POK-ABS composite material applied to sports ware and preparation method of POK-ABS composite material

Abstract

The invention provides a POK-ABS composite material applied to sports ware and a preparation method thereof.The POK-ABS composite material comprises a POK composite material shell and a plastic soft lining, the thickness of the POK composite material shell ranges from 1 mm to 5 mm, and the POK composite material shell comprises POK resin, ABS, a compatilizer, a wear-resisting agent, an antioxidant and a lubricating agent according to the preset weight; the plastic soft lining is tightly attached to the inner surface of the POK composite material shell, the thickness of the plastic soft lining ranges from 0.5 mm to 2 mm, and the plastic soft lining comprises EVA and plastic according to the preset weight. The material not only continues the excellent properties of POK, but also integrates the ABS plastic high polymer material with excellent wear resistance as well as a proper amount of auxiliary components such as the compatilizer and the wear-resistant agent. Through the innovative design of the composite material, on the basis that the original strength of a final product is maintained, more excellent wear resistance and more stable use experience are achieved. The composite material perfectly meets the requirements of protectors in diversified use environments, and provides safer and more comfortable protection for athletes and users.

Description

Technical Field

[0001] The present invention relates to the field of polymer protective gear composite materials, and in particular to a POK-ABS composite material used for sports protective gear and a preparation method thereof. Background Art

[0002] Polymer materials are materials composed of compounds with relatively high molecular mass. These materials include rubber, plastic, fiber, coating, adhesive, and polymer-based composite materials. They play an important role in our daily lives, especially in the fields of sports protective gear, assistive devices for the disabled, and other medical devices. For example, in sports, athletes often use various protective gear. The outer shells of these protective gear are usually made of high-strength, impact-resistant polymer materials to reduce the damage caused to the human body by external forces. The inner lining of the protective gear uses foam materials such as EVA and rubber. These materials can effectively disperse internal pressure, thereby preventing harm to the human body. On the market, polymer materials such as nylon and ABS are commonly used raw materials for making protective gear.

[0003] However, although polymer materials such as nylon perform well in some aspects, they also have some shortcomings. Because these materials contain hydrophilic amide groups, they easily absorb water. Once they absorb water, the shape and size of the material are easily deformed. In addition, water absorption will also cause the strength and resistivity of the material itself to decrease, which will become a bottleneck limiting the application of materials in scenarios with high temperature, high humidity or very strict requirements on dimensional accuracy. For the raw materials used to make protective gear, they usually need to have high strength, good wear resistance, stable shape and high temperature resistance to ensure reliable protection in various environments.

[0004] In view of the above problems, it is particularly important to find a polymer material with high strength, no water absorption and no deformation. To this end, researchers have developed a composite material with POK material as the main component. Summary of the Invention

[0005] To address the above technical challenges, the present invention discloses for the first time a POK-ABS composite material for use in sports protective gear and its preparation method. This material not only inherits the excellent properties of POK, but also integrates ABS plastic polymer materials with excellent wear resistance, as well as appropriate amounts of auxiliary ingredients such as compatibilizers and wear-resistant agents. Through the innovative design of this composite material, the final product achieves superior wear resistance and a more stable user experience while maintaining its original strength. This composite material perfectly adapts to the needs of protective gear in diverse usage environments, providing athletes and users with safer and more comfortable protection to adapt to various usage scenarios of sports protective gear.

[0006] In order to achieve the purpose of the present invention, the technical solution of the present invention is as follows:

[0007] The present invention first discloses a POK-ABS composite material for use in sports protective gear. The key features of the composite material are: a POK composite material shell and a soft plastic lining. The POK composite material shell has a thickness between 1-5 mm and includes POK resin, ABS, a compatibilizer, a wear-resistant agent, an antioxidant, and a lubricant weighed in predetermined amounts. The soft plastic lining is tightly attached to the inner surface of the POK composite material shell, has a thickness between 0.5-2 mm, and includes EVA and plastic weighed in predetermined amounts.

[0008] Furthermore, the components of the POK composite material shell, POK resin, ABS, compatibilizer, wear-resistant agent, antioxidant and lubricant, are as follows by weight:

[0009]

[0010] Furthermore, the chemical nature of the ABS is acrylonitrile-butadiene-styrene copolymer.

[0011] Furthermore, the chemical nature of the compatibilizer is EPDM rubber with unsaturated bonds.

[0012] Furthermore, the anti-wear agent is carbon black powder that has been subjected to vulcanization treatment, surface modification treatment and heat treatment; wherein:

[0013] Vulcanization treatment: Mix carbon black with a vulcanizing agent and react them to form sulfide carbon black to improve the strength and wear resistance of carbon black;

[0014] Surface modification: Surface modification is performed using the sol-gel precipitation method to enhance the bonding ability between carbon black and the matrix material;

[0015] Heat treatment: Place the treated carbon black powder into an oven and dry it at 120°C for 3-4 hours.

[0016] Furthermore, the antioxidant is prepared by mixing pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and DLTP in a ratio of 1:1.5.

[0017] Furthermore, the lubricant is magnesium stearate.

