Fluorine-free reinforced wear-resistant polyketone composite material, preparation method and application thereof

Abstract

The application discloses a fluorine-free reinforced wear-resistant polyketone composite material and a preparation method and application thereof, and relates to the technical field of polymer composites.The fluorine-free reinforced wear-resistant polyketone composite material comprises polyketone resin, glass fiber, modified ultrahigh molecular weight polyethylene, antioxidant and lubricant; the modified ultrahigh molecular weight polyethylene is obtained by modifying linear polyethylene without branches with a molecular weight of more than 2 million, and the amount of the modifier is 1% to 5% of the amount of the ultrahigh molecular weight polyethylene.The modified ultrahigh molecular weight polyethylene, the glass fiber and the polyketone resin are blended and modified, the polyketone resin has good wear resistance, and the glass fiber has high strength; meanwhile, the modified ultrahigh molecular weight polyethylene has low friction coefficient, the compatibility with the polyketone resin is improved, the polyketone resin is more uniformly dispersed, and the heat resistance and friction performance of the polyketone resin are comprehensively improved.In addition, the use of the fluorine-free material improves the safety of the polyketone composite material and expands the application market of the polyketone composite material.

Description

Technical Field

[0001] This invention relates to the field of polymer composite materials technology, and more specifically, to a fluorine-free reinforced wear-resistant polyketone composite material, its preparation method, and its application. Background Technology

[0002] Polytetrafluoroethylene (PTFE) is widely used in industrial applications such as ball valve seals due to its excellent self-lubricating properties, wear resistance, and resistance to high and low temperatures. However, PTFE has a high viscosity and no fluidity in its molten state at high temperatures, making it unsuitable for injection molding. It can only be formed through compression and sintering, which complicates the manufacturing process and increases costs significantly. In recent years, due to increasingly stringent environmental laws and regulations, PFAS regulations have emerged. As a typical fluorinated material, PTFE has gradually faced strict market restrictions (especially in the European market). The application of PTFE materials faces policy and environmental risks, further driving the exploration of alternative materials.

[0003] Polyketone (POK), a highly crystalline polymer, is a novel green polymer material synthesized from carbon monoxide and olefins (such as ethylene and propylene). Due to its low water absorption, good wear resistance, hydrolysis resistance, excellent chemical resistance, and superior flowability and processability, it has gained attention and widespread application in various industrial fields, such as automotive manufacturing, electronics, and medical devices. However, in certain specific applications, POK still falls short in terms of mechanical strength, high-temperature resistance, and durability, which limits its application in specific areas, such as sealing materials.

[0004] Therefore, there is an urgent need to explore and obtain a fluorine-free reinforced wear-resistant polyketone composite material that is fluorine-free, high-performance, and meets environmental protection requirements.

[0005] In view of this, the present invention is proposed. Summary of the Invention

[0006] The purpose of this invention is to provide a fluorine-free reinforced wear-resistant polyketone composite material, its preparation method, and its application, so as to solve the above-mentioned technical problems.

[0007] This invention is implemented as follows: In a first aspect, embodiments of the present invention provide a fluorine-free reinforced wear-resistant polyketone composite material, comprising the following components by weight: 79-89 parts of polyketone resin, 5-15 parts of glass fiber, 3-10 parts of modified ultra-high molecular weight polyethylene, 0.5-1.0 parts of antioxidant, and 0.3-0.5 parts of lubricant. Among them, modified ultra-high molecular weight polyethylene is obtained by modifying unbranched linear polyethylene with a molecular weight of more than 2 million, and the amount of modifier used is 1%-5% of the amount of ultra-high molecular weight polyethylene.

[0008] Secondly, embodiments of the present invention provide a method for preparing the aforementioned fluorine-free reinforced wear-resistant polyketone composite material, comprising the following steps: Polyketone, modified ultra-high molecular weight polyethylene, glass fiber, antioxidants, and lubricants are mixed according to the specified ratio and then extruded.

