Sulfonated polyetheretherketone powder, preparation method and application thereof

Abstract

This invention relates to a sulfonated polyether ether ketone (PEEEK) powder, its preparation method, and its applications. The preparation method involves dissolving a solid PEEEK in an alkaline aqueous solution to prepare a solution, which is then mixed with an organic solvent. During this mixing process, the PEEEK dissolved in the solution precipitates in the organic solvent, resulting in a solid-liquid mixture. The solid-liquid mixture is then subjected to solid-liquid separation, and the resulting solid phase is pulverized. In this preparation method, when the PEEEK precipitates in the organic solvent, the precipitated PEEEK is gel-like with a loose structure, making it easy to pulverize and obtain PEEEK powder with a relatively uniform particle size. This preparation method effectively reduces the agglomeration of the PEEEK product, yielding PEEEK powder with a relatively uniform particle size, thus promoting the widespread use and application of PEEEK.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a sulfonated polyether ether ketone powder, its preparation method, and its application. Background Technology

[0002] Polyetheretherketone (PEEK) exhibits stable properties and demonstrates good performance in terms of mechanical properties, corrosion resistance, and wear resistance. However, as the application range of PEEK expands, certain limitations have also emerged. For example, PEEK has poor affinity for aqueous solutions, which results in a weak ability to form a fluid lubricating film in friction pairs made from it under low-speed conditions, leading to poor lubrication. Therefore, modifying PEEK to enrich its properties is of great significance for its promotion and application.

[0003] Sulfonation with concentrated sulfuric acid is a commonly used method for modifying polyetheretherketone (PEEK). Sulfonation introduces sulfonic acid groups onto PEEK, thereby improving its properties. However, while this method effectively improves PEEK properties, the sulfonated PEEK product is difficult to disperse upon precipitation, easily forming particles of uneven size. These unevenly sized particles negatively impact the properties of sulfonated PEEK and the molding of PEEK products, thus hindering its widespread adoption and use. Summary of the Invention

[0004] Therefore, it is necessary to provide a sulfonated polyether ether ketone powder, its preparation method, and its application. This preparation method can effectively reduce the agglomeration degree of the sulfonated polyether ether ketone product, resulting in sulfonated polyether ether ketone powder with a more uniform particle size, thus promoting the widespread use of sulfonated polyether ether ketone.

[0005] To solve the above technical problems, the technical solution of the present invention is as follows:

[0006] A method for preparing sulfonated polyether ether ketone powder includes the following steps:

[0007] A solution was prepared by dissolving sulfonated polyether ether ketone solid in an alkaline aqueous solution.

[0008] The solution is mixed with an organic solvent, causing the sulfonated polyether ether ketone in the solution to precipitate in the organic solvent, resulting in a solid-liquid mixture; the organic solvent is immiscible with water;

[0009] The solid-liquid mixture is subjected to solid-liquid separation treatment;

[0010] The solid phase obtained from the solid-liquid separation process is then pulverized.

[0011] In one embodiment, the volume ratio of the solution to the organic solvent is 1:1 to 1:4.

[0012] In one embodiment, the organic solvent includes at least one selected from petroleum ether, benzene, toluene, n-octane, cyclohexane, and gasoline; and / or,

[0013] The alkaline aqueous solution includes at least one of sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, lithium hydroxide aqueous solution, and calcium hydroxide aqueous solution.

[0014] In one embodiment, the pulverizing process includes crushing and / or grinding.

[0015] In one embodiment, the sulfonated polyether ether ketone solid is prepared by a method comprising the following steps:

[0016] A sulfonation solution is prepared by dissolving polyetheretherketone powder in a sulfonating agent.

[0017] The sulfonated solution is mixed with water to precipitate sulfonated polyether ether ketone solid.

[0018] A sulfonated polyether ether ketone powder is prepared by the preparation method described in any of the above embodiments.

[0019] A method for preparing a sulfonated polyether ether ketone product includes the following steps:

[0020] The sulfonated polyether ether ketone powder is subjected to hot pressing molding.

[0021] In one embodiment, the pressure of the hot pressing process is 5 MPa to 15 MPa; and / or,

[0022] The temperature program for hot pressing includes: first holding at 320℃~340℃ for 30min~120min, and then holding at 230℃~270℃ for 20min~60min.