[0018] Furthermore, the soft lining comprises by weight:

[0019] EVA 60-70 parts

[0020] 30-40 parts of rubber

[0021] Secondly, the present invention also discloses a method for preparing the POK-ABS composite material for sports protective gear, the key of which is:

[0022] S1: Weighing raw materials: Prepare raw materials POK, ABS, compatibilizer, anti-wear agent, lubricant, and antioxidant according to the required weight parts;

[0023] S2: Mixing raw materials: Put the raw materials prepared in step S1 into a mixer and mix them until they are evenly mixed and set aside;

[0024] S3: Melt blending: The uniformly mixed raw materials are fed into a twin-screw extruder for melt blending, and the screw process parameters are adjusted to obtain a melt blend;

[0025] S4: Molding: The molten blend is fed into a mold and the desired POK composite shell embryo is obtained through molding processes such as injection molding and extrusion;

[0026] S5: Post-processing: Cooling the formed POK composite material shell, trimming the burrs and other post-processing to obtain the final POK composite material shell product;

[0027] The preparation method of the plastic soft lining comprises the following steps:

[0028] T1: Weighing raw materials: Prepare the raw materials EVA and rubber according to the required weight parts;

[0029] T2: Mixing the raw materials: Add the raw materials prepared in step T1 into a mixer and mix them until they are evenly mixed and set aside;

[0030] T3: Melt extrusion: The uniformly mixed raw materials are fed into a single-screw extruder for melt extrusion, and the screw process parameters are adjusted to obtain a molten extrudate;

[0031] T4: Laminating process: laminating the molten extrudate to the inner surface of the POK composite material shell with an adhesive, and then cooling and shaping the POK-ABS composite material;

[0032] T5: Quality Inspection: Perform quality inspection on the prepared POK-ABS composite material, including but not limited to performance tests on appearance, size, heat resistance, wear resistance, chemical corrosion resistance and impact strength to ensure that the shell quality meets the established standards.

[0033] Furthermore, the adhesive used in the laminating process in step T4 is hot melt adhesive.

[0034] Compared with the existing technology, the remarkable effects of this new method are:

[0035] 1. This invention utilizes POK material as its core component. POK is a polymer material that does not contain hydrophilic groups. It is non-water-absorbent and exhibits high strength, high heat resistance, and excellent wear and chemical resistance. Using POK as the core component can better meet the stringent material performance requirements of protective gear manufacturing.

[0036] 2. In the present invention, ABS material is used as a secondary core component, which significantly improves the impact resistance, heat resistance and low temperature resistance of the composite material.

[0037] 3. The composite material of the present invention uses EPDM rubber containing unsaturated bonds as a compatibilizer. This compatibilizer effectively improves the compatibility between different polymers such as ABS and POK, reduces interfacial tension, increases interfacial thickness, and prevents the aggregation of the dispersed phase, thereby forming a stable mixed structure.

[0038] 4. The present invention adds specially pre-treated carbon black powder into the composite material as a wear-resistant agent, which enhances the wear resistance of the polymer material to a certain extent.

[0039] 5. In the composite material of the present invention, a mixture of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and DLTP in a ratio of 1:1.5 is used as an antioxidant. This antioxidant can effectively capture free radicals, decompose peroxides, and block chain reactions, thereby improving the stability of the material and extending its service life.

[0040] 6. Magnesium stearate is used as a lubricant in the present invention, which can improve the processing fluidity of the material, reduce friction and adhesion, and thus optimize the overall performance of the product.

[0041] 7. The soft inner layer material of the present invention is essentially a mixture of EVA and rubber. This mixture takes advantage of the lightweight, thermally stable, and moderate elasticity of EVA, while also combining the strong elasticity and good wear resistance of rubber. This gives the soft inner lining excellent elasticity and wear resistance.

[0042] 8. Based on the above advantages, the POK-ABS composite material provided by the present invention exhibits excellent stability, wear resistance, high strength, high and low temperature resistance, chemical corrosion resistance and no water absorption. DETAILED DESCRIPTION

[0043] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. Additional aspects and advantages of the present invention will be partially given in the following description, partially become apparent from the following description, or be understood through practice of the present invention. It should be understood that the following description is only used to explain the present invention and is not intended to limit the present invention.

[0044] As used herein, the terms "comprises," "including," "having," "containing" or any other variations thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a listed element is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

[0045] Example 1:

[0046] Polymer materials are widely used in the manufacture of sports protective gear. However, traditional materials such as nylon, due to their hydrophilic groups, easily absorb water in humid environments, leading to deformation and reduced strength. Especially in high-temperature and high-humidity environments, the dimensional stability and mechanical properties of the protective gear shell are significantly reduced, affecting the protective effect on the user. For example, when football players compete in the rain, their knee pads absorb water and expand and deform, resulting in uneven stress on the joints and even the risk of secondary injury.

[0047] To address these issues, researchers discovered that polyketone resin possesses both hydrophobicity and high mechanical strength, but its use alone can be brittle and difficult to process. By analyzing the balance between mechanical load-bearing and wearing comfort required of protective gear materials, they proposed a composite structure combining a high-strength outer shell with an elastic lining. After multiple experiments, they determined that a blend of polyketone resin and acrylonitrile-butadiene-styrene copolymer would serve as the outer shell substrate, supplemented by an elastic foam lining. This results in a composite system that combines rigidity and flexibility, inhibiting deformation due to water absorption while enhancing cushioning performance.

