A foamed composite material, a method for producing the same, and use thereof in shoe materials

Abstract

The application discloses a kind of foamed composite material and its preparation method and its application in shoe material.Foamed composite material, it includes EVA, POE elastomer, nylon blend, elastomer microsphere and crosslinking agent, the content of the elastomer microsphere is 0.5~1%, the content of the crosslinking agent is 0.2~0.5%, and the crosslinking agent is bismaleimide.The elastomer microsphere of the application is easy to migrate and enrich in the cell wall area during mixing and foaming process due to the difference of its density and surface energy.The elastic properties of microsphere enable it to effectively absorb and disperse external stress during the formation of cell wall, improving the toughness and crack resistance of cell wall.Meanwhile, the crosslinking agent can react with the matrix resin during the foaming temperature rise stage to form a dense three-dimensional network structure.The synergistic effect of elastomer microsphere and crosslinking network makes the cell wall area have good flexibility, high strength and stability.

Description

Technical Field

[0001] This application relates to the field of polymer foaming materials, specifically to a foamed composite material, its preparation method, and its application in footwear materials. Background Technology

[0002] With the increasing demand for lightweight, high-strength, and highly elastic materials in the footwear market, including athletic and casual shoes, foamed composite materials are widely used in the footwear industry due to their excellent cushioning, shock absorption, and thermal insulation properties. Common foamed footwear materials, such as EVA, POE elastomers, and nylon blends, can balance elasticity and strength to a certain extent, meeting the basic needs of daily wear and sports.

[0003] However, while pursuing high foaming ratios and low specific gravity, existing foamed footwear materials often face the problem of decreased tensile strength and impact resistance. Especially in foamed structures, the cell walls are prone to becoming sites for the initiation and propagation of microcracks, leading to insufficient overall material durability and making it difficult to meet the requirements of high-performance footwear materials. Therefore, how to improve the mechanical properties of materials while ensuring lightweighting has become a key technical challenge for the industry. Summary of the Invention

[0004] To address the aforementioned technical problems, this application provides a foamed composite material, its preparation method, and its application in footwear materials.

[0005] The first aspect of this application provides a foamed composite material comprising EVA, POE elastomer, nylon blend, elastomer microspheres and a crosslinking agent, wherein the content of the elastomer microspheres is 0.5% to 1%, the content of the crosslinking agent is 0.2% to 0.5%, the elastomer microspheres are selected from EVA microspheres or POE microspheres, and the crosslinking agent is bismaleimide.

[0006] The elastomer microspheres of this application readily migrate and accumulate in the cell wall region due to differences in density and surface energy during mixing and foaming. The elastic properties of the microspheres enable them to effectively absorb and disperse external stress during cell wall formation, improving the toughness and crack resistance of the cell walls and inhibiting the initiation and propagation of microcracks. Simultaneously, the crosslinking agent (such as bismaleimide) can undergo a crosslinking reaction with the matrix resin during the foaming heating stage, forming a dense three-dimensional network structure. This crosslinked network not only enhances the overall strength of the matrix but also improves the structural integrity and thermal stability of the cell walls. The synergistic effect of the elastomer microspheres and the crosslinked network gives the cell wall region both good flexibility and high strength and stability.

[0007] Furthermore, the elastomeric microspheres are EVA microspheres. Using EVA microspheres allows for better compatibility with the matrix system, improving the uniformity of microsphere distribution on the cell walls and the toughening effect.

[0008] Furthermore, the elastomeric microspheres are POE microspheres. POE microspheres have good elasticity and dispersibility, which helps to improve the overall toughness of the material.

[0009] Furthermore, the crosslinking agent is a triazine crosslinking agent. Triazine crosslinking agents can provide different crosslinking reaction pathways, further enriching the ways to regulate the structure of materials.

[0010] Furthermore, the content of EVA is 20%~40%, the content of POE elastomer is 5%~15%, and the content of nylon blend is 30%~45%. By reasonably controlling the proportion of each component, the foaming properties, mechanical properties, and processing properties of the material can be balanced.

[0011] Furthermore, the foamed composite material also comprises calcium carbonate, polyvinylpyrrolidone, maleic anhydride-grafted polyethylene, calcium stearate, polyethylene glycol, azodicarbonamide, benzoyl peroxide, and γ-methacryloyloxypropyltrimethoxysilane. These additives help improve the dispersibility, foaming ratio, and processing rheology of the material.

