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

Abstract

The invention discloses a fluoride-free reinforced wear-resistant polyketone composite material as well as a preparation method and application thereof, and relates to the technical field of polymer composite materials. The fluoride-free reinforced wear-resistant polyketone composite material comprises polyketone resin, glass fibers, modified ultra-high molecular weight polyethylene, an antioxidant and a lubricant, wherein the modified ultra-high molecular weight polyethylene is obtained by modifying branched-chain-free linear polyethylene with the molecular weight of 2 million or more, and the dosage of the modifier is 1%-5% of that of the ultra-high molecular weight polyethylene. The modified ultra-high molecular weight polyethylene, the glass fiber and the polyketone resin are subjected to blending modification, and the characteristics of good wear resistance of the polyketone resin and high strength of the glass fiber are combined; meanwhile, the friction coefficient is low after the ultra-high molecular weight polyethylene is modified, the compatibility with the polyketone resin is enhanced, the dispersion is more uniform, and the heat resistance and friction performance of the polyketone resin are comprehensively improved. In addition, due to the use of fluorine-free, the safety of the polyketone composite material is improved, and meanwhile, the application market of the polyketone composite material is expanded.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer composite materials, in particular to a fluorine-free reinforced wear-resistant polyketone composite material and a preparation method and application thereof. BACKGROUND

[0002] Polytetrafluoroethylene (PTFE) is widely used in industrial fields such as ball valve sealing blocks due to its excellent self-lubricating property, wear resistance and high and low temperature resistance. However, PTFE has high viscosity in a molten state at high temperatures and no flowability, which results in that it cannot be formed by injection molding but only by pressing and sintering, which makes the PTFE manufacturing process complex and the cost extremely high. In recent years, due to increasingly stringent environmental protection laws and regulations, PFAS regulations have emerged as the times require, and PTFE, as one of the typical fluorine-containing materials, is gradually subject to strict restrictions by the market (especially the European market), and the application of PTFE materials faces policy and environmental risks, which further promotes the exploration of alternative materials.

[0003] Polyketone (POK) is a new green polymer material synthesized from carbon monoxide and olefins (such as ethylene and propylene), which has low water absorption, good wear resistance, hydrolysis resistance, excellent chemical resistance, excellent flowability and molding processability, and has been concerned and widely used in many industrial fields, such as automobile manufacturing, electronics and electrical appliances, medical devices and other industries. However, POK still has some shortcomings in mechanical strength, high temperature resistance and wear resistance in some specific application scenarios, which limits its application in some specific fields, such as sealing materials.

[0004] Therefore, it is urgent to explore a fluorine-free reinforced wear-resistant polyketone composite material which has the characteristics of being fluorine-free, high-performance and meeting environmental protection requirements.

[0005] In view of this, the present application is proposed. SUMMARY

[0006] The present application aims to provide a fluorine-free reinforced wear-resistant polyketone composite material and a preparation method and application thereof to solve the above technical problems.

[0007] The present application is implemented as follows: In a first aspect, an embodiment of the present application provides a fluorine-free reinforced wear-resistant polyketone composite material, which comprises the following components in parts 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. The modified ultra-high molecular weight polyethylene is linear polyethylene modified by a modifier with a molecular weight of more than 2 million, and the amount of the modifier is 1-5% of the amount of the ultra-high molecular weight polyethylene.

[0008] In a second aspect, embodiments of the present application provide a method for preparing the fluorine-free wear-resistant polyketone composite material as described above, comprising the following steps: The polyketone, modified ultra-high molecular weight polyethylene, glass fiber, antioxidant and lubricant are mixed according to the ratio, and then extruded.

[0009] In a third aspect, embodiments of the present application provide a ball valve sealing block made of the fluorine-free wear-resistant polyketone composite material as described above or prepared by the method as described above.

[0010] The present application has the following beneficial effects: The fluorine-free wear-resistant polyketone composite material, the preparation method and the application thereof provided by the embodiments of the present application have the following advantages: the modified ultra-high molecular weight polyethylene, the glass fiber and the polyketone resin are blended and modified, which combines the characteristics of good wear resistance of the polyketone resin and high strength of the glass fiber; at the same time, the friction coefficient of the modified ultra-high molecular weight polyethylene is low, which enhances the compatibility with the polyketone resin, the dispersion is more uniform, and the heat resistance and the friction performance of the polyketone resin are comprehensively improved. In addition, the use of fluorine improves the safety of the polyketone composite material and expands the application market thereof. BRIEF DESCRIPTION OF DRAWINGS

[0011] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following will briefly introduce the drawings needed to be used in the embodiments. It should be understood that the following drawings only show some embodiments of the present application, and therefore should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can also be obtained without creative labor on the basis of these drawings.