[0048] Therefore, this embodiment proposes a composite structure comprising a polyketone composite outer shell and a soft plastic inner lining. The polyketone composite outer shell (POK composite outer shell) is composed of polyketone resin (POK), acrylonitrile-butadiene-styrene copolymer (ABS), a compatibilizer, a wear-resistant agent, an antioxidant, and a lubricant, and its thickness can be controlled within a specific range. The soft plastic inner lining is composed of ethylene-vinyl acetate copolymer (EVA) and rubber, and is adhered to the inner surface of the outer shell at a specific thickness.

[0049] Among them, the polyketone composite shell refers to a polymer blend based on polyketone resin, which can be prepared by a twin-screw extrusion melt blending process. The shell blocks water penetration through the hydrophobic properties of the polyketone resin, while using acrylonitrile-butadiene-styrene copolymer to improve the toughness of the material. The compatibilizer is used to promote the interfacial bonding between the polyketone resin and the acrylonitrile-butadiene-styrene copolymer, and a polymer containing reactive functional groups can be used. The plastic soft lining refers to an elastomer layer with a closed-cell structure, which is bonded to the shell through a bonding process. The use of ethylene-vinyl acetate copolymer and rubber blends can form a gradient modulus structure to achieve a pressure dispersion function.

[0050] Specifically, when the polyketone composite shell is subjected to external impact, the rigid skeleton of the polyketone resin provides primary support, while the acrylonitrile-butadiene-styrene copolymer absorbs energy through the flexible deformation of its molecular chains. The synergistic effect of the two enables the material to maintain high strength while reducing the risk of brittle fracture. The soft plastic lining converts concentrated stress into distributed load through elastic deformation, avoiding discomfort caused by excessive local pressure. During the melt processing, the compatibilizer eliminates defects at the interface between the two phases through chemical bonding, improving the integrity of the material. The thickness ratio of the shell and lining has been optimized to ensure that the composite structure achieves a balance between mechanical performance and wearer comfort within a limited space.

[0051] Compared with existing technologies, conventional nylon protective gear experiences significantly higher dimensional changes due to water absorption and expansion under the same humidity conditions than this solution, and is also prone to strength degradation after repeated impacts. This solution utilizes the hydrophobic properties of polyketone resin to fundamentally block the water absorption pathway. Combined with a composite structural design, this solution allows the protective gear to maintain a stable shape even in humid environments. The introduction of acrylonitrile-butadiene-styrene copolymer increases the material's elongation at break, avoiding the brittle cracking of pure polyketone materials under impact.

[0052] Through the above-mentioned technical solution, this application effectively addresses the problem of reduced protective performance caused by water absorption and deformation of sports protective gear materials. While maintaining high strength and wear resistance, the composite outer shell reduces wear discomfort through the elastic deformation properties of the lining, making it suitable for competitive sports protective gear that requires long-term wear. The improved thermal stability and processing properties of the material system make it suitable for large-scale production processes such as injection molding.

[0053] Example 2:

[0054] This embodiment further proposes that the components of the POK composite material shell include POK resin, ABS, compatibilizer, wear-resistant agent, antioxidant and lubricant, and their weight parts are 45-60 parts, 15-30 parts, 4-10 parts, 2-5 parts, 0.5-0.8 parts and 0.3-0.6 parts respectively.

[0055] Among them, POK resin refers to a polyketone polymer compound, specifically a polyketone material with a non-polar molecular structure. Its regular arrangement of molecular chains forms a highly crystalline matrix, thereby providing the material's basic strength and water resistance. ABS refers to acrylonitrile-butadiene-styrene copolymer, specifically a copolymer with a butadiene content controlled at 15%-25%. Its styrene segments form physical entanglements with the POK resin, and the butadiene phase provides toughness compensation. A compatibilizer refers to an interface modifier, specifically EPDM rubber containing active functional groups, which promotes interfacial compatibility between POK and ABS through molecular chain grafting reactions. An anti-wear agent refers to a surface strengthening component, specifically carbon black powder with a particle size distribution of 50-100 nanometers. Its surface modification enhances its bonding strength to the matrix. An antioxidant refers to a free radical scavenger, specifically a combination of hindered phenols and thioesters, which synergistically slows down the oxidative degradation of the material. Lubricants refer to processing aids, which can be specifically realized by metal soap compounds. They improve the fluidity of the material during the molding process by reducing the viscosity of the melt.

[0056] Specifically, this technical solution optimizes material properties by constructing a synergistic system between the main matrix and the toughening phase. The continuous phase network structure formed by the POK resin provides anti-water absorption properties, and its non-polar molecular structure effectively blocks the penetration of water molecules; ABS is embedded in the matrix as a dispersed phase, and forms an interpenetrating network through the van der Waals force of the styrene chain segments and POK. The active groups of the compatibilizer undergo grafting reactions with the carbonyl groups of POK and the cyano groups of ABS during the melt blending process, eliminating phase interface defects. The nano-scale particles of the wear-resistant agent form a three-dimensional dispersed structure in the matrix, improving the surface hardness through mechanical interlocking. The compound system of antioxidants forms a synergistic protection during the heating process of the material, while scavenging alkoxy free radicals and peroxides. The polar molecules of the lubricant are directionally arranged on the surface of the material during processing, reducing the friction resistance between the melt and the processing equipment. The proportion of each component is determined based on rheological phase analysis. When the POK resin accounts for more than 45%, a continuous phase structure can be formed. ABS is controlled below 30% to avoid excessive introduction of hydrophilic groups. The lower limit of the compatibilizer dosage is 4% to ensure the interfacial bonding strength of the two phases.