[0009] Thirdly, embodiments of the present invention provide a ball valve sealing block, which is made of the aforementioned fluorine-free reinforced wear-resistant polyketone composite material or the fluorine-free reinforced wear-resistant polyketone composite material prepared by the aforementioned preparation method.

[0010] The present invention has the following beneficial effects: The fluorine-free reinforced wear-resistant polyketone composite material, its preparation method, and its application provided in this invention combine the advantages of good wear resistance of polyketone resin and high strength of glass fiber by blending modified ultra-high molecular weight polyethylene, glass fiber, and polyketone resin. Simultaneously, the modified ultra-high molecular weight polyethylene has a low coefficient of friction, enhancing its compatibility with polyketone resin and resulting in more uniform dispersion, thus comprehensively improving the heat resistance and friction performance of polyketone resin. Furthermore, the fluorine-free design improves the safety of the polyketone composite material while expanding its application market. Attached Figure Description

[0011] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0012] Figure 1 Comparison figures before and after wear resistance testing of composite materials: (a) Example 2, (b) Comparative Example 6. Detailed Implementation

[0013] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0014] In a first aspect, embodiments of the present invention provide a fluorine-free reinforced wear-resistant polyketone composite material, comprising the following components by weight: 79-89 parts of polyketone resin, 5-15 parts of glass fiber, 3-10 parts of modified ultra-high molecular weight polyethylene, 0.5-1.0 parts of antioxidant, and 0.3-0.5 parts of lubricant. Among them, modified ultra-high molecular weight polyethylene is obtained by modifying unbranched linear polyethylene with a molecular weight of more than 2 million, and the amount of modifier used is 1%-10% of the amount of ultra-high molecular weight polyethylene.

[0015] It should be noted that the fluorine-free reinforced wear-resistant polyketone composite material provided in this embodiment of the invention combines the advantages of good wear resistance of polyketone resin and high strength of glass fiber through blending modification of ultra-high molecular weight polyethylene, glass fiber, and polyketone resin. The low coefficient of friction of the modified ultra-high molecular weight polyethylene enhances its compatibility with the polyketone resin, resulting in more uniform dispersion and a comprehensive improvement in the heat resistance and friction performance of the polyketone resin. This significantly improves the mechanical strength, high-temperature resistance, and wear durability of POK.

[0016] Ultra-high molecular weight polyethylene (UHMWPE) is an unbranched linear polyethylene with a molecular weight of over 2 million. Its molecular chains are highly regular, with high crystallinity and high strength, i.e., mechanical properties. After modification with modifiers, its compatibility with polyketone resin is enhanced, and its dispersion is more uniform, which is beneficial to improving the heat resistance and friction properties of polyketone resin.

[0017] In an optional embodiment, the modified ultra-high molecular weight polyethylene is 5 to 10 parts by weight; for example, the amount of modified ultra-high molecular weight polyethylene can be selected from any one of 5 parts, 7 parts, 8 parts, 8.5 parts and 10 parts, or other values ​​in the range of 5 to 10 parts.

[0018] And / or, the modifier is selected from at least one of styrene-acrylonitrile copolymer, maleic anhydride, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-vinyl acetate copolymer, polymethyl methacrylate and glycidyl methacrylate.

[0019] In an optional embodiment, modified ultra-high molecular weight polyethylene (UHMWPE) is prepared by the following method: UHMWPE and a modifier are melt-blended using a single-screw extruder, extruded, and then granulated to obtain modified UHMWPE. The amount of modifier used is 1%-5% of the amount of UHMWPE. For example, it can be selected from any one of 1%, 2%, 3%, 4%, and 5%, or other values ​​within the range of 1%-5%. If the amount of modifier is too small, the grafting rate of the modifier will be low, resulting in poor compatibility between the modified UHMWPE and polyketone. When the amount of modifier exceeds a certain amount, the grafting rate of the modifier reaches its peak and cannot be further increased. Therefore, while ensuring the grafting rate, it is necessary to select an appropriate amount of modifier to add.