[0023] A sulfonated polyether ether ketone product is prepared from the sulfonated polyether ether ketone powder.

[0024] In one embodiment, the sulfonated polyether ether ketone product includes friction pairs, water-lubricated bearings, artificial joints, ion exchange membranes, or flocculants.

[0025] In the above-mentioned method for preparing sulfonated polyether ether ketone powder, a solution is prepared by dissolving solid sulfonated polyether ether ketone in an alkaline aqueous solution, and then mixing the solution with an organic solvent. During this mixing process, the sulfonated polyether ether ketone dissolved in the solution precipitates in the organic solvent, resulting in a solid-liquid mixture. The solid-liquid mixture is then subjected to solid-liquid separation, and the resulting solid phase is pulverized. In this preparation method, when the sulfonated polyether ether ketone precipitates in the organic solvent, the precipitated sulfonated polyether ether ketone is gel-like with a loose structure, making it easy to pulverize and obtain sulfonated polyether ether ketone powder with a relatively uniform particle size. This preparation method can effectively reduce the agglomeration degree of sulfonated polyether ether ketone products, prepare sulfonated polyether ether ketone powder with a relatively uniform particle size, and promote the application and use of sulfonated polyether ether ketone.

[0026] Furthermore, the sulfonated polyether ether ketone powder prepared by the above method has good grindability and can be pulverized to obtain sulfonated polyether ether ketone powder of appropriate particle size as needed. The above preparation method can obtain micron-sized sulfonated polyether ether ketone powder. Attached Figure Description

[0027] Figure 1 This is a schematic diagram of a method for preparing sulfonated polyether ether ketone powder according to an embodiment of the present invention;

[0028] Figure 2 This is a photograph of the sulfonated polyether ether ketone powder obtained in Example 1 of the present invention.

[0029] Figure 3 This is a schematic diagram of the temperature program for spark plasma sintering in the preparation method of sulfonated polyether ether ketone products in Example 1 of the present invention;

[0030] Figure 4 A physical image of the sulfonated polyether ether ketone product obtained in Example 1 of this invention;

[0031] Figure 5 This is a photograph of the sulfonated polyether ether ketone product obtained in Comparative Example 1 of the present invention.

[0032] Figure 6 for Figure 5 The image shows the sulfonated polyether ether ketone (PEEK) product after being treated with liquid nitrogen and then pulverized to obtain PEEK particles. Detailed Implementation

[0033] To make the above-mentioned objects, features, and advantages of the present invention more apparent and understandable, specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. Many specific details are set forth in the following description to provide a thorough understanding of the present invention. However, the present invention can be practiced in many other ways different from those described herein, and those skilled in the art can make similar modifications without departing from the spirit of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0034] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the specification of this invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0035] An embodiment of the present invention provides a method for preparing sulfonated polyether ether ketone powder. The preparation method includes the following steps: dissolving solid sulfonated polyether ether ketone in an alkaline aqueous solution to prepare a solution; mixing the solution with an organic solvent to precipitate the sulfonated polyether ether ketone from the solution into the organic solvent, obtaining a solid-liquid mixture; the organic solvent and water are immiscible. The solid-liquid mixture is subjected to solid-liquid separation treatment. The solid phase obtained from the solid-liquid separation treatment is then pulverized. In this embodiment, the organic solvent and water are immiscible. When the solution and organic solvent are mixed, a two-phase interface exists between the solution and the organic solvent. The sulfonated polyether ether ketone dissolved in the solution slowly precipitates and disperses into the organic solvent, i.e., the sulfonated polyether ether ketone in the solution precipitates into the organic solvent. When the sulfonated polyether ether ketone precipitates into the organic solvent, the precipitated sulfonated polyether ether ketone is gel-like, loosely structured, and easily pulverized, making it easy to obtain sulfonated polyether ether ketone powder with a relatively uniform particle size through pulverization. This preparation method can effectively reduce the agglomeration degree of sulfonated polyether ether ketone products, and prepare sulfonated polyether ether ketone powder with relatively uniform particle size, thereby promoting the application and use of sulfonated polyether ether ketone.

