sevenu, brand name MB300; The carbon fiber surface treatment agent is manufactured by Wanlixin and its brand name is WLX-PA. The black masterbatch is aniline black masterbatch, manufactured by Gao Lai, and its brand name is NACE N54 / 1033. PA612 medium viscosity resin, manufactured by Huitong Special Materials, grade HB30, with a relative viscosity of 2.4; All materials are commercially available, commonly used products.

[0025] It is understood that the above-mentioned raw materials and reagents are merely examples of some specific embodiments of the present invention, making the technical solution of the present invention clearer, and do not mean that the present invention can only use the above-mentioned reagents. The specific scope shall be determined by the claims. In addition, unless otherwise specified, "parts" in the examples and comparative examples refer to parts by weight.

[0026] Any range described in this invention includes the endpoint, any value between the endpoints, and any subrange consisting of the endpoint or any value between the endpoints.

[0027] Example 1 (1) Weighing: First, dry PA612 medium viscous resin HB30 at 80℃ for 4 hours for later use; then weigh the following raw materials: toughening agent 5 parts, carbon fiber 10 parts, compatibilizer 10 parts, nylon micro foam masterbatch 3 parts, lubricant 0.3 parts, main antioxidant 0.5 parts, auxiliary antioxidant 0.5 parts, carbon fiber surfactant 0.5 parts, PE substrate black masterbatch 2 parts, and medium viscous PA612 resin 68.2 parts; (2) Mixing: Add the weighed PA612 adhesive resin, toughening agent, compatibilizer, nylon microfoaming masterbatch, black masterbatch, and carbon fiber surfactant to a high-speed mixer and mix at high speed for 5 minutes. Then add the weighed lubricant, main antioxidant, and auxiliary antioxidant and continue to mix at high speed for 5 minutes to obtain the mixture. (3) Melt extrusion: The mixture is added to the main feed of the twin-screw extruder. The carbon fiber is fed in from the eighth zone. The temperature of the twin-screw extruder from the first zone to the die head is 65℃ (to prevent resin from clumping at the feed port), 215℃, 235℃, 235℃, 235℃, 230℃, 230℃, 230℃, 230℃, 230℃, 230℃, 245℃; the screw speed is 500 rpm, and the feed rate is 25-40 rpm.

[0028] (4) Extrusion pelletizing: The extruded material is cooled, dried, pelletized, passed through a vibrating screen, homogenized in a homogenizing tank, and packaged to obtain the finished product, which is the corresponding carbon plate material.

[0029] Example 2 (1) Weighing: First, dry PA612 medium viscous resin HB30 at 80℃ for 4 hours for later use; then weigh the following raw materials: toughening agent 5 parts, carbon fiber 20 parts, compatibilizer 10 parts, nylon micro foam masterbatch 3 parts, lubricant 0.3 parts, main antioxidant 0.5 parts, auxiliary antioxidant 0.5 parts, carbon fiber surfactant 0.5 parts, PE substrate black masterbatch 2 parts, and medium viscous PA612 resin 58.2 parts; (2) Mixing: Add the weighed PA612 adhesive resin, toughening agent, compatibilizer, nylon microfoaming masterbatch, black masterbatch, and carbon fiber surfactant to a high-speed mixer and mix at high speed for 5 minutes. Then add the weighed lubricant, main antioxidant, and auxiliary antioxidant and continue to mix at high speed for 5 minutes to obtain the mixture. (3) Melt extrusion: The mixture is added to the main feed of the twin-screw extruder. The carbon fiber is fed in from the eighth zone. The temperature of the twin-screw extruder from the first zone to the die head is 65℃ (to prevent resin from clumping at the feed port), 215℃, 235℃, 235℃, 235℃, 230℃, 230℃, 230℃, 230℃, 230℃, 230℃, 245℃; the screw speed is 500 rpm, and the feed rate is 25-40 rpm.

[0030] (4) Extrusion pelletizing: The extruded material is cooled, dried, pelletized, passed through a vibrating screen, homogenized in a homogenizing tank, and packaged to obtain the finished product, which is the corresponding carbon plate material.

[0031] Example 3 (1) Weighing: First, dry PA612 medium viscous resin HB30 at 80℃ for 4 hours for later use; then weigh the following raw materials: toughening agent 10 parts, carbon fiber 10 parts, compatibilizer 5 parts, nylon micro foam masterbatch 8 parts, lubricant 0.3 parts, main antioxidant 0.5 parts, auxiliary antioxidant 0.5 parts, carbon fiber surfactant 0.5 parts, PE substrate black masterbatch 2 parts, and medium viscous PA612 resin 63.2 parts; (2) Mixing: Add the weighed PA612 adhesive resin, toughening agent, compatibilizer, nylon microfoaming masterbatch, black masterbatch, and carbon fiber surfactant to a high-speed mixer and mix at high speed for 5 minutes. Then add the weighed lubricant, main antioxidant, and auxiliary antioxidant and continue to mix at high speed for 5 minutes to obtain the mixture. (3) Melt extrusion: The mixture is added to the main feed of the twin-screw extruder. The carbon fiber is fed in from the eighth zone. The temperature of the twin-screw extruder from the first zone to the die head is 65℃ (to prevent resin from clumping at the feed port), 215℃, 235℃, 235℃, 235℃, 230℃, 230℃, 230℃, 230℃, 230℃, 230℃, 245℃; the screw speed is 500 rpm, and the feed rate is 25-40 rpm.

