Nylon composite material and preparation method and application thereof

Abstract

The present application relates to a kind of nylon composite material and its preparation method and application, belong to polymer material technical field.The nylon composite material provided by the present application includes the following weight parts of component: polyamide 80-95 parts, toughening agent 0.01-10 parts, reinforcing material 0.01-20 parts, other auxiliary agent 0.01-5 parts;The reinforcing material includes at least one in glass fiber, whisker, lamellar mineral;The particle size of reinforcing material is greater than or equal to 5000 mesh.The nylon composite material of the present application has excellent bending and resilient performance, has good mechanical strength and supporting performance simultaneously, while preparation process is simple, cost is low, shoe industry manufacturing field such as sports shoes, leisure shoes has higher practical value.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a nylon composite material, its preparation method, and its application. Background Technology

[0002] To enhance the support and rebound performance of shoe soles, carbon fiber plates are often incorporated as a framework during the sole manufacturing process. Currently, the most widely used carbon fiber plates in the industry are formed by impregnating and curing carbon fibers aligned in the same direction with thermoplastic epoxy resin to create carbon fiber sheets. Other methods utilize thermoplastic polyurethane and thermoplastic epoxy to prepare rigid and flexible carbon fiber plates respectively, which are then hot-pressed to obtain carbon fiber plates for both rigid and flexible shoe materials. CN117024949A discloses a method of mixing nylon and carbon fiber, extruding and granulating the mixture, and then injection molding the granulated mixture to obtain a carbon fiber plate for footwear.

[0003] Existing technologies mostly use thermoplastic epoxy resins for impregnation and curing to form carbon fiber sheets, resulting in long production cycles and high material costs. Furthermore, because the carbon fibers are uniformly aligned, the stiffness of different areas of the shoe material is the same, leading to poor wearing comfort and difficulty in meeting customized needs. Using thermoplastic polyurethane and thermoplastic epoxy to prepare rigid and flexible carbon sheets respectively requires different materials, increasing material costs. Moreover, carbon sheets are expensive and generally only used in racing shoes, with limited applicability in ordinary sports shoes or casual shoes. On the other hand, carbon sheets are not resistant to bending and are prone to breakage after repeated bending, making them unsuitable as a sole material for sports or casual shoes.

[0004] Given the high cost, cumbersome manufacturing process, and poor economic applicability of existing carbon fiber plates used in shoe sole frames, there is an urgent need to develop a shoe sole material with a simplified preparation process, affordable price, and good overall performance. This material should be resistant to bending and elasticity, better suited to the needs of ordinary sports and casual shoes, and have high application value. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of existing technologies and provide a nylon composite material, its preparation method, and its applications. The nylon composite material provided by this invention effectively combines bending resistance, resilience, and good mechanical and support properties, making it highly valuable as a material for sports and casual shoe soles.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] In a first aspect, the present invention provides a nylon composite material comprising the following components in parts by weight: 80-95 parts polyamide, 0.01-10 parts toughening agent, 0.01-20 parts reinforcing material, and 0.01-5 parts other additives; wherein the reinforcing material comprises at least one of glass fiber, whiskers, and flaky minerals; and wherein the particle size of the reinforcing material is ≥5000 mesh.

[0008] This invention provides a nylon composite material, which is formulated with polyamide, toughening agent, specific reinforcing material and other additives in a specific ratio to comprehensively control the mechanical properties, resilience and bending properties of the composite material, resulting in a material suitable for the footwear manufacturing industry that can balance bending resistance, resilience, good mechanical properties and good support performance.

[0009] Within the specified ratio range of polyamide, toughening agent, and specific reinforcing materials, the overall performance is optimal. When too little polyamide is used in the composite material, the tensile strength, bending performance, hardness support performance, and springback after bending all deteriorate significantly; similarly, excessive use of polyamide in the composite material leads to a decrease in tensile strength, bending performance, and hardness support performance.

[0010] Furthermore, the specific reinforcing materials selected in this invention have a significant impact on the overall flexural resistance of the composite material. Selecting reinforcing materials with excessively low particle size significantly reduces the elongation and flexural modulus of the composite material, and causes fracture after flexural resistance testing. Using other reinforcing materials in the same proportions as other components may lead to a substantial decrease in elongation at break and flexural modulus, as well as substandard hardness support performance.

[0011] The nylon composite material provided by this invention has a tensile strength of 60-68 MPa, a flexural strength of 80-88 MPa, and a flexural modulus of 2800-3300 MPa. It does not break after being subjected to a notched impact from a cantilever beam, and its hardness support and rebound performance after bending are qualified. At the same time, the material does not break after being folded at 120° 5 times or 50° 100,000 times. Its strength support, rebound performance and bending resistance are excellent, and it has high application value as a sole material in the manufacture of sports and casual shoes.