[0036] Furthermore, the sulfonated polyether ether ketone powder prepared by the above method has good grindability and can be pulverized to obtain sulfonated polyether ether ketone powder of the corresponding particle size according to requirements. The above preparation method can obtain micron-sized sulfonated polyether ether ketone powder. When pulverizing the solid phase obtained from the solid-liquid separation process, the precipitated gel-like sulfonated polyether ether ketone can be manually crushed or crushed using a mixer, then dried, and then milled in a mortar or ball mill to prepare micron-sized sulfonated polyether ether ketone powder. The drying temperature can be selected from 100℃ to 150℃, and the drying time is 2h to 5h. Furthermore, in the preparation method of sulfonated polyether ether ketone powder in this embodiment, the sulfonated polyether ether ketone solid is first dissolved in an alkaline aqueous solution, and then when mixed with an organic solvent, the sulfonated polyether ether ketone in the solution precipitates in the organic solvent. By combining dissolution and precipitation, sulfonated groups can be distributed inside and on the surface of polyether ether ketone powder. During use, the sulfonated groups are not easily lost, which can effectively maintain and improve the performance stability of sulfonated polyether ether ketone powder and sulfonated polyether ether ketone products.

[0037] In a specific example, the density of the organic solvent is less than that of water. Thus, when the solution is mixed with the organic solvent, the organic solvent containing sulfonated polyether ether ketone is located on top of the alkaline aqueous solution, which facilitates the subsequent separation of the organic solvent and the alkaline aqueous solution, especially the separation of the gel-like sulfonated polyether ether ketone from the solid-liquid mixture.

[0038] Optionally, when mixing the solution with the organic solvent, the solution can be added to the organic solvent. Since the density of the organic solvent is less than that of water, the solution will sink when added, allowing for more thorough interaction between the solution and the organic solvent, which facilitates better precipitation of sulfonated polyether ether ketone into the organic solvent. Further, optionally, when mixing the solution with the organic solvent, stirring can promote mixing, ensuring more thorough and efficient mixing, increasing the precipitation rate of sulfonated polyether ether ketone in the organic solvent, and thus improving the yield and production efficiency of polyether ether ketone powder. Furthermore, after the sulfonated polyether ether ketone precipitates in the organic solvent, it forms a gel-like solid. Stirring can break up this gel-like solid, facilitating subsequent solid-phase pulverization.

[0039] In a specific example, when sulfonated polyether ether ketone solid is dissolved in an alkaline aqueous solution, the amount of sulfonated polyether ether ketone solid in the alkaline aqueous solution is 5 g / L to 50 g / L. Optionally, the amount of sulfonated polyether ether ketone solid in the alkaline aqueous solution can be 5 g / L, 10 g / L, 15 g / L, 20 g / L, 25 g / L, 30 g / L, 35 g / L, 40 g / L, 45 g / L, or 50 g / L. It is understood that other suitable choices can be made within the range of 5 g / L to 50 g / L for the amount of sulfonated polyether ether ketone solid in the alkaline aqueous solution.

[0040] It is understandable that when sulfonated polyether ether ketone solids are dissolved in an alkaline aqueous solution, the amount of alkaline aqueous solution used is excessive to ensure that the sulfonated polyether ether ketone solids are fully dissolved.

[0041] Optionally, the pH value of the alkaline aqueous solution is controlled between 10 and 14. For example, the pH of the alkaline aqueous solution can be 10, 11, 12, 13 or 14.

[0042] Understandably, the solid-liquid mixture is further subjected to the following steps before solid-liquid separation: allowing the mixture to stand. This standing process allows the organic solvent and aqueous solution to separate into layers, enabling the sulfonated polyether ether ketone to be fully separated.

[0043] It is also understandable that filtration can be used to separate solid-liquid mixtures.

[0044] In a specific example, the volume ratio of the solution to the organic solvent is 1:1 to 1:4. For example, the volume ratio of the solution to the organic solvent can be controlled to be 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, or 1:4. It is understood that when mixing the solution and the organic solvent, other suitable choices can be made within the range of 1:1 to 1:4. When the amount of organic solvent is insufficient, the sulfonated polyether ether ketone (PEEEK) may not precipitate completely. When there is too much organic solvent, on the one hand, the organic solvent is wasted, and on the other hand, the precipitated PEEEEK is difficult to form a gel, making it inconvenient to collect and pulverize.