[0012] The second aspect of this application provides a method for preparing a foamed composite material, comprising the following steps: blending nylon 6, polyvinylpyrrolidone, maleic anhydride-grafted polyethylene, polypropylene, and calcium carbonate to obtain a nylon blend; mixing and kneading EVA, POE elastomer, the nylon blend, calcium carbonate, and polyethylene glycol, then sequentially adding elastomer microspheres, azodicarbonamide, benzoyl peroxide, γ-methacryloyloxypropyltrimethoxysilane, and a crosslinking agent, mixing evenly, and granulating; and foaming the obtained material to obtain a foamed composite material.

[0013] The above preparation method can achieve uniform dispersion and effective synergy of each component, ensuring the structure and performance of the foamed composite material.

[0014] Furthermore, the foaming process includes: at 175°C, for 9 minutes, and at a density of 150 kg / cm³. 2 The first foaming is carried out at 150℃ for 8 minutes at 150 kg / cm². 2 A second foaming process is then performed. This step-by-step foaming process helps to obtain a uniform cell structure and excellent mechanical properties.

[0015] A third aspect of this application provides the application of a foamed composite material in footwear materials, wherein the foamed composite material is used for soles or insoles. This material is suitable for various footwear materials, including athletic shoes, casual shoes, and safety shoes, and can significantly improve the durability and comfort of footwear materials. Detailed Implementation

[0016] To facilitate understanding of this application, a more complete description will be provided below. This application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of this application.

[0017] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of that feature. In the description of the application, "multiple" means at least two, such as two, three, etc., unless otherwise explicitly specified. In the description of this application, "several" means at least one, such as one, two, etc., unless otherwise explicitly specified.

[0018] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0019] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.

[0020] In this application, numerical ranges are referred to as continuous unless otherwise specified, and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0021] Unless otherwise specified, the percentage content mentioned in this application refers to mass percentage for solid-liquid mixtures and solid-phase-solid mixtures, and volume percentage for liquid-phase-liquid mixtures.

[0022] Unless otherwise specified, all percentage concentrations mentioned in this application refer to the final concentration. The final concentration refers to the proportion of the added component in the system after the addition of that component.

[0023] Unless otherwise specified, the temperature parameters in this application may be either constant temperature processing or processing within a certain temperature range. The constant temperature processing allows for temperature fluctuations within the precision range controlled by the instrument.

[0024] The term "particle" as used in this application, or a substance with a defined particle size distribution, is not necessarily spherical in shape; it may be irregular and can be either primary or secondary particles. The particle size of irregular particles is calculated as the average of their maximum and minimum diameters.

[0025] Example 1: This example provides a foamed composite material and its preparation method.

[0026] Formula: EVA (Mitsui, Japan, item number: 40W) 30 wt%, POE elastomer (Wanhua, item number: 5057) 10 wt%, nylon blend 38 wt% (prepared from nylon 6 (Huashida, PA6), polyvinylpyrrolidone (CAS: 9003-39-8), maleic anhydride grafted polyethylene (CAS: 9006-26-2), polypropylene (Yanshan Petrochemical, item number: K8303), calcium carbonate (Shengyuan, item number: SY-017), calcium carbonate 8 wt%, calcium stearate (CAS: 1592-23-0) 1.2 wt%, polyethylene glycol (PEG 400) 0.8 wt%, azodicarbonamide (CAS: 123-77-3) 9 wt%, benzoyl peroxide (CAS: 94-36-0) 1 wt%, γ-methacryloyloxypropyltrimethoxysilane (KH570) 2 wt%, elastomer microspheres (EVA microspheres, prepared by spray cooling method, with an average particle size of 100 μm, material is Dow 3120) 0.8 wt%, crosslinking agent (bismaleimide, CAS: 13676-54-5) 0.3 wt%.

[0027] Preparation method: Nylon 6, polyvinylpyrrolidone, maleic anhydride-grafted polyethylene, polypropylene, and calcium carbonate are blended in a screw extruder for 4 minutes at 230℃ to obtain a nylon blend. EVA, POE elastomer, nylon blend, calcium carbonate, and polyethylene glycol are added to a mixer and mixed at 130℃ for 8 minutes. Elastomer microspheres, azodicarbonamide, benzoyl peroxide, KH570, and bismaleimide are added sequentially, and mixing continues for 3 minutes. The mixture is then thinned into sheets (85℃, 4 minutes, 8mm thickness) using an open mill and fed into a granulator for three-stage granulation (95℃ / 100℃ / 90℃). The resulting material is then processed in a foaming machine at 175℃ for 9 minutes at 150 kg / cm³. 2 The first foaming was performed by placing the rough blank in the shoe mold at 150℃ for 8 minutes at 150kg / cm². 2 Secondary foaming molding.

[0028] Example 2: This example provides a foamed composite material and its preparation method.