[0057] Compared with the existing technology, traditional protective gear materials such as nylon-based composite materials have a water absorption rate of more than 2.5% due to the excessive content of amide groups. This solution reduces the water absorption rate of the material to less than 0.8% by controlling the total content of hydrophilic components below 30%. Compared with pure ABS materials, the introduction of the POK matrix increases the tensile strength to more than 65MPa, and the Vicat softening temperature is increased to 160°C. In terms of processing performance, the use of lubricants enables the melt flow index to reach 25g / 10min, which is better than the 15g / 10min of conventional POK materials. Compared with the control sample without the addition of compatibilizer, the improvement in interfacial bonding strength increases the impact toughness value by about 40%.

[0058] Through the above technical solution, this application achieves the dimensional stability of sports protective gear materials in humid environments, solving the problem of protection failure caused by water absorption and deformation of traditional materials. The flexural modulus of the material reaches more than 2800MPa, and it can withstand repeated impact loads without plastic deformation. The surface Rockwell hardness is maintained at 110R scale, maintaining good appearance integrity under long-term friction conditions. The improvement of melt fluidity during processing increases the molding qualification rate of complex structure protective gear to more than 95%, and the thermal stability of the material enables it to withstand conventional sterilization processing temperatures.

[0059] Example 3:

[0060] This embodiment further emphasizes acrylonitrile-butadiene-styrene copolymer as a component of the composite material.

[0061] Acrylonitrile-butadiene-styrene copolymer (ABS) is a thermoplastic polymer formed by the copolymerization of acrylonitrile, butadiene, and styrene, typically via bulk or emulsion polymerization. Acrylonitrile enhances the material's chemical resistance by introducing cyano groups, butadiene improves impact strength by forming a rubber phase, and styrene improves processing fluidity through its rigid chain segments. The synergistic effect of these three elements ensures that the copolymer maintains both rigidity and toughness within the composite material system.

[0062] Specifically, the polar groups of acrylonitrile form hydrogen bonds with the POK resin molecular chains, the elastic segments of butadiene absorb energy through molecular chain slippage when impacted, and the rigidity of styrene forms an interpenetrating network with the crystalline regions of the POK resin. This molecular-level interaction enables the components to form a uniformly dispersed microphase during melt blending, avoiding phase separation due to polarity differences.

[0063] Compared to existing technologies, existing composite materials generally describe the use of ABS without specifying its chemical structure. This leads to problems such as unstable interfacial bonding and fluctuating water absorption rates due to differences in monomer ratios between ABS suppliers. By specifying ABS as an acrylonitrile-butadiene-styrene copolymer, the polar group content and rubber phase ratio are precisely controlled, ensuring the material maintains phase stability during high-temperature processing.

[0064] Through the above technical solution, this application solves the problems of insufficient interface bonding strength and performance fluctuations of ABS materials due to unclear chemical structure, so that the composite material maintains dimensional stability in a hot and humid environment, while having both chemical corrosion resistance and impact resistance, meeting the dual requirements of sports protective gear for mechanical strength and weather resistance of materials.

[0065] Example 4:

[0066] This embodiment further proposes that the chemical nature of the compatibilizer is EPDM rubber having unsaturated bonds.

[0067] Unsaturated EPDM refers to a polymer with a saturated backbone and double bonds in the side chains. It can be prepared through solution polymerization of ethylene, propylene, and non-conjugated diene monomers. The unsaturated bonds in this material can undergo a grafting reaction with the styrene phase in ABS, while the non-polar structure of the backbone forms a physical entanglement with the POK resin.

[0068] Specifically, during the melt blending process, the double bonds in the EPDM side chains react with the styrene groups in ABS through free radical reactions to form a chemical grafting structure. Simultaneously, the non-polar segments of its main chain entangle with the carbon-oxygen backbone of the POK resin to form a molecular chain. This dual bonding mechanism forms an interpenetrating network structure at the interface between the POK and ABS phases, creating a stable interfacial bonding layer between the originally incompatible components. The presence of this interfacial bonding layer effectively blocks the permeation path of water molecules along the phase interface, while the enhanced interfacial strength inhibits interlayer delamination caused by differences in swelling stress within the material after water absorption.

[0069] Compared with existing technologies, traditional compatibilizers often use polar modified materials such as maleic anhydride grafted polyolefins, which improve compatibility solely through physical adsorption of polar groups with POK and are unable to form chemical bonds with ABS. However, the EPDM rubber in this solution chemically reacts with ABS through unsaturated bonds, improving interfacial bonding while maintaining the compatibility of the non-polar backbone with POK, thus resolving the weak interfacial bonding problem caused by simple physical mixing.