[0045] In some specific examples, as examples of choices for organic solvents, the organic solvent includes at least one selected from petroleum ether, benzene, toluene, n-octane, cyclohexane, and gasoline. Alternatively, the organic solvent is at least one selected from petroleum ether, benzene, toluene, n-octane, cyclohexane, and gasoline. Alternatively, the organic solvent is petroleum ether, benzene, toluene, n-octane, cyclohexane, or gasoline. Further alternatively, the organic solvent is petroleum ether.

[0046] As an example of an alkaline aqueous solution, the alkaline aqueous solution includes at least one selected from sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, lithium hydroxide aqueous solution, and calcium hydroxide aqueous solution. Optionally, the alkaline aqueous solution is at least one selected from sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, lithium hydroxide aqueous solution, and calcium hydroxide aqueous solution. Alternatively, the alkaline aqueous solution is an aqueous solution of sodium hydroxide, potassium hydroxide, lithium hydroxide, or calcium hydroxide. More preferably, the alkaline aqueous solution is an aqueous solution of sodium hydroxide.

[0047] In a specific example, the pulverization process includes crushing and / or grinding. Optionally, crushing can be performed using equipment such as a high-speed blender or a crusher. Grinding includes ball mills, column mills, rod mills, etc.

[0048] In a specific example, sulfonated polyether ether ketone solid is dissolved in an alkaline aqueous solution, with the dissolution temperature controlled between 60°C and 90°C. By controlling the dissolution temperature, the dissolution rate of sulfonated polyether ether ketone can be improved. Optionally, the dissolution temperature can be controlled at 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, or 90°C. It is understood that other suitable choices can be made within the range of 60°C to 90°C. Further, the dissolution time is controlled between 2 hours and 5 hours when the sulfonated polyether ether ketone solid is dissolved in the alkaline aqueous solution. Optionally, the dissolution time can be controlled at 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, or 5 hours. It is understood that other suitable choices can be made within the range of 2 hours to 5 hours. It is also understandable that when dissolving sulfonated polyether ether ketone solids in an alkaline aqueous solution, stirring can be used to promote the dissolution of the sulfonated polyether ether ketone solids in the alkaline aqueous solution.

[0049] In a specific example, sulfonated polyetheretherketone (PEEK) solids are prepared by a method comprising the following steps: dissolving PEEK powder in a sulfonating agent to prepare a sulfonation solution; mixing the sulfonation solution with water to precipitate sulfonated PEEK solids. In this example, PEEK powder is dissolved in a sulfonating agent to perform sulfonic acid group grafting modification on the PEEK powder. The sulfonation solution is added to water to precipitate sulfonated PEEK solids, providing a basis for the subsequent preparation of sulfonated PEEK powder.

[0050] As an alternative example of a sulfonating agent, the sulfonating agent includes at least one selected from concentrated sulfuric acid, fuming sulfuric acid, and chlorosulfonic acid. Specifically, the sulfonating agent is at least one selected from concentrated sulfuric acid, fuming sulfuric acid, and chlorosulfonic acid. Further, the sulfonating agent is concentrated sulfuric acid, fuming sulfuric acid, or chlorosulfonic acid. Still further, the sulfonating agent is concentrated sulfuric acid.

[0051] In a specific example, the amount of polyetheretherketone (PEEK) powder as a percentage of the sulfonating agent is 0.02 g / mL to 0.1 g / mL. Optionally, the amount of PEEK powder as a percentage of the sulfonating agent is 0.02 g / mL, 0.03 g / mL, 0.04 g / mL, 0.05 g / mL, 0.06 g / mL, 0.07 g / mL, 0.08 g / mL, 0.09 g / mL, or 0.1 g / mL. Of course, other suitable choices can be made within the range of 0.02 g / mL to 0.1 g / mL for the PEEK powder as a percentage of the sulfonating agent.