[0029] Formula: EVA (Mitsui, Japan, item number: 40W) 30 wt%, POE elastomer (Wanhua, item number: 5057) 10 wt%, nylon blend 38 wt% (prepared from nylon 6 (Huashida, PA6), polyvinylpyrrolidone (CAS: 9003-39-8), maleic anhydride grafted polyethylene (CAS: 9006-26-2), polypropylene (Yanshan Petrochemical, item number: K8303), calcium carbonate (Shengyuan, item number: SY-017), calcium carbonate 8 wt%, calcium stearate (CAS: 1592-23-0) 1.2 wt%, polyethylene glycol (PEG 400) 0.8 wt%, azodicarbonamide (CAS: 123-77-3) 9 wt%, benzoyl peroxide (CAS: 94-36-0) 1 wt%, γ-methacryloyloxypropyltrimethoxysilane (KH570) 2 wt%, elastomer microspheres (EVA microspheres, prepared by spray cooling method, with an average particle size of 100 μm, material is Dow 3120) 0.5 wt%, crosslinking agent (bismaleimide, CAS: 13676-54-5) 0.5 wt%.

[0030] Preparation method: Nylon 6, polyvinylpyrrolidone, maleic anhydride-grafted polyethylene, polypropylene, and calcium carbonate are blended in a screw extruder for 4 minutes at 230℃ to obtain a nylon blend. EVA, POE elastomer, nylon blend, calcium carbonate, and polyethylene glycol are added to a mixer and mixed at 130℃ for 8 minutes. Elastomer microspheres, azodicarbonamide, benzoyl peroxide, KH570, and bismaleimide are added sequentially, and mixing continues for 3 minutes. The mixture is then thinned into sheets (85℃, 4 minutes, 8mm thickness) using an open mill and fed into a granulator for three-stage granulation (95℃ / 100℃ / 90℃). The resulting material is then processed in a foaming machine at 175℃ for 9 minutes at 150 kg / cm³. 2 The first foaming was performed by placing the rough blank in the shoe mold at 150℃ for 8 minutes at 150kg / cm². 2 Secondary foaming molding.

[0031] Example 3: This example provides a foamed composite material and its preparation method.

[0032] Formula: EVA (Mitsui, Japan, item number: 40W) 30 wt%, POE elastomer (Wanhua, item number: 5057) 10 wt%, nylon blend 38 wt% (prepared from nylon 6 (Huashida, PA6), polyvinylpyrrolidone (CAS: 9003-39-8), maleic anhydride grafted polyethylene (CAS: 9006-26-2), polypropylene (Yanshan Petrochemical, item number: K8303), calcium carbonate (Shengyuan, item number: SY-017), calcium carbonate 8 wt%, calcium stearate (CAS: 1592-23-0) 1.2 wt%, polyethylene glycol (PEG 400) 0.8 wt%, azodicarbonamide (CAS: 123-77-3) 9 wt%, benzoyl peroxide (CAS: 94-36-0) 1 wt%, γ-methacryloyloxypropyltrimethoxysilane (KH570) 2 wt%, elastomer microspheres (prepared by spray cooling method, average particle size of 200 μm, material is Dow 8150) 0.8 wt%, crosslinking agent (bismaleimide, CAS: 13676-54-5) 0.3 wt%.

[0033] Preparation method: Nylon 6, polyvinylpyrrolidone, maleic anhydride-grafted polyethylene, polypropylene, and calcium carbonate are blended in a screw extruder for 4 minutes at 230℃ to obtain a nylon blend. EVA, POE elastomer, nylon blend, calcium carbonate, and polyethylene glycol are added to a mixer and mixed at 130℃ for 8 minutes. Elastomer microspheres, azodicarbonamide, benzoyl peroxide, KH570, and bismaleimide are added sequentially, and mixing continues for 3 minutes. The mixture is then thinned into sheets (85℃, 4 minutes, 8mm thickness) using an open mill and fed into a granulator for three-stage granulation (95℃ / 100℃ / 90℃). The resulting material is then processed in a foaming machine at 175℃ for 9 minutes at 150 kg / cm³. 2 The first foaming was performed by placing the rough blank in the shoe mold at 150℃ for 8 minutes at 150kg / cm². 2 Secondary foaming molding.

[0034] Example 4: This example provides a foamed composite material and its preparation method.

[0035] Formula: EVA (Mitsui, Japan, item number: 40W) 30 wt%, POE elastomer (Wanhua, item number: 5057) 10 wt%, nylon blend 38 wt% (prepared from nylon 6 (Huashida, PA6), polyvinylpyrrolidone (CAS: 9003-39-8), maleic anhydride grafted polyethylene (CAS: 9006-26-2), polypropylene (Yanshan Petrochemical, item number: K8303), calcium carbonate (Shengyuan, item number: SY-017), calcium carbonate 8 wt%, calcium stearate (CAS: 1592-23-0) 1.2 wt%, polyethylene glycol (PEG 400) 0.8 wt%, azodicarbonamide (CAS: 123-77-3) 9 wt%, benzoyl peroxide (CAS: 94-36-0) 1 wt%, γ-methacryloyloxypropyltrimethoxysilane (KH570) 2 wt%, elastomer microspheres (EVA microspheres, prepared by spray cooling method, average particle size of 100 μm, material is Dow 3120) 0.8 wt%, crosslinking agent (bismaleimide, CAS: 13676-54-5) 0.2 wt%.