[0020] In the preferred embodiment, the amount of modifier is 2%; in other embodiments of the present invention, the type of modifier may be selected from at least one of maleic anhydride, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-vinyl acetate copolymer, polymethyl methacrylate and glycidyl methacrylate, depending on actual needs.

[0021] In an optional embodiment, the number average molecular weight of the polyketone resin is 60,000-120,000; exemplaryly, the number average molecular weight of the polyketone resin may be selected from at least one of 60,000, 70,000, 80,000, 90,000, 100,000, 110,000, and 120,000, or other values ​​in the range of 60,000-120,000.

[0022] Furthermore, the number average molecular weight of the polyketone resin is 70,000-80,000.

[0023] It should be noted that a suitable number-average molecular weight ensures that polyketone resin has good molecular chain entanglement properties, good crystallinity and toughness, thus exhibiting better wear resistance. If the number-average molecular weight is too small, the following problems may occur: the molecular chains cannot effectively absorb impact energy, increasing brittleness; weak crystallization ability, easily softening and deforming at high temperatures; easy melt fracture during blow molding or extrusion, making it difficult to mold complex parts and failing to meet the requirements of engineering plastics. If the number-average molecular weight is too large, the following problems may occur: severe entanglement of ultra-long molecular chains, poor flowability, making injection molding or extrusion difficult; prolonged melting and plasticizing time, reducing production efficiency; poor long chain mobility, incomplete crystallization, which may lead to fluctuations in mechanical properties; difficulty in macromolecular chain orientation, easy generation of residual stress in products, causing warping or cracking; poor versatility and increased processing costs.

[0024] And / or, polyketides include polymers synthesized from carbon monoxide and olefins.

[0025] And / or, the glass fiber is modified with a silane coupling agent, and the length of the glass fiber is 3.0mm-4.0mm and the diameter is 8μm-15μm.

[0026] Glass fibers modified with silane coupling agents can significantly improve their interfacial bonding performance with polyketone resins. For example, glass fibers are prone to reacting with moisture in humid environments, but the hydrophobic layer formed by the silane coupling agent can prevent water molecules from penetrating. The silane layer can resist the erosion of the fiber surface by acid and alkali media, extending the service life of the composite material in chemical environments. It also reduces the surface energy of the fiber, improves its dispersion uniformity in the resin, and makes injection molding or extrusion processing smoother, thereby improving the overall performance of the composite material.

[0027] The length and diameter of the glass fiber can be reasonably selected according to actual needs; for example, the length of the glass fiber can be selected from any one of 3.0mm, 3.2mm, 3.5mm, 3.8mm and 4.0mm, or other values ​​in the range of 3.0mm-4.0mm; the diameter can be selected from any one of 8μm, 9μm, 10μm, 11μm, 12μm, 13μm and 15μm, or other values ​​in the range of 8μm-15μm.

[0028] In an optional embodiment, the amount of glass fiber used is 8 to 12 parts. Exemplarily, it can be selected from any one of 8, 8.5, 9, 9.5, 10, 11, and 12 parts, or other values ​​within the range of 8 to 12 parts. If the amount used is increased, the wear of the product will increase; if the amount used is decreased, the performance of the product will be affected, such as a significant change in the heat distortion temperature of the product.

[0029] In an optional embodiment, the antioxidant is selected from at least one of 3-(1,1-dimethylethyl)-β-[3-(1,1-dimethylethyl)-4-hydroxyphenyl]-4-hydroxy-β-methylbenzoic acid-1,2-ethylene ester, 3,9-bis(2,4-dicumylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, and N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-phenylenediamide.

[0030] In an optional embodiment, the antioxidant comprises 3-(1,1-dimethylethyl)-β-[3-(1,1-dimethylethyl)-4-hydroxyphenyl]-4-hydroxy-β-methylbenzoic acid-1,2-ethylene ester, 3,9-bis(2,4-dicumylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane and N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-phenylenediamide in a mass ratio of (0.6-0.8):2:(0.8-1.0).