[0012] Figure 1 The comparative diagrams of the composite material before and after wear resistance test: (a) Example 2, (b) Comparative Example 6. DETAILED DESCRIPTION

[0013] In order to make the purpose, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be described clearly and completely in the following. The specific conditions not mentioned in the embodiments are carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments not mentioned by the manufacturer are all conventional products that can be obtained by market purchase.

[0014] In a first aspect, embodiments of the present application provide a fluorine-free wear-resistant polyketone composite material, which comprises the following components in terms of weight fraction: 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, the 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 the modifier used is 1%-10% of the amount of the ultra-high molecular weight polyethylene used.

[0015] It should be noted that the fluorine-free reinforced wear-resistant polyketone composite material provided by the embodiments of the present invention combines the good wear resistance of polyketone resin with the high strength of glass fiber by blending modified ultra-high molecular weight polyethylene and glass fiber. The modified ultra-high molecular weight polyethylene has a low friction coefficient, enhanced compatibility with the polyketone resin, and more uniform dispersion, comprehensively improving the heat resistance and friction performance of the polyketone resin. This significantly improves the mechanical strength, high temperature resistance, and wear resistance of POK.

[0016] Ultra-high molecular weight polyethylene is an unbranched linear polyethylene with a molecular weight of more than 2 million. Its molecular chain is highly regular, with high crystallinity and high strength and mechanical properties. After modification with a modifier, its compatibility with polyketone resin is enhanced, and the dispersion is more uniform, which is beneficial to improving the heat resistance and friction performance of polyketone resin.

[0017] In an optional embodiment, the amount of modified ultra-high molecular weight polyethylene is 5-10 parts by weight; illustratively, 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 ​​within the range of 5-10 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, the modified ultra-high molecular weight polyethylene is prepared by the following method: ultra-high molecular weight polyethylene and a modifier are melt-blended with a single screw, and granulated after extrusion to obtain the modified ultra-high molecular weight polyethylene. The amount of the modifier is 1%-5% of the amount of ultra-high molecular weight polyethylene. 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 the modifier is small, the grafting rate of the modifier is low, and the compatibility of the obtained modified ultra-high molecular weight polyethylene with polyketone will be poor; when the amount of the modifier exceeds a certain amount, the grafting rate of the modifier reaches a peak and cannot be further improved. Therefore, while ensuring the grafting rate, it is necessary to select a suitable amount of modifier addition.

[0020] In the optimal embodiment, the amount of the modifier is 2%; in other embodiments of the present application, the type of the modifier can 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 according to actual needs.

[0021] In the optional embodiment, the number average molecular weight of the polyketone resin is 60000-120000; illustratively, the number average molecular weight of the polyketone resin can be selected from at least one of 60000, 70000, 80000, 90000, 100000, 110000 and 120000, or other values within the range of 60000-120000.

[0022] Further, the number average molecular weight of the polyketone resin is 70000-80000.

[0023] It should be noted that a suitable number average molecular weight can ensure that the polyketone resin has better molecular chain entanglement performance, better crystallinity and toughness, so as to exhibit better wear resistance. If the number average molecular weight is too small, the following problems may occur: the molecular chain cannot effectively absorb impact energy, the brittleness increases; the crystallization ability is weak, and the deformation is easy to soften at high temperature; the melt rupture is easy to occur during blow molding or extrusion, it is difficult to form complex parts, and it cannot meet the requirements of engineering plastics. If the number average molecular weight is too large, the following problems may occur: the long molecular chain is severely entangled, the flowability is poor, and it is difficult to be injection molded or extruded; the melting and plasticizing time is prolonged, and the production efficiency is reduced; the long chain movement ability is poor, the crystallization is imperfect, which may cause mechanical property fluctuation, the macromolecular chain orientation is difficult, and the product is easy to produce residual stress, which may cause warping or cracking; the general type is poor and the processing cost is increased.

[0024] And / or, the polyketone includes a polymer synthesized from carbon monoxide and olefin.

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

[0026] The glass fiber modified by the silane coupling agent can significantly improve the interfacial bonding performance with the polyketone resin. For example, the glass fiber is easy to react with water in a humid environment, the hydrophobic layer formed by the silane coupling agent can block the penetration of water molecules; the silane layer can resist the erosion of acid and alkali medium on the surface of the fiber, prolonging the service life of the composite material in the chemical environment; reducing the surface energy of the fiber, improving the dispersion uniformity thereof in the resin, making the injection molding or extrusion processing more smooth, thereby improving the comprehensive 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 3.0 mm, 3.2 mm, 3.5 mm, 3.8 mm and 4.0 mm, or other values within the range of 3.0 mm-4.0 mm; the diameter can be selected from any one of 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm and 15 μm, or other values within the range of 8 μm-15 μm.