[0036] Preparation method: Nylon 6, polyvinylpyrrolidone, maleic anhydride-grafted polyethylene, polypropylene, and calcium carbonate are blended in a screw extruder for 4 minutes at 230℃ to obtain a nylon blend. EVA, POE elastomer, nylon blend, calcium carbonate, and polyethylene glycol are added to a mixer and mixed at 130℃ for 8 minutes. Elastomer microspheres, azodicarbonamide, benzoyl peroxide, KH570, and bismaleimide are added sequentially, and mixing continues for 3 minutes. The mixture is then thinned into sheets (85℃, 4 minutes, 8mm thickness) using an open mill and fed into a granulator for three-stage granulation (95℃ / 100℃ / 90℃). The resulting material is then processed in a foaming machine at 175℃ for 9 minutes at 150 kg / cm³. 2 The first foaming was performed by placing the rough blank in the shoe mold at 150℃ for 8 minutes at 150kg / cm². 2 Secondary foaming molding.

[0037] Example 5: This example provides a foamed composite material and its preparation method.

[0038] Formula: EVA (Mitsui, Japan, item number: 40W) 30 wt%, POE elastomer (Wanhua, item number: 5057) 10 wt%, nylon blend 38 wt% (prepared from nylon 6 (Huashida, PA6), polyvinylpyrrolidone (CAS: 9003-39-8), maleic anhydride grafted polyethylene (CAS: 9006-26-2), polypropylene (Yanshan Petrochemical, item number: K8303), calcium carbonate (Shengyuan, item number: SY-017), calcium carbonate 8 wt%, calcium stearate (CAS: 1592-23-0) 1.2 wt%, polyethylene glycol (PEG 400) 0.8 wt%, azodicarbonamide (CAS: 123-77-3) 9 wt%, benzoyl peroxide (CAS: 94-36-0) 1 wt%, γ-methacryloyloxypropyltrimethoxysilane (KH570) 2 wt%, elastomer microspheres (EVA microspheres, prepared by spray cooling method, average particle size of 100 μm, material is Dow 3120) 1 wt%, crosslinking agent (bismaleimide, CAS: 13676-54-5) 0.5 wt%.

[0039] Preparation method: Nylon 6, polyvinylpyrrolidone, maleic anhydride-grafted polyethylene, polypropylene, and calcium carbonate are blended in a screw extruder for 4 minutes at 230℃ to obtain a nylon blend. EVA, POE elastomer, nylon blend, calcium carbonate, and polyethylene glycol are added to a mixer and mixed at 130℃ for 8 minutes. Elastomer microspheres, azodicarbonamide, benzoyl peroxide, KH570, and bismaleimide are added sequentially, and mixing continues for 3 minutes. The mixture is then thinned into sheets (85℃, 4 minutes, 8mm thickness) using an open mill and fed into a granulator for three-stage granulation (95℃ / 100℃ / 90℃). The resulting material is then processed in a foaming machine at 175℃ for 9 minutes at 150 kg / cm³. 2 The first foaming was performed by placing the rough blank in the shoe mold at 150℃ for 8 minutes at 150kg / cm². 2 Secondary foaming molding.

[0040] Example 6: This example provides a foamed composite material and its preparation method.

[0041] Formula: EVA (Mitsui, Japan, item number: 40W) 25wt%, POE elastomer (Wanhua, item number: 5057) 12wt%, nylon blend 43wt% (prepared from nylon 6 (Huashida, PA6), polyvinylpyrrolidone (CAS: 9003-39-8), maleic anhydride grafted polyethylene (CAS: 9006-26-2), polypropylene (Yanshan Petrochemical, item number: K8303), calcium carbonate (Shengyuan, item number: SY-017), calcium carbonate 8wt%, calcium stearate (CAS: 1592-23-0) 1.2wt%, polyethylene glycol (PEG 400) 0.8wt%, azodicarbonamide (CAS: 123-77-3) 9wt%, benzoyl peroxide (CAS: 94-36-0) 1 wt%, γ-methacryloyloxypropyltrimethoxysilane (KH570) 2 wt%, elastomer microspheres (EVA microspheres, prepared by spray cooling method, average particle size of 100 μm, material is Dow 3120) 0.7 wt%, crosslinking agent (bismaleimide, CAS: 13676-54-5) 0.3 wt%.