[0031] It should be noted that the selection of antioxidants mentioned above helps prevent oxidative degradation of materials during use and improves the thermal stability of composite materials during high-temperature processing. Furthermore, the use of antioxidants also enhances the weather resistance and processing performance of polyketide-modified composite materials. Using a combination of multiple antioxidants can improve their effectiveness. For example, the mass ratio of antioxidant substances can be selected from any one of 0.6:2:0.8, 0.6:2:1.0, 0.7:2:0.9, 0.7:2:0.8, 0.8:2:0.9, and 0.8:2:1.0, or other values ​​within the range of (0.6-0.8):2:(0.8-1.0).

[0032] In an optional embodiment, the lubricant is selected from at least one of calcium stearate, polyethylene wax, and pentaerythritol tetrastearate.

[0033] In an optional embodiment, the lubricant comprises polyethylene wax and pentaerythritol tetrastearate in a mass ratio of 1:(1.5-2.0).

[0034] It should be noted that by rationally selecting the specific proportions of the above-mentioned compounded lubricants, the frictional force between molecular chains in the composite material can be effectively improved during processing, making the material flow more easily. Furthermore, the lubricant also helps prevent excessive adhesion between the polyketone modified composite material and the mold during processing and molding. For example, the mass ratio of the lubricant substances can be selected from any one of 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, and 1:2, or other values ​​within the range of 1:(1.5-2.0).

[0035] Secondly, embodiments of the present invention provide a method for preparing the aforementioned fluorine-free reinforced wear-resistant polyketone composite material, comprising the following steps: The polyketone resin, modified ultra-high molecular weight polyethylene, glass fiber, antioxidant, and lubricant are mixed according to the specified ratio and then extruded.

[0036] In an optional embodiment, extrusion, cooling, and granulation are performed using a twin-screw extruder; And / or, the temperatures of the 11 zones of the twin-screw extruder are set to 100℃-110℃, 225℃-235℃, 225℃-235℃, 225℃-235℃, 215℃-225℃, 215℃-225℃, 215℃-225℃, 205℃-215℃, 205℃-215℃, 205℃-215℃ and 225℃-235℃ respectively, and the main extruder speed is 200rpm-300rpm.

[0037] It should be noted that the temperature settings of the 11 zones of a twin-screw extruder are key process parameters in the plastics processing, directly affecting the melting, mixing, plasticizing, venting, and final product performance of the material. The settings of each temperature zone are not arbitrary, but are scientifically optimized based on material characteristics, screw combination, and processing objectives (such as compounding, reactive extrusion, devolatilization, etc.).

[0038] Thirdly, embodiments of the present invention provide a ball valve sealing block, which is made of the aforementioned fluorine-free reinforced wear-resistant polyketone composite material or the fluorine-free reinforced wear-resistant polyketone composite material prepared by the aforementioned preparation method.

[0039] A ball valve consists of a valve core, a sealing block, and a housing. The valve core controls the closure and flow rate of the coolant flow channel by rotating. The housing remains stationary while the valve core rotates, and the sealing block provides a seal between the valve core and the housing. Applications require the sealing block material to have sufficient lubricity, wear resistance, and resistance to high and low temperatures.

[0040] The fluorine-free reinforced wear-resistant polyketone composite material provided in this invention significantly improves the mechanical strength, high temperature resistance, and wear resistance of POK by blending modified ultra-high molecular weight polyethylene, glass fiber, and polyketone resin.

[0041] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0042] It should be noted that, specifically in the embodiments of the present invention, the types of materials used are as follows: the polyketone resin is a polymer synthesized from carbon monoxide and olefins (ethylene, propylene), provided by Hyosung Group of South Korea, and its type is M330A; the glass fiber is ECS301HP-3-K; and the ultra-high molecular weight polyethylene is Mitsui Chemicals Lubmer L5000. In other embodiments of the present invention, the types of materials used can be reasonably selected according to actual needs, either purchased or self-made.