[0070] Through the above technical solution, the present application achieves the densification of the interface microstructure of the composite material, reduces the risk of deformation caused by internal stress concentration of the material after water absorption, and enables the prepared sports protective gear to still maintain stable mechanical strength and dimensional accuracy in a humid environment.

[0071] Embodiment 5:

[0072] This embodiment further proposes that the wear-resistant agent is carbon black powder that has been subjected to vulcanization, surface modification, and heat treatment. The vulcanization treatment involves mixing carbon black with a vulcanizing agent to form vulcanized carbon black. The surface modification treatment is performed using a sol-gel precipitation method. The heat treatment involves drying the treated carbon black powder at 120°C for 3-4 hours.

[0073] Among them, vulcanization treatment refers to the introduction of sulfide cross-linking structures between carbon black particles through chemical reactions. Specifically, it can be achieved by using sulfur or peroxide as a vulcanizing agent to react with carbon black at high temperature, thereby enhancing the mechanical strength and wear resistance of the carbon black itself through the formation of a cross-linked network.

[0074] Among them, surface modification treatment refers to the formation of an interfacial transition layer on the surface of carbon black by chemical or physical methods. Specifically, it can be achieved by mixing the silica precursor solution with carbon black and then hydrolyzing and precipitating it using the sol-gel method, and improving the interfacial bonding ability between carbon black and the matrix material through the surface coating layer.

[0075] Among them, heat treatment refers to the removal of volatile substances remaining inside the material through temperature control. Specifically, it can be achieved by using a hot air circulation oven to continuously dry at a specific temperature. The evaporation of water and solvents eliminates the risk of pores or interface defects in carbon black powder during subsequent processing.

[0076] Specifically, the cross-linked structure formed during the vulcanization stage gives the carbon black particles a higher shear resistance, which can effectively resist external force damage when the composite material is subjected to friction. The silica coating formed during the surface modification stage chemically bonds with the polar groups in the matrix material through hydroxyl groups, thereby enhancing the dispersion of carbon black in the matrix and the interfacial bonding strength. The heat treatment stage ensures the complete evaporation of adsorbed water and avoids the decomposition of the carbon black surface modification layer due to high temperature by precisely controlling the temperature and time parameters, thereby ensuring the integrity of the interface structure during the material molding process. The three stages are implemented in sequence to form a systematic solution from core strengthening, interface optimization to processing stability assurance.

[0077] Compared to existing technologies, traditional carbon black modification methods typically rely solely on single surface treatments or simple drying processes, failing to address the inherent strength issues of carbon black and interfacial defects caused by processing residues. For example, existing approaches using silane coupling agents to treat carbon black do not address crosslinking and moisture control. This approach, through a three-stage synergistic treatment, achieves for the first time the simultaneous optimization of the three dimensions of carbon black modification: the particle core, the interface, and processing stability.

[0078] Through the above technical solution, the present application enables the carbon black to form a stable chemically bonded interface with the matrix material while maintaining high wear resistance, thus preventing wear resistance degradation caused by interfacial delamination. This also eliminates the impact of residual moisture within the carbon black on the molding process, ensuring that the composite material does not generate bubbles or structural defects due to the escape of volatiles during the injection molding or extrusion process, ultimately resulting in a wear-resistant composite material with a uniform and dense structure.

[0079] Example 6:

[0080] This embodiment further proposes that the antioxidant is prepared by mixing pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and DLTP in a ratio of 1:1.5.

[0081] Among them, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] refers to a phenolic primary antioxidant, which can be prepared by an organic synthesis method. It captures free radicals through the hydrogen donation effect of the phenolic hydroxyl group, thereby interrupting the oxidation chain reaction.

[0082] DLTP refers to dilauryl thiodipropionate, which can be prepared by esterification reaction, and the continued oxidation reaction is inhibited by decomposing peroxides.

[0083] Among them, the ratio of 1:1.5 refers to the mass ratio of the two components. For example, 1 part by weight of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] can be selected, and 1.5 parts by weight of DLTP can be selected. This ratio can optimize the synergistic effect of the two antioxidant mechanisms.

[0084] Specifically, during high-temperature processing and long-term use, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] preferentially reacts with free radicals to form a stable structure, preventing the propagation of the oxidative chain initiation stage; while DLTP blocks the continuation of the chain growth stage by decomposing hydrogen peroxide. The synergistic ratio of the two allows the primary and secondary antioxidants to form a complementary network within the material matrix, covering the different stages of oxidative degradation while avoiding crystallization or interfacial defects caused by excessive amounts of a single component. This ratio further ensures molecular dispersion of the two components during melt blending, thereby maintaining thermal stability during material processing.

[0085] Compared to existing technologies, traditional approaches typically use either phenolic or thioester antioxidants alone. However, these single components cannot simultaneously inhibit both free radical initiation and peroxide decomposition. This solution's blended system, designed with a specific ratio, allows the two components to form a stable blend in the molten state. This overcomes the phase separation issue often associated with traditional blends while also multiplying oxidation inhibition efficiency.

[0086] Through the above technical solution, this application effectively delays the oxidative degradation rate of composite materials during processing and use environment, significantly improves the stability of the material under high temperature conditions, and at the same time avoids the negative impact of excessive addition of antioxidants on the mechanical properties of the material, thereby extending the service life of sports protective gear products.