[0042] Preparation method: Nylon 6, polyvinylpyrrolidone, maleic anhydride-grafted polyethylene, polypropylene, and calcium carbonate are blended in a screw extruder for 4 minutes at 230℃ to obtain a nylon blend. EVA, POE elastomer, nylon blend, calcium carbonate, and polyethylene glycol are added to a mixer and mixed at 130℃ for 8 minutes. Elastomer microspheres, azodicarbonamide, benzoyl peroxide, KH570, and bismaleimide are added sequentially, and mixing continues for 3 minutes. The mixture is then thinned into sheets (85℃, 4 minutes, 8mm thickness) using an open mill and fed into a granulator for three-stage granulation (95℃ / 100℃ / 90℃). The resulting material is then processed in a foaming machine at 175℃ for 9 minutes at 150 kg / cm³. 2 The first foaming was performed by placing the rough blank in the shoe mold at 150℃ for 8 minutes at 150kg / cm². 2 Secondary foaming molding.

[0043] Example 7: This example provides a foamed composite material and its preparation method.

[0044] Formula: EVA (Mitsui, Japan, item number: 40W) 35 wt%, POE elastomer (Wanhua, item number: 5057) 8 wt%, nylon blend 35 wt% (prepared from nylon 6 (Huashida, PA6), polyvinylpyrrolidone (CAS: 9003-39-8), maleic anhydride grafted polyethylene (CAS: 9006-26-2), polypropylene (Yanshan Petrochemical, item number: K8303), calcium carbonate (Shengyuan, item number: SY-017), calcium carbonate 8 wt%, calcium stearate (CAS: 1592-23-0) 1.2 wt%, polyethylene glycol (PEG 400) 0.8 wt%, azodicarbonamide (CAS: 123-77-3) 9 wt%, benzoyl peroxide (CAS: 94-36-0) 1 wt%. wt%, γ-methacryloyloxypropyltrimethoxysilane (KH570) 2 wt%, elastomer microspheres (EVA microspheres, prepared by spray cooling method, with an average particle size of 100 μm, material is Dow 3120) 0.9 wt%, crosslinking agent (bismaleimide, CAS: 13676-54-5) 0.4 wt%.

[0045] Preparation method: Nylon 6, polyvinylpyrrolidone, maleic anhydride-grafted polyethylene, polypropylene, and calcium carbonate are blended in a screw extruder for 4 minutes at 230℃ to obtain a nylon blend. EVA, POE elastomer, nylon blend, calcium carbonate, and polyethylene glycol are added to a mixer and mixed at 130℃ for 8 minutes. Elastomer microspheres, azodicarbonamide, benzoyl peroxide, KH570, and bismaleimide are added sequentially, and mixing continues for 3 minutes. The mixture is then thinned into sheets (85℃, 4 minutes, 8mm thickness) using an open mill and fed into a granulator for three-stage granulation (95℃ / 100℃ / 90℃). The resulting material is then processed in a foaming machine at 175℃ for 9 minutes at 150 kg / cm³. 2 The first foaming was performed by placing the rough blank in the shoe mold at 150℃ for 8 minutes at 150kg / cm². 2 Secondary foaming molding.

[0046] Example 8: This example provides a foamed composite material and its preparation method.

[0047] Formula: EVA (Mitsui, Japan, item number: 40W) 28 wt%, POE elastomer (Wanhua, item number: 5057) 10 wt%, nylon blend 40 wt% (prepared from nylon 6 (Huashida, PA6), polyvinylpyrrolidone (CAS: 9003-39-8), maleic anhydride grafted polyethylene (CAS: 9006-26-2), polypropylene (Yanshan Petrochemical, item number: K8303), calcium carbonate (Shengyuan, item number: SY-017), calcium carbonate 8 wt%, calcium stearate (CAS: 1592-23-0) 1.2 wt%, polyethylene glycol (PEG 400) 0.8 wt%, azodicarbonamide (CAS: 123-77-3) 9 wt%, benzoyl peroxide (CAS: 94-36-0) 1 wt%, γ-methacryloyloxypropyltrimethoxysilane (KH570) 2 wt%, elastomer microspheres (EVA microspheres, prepared by spray cooling method, average particle size of 100 μm, material is Dow 3120) 0.6 wt%, crosslinking agent is triazine crosslinking agent (2,4-dichloro-1,3,5-triazine, CAS: 2831-66-5) 0.3 wt%.