[0012] Preferably, the components comprising the following parts by weight are: 85-95 parts polyamide, 0.01-5 parts toughening agent, 0.01-10 parts reinforcing material, and 0.01-2 parts other additives.

[0013] Within this range, the bending resistance, resilience, mechanical strength, and support performance can be better balanced.

[0014] Preferably, the polyamide is at least one of PA6, PA66, PA46, PA56, PA610, PA612, PA513, PA11, PA12, PA1010, PA1012, PA4T, PA6T, PA9T, PA10T, and PA MXD6.

[0015] The polyamides selected in this invention include polymers composed of carboxyl and amino groups polymerized via amide bonds.

[0016] Preferably, the viscosity of the polyamide is ≥2.7 cP.

[0017] The viscosity is measured using a viscometer at 25°C. When the selected polyamide has a viscosity ≥ 2.7 cP, the material strength can be increased.

[0018] Preferably, the toughening agent is at least one of polyolefin elastomer, ethylene propylene rubber, ethylene-vinyl acetate copolymer, ethylene copolymer ionomer, SBS resin and its grafts.

[0019] Preferably, the reinforcing material is at least one of talc, montmorillonite, and mica.

[0020] As a preferred embodiment, the reinforcing material is talc.

[0021] Preferably, the other additives are at least one of antioxidants, lubricants, nucleating agents, and pigments.

[0022] As a preferred embodiment, the other additives include 0.2 parts by weight of antioxidant 1098, 0.3 parts by weight of antioxidant 168, and 0.5 parts by weight of lubricant calcium stearate.

[0023] Secondly, the present invention provides a method for preparing the above-mentioned nylon composite material, comprising the following steps:

[0024] Polyamide, toughening agent and other additives are mixed and extruded into granules using a twin-screw extruder. Reinforcing material is added from the rear side and the mixture is then kneaded to obtain the nylon composite material.

[0025] The method for preparing the nylon composite material of this invention employs twin-screw extrusion granulation: the components are first added to a high-speed mixer and mixed evenly, and then added to a twin-screw extruder for compounding. Furthermore, the reinforcing material is fed in from the rear side, which effectively reduces damage to the reinforcing material caused by screw shearing, ensuring the reinforcing effect of the material and thus improving the strength properties of the composite material.

[0026] The mixing temperature is 200-230℃ and the rotation speed is 280-320rpm.

[0027] Thirdly, the present invention provides the application of the above-mentioned nylon composite material in the footwear manufacturing industry.

[0028] Preferably, the footwear manufacturing industry includes the manufacturing of sports shoes and casual shoes.

[0029] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0030] This invention uses polyamide, toughening agent, specific reinforcing material and other additives in a specific ratio, which is low cost and simple to prepare. The nylon composite material provided has good support and resilience properties, as well as good bending resistance, and has high application value in the manufacture of sports and leisure shoes. Detailed Implementation

[0031] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments. Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods; the materials and reagents used, unless otherwise specified, are commercially available reagents and materials.

[0032] Example 1

[0033] An embodiment of the nylon composite material of the present invention is provided, wherein the nylon composite material of the present invention is composed of the following components in parts by weight: 87 parts of polyamide, 2 parts of toughening agent, 10 parts of reinforcing material, and 1 part of other additives.

[0034] The polyamide is PA6 (polymerized cis J2700, viscosity 2.75 cP), the toughening agent is ethylene-octene grafted maleic anhydride (POE-g-MAH, N493), the reinforcing material is 5000 mesh talc powder; other additives include 0.2 parts by weight of antioxidant 1098, 0.3 parts by weight of antioxidant 168 and 0.5 parts by weight of lubricant calcium stearate.

[0035] The preparation method of the nylon composite material in this embodiment is as follows:

[0036] The reinforcing material is first made into a reinforcing material masterbatch by twin-screw extrusion; polyamide, toughening agent and other additives are added to a high-speed mixer and mixed evenly, and then fed into a twin-screw extruder for extrusion granulation. The reinforcing material masterbatch is then fed in from the rear side for mixing at a temperature of 220℃ and a speed of 300rpm to obtain a nylon composite material.

[0037] Example 2

[0038] An embodiment of the nylon composite material of the present invention differs from Embodiment 1 only in that the reinforcing material is 8000 mesh talc powder.