[0087] Embodiment seven:

[0088] This embodiment further proposes a technical solution in which the lubricant is magnesium stearate.

[0089] Magnesium stearate is a metallic soap compound formed from stearic acid and magnesium ions. Specifically, it can be achieved using industrial-grade powdered magnesium stearate. Its polar molecular structure forms an interfacial compatibility layer with the resin matrix, thereby reducing internal friction within the melt blend. Magnesium stearate's low hygroscopicity prevents dimensional deformation caused by water absorption in traditional lubricants.

[0090] Specifically, magnesium stearate is uniformly dispersed in the POK resin and ABS mixture during melt blending, forming a lubricating interface layer through the interaction between polar groups and the resin molecular chains. This interface layer effectively reduces the material's adhesion to the metal surface of the molding equipment during extrusion or injection molding, reducing melt flow resistance. Magnesium stearate's thermal stability prevents it from decomposing to produce gas or residue within the processing temperature range, thus avoiding molding defects caused by lubricant failure. Its low hygroscopicity maintains the stability of the material's internal structure even in high-temperature and high-humidity environments, preventing degradation of lubrication properties caused by moisture intrusion.

[0091] Compared to existing technologies, traditional lubricants such as silicone oil and paraffin waxes tend to volatilize or carbonize during high-temperature processing, resulting in unstable lubrication. Some lubricants contain hydrophilic groups, which can absorb water in high-humidity environments, causing material swelling or interfacial delamination. Magnesium stearate overcomes these limitations through its stable chemical structure, and the coordination of its metal ions with the resin further enhances interfacial bonding strength.

[0092] Through the above technical solution, the present application effectively reduces the flow resistance of the molten blend, avoiding molding defects caused by uneven local shear forces. The demolding performance of the material is significantly improved during processing, reducing surface defects after the protective gear shell is molded. The low moisture absorption properties of magnesium stearate ensure the dimensional stability of the composite material in hot and humid environments, avoiding product performance fluctuations caused by water absorption by the lubricant.

[0093] Embodiment 8:

[0094] This embodiment further proposes a composite structure design in which the soft liner includes 60-70 parts of EVA and 30-40 parts of rubber by weight.

[0095] EVA refers to an ethylene-vinyl acetate copolymer material, which can be foamed into a closed-cell cushioning layer. The vinyl acetate content in its molecular chains can adjust the material's softness and resilience. Rubber refers to a highly elastic polymer with a three-dimensional cross-linked network structure, specifically styrene-butadiene rubber (SBR) or natural rubber. The entanglement of its molecular chains imparts resistance to permanent deformation. In this system, EVA, as the matrix phase, primarily dissipates pressure, while rubber, as the reinforcing phase, maintains the stability of the material structure.

[0096] Specifically, when the EVA content is between 60 and 70 parts, the closed-cell foam structure can effectively absorb impact energy and avoid local stress concentration that causes pressure on the human body. When the rubber content is controlled within the range of 30 to 40 parts, its cross-linked network can not only limit excessive deformation of the EVA, but also maintain the original shape of the lining through elastic recovery. The interpenetrating network structure formed by the two materials during the melt processing allows the impact energy to be dissipated through the dual mechanisms of deformation absorption by EVA and elastic support by rubber. By adjusting the mixing temperature and time, the rubber phase forms a continuously distributed second phase structure in the EVA matrix, thereby improving creep resistance while maintaining cushioning performance.

[0097] Compared to existing technologies, traditional protective gear linings often use a single EVA or rubber material. The former is prone to permanent dents after prolonged pressure, while the latter's high hardness reduces wearing comfort. This solution, through a composite material design with a specific ratio, creates a synergistic effect between the cushioning properties of EVA and the morphological stability of rubber. This avoids the functional limitations of a single material and addresses the issue of insufficient interfacial bonding strength in the composite system.

[0098] Through the above technical solution, this application achieves a dynamic balance between impact energy absorption and structural support in the protective gear lining material, ensuring that the impact force of movement is effectively dispersed while preventing the material from irreversibly deforming after repeated stress. Furthermore, this ratio design ensures that the lining material maintains a moderate softness when in contact with the human body, avoiding skin indentations or blood circulation obstruction caused by excessively hard materials.

[0099] Embodiment 9:

[0100] This example discloses a method for preparing a POK-ABS composite material, including a phased process for preparing an outer shell and an inner liner, followed by their final composite. The outer shell preparation method includes raw material weighing, mixing, twin-screw melt blending, injection molding, and post-processing; the inner liner preparation method includes raw material mixing, single-screw melt extrusion, hot melt adhesive lamination, and multi-dimensional testing.

[0101] Among them, a twin-screw extruder refers to a continuous mixing device with two parallel intermeshing screws. Specifically, it can be achieved by adopting an intermeshing twin-screw structure with segmented temperature control. The interface bonding state of POK and ABS is optimized by adjusting the screw speed and shear strength. A single-screw extruder refers to a plasticizing extrusion device with a single rotating screw. Specifically, it can be achieved by adopting a gradient compression section structure to avoid overheating and degradation of high-viscosity rubber materials during processing. Hot melt adhesive bonding refers to the process of using thermoplastic adhesives to achieve interlayer bonding of materials. Specifically, it can be achieved by using ethylene-vinyl acetate copolymer-based adhesives to complete rapid bonding within a temperature range of 150-180°C. Multi-dimensional testing refers to a test system covering physical properties and chemical stability. Specifically, it can be achieved by combining non-destructive testing with laboratory analysis. For example, the material composition is verified by infrared spectroscopy and the impact resistance is evaluated by a pendulum impact tester.