[0043] Example 1 This embodiment provides a fluorine-free reinforced wear-resistant polyketone composite material, the preparation of which includes the following steps: By weight, 89 parts of polyketone resin, 5 parts of modified ultra-high molecular weight polyethylene, 5 parts of glass fiber, 0.7 parts of antioxidant, and 0.3 parts of lubricant are mixed and then extruded, cooled, and granulated using a twin-screw extruder. The temperatures of the 11 zones of the twin-screw extruder are set to 110℃, 225℃, 225℃, 235℃, 220℃, 220℃, 200℃, 210℃, 210℃, 210℃, and 230℃, respectively, and the main extruder speed is 200rpm-300rpm.

[0044] The antioxidants include 3-(1,1-dimethylethyl)-β-[3-(1,1-dimethylethyl)-4-hydroxyphenyl]-4-hydroxy-β-methylbenzoic acid-1,2-ethylene ester, 3,9-bis(2,4-dicumylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosspiro[5,5]undecane and N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-phenylenediamide in a mass ratio of 0.8:2:1.0; The lubricant consists of polyethylene wax and pentaerythritol tetrastearate in a mass ratio of 1:2.0; Ultra-high molecular weight polyethylene (UHMWPE) is unbranched linear polyethylene with a molecular weight of over 2 million. The modifier is styrene-acrylonitrile copolymer, and the amount of modifier used is 2% of the amount of UHMWPE. The glass fiber is 4 mm long and 13 μm in diameter.

[0045] The specific amounts of each substance in the formula are shown in Table 1.

[0046] Example 2 This embodiment provides a fluorine-free reinforced wear-resistant polyketone composite material, the preparation of which includes the following steps: By weight, the composition includes: 84 parts polyketone resin, 10 parts glass fiber, and the remaining substances and process parameters are the same as in Example 1.

[0047] Example 3 This embodiment provides a fluorine-free reinforced wear-resistant polyketone composite material, the preparation of which includes the following steps: By weight, the composition includes: 79 parts polyketone resin, 15 parts glass fiber, and the remaining substances and process parameters are the same as in Example 1.

[0048] Example 4 This embodiment provides a fluorine-free reinforced wear-resistant polyketone composite material, the preparation of which includes the following steps: By weight, the composition includes: 86 parts polyketone resin, 3 parts modified ultra-high molecular weight polyethylene, 10 parts glass fiber, and the remaining substances and process parameters are the same as in Example 1.

[0049] Example 5 This embodiment provides a fluorine-free reinforced wear-resistant polyketone composite material, the preparation of which includes the following steps: By weight, the composition includes: 81 parts polyketone resin, 8 parts modified ultra-high molecular weight polyethylene, 10 parts glass fiber, and the remaining substances and process parameters are the same as in Example 1.

[0050] Comparative Example 1 This comparative example provides a fluorine-free reinforced wear-resistant polyketone composite material, the preparation of which includes the following steps: By weight, 94 parts of polyketone resin, 5 parts of modified ultra-high molecular weight polyethylene, 0.7 parts of antioxidant and 0.3 parts of lubricant were mixed and then extruded, cooled and granulated by a twin-screw extruder; glass fiber was missing, and the other process parameters were the same as in Example 1.

[0051] Comparative Example 2 This comparative example provides a fluorine-free reinforced wear-resistant polyketone composite material, the preparation of which includes the following steps: By weight, 89 parts of polyketone resin, 10 parts of glass fiber, 0.7 parts of antioxidant and 0.3 parts of lubricant were mixed and then extruded, cooled and granulated by a twin-screw extruder; modified ultra-high molecular weight polyethylene was omitted, and the other process parameters were the same as in Example 1.

[0052] Comparative Example 3 This comparative example provides a fluorine-free reinforced wear-resistant polyketone composite material, the preparation of which includes the following steps: By weight, 84 parts of polyketone resin, 10 parts of glass fiber, 5 parts of ultra-high molecular weight polyethylene (unmodified), 0.7 parts of antioxidant and 0.3 parts of lubricant were mixed and then extruded, cooled and granulated by a twin-screw extruder; the remaining process parameters were the same as in Example 1.