[0032] (4) Extrusion pelletizing: The extruded material is cooled, dried, pelletized, passed through a vibrating screen, homogenized in a homogenizing tank, and packaged to obtain the finished product, which is the corresponding carbon plate material.

[0033] Example 4 (1) Weighing: First, dry PA612 medium viscous resin HB30 at 80℃ for 4 hours for later use; then weigh the following raw materials: toughening agent 10 parts, carbon fiber 20 parts, compatibilizer 5 parts, nylon micro foam masterbatch 8 parts, lubricant 0.3 parts, main antioxidant 0.5 parts, auxiliary antioxidant 0.5 parts, carbon fiber surfactant 0.5 parts, PE substrate black masterbatch 2 parts, and medium viscous PA612 resin 53.2 parts; (2) Mixing: Add the weighed PA612 adhesive resin, toughening agent, compatibilizer, nylon microfoaming masterbatch, black masterbatch, and carbon fiber surfactant to a high-speed mixer and mix at high speed for 5 minutes. Then add the weighed lubricant, main antioxidant, and auxiliary antioxidant and continue to mix at high speed for 5 minutes to obtain the mixture. (3) Melt extrusion: The mixture is added to the main feed of the twin-screw extruder. The carbon fiber is fed in from the eighth zone. The temperature of the twin-screw extruder from the first zone to the die head is 65℃ (to prevent resin from clumping at the feed port), 215℃, 235℃, 235℃, 235℃, 230℃, 230℃, 230℃, 230℃, 230℃, 230℃, 245℃; the screw speed is 500 rpm, and the feed rate is 25-40 rpm.

[0034] (4) Extrusion pelletizing: The extruded material is cooled, dried, pelletized, passed through a vibrating screen, homogenized in a homogenizing tank, and packaged to obtain the finished product, which is the corresponding carbon plate material.

[0035] Comparative Example 1 (1) Weighing: First, dry the PA612 medium viscous resin HB30 at 80℃ for 4 hours for later use; then weigh the following raw materials: 5 parts toughening agent, 9 parts carbon fiber, 10 parts compatibilizer, 3 parts nylon micro foam masterbatch, 0.3 parts lubricant, 0.5 parts main antioxidant, 0.5 parts auxiliary antioxidant, 0.5 parts carbon fiber surfactant, 2 parts PE substrate black masterbatch, and 69.2 parts medium viscous PA612 resin; the subsequent steps are the same as in Example 1.

[0036] Comparative Example 2 (1) Weighing: First, dry the PA612 medium viscous resin HB30 at 80℃ for 4 hours for later use; then weigh the following raw materials: 5 parts toughening agent, 21 parts carbon fiber, 10 parts compatibilizer, 3 parts nylon micro foam masterbatch, 0.3 parts lubricant, 0.5 parts main antioxidant, 0.5 parts auxiliary antioxidant, 0.5 parts carbon fiber surfactant, 2 parts PE substrate black masterbatch, and 57.2 parts medium viscous PA612 resin; the subsequent steps are the same as in Example 1.

[0037] Comparative Example 3 (1) Weighing: First, dry the PA612 medium viscous resin HB30 at 80℃ for 4 hours for later use; then weigh the following raw materials: 5 parts toughening agent, 20 parts carbon fiber, 10 parts compatibilizer, 2 parts nylon micro foam masterbatch, 0.3 parts lubricant, 0.5 parts main antioxidant, 0.5 parts auxiliary antioxidant, 0.5 parts carbon fiber surfactant, 2 parts PE substrate black masterbatch, and 59.2 parts medium viscous PA612 resin; the subsequent steps are the same as in Example 1.

[0038] Comparative Example 4 (1) Weighing: First, dry the PA612 medium viscous resin HB30 at 80℃ for 4 hours for later use; then weigh the following raw materials: 5 parts toughening agent, 10 parts carbon fiber, 10 parts compatibilizer, 9 parts nylon micro foam masterbatch, 0.3 parts lubricant, 0.5 parts main antioxidant, 0.5 parts auxiliary antioxidant, 0.5 parts carbon fiber surfactant, 2 parts PE substrate black masterbatch, and 62.2 parts medium viscous PA612 resin; the subsequent steps are the same as in Example 1.

[0039] The mechanical properties and molding conditions of the carbon plate materials prepared in Examples 1-4 and Comparative Examples 1-4 were tested. The test results are shown in Table 1, and the test methods and conditions are shown in Table 2.

[0040] Table 1 Performance Test Results

[0041] Table 2 Test Standards and Condition Boundaries

[0042] As shown in Table 1, Examples 1-4 used materials composed of PA612 binder, toughening agent, carbon fiber and compatibilizer. The extrusion was smooth, the material had good mechanical properties, the flexural modulus was between 6000-8000MPa, and the notched impact strength was between 12-20KJ / m². The finished products made by the customer also met the product requirements.