[0028] In an optional embodiment, the amount of glass fiber is 8-12 parts, for example, can be selected from any one of 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts, 11 parts and 12 parts, or other values within the range of 8-12 parts. If the amount is increased, the product wear will increase; if the amount is reduced, the performance of the product will be affected, such as the heat distortion temperature of the product changes significantly.

[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-piperidyl)-1,3-benzene dicarboxamide.

[0030] In an optional embodiment, the antioxidant includes 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-piperidyl)-1,3-benzene dicarboxamide in a mass ratio of (0.6-0.8):2:(0.8-1.0).

[0031] It should be noted that the above selection of antioxidants is beneficial to prevent oxidative degradation of the material during use, and is beneficial to the thermal stability of the composite material during high-temperature processing, in addition, the use of antioxidants is also beneficial to enhance the weather resistance of the polyketone modified composite material and improve its processing performance, etc. The use of multiple antioxidants in combination can enhance the effect of the antioxidant. For example, the mass ratio of the antioxidant substance 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 alternative embodiment, the lubricant is selected from at least one of calcium stearate, polyethylene wax, and pentaerythritol tetra stearate.

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

[0034] It should be noted that by reasonably selecting the above compounded specific ratio of lubricant, the friction between the molecular chains of the composite material during processing can be effectively improved, so that the material flows more easily during processing. In addition, the lubricant is also beneficial to prevent the polyketone modified composite material from excessive adhesion with the mold during processing. Exemplarily, the mass ratio of the lubricant substance 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] In a second aspect, embodiments of the present application provide a preparation method of the fluorine-free reinforced wear-resistant polyketone composite material as described above, comprising the following steps: The polyketone resin, modified ultra-high molecular weight polyethylene, glass fiber, antioxidant, and lubricant are mixed according to the ratio, and then extruded.

[0036] In an alternative embodiment, the extrusion, cooling, and granulation are performed by a twin-screw extruder. And / or, the temperature of the 11th zone of the twin-screw extruder is set to 100-110°C, 225-235°C, 225-235°C, 225-235°C, 215-225°C, 215-225°C, 215-225°C, 205-215°C, 205-215°C, 205-215°C, and 225-235°C, respectively, and the main machine speed is 200-300 rpm.

[0037] It should be noted that the temperature setting of the 11th zone of the twin-screw extruder is a key process parameter in plastic processing, which directly affects the melting, mixing, plasticizing, degassing, and performance of the final product of the material. The setting of each temperature zone is not arbitrary, but is scientifically optimized according to the material properties, screw combination, and processing target (such as mixing, reaction extrusion, and devolatilization).

[0038] In a third aspect, embodiments of the present application provide a ball valve sealing block made of the fluorine-free reinforced wear-resistant polyketone composite material as described above or prepared by the preparation method as described above.

[0039] The ball valve structure is composed of a valve core, a sealing block and a shell, wherein the ball valve core controls the cooling liquid flow passage to be closed and the flow by rotating. The shell is fixed, the valve core rotates, and the sealing block realizes the sealing between the valve core and the shell. The use requires that the sealing block material has sufficient lubricity, wear resistance and high and low temperature resistance.

[0040] The fluorine-free reinforced wear-resistant polyketone composite provided by the embodiment of the present application is obtained by blending and modifying the modified ultra-high molecular weight polyethylene, glass fiber and polyketone resin, so that the POK is significantly improved in mechanical strength, high temperature resistance and wear resistance.

[0041] The features and properties of the present application are further described in detail below in combination with the embodiments.

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

[0043] Embodiment 1 The present embodiment provides a fluorine-free reinforced wear-resistant polyketone composite, and the preparation thereof comprises the following steps: According to the weight fraction, 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 by a double screw extruder; wherein the temperature of the 11 zones of the double screw extruder is set to 110℃, 225℃, 225℃, 235℃, 220℃, 220℃, 200℃, 210℃, 210℃, 210℃ and 230℃ respectively, and the main machine speed is 200rpm-300rpm.