[0052] In a specific example, polyetheretherketone (PEEK) powder is dissolved in a sulfonating agent, with the dissolution temperature controlled at 80°C to 100°C. Optionally, the dissolution temperature can be controlled at 80°C, 85°C, 90°C, 95°C, or 100°C. It is understood that other suitable choices can be made within the range of 80°C to 100°C. Further, when dissolving the PEEK powder in the sulfonating agent, the dissolution time is controlled at 3 hours to 6 hours. Optionally, the dissolution time can be controlled at 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, or 6 hours. It is understood that other suitable choices can be made within the range of 3 hours to 6 hours. It is also understood that when dissolving the PEEK powder in the sulfonating agent, stirring can be used to promote the dissolution of the PEEK powder in the sulfonating agent.

[0053] In a specific example, mixing the sulfonation solution with water involves adding the sulfonation solution to the water. When adding the sulfonation solution to the water, the addition rate is 50 mL / min to 500 mL / min. Optionally, the addition rate can be 50 mL / min, 100 mL / min, 150 mL / min, 200 mL / min, 250 mL / min, 300 mL / min, 350 mL / min, 400 mL / min, 450 mL / min, or 500 mL / min. Of course, other suitable choices can be made within the range of 50 mL / min to 500 mL / min. Further, the sulfonation solution is added to the water at a temperature of 0°C to 30°C. Optionally, the water is ultrapure water. Optionally, the water temperature can be 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, or 30°C. Of course, other suitable choices can be made within the range of 0°C to 30°C. Furthermore, the sulfonation solution is added to water, and the stirring speed is controlled at 100 rpm to 400 rpm. Optionally, the stirring speed can be 100 rpm, 150 rpm, 200 rpm, 250 rpm, 300 rpm, 350 rpm, or 400 rpm. Of course, other suitable stirring speeds can also be selected within the range of 100 rpm to 400 rpm.

[0054] See also Figure 1 The invention illustrates a method for preparing sulfonated polyether ether ketone powder according to an embodiment of the present invention, which includes the following steps:

[0055] S101: Dissolve polyetheretherketone powder in a sulfonating agent to prepare a sulfonation solution.

[0056] S102: Add the sulfonation solution to water to precipitate sulfonated polyether ether ketone solid.

[0057] S103: Dissolve sulfonated polyether ether ketone solid in an alkaline aqueous solution to prepare a solution.

[0058] S104: The solution is mixed with an organic solvent, causing the sulfonated polyether ether ketone in the solution to precipitate in the organic solvent, resulting in a solid-liquid mixture. The precipitated sulfonated polyether ether ketone is in a gel state.

[0059] S105: Solid-liquid separation treatment is performed on the solid-liquid mixture. S105 is not shown in the figure.

[0060] S106: The solid phase obtained from the solid-liquid separation process is pulverized. S106 is not shown in the figure.

[0061] Another embodiment of the present invention provides a sulfonated polyether ether ketone powder. This sulfonated polyether ether ketone powder is prepared by the above-described preparation method.

[0062] Another embodiment of the present invention provides a method for preparing a sulfonated polyether ether ketone (PEEK) product. The method for preparing the PEEK product includes the following steps: hot-pressing the above-mentioned sulfonated PEEK powder.

[0063] Specifically, the hot pressing forming process is a hot pressing sintering process. Optionally, the hot pressing forming process is carried out in a vacuum sintering furnace or a spark plasma sintering furnace.

[0064] In a specific example, the pressure for hot pressing is between 5 MPa and 15 MPa. For instance, the pressure for hot pressing can be 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa, 10 MPa, 11 MPa, 12 MPa, 13 MPa, 14 MPa, or 15 MPa. It is understood that other suitable choices can be made within the range of 5 MPa to 15 MPa for the hot pressing process.

[0065] Furthermore, the temperature procedure for hot pressing includes: first holding at 320℃~340℃ for 30min~120min, and then holding at 230℃~270℃ for 20min~60min. Using a lower pressing temperature during the hot pressing process helps to ensure the stable presence of sulfonate groups in the sulfonated polyether ether ketone (PEEEK) product, thus improving its performance. Specifically, holding at 320℃~340℃ for 30min~120min can be considered the powder forming stage of the sulfonated PEEK powder, allowing for thorough fusion. Holding at 230℃~270℃ for 20min~60min can be considered the crystallizing stage of the sulfonated PEEK powder, allowing for stable crystallization of the fused powder, thereby forming a stable sulfonated PEEK product. Optionally, during the fusion stage, the temperature can be 320℃, 322℃, 325℃, 330℃, 335℃, 338℃, or 400℃; the holding time can be 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, or 120min. During the crystallization stage, the temperature can be 230℃, 235℃, 240℃, 245℃, 250℃, 255℃, 260℃, 265℃, or 270℃; the holding time can be 20min, 30min, 40min, 50min, or 60min, etc. It is understood that the temperature and holding time for each stage can also be selected from the temperature and holding time ranges listed above.