[0039] Example 3

[0040] An embodiment of the nylon composite material of the present invention differs from Embodiment 1 only in that it is composed of the following components in parts by weight: 88 parts polyamide, 0.01 parts toughening agent, 5 parts reinforcing material, and 1 part other additives; the reinforcing material is 8000 mesh talc powder.

[0041] Example 4

[0042] An embodiment of the nylon composite material of the present invention is provided. The nylon composite material of this embodiment is composed of the following components in parts by weight: 87 parts of polyamide, 10 parts of toughening agent, 0.01 parts of reinforcing material, and 1 part of other additives.

[0043] The polyamide is PA6 (Alphamid) TM A140LN (viscosity 4.0 cP), toughening agent is ionomer of ethylene copolymer (surlyn-9120), reinforcing material is 8000 mesh talc powder; other additives include 0.2 parts by weight of antioxidant 1098, 0.3 parts by weight of antioxidant 168 and 0.5 parts by weight of lubricant calcium stearate.

[0044] The preparation method of the nylon composite material in this embodiment is the same as that in Example 1.

[0045] Example 5

[0046] An embodiment of the nylon composite material of the present invention is provided, wherein the nylon composite material of this embodiment is composed of the following components in parts by weight: 87 parts of polyamide, 5 parts of toughening agent, 20 parts of reinforcing material, and 1 part of other additives.

[0047] The polyamide is PA6 (Alphamid) TM A136LN (viscosity 3.6 cP), toughening agent is ethylene-octene grafted maleic anhydride (POE-g-MAH, N493), reinforcing material is 8000 mesh talc; other additives include 0.2 parts by weight of antioxidant 1098, 0.3 parts by weight of antioxidant 168 and 0.5 parts by weight of lubricant calcium stearate.

[0048] The preparation method of the nylon composite material in this embodiment is the same as that in Example 1.

[0049] Example 6

[0050] An embodiment of the nylon composite material of the present invention differs from Embodiment 1 only in that it is composed of the following components in parts by weight: 82 parts polyamide, 10 parts toughening agent, 15 parts reinforcing material, and 1 part other additives.

[0051] Comparative Example 1

[0052] The only difference between the composite material of Comparative Example 1 and Example 1 is that the weight parts of polyamide are changed to 79 parts and the weight parts of toughening agent are changed to 10 parts.

[0053] Comparative Example 2

[0054] The only difference between the composite material of Comparative Example 2 and Example 1 is that the reinforcing material is replaced with 2000-mesh talc.

[0055] Comparative Example 3

[0056] The only difference between the composite material of Comparative Example 3 and Example 1 is that the weight parts of polyamide are changed to 100 parts, the weight parts of toughening agent are 0.01 parts, and the weight parts of reinforcing material are 0.01 parts.

[0057] Comparative Example 4

[0058] The only difference between the composite material of Comparative Example 4 and Example 1 is that the reinforcing material is replaced with 5000-mesh calcium carbonate.

[0059] The component composition comparison of the above embodiments and comparative examples is shown in Table 1 below.

[0060] Table 1 Comparison of component composition in the examples and comparative examples.

[0061]

[0062] Example of effect

[0063] To investigate the performance of the nylon composite material provided by this invention, the following performance tests were conducted:

[0064] a. Tensile strength and elongation at break: The test standard is GB / T 1040;

[0065] b. Bending strength and bending modulus: The test standard is GB / T 9341-2008;

[0066] c. Unnotched beam impact test: The test standard is GB / T 1043;

[0067] d. Hardness support test: flexural modulus ≥ 2700MPa, which is considered a qualified hardness support test;

[0068] e. Fold the material at 120° five times and observe whether it breaks;

[0069] f. Fold the material at 50° for 100,000 times and observe whether it breaks.

[0070] g. Bending rebound test: Bend the tensile specimen uniformly and continuously 10 times at 90° within 10 seconds, and then immediately lay the specimen flat to test the height of the arch. A height less than 10mm is considered qualified.

[0071] The test results of the above-mentioned performance of the composite materials in Examples 1-5 and Comparative Examples 1-4 are shown in Tables 2-1 and 2-2.

[0072] Combining Table 1 and Table 2, we can see that:

[0073] (1) Compared with the composite material in the comparative example, the nylon composite material in the embodiment within the scope of the present invention can better balance higher tensile strength, flexural strength and flexural modulus, and the overall mechanical strength is significantly higher than that of the comparative example; in addition, the material does not break in the cantilever beam unnotched impact test, and the hardness support and rebound test results after bending are qualified. It does not break after being folded at 120° 5 times and 50° 100,000 times. Its support performance, rebound performance and bending resistance as a sole material are significantly better than those of the comparative example, and it can better adapt to the application scenarios of sports shoes and casual shoes as a sole material.