[0102] Specifically, during the shell production process, the raw material weighing stage uses an electronic balance to precisely control the proportions of each component to ensure that the POK resin and ABS form a continuous phase structure. The twin-screw extruder stage adopts a segmented temperature control mode, maintaining 180°C in the feed section to prevent premature plasticization, raising the temperature to 230°C in the mixing section to promote molecular chain entanglement, and cooling the discharge port to 200°C to prevent material oxidation. The molding process uses an injection molding process with a mold temperature controlled at 60°C to ensure uniform flow and filling of the melt in the mold. During the lining preparation process, the mixer rotor plasticizes the EVA and rubber at a speed of 25 rpm, and the single-screw extruder uses a 3:1 compression ratio to ensure material density. The laminating process applies a layer of hot melt adhesive under an air pressure of 0.5 MPa, and the pressure is maintained for 30 seconds to achieve complete interface bonding. The quality inspection stage subjects the samples to a 72-hour moisture and heat cycle test to verify dimensional stability.

[0103] Compared to existing technologies, traditional nylon protective gear utilizes a single-shot injection molding process, resulting in a material water absorption rate as high as 2.5%, leading to dimensional deformation. This solution, however, utilizes a POK-ABS composite system to control water absorption to below 0.3%. Existing linings often utilize direct bonding of foam materials, resulting in insufficient interfacial bonding strength and prone to delamination. This solution achieves gradient modulus matching between the outer shell and lining through a step-by-step preparation process. Conventional testing focuses solely on appearance and hardness indicators, while this solution adds a new chemical corrosion resistance test to simulate a sweat environment to verify material durability.

[0104] This technical solution effectively addresses the issues of water absorption and deformation of the outer shell and loose lining adhesion in sports protective gear. The outer shell material maintains high strength while also offering dimensional stability. Testing has shown that the morphological deviation remains within 0.1mm in a 95% humidity environment. The peel strength between the inner lining and the outer shell has been increased to 15N / cm, ensuring that the layers remain intact during intense exercise. The entire manufacturing process enables continuous production, with a single-batch qualification rate exceeding 98%, meeting the requirements of large-scale manufacturing.

[0105] Embodiment 10:

[0106] This application further proposes a technical solution of using hot melt adhesive as an adhesive during the bonding process.

[0107] Hot melt adhesives are thermoplastic resin-based materials that solidify upon cooling after being applied in a molten state. Specifically, ethylene-vinyl acetate copolymer-based hot melt adhesives are used. They contain no volatile solvents and require no chemical reaction during the curing process. This feature prevents interfacial stress concentration caused by water absorption by the material by avoiding the introduction of moisture.

[0108] Specifically, the hot melt adhesive in its solid form is heated to a molten state during processing and evenly applied to the surface of the soft plastic lining through an extruder. During the cooling and setting phase, it forms a physical bond with the POK composite shell. Because the hot melt adhesive's melting temperature range matches the shell's molding temperature, it maintains its adhesiveness during the bonding process without causing thermal deformation of the shell material. The cured hot melt adhesive layer forms a continuous interface with an elastic modulus intermediate between the shell and lining materials, enabling the composite structure to achieve a stress gradient transition under impact.

[0109] Compared to existing technologies, traditional protective gear manufacturing often uses solvent-based adhesives or reactive glues, which can lead to porosity defects and water swelling caused by solvent evaporation. Hot melt adhesives, however, have zero water content, eliminating the risk of interfacial deformation caused by water absorption. Their rapid curing properties shorten the lamination process by approximately 40%, while also eliminating the need for solvent recovery equipment, simplifying the production process.

[0110] Through the above technical solution, the present application achieves an improvement in the interface bonding strength between the outer shell and the lining of sports protective gear, enables the composite structure to maintain dimensional stability in a hot and humid environment, avoids the problem of deformation and failure of protective gear caused by water absorption of the adhesive, and at the same time meets the process efficiency requirements of large-scale production.