[0066] Furthermore, the temperature procedure for hot pressing also includes: heating from the initial temperature to 320℃ to 340℃ at a rate of 4℃ / min to 8℃ / min and holding at that temperature, followed by cooling to 230℃ to 270℃ at a rate of 3℃ / min to 5℃ / min. That is, during hot pressing, the sulfonated polyether ether ketone powder is first heated from the initial temperature to 320℃ to 340℃ at a rate of 4℃ / min to 8℃ / min and held at 320℃ to 340℃ for 30 min to 120 min, then cooled to 230℃ to 270℃ at a rate of 3℃ / min to 5℃ / min and held at 230℃ to 270℃ for 20 min to 60 min. Optionally, during the heating stage, the heating rate can be 4℃ / min, 5℃ / min, 6℃ / min, 7℃ / min, or 8℃ / min, etc. During the cooling phase, the cooling rate can be 3℃ / min, 3.5℃ / min, 4℃ / min, 4.5℃ / min, or 5℃ / min, etc.

[0067] Specifically, the starting temperature is 20℃ to 30℃. It is understood that room temperature can be used as the starting temperature during the hot pressing process. Optionally, the starting temperature can be 20℃, 21℃, 22℃, 23℃, 24℃, 25℃, 26℃, 27℃, 28℃, 29℃, or 30℃. Of course, other suitable choices can also be made within the range of 20℃ to 30℃.

[0068] Understandably, before hot pressing the sulfonated polyether ether ketone powder, the following steps are included: drying the sulfonated polyether ether ketone powder. Specifically, the drying temperature is 110℃~150℃, and the drying time is 2h~5h. For example, the drying temperature can be 110℃, 120℃, 130℃, 140℃, or 150℃, and the drying time can be 2h, 3h, 4h, or 5h, etc. After drying, the sulfonated polyether ether ketone powder is then hot pressed.

[0069] In a specific example, the preparation method of sulfonated polyether ether ketone includes the following steps:

[0070] S201: Dissolve polyetheretherketone powder in a sulfonating agent to prepare a sulfonation solution.

[0071] S202: Add the sulfonation solution to water to precipitate sulfonated polyether ether ketone solid.

[0072] S203: Dissolve sulfonated polyether ether ketone solid in an alkaline aqueous solution to prepare a solution.

[0073] S204: Mix the solution with an organic solvent to precipitate the sulfonated polyether ether ketone in the solution into the organic solvent, thus obtaining a solid-liquid mixture.

[0074] S205: Solid-liquid separation treatment for solid-liquid mixtures.

[0075] S206: The solid phase obtained from the solid-liquid separation process is pulverized.

[0076] S207: The sulfonated polyether ether ketone powder obtained after pulverization is subjected to hot pressing molding.

[0077] Another embodiment of the present invention provides a sulfonated polyether ether ketone product comprising the above-mentioned sulfonated polyether ether ketone powder.

[0078] Another embodiment of the present invention provides a sulfonated polyether ether ketone product, which is prepared by the above-mentioned sulfonated polyether ether ketone powder.

[0079] In a specific example, sulfonated polyetheretherketone products include friction pairs, water-lubricated bearings, artificial joints, ion exchange membranes, or flocculants.

[0080] The following are specific examples.

[0081] In the following examples, the polyetheretherketone (PEEK) powder is a commercially available PEEK powder manufactured by Vigers. Alternatively, other manufacturers of commercial PEEK powder may include China Research Institute of Polymer Materials, Solvay, etc.