[0048] Preparation method: Nylon 6, polyvinylpyrrolidone, maleic anhydride-grafted polyethylene, polypropylene, and calcium carbonate are blended in a screw extruder for 4 minutes at 230℃ to obtain a nylon blend. EVA, POE elastomer, nylon blend, calcium carbonate, and polyethylene glycol are added to a mixer and mixed at 130℃ for 8 minutes. Elastomer microspheres, azodicarbonamide, benzoyl peroxide, KH570, and a crosslinking agent are added sequentially, and mixing continues for 3 minutes. The mixture is then sheeted using an open mill (85℃, 4 minutes, 8mm thickness) and fed into a granulator for three-stage granulation (95℃ / 100℃ / 90℃). The resulting material is then processed in a foaming machine at 175℃ for 9 minutes at 150 kg / cm³. 2 The first foaming was performed by placing the rough blank in the shoe mold at 150℃ for 8 minutes at 150kg / cm². 2 Secondary foaming molding.

[0049] Example 9: This example provides a foamed composite material and its preparation method.

[0050] Formula: EVA (Mitsui, Japan, item number: 40W) 32 wt%, POE elastomer (Wanhua, item number: 5057) 9 wt%, nylon blend 39 wt% (prepared from nylon 6 (Huashida, PA6), polyvinylpyrrolidone (CAS: 9003-39-8), maleic anhydride grafted polyethylene (CAS: 9006-26-2), polypropylene (Yanshan Petrochemical, item number: K8303), calcium carbonate (Shengyuan, item number: SY-017), calcium carbonate 8 wt%, calcium stearate (CAS: 1592-23-0) 1.2 wt%, polyethylene glycol (PEG 400) 0.8 wt%, azodicarbonamide (CAS: 123-77-3) 9 wt%, benzoyl peroxide (CAS: 94-36-0) 1 wt%, γ-methacryloyloxypropyltrimethoxysilane (KH570) 2 wt%, elastomer microspheres (EVA microspheres, prepared by spray cooling method, average particle size of 100 μm, material is Dow 3120) 0.8 wt%, crosslinking agent (bismaleimide, CAS: 13676-54-5) 0.3 wt%.

[0051] Preparation method: Nylon 6, polyvinylpyrrolidone, maleic anhydride-grafted polyethylene, polypropylene, and calcium carbonate are blended in a screw extruder for 4 minutes at 230℃ to obtain a nylon blend. EVA, POE elastomer, nylon blend, calcium carbonate, and polyethylene glycol are added to a mixer and mixed at 130℃ for 8 minutes. Elastomer microspheres, azodicarbonamide, benzoyl peroxide, KH570, and bismaleimide are added sequentially, and mixing continues for 3 minutes. The mixture is then thinned into sheets (85℃, 4 minutes, 8mm thickness) using an open mill and fed into a granulator for three-stage granulation (95℃ / 100℃ / 90℃). The resulting material is then processed in a foaming machine at 175℃ for 9 minutes at 150 kg / cm³. 2 The first foaming was performed by placing the rough blank in the shoe mold at 150℃ for 8 minutes at 150kg / cm². 2 Secondary foaming molding.

[0052] Comparative Example 1: This embodiment provides a foamed composite material and its preparation method.

[0053] Formula: EVA (Mitsui, Japan, item number: 40W) 30 wt%, POE elastomer (Wanhua, item number: 5057) 10 wt%, nylon blend 39.3 wt% (prepared from nylon 6 (Huashida, PA6), polyvinylpyrrolidone (CAS: 9003-39-8), maleic anhydride grafted polyethylene (CAS: 9006-26-2), polypropylene (Yanshan Petrochemical, item number: K8303), calcium carbonate (Shengyuan, item number: SY-017), calcium carbonate 8 wt%, calcium stearate (CAS: 1592-23-0) 1.2 wt%, polyethylene glycol (PEG 400) 0.8 wt%, azodicarbonamide (CAS: 123-77-3) 9 wt%, benzoyl peroxide (CAS: 94-36-0) 1 wt%, γ-methacryloyloxypropyltrimethoxysilane (KH570) 2 wt%.

[0054] Preparation method: Nylon 6, polyvinylpyrrolidone, maleic anhydride-grafted polyethylene, polypropylene, and calcium carbonate are blended in a screw extruder for 4 minutes at 230℃ to obtain a nylon blend. EVA, POE elastomer, nylon blend, calcium carbonate, and polyethylene glycol are added to a mixer and mixed at 130℃ for 8 minutes. Elastomer microspheres, azodicarbonamide, benzoyl peroxide, KH570, and bismaleimide are added sequentially, and mixing continues for 3 minutes. The mixture is then thinned into sheets (85℃, 4 minutes, 8mm thickness) using an open mill and fed into a granulator for three-stage granulation (95℃ / 100℃ / 90℃). The resulting material is then processed in a foaming machine at 175℃ for 9 minutes at 150 kg / cm³. 2 The first foaming was performed by placing the rough blank in the shoe mold at 150℃ for 8 minutes at 150kg / cm². 2 Secondary foaming molding.