[0053] Comparative Example 4 This comparative example provides a composite material prepared from 100 parts of polyketone resin, with process parameters as described in Example 1.

[0054] Comparative Example 5 This comparative example provides a composite material prepared from 100 parts of polytetrafluoroethylene, with process parameters as described in Example 1.

[0055] Comparative Example 6 This comparative example provides a fluorine-free reinforced wear-resistant polyketone composite material, the only difference in its preparation steps from Example 2 is: The modifier for modified ultra-high molecular weight polyethylene is maleic anhydride.

[0056] Comparative Example 7 This comparative example provides a fluorine-free reinforced wear-resistant polyketone composite material, the only difference in its preparation steps from Example 2 is: The modifier for modified ultra-high molecular weight polyethylene is ethylene-acrylic acid copolymer.

[0057] Comparative Example 8 This comparative example provides a fluorine-free reinforced wear-resistant polyketone composite material, the only difference in its preparation steps from Example 2 is: The modifier for modified ultra-high molecular weight polyethylene is ethylene-methyl acrylate copolymer.

[0058] Comparative Example 9 This comparative example provides a fluorine-free reinforced wear-resistant polyketone composite material, the only difference in its preparation steps from Example 2 is: The modifier for modified ultra-high molecular weight polyethylene is glycidyl methacrylate.

[0059] Table 1. Amount of each component in fluorine-free reinforced wear-resistant polyketone composite material (in parts by weight)

[0060] Note: "-" in the table indicates that the corresponding substance was not added.

[0061] Experimental Example 1 This experiment tested the performance of the composite materials prepared in Examples 1-5 and Comparative Examples 1-9. The relevant test results are shown in Table 2. The tensile strength test method followed ISO 527, and the flexural strength test method followed ISO 178. The abrasion resistance test method followed JIS K 7218 Method B, with a test speed of 0.5 m / s, a load of 100 N, and a sliding distance of 3 km. Comparison figures of the composite materials before and after the abrasion resistance test are shown below. Figure 1 (a) Example 2, (b) Comparative Example 6.

[0062] The formula for calculating the volumetric wear rate is: (Equation-1).

[0063] In Equation-1: K - volumetric wear rate, 10 -3 ·mm 3 / (N·km); Δm - difference in sample mass before and after wear, mg; ρ - sample density, g / cm³ 3 N - load, N; L - sliding friction distance, km; Specifically, in this embodiment, the load N is a constant value of 100N, and the sliding friction distance L is a constant value of 3km.

[0064] Table 2 Performance Test Results

[0065] As can be seen from the data results in Table 2, the wear will increase with the increase of glass fiber filling. Specifically, glass fiber can significantly increase the heat resistance of the material. With the increase of glass fiber content, the heat resistance of the product is enhanced. The heat distortion temperature of Example 1 increased by 19.3% compared with Comparative Example 1 (without glass fiber), and the heat distortion temperature of Example 3 increased by 130.1% compared with Comparative Example 1 (without glass fiber).

[0066] Excessive modification of ultra-high molecular weight polyethylene (UHMWPE) leads to uneven dispersion and agglomeration, resulting in increased wear and a decrease in its heat distortion temperature. Specifically, as seen in Examples 2 and Comparative Examples 6-9, styrene-acrylonitrile modified UHMWPE exhibits good compatibility with polyketone resin, resulting in products with relatively low wear. The volumetric wear rate of Example 2 is 40% lower than that of Comparative Example 6 and 51.2% lower than that of Comparative Example 7. Furthermore, from... Figure 1It can also be seen that the wear of the composite material prepared in Example 2 is significantly lower than that of the composite material prepared in Comparative Example 6. Changing the type of modifier will change the color of the final composite material; the composite material of Example 2 is more yellow, while the composite material of Comparative Example 6 is more whitish.