[0082] Example 1

[0083] The preparation method of sulfonated polyether ether ketone powder in this embodiment includes the following steps:

[0084] S301: Dissolve 15g of polyetheretherketone powder in 300mL of concentrated sulfuric acid, control the dissolution temperature at 90℃ and the dissolution time at 4h to prepare a sulfonation solution.

[0085] S302: Under a stirring speed of 200 rpm, the sulfonation solution is added to 3000 mL of ultrapure water at 10 °C at a stirring rate of 200 mL / min, and sulfonated polyether ether ketone solid is precipitated.

[0086] S303: Sulfonated polyether ether ketone solid is dissolved in an excess of sodium hydroxide aqueous solution, with the dissolution temperature controlled at 70℃ and the dissolution time at 3h to prepare a solution.

[0087] S304: Mix the solution with petroleum ether to precipitate the sulfonated polyether ether ketone in the solution into the petroleum ether. The volume ratio of the solution to the petroleum ether is 1:2 to obtain a solid-liquid mixture. Let the solid-liquid mixture stand.

[0088] S305: Filter and dry the solid-liquid mixture to obtain the solid phase.

[0089] S306: The solid phase is ground. After grinding, the sulfonated polyether ether ketone powder of this embodiment is obtained. The sulfonated polyether ether ketone powder is as follows: Figure 2 As shown, the sulfonated polyether ether ketone powder has a sulfonation degree of approximately 90% and an average particle size of approximately 20 μm. It also exhibits good thermal stability; after heating at 400°C for 0.5 h, the mass loss rate remains below 0.5%.

[0090] The preparation method of the sulfonated polyether ether ketone product in this embodiment includes the following steps:

[0091] S307: The sulfonated polyether ether ketone powder obtained from S306 is dried at 120°C for 3 hours.

[0092] S308: The dried sulfonated polyether ether ketone powder of S307 is hot-pressed in a spark plasma sintering furnace. The pressure for hot-pressing is 8 MPa. The temperature program is as follows: Figure 3As shown, the temperature is increased from 25°C to 325°C at a rate of 6°C / min, held at 325°C for 60 min, then decreased to 250°C at a rate of 3.75°C / min, and held at 250°C for 30 min. After hot pressing, sulfonated polyetheretherketone (PEEK) products are obtained. Sulfonated PEEK products are as follows... Figure 4 As shown, the coefficient of friction of this polyetheretherketone (PEEK) product is as low as approximately 0.01. Specifically, the coefficient of friction is approximately 0.015 at a sliding speed of 12.5 mm / s; 0.012 at a sliding speed of 25 mm / s; and approximately 0.011 at a sliding speed of 50 mm / s.

[0093] Example 2

[0094] The preparation method of sulfonated polyether ether ketone powder in this embodiment includes the following steps:

[0095] S301: Dissolve 15g of polyetheretherketone powder in 300mL of concentrated sulfuric acid, control the dissolution temperature at 90℃ and the dissolution time at 4h to prepare a sulfonation solution.

[0096] S302: Under a stirring speed of 200 rpm, the sulfonation solution is added to 3000 mL of ultrapure water at 10 °C at a stirring rate of 200 mL / min, and sulfonated polyether ether ketone solid is precipitated.

[0097] S303: Sulfonated polyether ether ketone solid is dissolved in an excess of sodium hydroxide aqueous solution, with the dissolution temperature controlled at 70℃ and the dissolution time at 3h to prepare a solution.

[0098] S304: Mix the solution with cyclohexane to precipitate the sulfonated polyether ether ketone in the solution into the cyclohexane. The volume ratio of the solution to cyclohexane is 1:2 to obtain a solid-liquid mixture, and then let the solid-liquid mixture stand.

[0099] S305: Filter and dry the solid-liquid mixture to obtain the solid phase.

[0100] S306: The solid phase is ground. After grinding, the sulfonated polyether ether ketone powder of this embodiment is obtained. The degree of sulfonation of this sulfonated polyether ether ketone powder is approximately 90%, and the average particle size is approximately 20 μm. It also exhibits good thermal stability; after heating at 400°C for 0.5 h, the mass loss rate remains below 0.5%.

[0101] The preparation method of the sulfonated polyether ether ketone product in this embodiment includes the following steps:

[0102] S307: The sulfonated polyether ether ketone powder obtained from S306 is dried at 120°C for 3 hours.