[0111] In summary, the present invention adopts POK material as the core component. POK material is a polymer material that does not contain hydrophilic groups. It has the characteristics of non-water absorption and exhibits high strength, high heat resistance, excellent wear resistance and chemical corrosion resistance. Using POK material as the core component can better meet the strict requirements for material properties when making protective gear. In the present invention, ABS material is used as a secondary core component, which significantly improves the impact resistance, heat resistance and low temperature resistance of the composite material. In the composite material of the present invention, EPDM rubber containing unsaturated bonds is used as a compatibilizer. This compatibilizer effectively improves the compatibility between different polymers such as ABS and POK, reduces interfacial tension, increases interfacial thickness, and can prevent the agglomeration of the dispersed phase, thereby forming a stable mixed structure. The present invention adds specially pre-treated carbon black powder to the composite material as a wear-resistant agent, which enhances the wear resistance of the polymer material to a certain extent. In the composite material of the present invention, a mixed reagent of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and DLTP in a ratio of 1:1.5 is used as an antioxidant. This antioxidant can effectively capture free radicals, decompose peroxides, and block chain reactions, thereby improving the stability of the material and extending its service life. Magnesium stearate is used as a lubricant in the present invention, which can improve the processing fluidity of the material, reduce friction and adhesion, and thus optimize the overall performance of the product. The soft inner layer material in the present invention is essentially a mixture of EVA material and rubber material. This mixture not only utilizes the characteristics of EVA material being light, thermally stable and moderately elastic, but also combines the advantages of rubber material being strong elasticity and good wear resistance, so that the soft lining has both good elasticity and wear resistance. Based on the above advantages, the POK-ABS composite material provided by the present invention exhibits the advantages of excellent stability, wear resistance, high strength, high and low temperature resistance, chemical corrosion resistance, and no water absorption.

[0112] The above disclosures are merely some preferred embodiments of the present invention, and certainly cannot be used to limit the scope of the present invention. A person skilled in the art will understand that all or part of the processes of the above embodiments and equivalent changes made in accordance with the claims of the present invention are still within the scope of the invention.

Claims

1. A POK-ABS composite material for sports protective gear, characterized by: It includes a POK composite material shell and a soft plastic lining. The thickness of the POK composite material shell is between 1-5 mm, and it includes POK resin, ABS, compatibilizer, wear-resistant agent, antioxidant and lubricant weighed according to predetermined proportions. The soft plastic lining is tightly attached to the inner surface of the POK composite material shell, its thickness is between 0.5-2 mm, and it includes EVA and plastic weighed according to predetermined proportions.

2. The POK-ABS composite material shell for sports protective gear according to claim 1, characterized in that: The components of the POK composite material shell, POK resin, ABS, compatibilizer, wear-resistant agent, antioxidant and lubricant, are as follows:

3. The POK-ABS composite material for sports protective gear according to claim 2, characterized in that: The chemical nature of the ABS is acrylonitrile-butadiene-styrene copolymer.

4. The POK-ABS composite material for sports protective gear according to claim 3, characterized in that: The chemical nature of the compatibilizer is ethylene propylene diene monomer rubber with unsaturated bonds.

5. The POK-ABS composite material for sports protective gear according to claim 4, characterized in that: The anti-wear agent is carbon black powder that has been subjected to vulcanization treatment, surface modification treatment and heat treatment; wherein: Vulcanization treatment: Mix carbon black with a vulcanizing agent and react them to form sulfide carbon black to improve the strength and wear resistance of carbon black; Surface modification: Surface modification is performed using the sol-gel precipitation method to enhance the bonding ability between carbon black and the matrix material; Heat treatment: Place the treated carbon black powder into an oven and dry it at 120°C for 3-4 hours.

6. The POK-ABS composite material for sports protective gear according to claim 5, characterized in that: The antioxidant is prepared by mixing pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and DLTP in a ratio of 1:1.

5.

7. The POK-ABS composite material for sports protective gear according to claim 6, characterized in that: The lubricant is magnesium stearate.

8. The POK-ABS composite material for sports protective gear according to any one of claims 1 to 7, characterized in that: The soft lining comprises by weight: EVA 60-70 parts 30-40 parts of rubber.

9. A method for preparing a POK-ABS composite material for sports protective gear according to any one of claims 2 to 7, characterized in that: The preparation method of the POK composite shell material comprises the following steps: S1: Weighing raw materials: Prepare raw materials POK, ABS, compatibilizer, anti-wear agent, lubricant, and antioxidant according to the required weight parts; S2: Mixing raw materials: Put the raw materials prepared in step S1 into a mixer and mix them until they are evenly mixed and set aside; S3: Melt blending: The uniformly mixed raw materials are fed into a twin-screw extruder for melt blending, and the screw process parameters are adjusted to obtain a melt blend; S4: Molding: The molten blend is fed into a mold and the desired POK composite shell embryo is obtained through molding processes such as injection molding and extrusion; S5: Post-processing: Cooling the formed POK composite material shell, trimming the burrs and other post-processing to obtain the final POK composite material shell product; The preparation method of the plastic soft lining comprises the following steps: T1: Weighing raw materials: Prepare the raw materials EVA and rubber according to the required weight parts; T2: Mixing the raw materials: Add the raw materials prepared in step T1 into a mixer and mix them until they are evenly mixed and set aside; T3: Melt extrusion: The uniformly mixed raw materials are fed into a single-screw extruder for melt extrusion, and the screw process parameters are adjusted to obtain a molten extrudate; T4: Laminating process: laminating the molten extrudate to the inner surface of the POK composite material shell with an adhesive, and then cooling and shaping the POK-ABS composite material; T5: Quality Inspection: Perform quality inspection on the prepared POK-ABS composite material, including but not limited to performance tests on appearance, size, heat resistance, wear resistance, chemical corrosion resistance and impact strength to ensure that the shell quality meets the established standards.

10. The preparation method according to claim 9, characterized in that: The adhesive used in the laminating process in step T4 is hot melt adhesive.

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