[0067] In summary, blending polyketone (POK) with modified ultra-high molecular weight polyethylene (UHMWPE) and glass fiber combines the excellent wear resistance of POK with the low coefficient of friction of UHMWPE, resulting in a fluorine-free reinforced wear-resistant POK composite material for ball valve sealing blocks. The fluorine-free design improves the safety of the POK composite material while expanding its application market. Grafting UHMWPE with styrene-acrylonitrile copolymer significantly improves its compatibility with POK and results in more uniform dispersion. Furthermore, glass fiber significantly enhances the material's heat resistance.

[0068] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A fluorine-free reinforced wear-resistant polyketone composite material, characterized in that, By weight, it comprises the following components: 79-89 parts polyketone resin, 5-15 parts glass fiber, 3-10 parts modified ultra-high molecular weight polyethylene, 0.5-1.0 parts antioxidant, and 0.3-0.5 parts lubricant. The modified ultra-high molecular weight polyethylene is obtained by modifying unbranched linear polyethylene with a molecular weight of over 2 million, and the amount of modifier used is 1%-5% of the amount of ultra-high molecular weight polyethylene. The modifier is a styrene-acrylonitrile copolymer; the number average molecular weight of the polyketone resin is 60,000-120,000.

2. The fluorine-free reinforced wear-resistant polyketone composite material according to claim 1, characterized in that, The modified ultra-high molecular weight polyethylene is 5-10 parts by weight.

3. The fluorine-free reinforced wear-resistant polyketone composite material according to claim 1, characterized in that, The polyketone resin comprises a polymer synthesized from carbon monoxide and olefins; And / or, the glass fiber is modified with a silane coupling agent, and the glass fiber has a length of 3.0 mm-4.0 mm and a diameter of 8 μm-15 μm.

4. The fluorine-free reinforced wear-resistant polyketone composite material according to claim 1, characterized in that, The antioxidant is selected from at least one of 3-(1,1-dimethylethyl)-β-[3-(1,1-dimethylethyl)-4-hydroxyphenyl]-4-hydroxy-β-methylbenzoic acid-1,2-ethylene ester, 3,9-bis(2,4-dicumylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosspiro[5,5]undecane and N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-phenylenediamide.

5. The fluorine-free reinforced wear-resistant polyketone composite material according to claim 4, characterized in that, The antioxidants comprise 3-(1,1-dimethylethyl)-β-[3-(1,1-dimethylethyl)-4-hydroxyphenyl]-4-hydroxy-β-methylbenzoic acid-1,2-ethylene ester, 3,9-bis(2,4-dicumylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane and N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-phenylenediamide in a mass ratio of (0.6-0.8):2:(0.8-1.0).

6. The fluorine-free reinforced wear-resistant polyketone composite material according to claim 1, characterized in that, The lubricant is selected from at least one of calcium stearate, polyethylene wax, and pentaerythritol tetrastearate.

7. The fluorine-free reinforced wear-resistant polyketone composite material according to claim 6, characterized in that, The lubricant comprises polyethylene wax and pentaerythritol tetrastearate in a mass ratio of 1:(1.5-2.0).

8. A method for preparing a fluorine-free reinforced wear-resistant polyketone composite material as described in any one of claims 1-7, characterized in that, Includes the following steps: The polyketone resin, modified ultra-high molecular weight polyethylene, glass fiber, antioxidant, and lubricant are mixed according to the specified ratio and then extruded.

9. The method for preparing the fluorine-free reinforced wear-resistant polyketone composite material according to claim 8, characterized in that, Extrusion, cooling, and granulation are performed using a twin-screw extruder; And / or, the temperatures of the 11 zones of the twin-screw extruder are set to 100℃-110℃, 225℃-235℃, 225℃-235℃, 225℃-235℃, 215℃-225℃, 215℃-225℃, 215℃-225℃, 205℃-215℃, 205℃-215℃, 205℃-215℃ and 225℃-235℃ respectively, and the main extruder speed is 200rpm-300rpm.

10. A ball valve sealing block, characterized in that, The composite material is prepared by using the fluorine-free reinforced wear-resistant polyketone composite material as described in any one of claims 1-7 or by the preparation method described in any one of claims 8-9.

Images