[0055] Comparative Example 2: This embodiment provides a foamed composite material and its preparation method.

[0056] Formula: EVA (Mitsui, Japan, item number: 40W) 30 wt%, POE elastomer (Wanhua, item number: 5057) 10 wt%, nylon blend 38.3 wt% (prepared from nylon 6 (Huashida, PA6), polyvinylpyrrolidone (CAS: 9003-39-8), maleic anhydride grafted polyethylene (CAS: 9006-26-2), polypropylene (Yanshan Petrochemical, item number: K8303), calcium carbonate (Shengyuan, item number: SY-017), calcium carbonate 8 wt%, calcium stearate (CAS: 1592-23-0) 1.2 wt%, polyethylene glycol (PEG 400) 0.8 wt%, azodicarbonamide (CAS: 123-77-3) 9 wt%, benzoyl peroxide (CAS: 94-36-0) 1 wt%, γ-methacryloyloxypropyltrimethoxysilane (KH570) 2 wt%, elastomer microspheres (EVA microspheres, prepared by spray cooling method, with an average particle size of 100 μm, and the material is Dow 3120) 0.8 wt%.

[0057] Preparation method: Nylon 6, polyvinylpyrrolidone, maleic anhydride-grafted polyethylene, polypropylene, and calcium carbonate are blended in a screw extruder for 4 minutes at 230℃ to obtain a nylon blend. EVA, POE elastomer, nylon blend, calcium carbonate, and polyethylene glycol are added to a mixer and mixed at 130℃ for 8 minutes. Elastomer microspheres, azodicarbonamide, benzoyl peroxide, KH570, and bismaleimide are added sequentially, and mixing continues for 3 minutes. The mixture is then thinned into sheets (85℃, 4 minutes, 8mm thickness) using an open mill and fed into a granulator for three-stage granulation (95℃ / 100℃ / 90℃). The resulting material is then processed in a foaming machine at 175℃ for 9 minutes at 150 kg / cm³. 2 The first foaming was performed by placing the rough blank in the shoe mold at 150℃ for 8 minutes at 150kg / cm². 2 Secondary foaming molding.

[0058] Comparative Example 3: This embodiment provides a foamed composite material and its preparation method.

[0059] Formula: EVA (Mitsui, Japan, item number: 40W) 30 wt%, POE elastomer (Wanhua, item number: 5057) 10 wt%, nylon blend 38.8 wt% (prepared from nylon 6 (Huashida, PA6), polyvinylpyrrolidone (CAS: 9003-39-8), maleic anhydride grafted polyethylene (CAS: 9006-26-2), polypropylene (Yanshan Petrochemical, item number: K8303), calcium carbonate (Shengyuan, item number: SY-017), calcium carbonate 8 wt%, calcium stearate (CAS: 1592-23-0) 1.2 wt%, polyethylene glycol (PEG 400) 0.8 wt%, azodicarbonamide (CAS: 123-77-3) 9 wt%, benzoyl peroxide (CAS: 94-36-0) 1 wt%, γ-methacryloyloxypropyltrimethoxysilane (KH570) 2 wt%, crosslinking agent (bismaleimide, CAS: 13676-54-5) 0.3 wt%.

[0060] Preparation method: Nylon 6, polyvinylpyrrolidone, maleic anhydride-grafted polyethylene, polypropylene, and calcium carbonate are blended in a screw extruder for 4 minutes at 230℃ to obtain a nylon blend. EVA, POE elastomer, nylon blend, calcium carbonate, and polyethylene glycol are added to a mixer and mixed at 130℃ for 8 minutes. Elastomer microspheres, azodicarbonamide, benzoyl peroxide, KH570, and bismaleimide are added sequentially, and mixing continues for 3 minutes. The mixture is then thinned into sheets (85℃, 4 minutes, 8mm thickness) using an open mill and fed into a granulator for three-stage granulation (95℃ / 100℃ / 90℃). The resulting material is then processed in a foaming machine at 175℃ for 9 minutes at 150 kg / cm³. 2 The first foaming was performed by placing the rough blank in the shoe mold at 150℃ for 8 minutes at 150kg / cm². 2 Secondary foaming molding.

[0061] Only 0.3 wt% crosslinking agent was added, without adding elastomer microspheres, and the rest was the same as in Example 1.

[0062] Performance testing methods

[0063] Tensile strength: Tested in accordance with GB / T 1040.3-2006 "Determination of tensile properties of plastics - Part 3: Test conditions for films and sheets".