[0044] The antioxidant includes 3-(1,1-dimethyl ethyl)-β-[3-(1,1-dimethyl ethyl)-4-hydroxyphenyl]-4-hydroxy-β-methyl benzoic acid-1,2-ethylene ester, 3,9-di(2,4-dicumyl phenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane and N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,3-benzene dicarboxamide with a mass ratio of 0.8:2:1.0; The lubricant includes polyethylene wax and pentaerythritol tetrastearate with a mass ratio of 1:2.0; The super high molecular weight polyethylene is linear polyethylene with a molecular weight of 2 million or more without branch, and the modifier is styrene-acrylonitrile copolymer, and the amount of the modifier is 2% of the amount of the super high molecular weight polyethylene; The length of the glass fiber is 4 mm, and the diameter is 13 μm.

[0045] The specific amount of each substance in the formula is shown in Table 1.

[0046] Example 2 The present example provides a fluorine-free reinforced wear-resistant polyketone composite, and the preparation comprises the following steps: According to the weight fraction, the components include 84 parts of polyketone resin, 10 parts of glass fiber, and the remaining substances and process parameters are the same as those in Example 1.

[0047] Example 3 The present example provides a fluorine-free reinforced wear-resistant polyketone composite, and the preparation comprises the following steps: According to the weight fraction, the components include 79 parts of polyketone resin, 15 parts of glass fiber, and the remaining substances and process parameters are the same as those in Example 1.

[0048] Example 4 The present example provides a fluorine-free reinforced wear-resistant polyketone composite, and the preparation comprises the following steps: According to the weight fraction, the components include 86 parts of polyketone resin, 3 parts of modified super high molecular weight polyethylene, 10 parts of glass fiber, and the remaining substances and process parameters are the same as those in Example 1.

[0049] Example 5 The present example provides a fluorine-free reinforced wear-resistant polyketone composite, and the preparation comprises the following steps: According to the weight fraction, the components include 81 parts of polyketone resin, 8 parts of modified super high molecular weight polyethylene, 10 parts of glass fiber, and the remaining substances and process parameters are the same as those in Example 1.

[0050] Comparative Example 1 The present example provides a fluorine-free reinforced wear-resistant polyketone composite, and the preparation comprises the following steps: According to the weight fraction, 94 parts of polyketone resin, 5 parts of modified super high molecular weight polyethylene, 0.7 parts of antioxidant and 0.3 parts of lubricant are mixed, and then extruded by a double screw extruder, cooled and granulated; the glass fiber is omitted, and the remaining process parameters are the same as those in Example 1.

[0051] Comparative Example 2 The present example provides a fluorine-free reinforced wear-resistant polyketone composite, and the preparation comprises the following steps: 89 parts of polyketone resin, 10 parts of glass fiber, 0.7 part of antioxidant and 0.3 part of lubricant were mixed by weight fraction, and then extruded, cooled and granulated by a double screw extruder; the rest of the process parameters were the same as those in Example 1.

[0052] Comparative Example 3 The present comparative example provides a fluorine-free reinforced wear-resistant polyketone composite, and the preparation thereof comprises the following steps: 84 parts of polyketone resin, 10 parts of glass fiber, 5 parts of ultra-high molecular weight polyethylene (unmodified), 0.7 part of antioxidant and 0.3 part of lubricant were mixed by weight fraction, and then extruded, cooled and granulated by a double screw extruder; the rest of the process parameters were the same as those in Example 1.

[0053] Comparative Example 4 The present comparative example provides a composite, which is prepared by using 100 parts of polyketone resin, and the process parameters are the same as those in Example 1.

[0054] Comparative Example 5 The present comparative example provides a composite, which is prepared by using 100 parts of polytetrafluoroethylene, and the process parameters are the same as those in Example 1.

[0055] Comparative Example 6 The present comparative example provides a fluorine-free reinforced wear-resistant polyketone composite, and the difference between the preparation steps thereof and those in Example 1 is only that: The modifier of the modified ultra-high molecular weight polyethylene is maleic anhydride.

[0056] Comparative Example 7 The present comparative example provides a fluorine-free reinforced wear-resistant polyketone composite, and the difference between the preparation steps thereof and those in Example 1 is only that: The modifier of the modified ultra-high molecular weight polyethylene is ethylene-acrylic acid copolymer.

[0057] Comparative Example 8 The present comparative example provides a fluorine-free reinforced wear-resistant polyketone composite, and the difference between the preparation steps thereof and those in Example 1 is only that: The modifier of the modified ultra-high molecular weight polyethylene is ethylene-methyl acrylate copolymer.

[0058] Comparative Example 9 The present comparative example provides a fluorine-free reinforced wear-resistant polyketone composite, and the difference between the preparation steps thereof and those in Example 1 is only that: The modifier of the modified ultra-high molecular weight polyethylene is glycidyl methacrylate.