[0043] As shown in Table 1, the test results of Examples 1-4 indicate that the amount of carbon fiber added significantly affects the flexural modulus of the material: when the carbon fiber content is 10%, the flexural modulus is approximately 6200-6340 MPa; when the carbon fiber content is 20%, the flexural modulus is approximately 7850-7920 MPa. Within the 10-20% range required by this invention, the flexural modulus can reach the target range of 6000-8000 MPa. In Comparative Example 1, the carbon fiber content is 9%, and the flexural modulus is below 6000 MPa, which does not meet the requirements; in Comparative Example 2, the carbon fiber content is 21%, and the flexural modulus exceeds 8100 MPa. The injection-molded carbon plate has excessively high hardness, posing a risk of injury to the ankle.

[0044] As shown in Table 1, the test results of Examples 1-4 indicate that the amount of compatibilizer and toughening agent added significantly affects the notched impact performance of the material. When the toughening agent content is 5% and the compatibilizer content is 10%, the notched impact strength is 15-19 KJ / m², and when the toughening agent content is 10% and the compatibilizer content is 5%, the notched impact strength is 13-15 KJ / m².

[0045] As shown in Table 1, the test results of Examples 1-4 indicate that the amount of nylon microfoam masterbatch added significantly affects the material density: when the masterbatch content is 3%, the density is approximately 1.03-1.07 g / cm³; when the masterbatch content is 8%, the density is approximately 1.01-1.03 g / cm³. Within the 3-8% range required by this invention, a significant weight reduction effect can be achieved. In Comparative Example 3, the masterbatch content is 2%, and the material density is 1.094 g / cm³, indicating no significant weight reduction effect and failing to meet the lightweight design requirements; in Comparative Example 4, the masterbatch content is 9%, resulting in severe breakage and discontinuous production.

[0046] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A lightweight, highly elastic long-chain carbon nylon carbon sheet material, characterized in that, It is prepared from the following components in mass percentage, where the sum of the mass percentages of each component is 100%: Toughening agent 5-10%, Carbon fiber 10-20%, Compatibilizer 5-10%, Nylon microfoaming masterbatch 3-8%, Carbon fiber surface treatment agent 0.5-3%, Antioxidant 0.2-1%, Lubricant 0.2-0.7%, Colorant 1-3%, The remainder is long-chain nylon resin; The long-chain nylon resin is PA612 medium viscosity resin with a relative viscosity of 2.3-2.

5.

2. The lightweight, highly elastic long-chain carbon nylon carbon plate material according to claim 1, characterized in that, The toughening agent is at least one of POE, LDPE, EPDM and SEBS; the compatibilizer is a grafted compatibilizer.

3. The lightweight, highly elastic long-chain carbon nylon carbon plate material according to claim 1, characterized in that, The carbon fiber is at least one of SYT45, T700, HF-30 and T700DPA.

4. The lightweight, highly elastic long-chain carbon nylon carbon plate material according to claim 1, characterized in that, The carbon fiber surface treatment agent is at least one of Hydrosize 200, HY-512 and WLX-PA.

5. The lightweight, highly elastic long-chain carbon nylon carbon sheet material according to claim 1, characterized in that, The colorant is at least one of aniline black masterbatch and nylon carrier aniline black masterbatch; the nylon microfoamed masterbatch includes at least one of A1030GSF, HT233 and MB300.

6. The lightweight, highly elastic long-chain carbon nylon carbon plate material according to claim 1, characterized in that, The material has a flexural modulus of 6000-8000MPa, a notched impact strength of 12-20KJ / m², and a density of 1.01-1.07g / cm³.

7. The method for preparing the lightweight, highly elastic long-chain carbon nylon carbon plate material according to any one of claims 1-6, characterized in that, Includes the following steps: Step 1: Weighing Materials: Dry the resin in PA612, and then weigh each raw material. Step 2, Mixing: Add the PA612 adhesive resin, toughening agent, compatibilizer, nylon microfoaming masterbatch, black masterbatch, and carbon fiber surface treatment agent to a high-speed mixer and mix. Then add lubricant and antioxidant and continue mixing to obtain the mixture. Step 3, Melt Extrusion: The mixture is added to the main feed port of the twin-screw extruder, and carbon fibers are added from the side feed port for melt extrusion. Step 4, Extrusion and Pelletizing: The extruded material is cooled, dried, pelletized, sieved, homogenized, and packaged to obtain the lightweight, highly elastic long-chain nylon carbon sheet material.

8. The preparation method according to claim 7, characterized in that, The drying temperature in step one is 80±5℃, and the drying time is 4±0.5 hours.

9. The preparation method according to claim 7, characterized in that, The mixing time in step two is 3-8 minutes; the temperature settings of the twin-screw extruder in step three are: 60-70℃ in zone one, 210-250℃ in zones two to ten and the die head, 400-600 rpm for the screw speed, and 25-40 rpm for the feed speed.

10. The application of the lightweight, highly elastic long-chain carbon nylon carbon plate material according to any one of claims 1-6 in the preparation of carbon plates for sports shoes.

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