[0064] Specific gravity: Tested in accordance with GB / T 1033-2008 "Determination of density and relative density of non-foamed plastics".

[0065] Impact resistance: Tested according to GB / T 1843-2008 "Plastic Cantilever Beam Impact Test Method".

[0066] Table 1 Performance test results of the examples and comparative examples

[0067] serial number Tensile strength (MPa) Impact resistance (kJ / m²) Specific gravity (g / cm³) Example 1 22.5 28.3 0.5 Example 2 21.8 27.1 0.51 Example 3 22.1 27.9 0.5 Example 4 21.9 27.5 0.49 Example 5 23 29 0.52 Example 6 22.3 28 0.5 Example 7 22.7 28.5 0.51 Example 8 22.4 28.2 0.5 Example 9 22.6 28.4 0.5 Comparative Example 1 13.2 15 0.48 Comparative Example 2 16.5 19.2 0.49 Comparative Example 3 17.8 20.5 0.49

[0068] As can be seen from Table 1, the tensile strength and impact strength of all embodiments are significantly higher than those of the comparative example, and the specific gravity remains basically between 0.49 and 0.52 g / cm³. 3 The lower level of tensile strength indicates that the mechanical properties of this foamed composite material are effectively improved while achieving lightweighting. This is because the elastomer microspheres of this application easily migrate and accumulate in the cell wall region due to differences in density and surface energy during the mixing and foaming process. The elastic properties of the microspheres enable them to effectively absorb and disperse external stress during the cell wall formation process, improving the toughness and crack resistance of the cell wall and inhibiting the initiation and propagation of microcracks. At the same time, the crosslinking agent (such as bismaleimide) can undergo a crosslinking reaction with the matrix resin during the foaming heating stage to form a dense three-dimensional network structure. This crosslinking network not only enhances the overall strength of the matrix but also improves the structural integrity and thermal stability of the cell wall. The synergistic effect of the elastomer microspheres and the crosslinking network gives the cell wall region both good flexibility and high strength and stability. Comparative Example 1, without the addition of elastomer microspheres and crosslinking agent, has the lowest tensile strength and impact strength, at 13.2 MPa and 15.0 kJ / m, respectively. 2 This indicates that the matrix material itself cannot simultaneously achieve high strength and lightweight. Comparative Example 2, which only added elastomer microspheres, showed a slight improvement in tensile strength and impact strength, but these were still lower than those of the examples, indicating that the toughening effect of adding only an elastomer microsphere was limited. Comparative Example 3, which only added a crosslinking agent, also showed a limited improvement in performance, indicating that single crosslinking is insufficient to fully suppress cell wall cracks. In contrast, Examples 1-10 all used elastomer microspheres and crosslinking agents for synergistic toughening, resulting in a denser cell wall structure that effectively dispersed stress and suppressed crack propagation, thus exhibiting excellent overall performance.

[0069] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0070] 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 foamed composite material, characterized by, A blend comprising the following components: EVA, POE elastomer, nylon blend, elastomer microspheres and crosslinking agent, wherein the content of the elastomer microspheres is 0.5-1% by total weight, the content of the crosslinking agent is 0.2-0.5%, the crosslinking agent is bismaleimide, the elastomer microspheres are EVA microspheres, the content of the EVA is 20-40%, the content of the POE elastomer is 5-15%, the content of the nylon blend is 30-45%, further comprising calcium carbonate, polyvinylpyrrolidone, maleic anhydride grafted polyethylene, calcium stearate, polyethylene glycol, azodicarbonamide, dibenzoyl peroxide and gamma-methacryloyloxypropyltrimethoxysilane.

2. A process for the production of a foamed composite material according to claim 1, characterized in that The method comprises the following steps: Blending nylon 6, polyvinylpyrrolidone, maleic anhydride grafted polyethylene, polypropylene and calcium carbonate to obtain a nylon blend; mixing EVA, POE elastomer, the nylon blend, calcium carbonate and polyethylene glycol in an internal mixer, then sequentially adding elastomer microspheres, azodicarbonamide, dibenzoyl peroxide, y-methacryloyloxypropyltrimethoxysilane and crosslinking agent, and granulating after uniform mixing; and foaming and molding the obtained material to obtain a foamed composite material.

3. The production method according to claim 2, characterized by, The foaming and molding comprises: first foaming at 175℃, 9min, 150kg / cm2; and second foaming and molding of the rough blank at 150℃, 8min, 150kg / cm2.

4. Use of the foamed composite material according to claim 1 in shoe materials, characterized by, The foamed composite material is used for shoe soles or insoles.

5. Use according to claim 4, characterized in that, The shoe material is sports shoes, casual shoes or safety shoes.