[0074] (2) Comparative Examples and Comparative Examples 1 and 3: In Comparative Example 1, reducing the amount of polyamide, making its ratio with the toughening agent outside the scope defined by this invention, resulted in a significant decrease in tensile strength, flexural strength, and flexural modulus. Furthermore, the hardness support and springback test results were all unqualified, indicating a significant deterioration in mechanical strength and resilience. In Comparative Example 3, increasing the amount of polyamide, making its ratio with the toughening agent and reinforcing material outside the scope defined by this invention, resulted in a significant decrease in the elongation at break and flexural modulus of the prepared composite material, a deterioration in toughness, and an unqualified hardness support, indicating a significant deterioration in performance. The specific ratio of polyamide, toughening agent, and reinforcing material defined by this invention can effectively balance the mechanical strength, toughness, springback after bending, and flexural resistance of the composite material, significantly improving material properties and meeting the application requirements in related fields.

[0075] (3) Comparative Examples and Comparative Examples 2 and 4: In Comparative Example 2, the reinforcing material was replaced with 2000-mesh talc powder. The elongation at break and flexural modulus of the composite material decreased significantly. After 100,000 50° bends, the material fractured, its flexural resistance decreased significantly, and its hardness support was unsatisfactory, resulting in poor durability as a shoe sole material. In Comparative Example 4, the reinforcing material was replaced with calcium carbonate. The elongation at break and flexural modulus of the composite material decreased significantly, and its hardness support was unsatisfactory. It can be seen that the present invention selects specific reinforcing materials and uses them in proportion with other components to significantly improve the mechanical properties of the balanced composite material and better apply it to the preparation of shoe sole materials.

[0076] Table 2-1 Performance test results of nylon composite materials in the examples

[0077] Performance test results Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Tensile strength (MPa) 60 63 65 65 68 60 Elongation at break (%) 30 45 40 105 32 40 Bending strength (MPa) 80 85 85 85 88 83 Flexural modulus (MPa) 3000 3200 3200 2800 3300 3100 Cantilever beam impact without notch Unbreakable Unbreakable Unbreakable Unbreakable Unbreakable Unbreakable Hardness support qualified qualified qualified qualified qualified qualified Fold 120° five times Unbreakable Unbreakable Unbreakable Unbreakable Unbreakable Unbreakable 50° bend 100,000 times Unbreakable Unbreakable Unbreakable Unbreakable Unbreakable Unbreakable Springback after bending qualified qualified qualified qualified qualified qualified

[0078] Table 2-2 Performance test results of composite materials in comparative examples

[0079] Performance test results Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Tensile strength (MPa) 50 55 65 50 Elongation at break (%) 50 20 10 8 Bending strength (MPa) 40 75 90 75 Flexural modulus (MPa) 1800 2500 2200 200 Cantilever beam impact without notch Unbreakable Unbreakable Unbreakable Unbreakable Hardness support Unqualified Unqualified Unqualified Unqualified Fold 120° five times Unbreakable Unbreakable Unbreakable Unbreakable 50° bend 100,000 times Unbreakable fracture Unbreakable Unbreakable Springback after bending Unqualified qualified qualified qualified

[0080] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A nylon composite material, characterized in that, It is composed of the following components in parts by weight: 80-95 parts polyamide, 0.01-10 parts toughening agent, 0.01-20 parts reinforcing material, and 0.01-5 parts other additives; the reinforcing material is talc; the particle size of the talc is ≥5000 mesh; the polyamide is PA6; the additives are antioxidants and lubricants; the toughening agent is an ionomer of ethylene-octene grafted maleic anhydride or ethylene copolymer.

2. The nylon composite material as described in claim 1, characterized in that, It includes the following components in parts by weight: 85-95 parts polyamide, 0.01-5 parts toughening agent, 0.01-10 parts reinforcing material, and 0.01-2 parts other additives.

3. The method for preparing the nylon composite material according to any one of claims 1-2, characterized in that, Includes the following steps: Polyamide, toughening agent and other additives are mixed and extruded into granules using a twin-screw extruder. Reinforcing material is added from the rear side and the mixture is then kneaded to obtain the nylon composite material.

4. The method for preparing the nylon composite material as described in claim 3, characterized in that, The mixing temperature is 200-230℃ and the rotation speed is 280-320rpm.

5. The application of the nylon composite material as described in any one of claims 1-2 in the footwear manufacturing industry.

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