[0059] Table 1 Dosage of each component in fluorine-free reinforced wear-resistant polyketone composite (by weight fraction)

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

[0061] Experimental Example 1 The performance of the composite materials prepared in Examples 1-5 and Comparative Examples 1-9 was tested in this experimental example, and the relevant test results are shown in Table 2. Among them, the tensile strength test method refers to ISO527, the bending strength test method refers to ISO178; the wear resistance test method refers to standard JIS K7218 method B, the test speed is 0.5 m / s, the load is 100 N, and the sliding distance is 3 km. The comparison chart of the composite material before and after wear resistance test is shown in Figure 1 , (a) Example 2, (b) Comparative Example 6.

[0062] The calculation formula of the volume wear rate is: (Formula-1).

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

[0064] Table 2 Performance test results

[0065] As can be seen from the data results in Table 2, the increase in glass fiber filling will also increase the wear; specifically, glass fiber can significantly increase the heat resistance of the material, and as the amount of glass fiber increases, the heat resistance of the product is enhanced, among which the heat distortion temperature of Example 1 is increased by 19.3% compared with Comparative Example 1 (lacking glass fiber), and the heat distortion temperature of Example 3 is increased by 130.1% compared with Comparative Example 1 (lacking glass fiber).

[0066] Excessive modified ultra-high molecular weight polyethylene, uneven dispersion, and easy agglomeration will also cause the wear to increase, and the heat distortion temperature will also decrease; specifically, as can be seen from Examples 2 and Comparative Examples 6-9, the ultra-high molecular weight polyethylene modified by styrene-acrylonitrile has good compatibility with polyketone resin, and the corresponding product has relatively low wear, among which the volume wear rate of Example 2 is 40% lower than that of Comparative Example 6, and 51.2% lower than that of Comparative Example 7; in addition, as can be seen from Figure 1It can also be seen that the abrasion of the composite material prepared in Example 2 is significantly lower than that of the composite material prepared in Comparative Example 6. The change of the modifier type will change the color of the final composite material; among them, the composite material of Example 2 is yellowish, and the composite material of Comparative Example 6 is white.

[0067] In summary, the polyketone (POK) is blended and modified with modified ultra-high molecular weight polyethylene and glass fiber, which combines the good wear resistance of polyketone and the low friction coefficient of ultra-high molecular weight polyethylene, to obtain a fluorine-free reinforced wear-resistant polyketone composite material for sealing block of ball valve. The use of fluorine-free improves the safety of the polyketone composite material and expands its application market. The graft modification of ultra-high molecular weight polyethylene and styrene-acrylonitrile copolymer greatly improves the compatibility of polyketone and makes the dispersion more uniform. In addition, the glass fiber can significantly increase the heat resistance of the material.

[0068] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A fluorine-free reinforced wear-resistant polyketone composite material, characterized in that: The composition comprises the following components in parts 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; The 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 the modifier used is 1%-5% of the amount of the ultra-high molecular weight polyethylene used.

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

3. The fluorine-free reinforced wear-resistant polyketone composite material according to claim 1, characterized in that: The number average molecular weight of the polyketone resin is 60,000-120,000; and / or, the polyketone resin comprises a polymer synthesized from carbon monoxide and an olefin; And / or, the glass fiber is modified with a silane coupling agent, and the length of the glass fiber is 3.0 mm to 4.0 mm, and the diameter is 8 μm to 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-diphosphaspiro[5.5]undecane and N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-benzenedicarboxamide.

5. The fluorine-free reinforced wear-resistant polyketone composite material according to claim 4, characterized in that: The antioxidant includes 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-benzenedicarboxamide 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 the fluorine-free reinforced wear-resistant polyketone composite material according to any one of claims 1 to 7, characterized in that: The steps include: The polyketone resin, modified ultra-high molecular weight polyethylene, glass fiber, antioxidant and lubricant are mixed according to a proportion and then extruded.

9. The method for preparing the fluorine-free reinforced wear-resistant polyketone composite material for ball valve sealing blocks according to claim 8, characterized in that: Extrusion, cooling and granulation are carried out through a twin-screw extruder; And / or, the temperatures of 11 zones of the twin-screw extruder are set to 100°C-110°C, 225°C-235°C, 225°C-235°C, 215°C-225°C, 215°C-225°C, 215°C-225°C, 205°C-215°C, 205°C-215°C, 205°C-215°C and 225°C-235°C, respectively, and the main engine 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 claimed in any one of claims 1 to 7 or the fluorine-free reinforced wear-resistant polyketone composite material prepared by the preparation method as claimed in any one of claims 8 to 9.

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