[0103] S308: The dried sulfonated polyether ether ketone powder of S307 is hot-pressed in a spark plasma sintering furnace. The pressure for hot-pressing is 8 MPa. The temperature program is as follows: Figure 3 As shown, the temperature is increased from 25°C to 325°C at a rate of 6°C / min, held at 325°C for 60 min, then decreased to 250°C at a rate of 3.75°C / min, and held at 250°C for 30 min. After hot pressing, a sulfonated polyetheretherketone (PEEK) product is obtained. The coefficient of friction of this PEEK product is as low as approximately 0.01. Specifically, the coefficient of friction is approximately 0.018 at a sliding speed of 12.5 mm / s; 0.016 at a sliding speed of 25 mm / s; and approximately 0.011 at a sliding speed of 50 mm / s.

[0104] Comparative Example 1

[0105] In this comparative example, sulfonated polyetheretherketone (PEEK) was prepared using the traditional concentrated sulfuric acid sulfonation method. PEEK powder was dissolved in concentrated sulfuric acid, and then sulfonated PEEK solid precipitated in water. The precipitated sulfonated PEEK solid was as follows: Figure 5 As shown. By Figure 5 It can be seen that the precipitated sulfonated polyether ether ketone solid is agglomerated and difficult to form into powder. Even after immersion in liquid ammonia and subsequent pulverization, the resulting product still exhibits uneven particle size and is difficult to further pulverize, making it hard to form powdered sulfonated polyether ether ketone. The pulverized particles are as follows... Figure 6 As shown, the coefficient of friction of the sample prepared from the sulfonated polyether ether ketone particles is above 0.1. Specifically, the coefficient of friction is approximately 0.20 at a sliding speed of 12.5 mm / s; 0.15 at a sliding speed of 25 mm / s; and approximately 0.13 at a sliding speed of 50 mm / s.

[0106] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0107] The above-described embodiments merely represent several implementation methods of the present invention, and their descriptions are relatively specific and detailed, but they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art may make several modifications and improvements without departing from the concept of the present invention, and these modifications and improvements fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be based on the appended claims, and the description and drawings may be used to interpret the content of the claims.

Claims

1. A method for preparing sulfonated polyetheretherketone powder, characterized in that, Includes the following steps: A solution is prepared by dissolving sulfonated polyether ether ketone solid in an alkaline aqueous solution; the alkaline aqueous solution includes at least one of sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, lithium hydroxide aqueous solution, and calcium hydroxide aqueous solution. The solution is mixed with an organic solvent to precipitate the sulfonated polyether ether ketone in the solution into the organic solvent, resulting in a solid-liquid mixture; the organic solvent is immiscible with water; the volume ratio of the solution to the organic solvent is 1:1 to 1:

4. The solid-liquid mixture is subjected to solid-liquid separation treatment; The solid phase obtained from the solid-liquid separation process is then pulverized.

2. The method for preparing sulfonated polyether ether ketone powder according to claim 1, characterized in that, The organic solvent includes at least one of petroleum ether, benzene, toluene, n-octane, cyclohexane, and gasoline.

3. The method for preparing sulfonated polyetheretherketone powder according to claim 1, characterized in that, The pulverization process includes crushing and / or grinding.

4. The method for preparing sulfonated polyether ether ketone powder according to any one of claims 1 to 3, characterized in that, The sulfonated polyether ether ketone solid is prepared by a method comprising the following steps: A sulfonation solution is prepared by dissolving polyetheretherketone powder in a sulfonating agent. The sulfonated solution is mixed with water to precipitate sulfonated polyether ether ketone solid.

5. A sulfonated polyetheretherketone powder, characterized in that, Prepared by the preparation method according to any one of claims 1 to 4.

6. A method for preparing a sulfonated polyether ether ketone product, characterized in that, Includes the following steps: The sulfonated polyether ether ketone powder according to claim 5 is subjected to hot pressing molding.

7. The method for preparing the sulfonated polyether ether ketone product according to claim 6, characterized in that, The pressure of the hot pressing process is 5MPa~15MPa.

8. The method for preparing the sulfonated polyether ether ketone product according to claim 6 or 7, characterized in that, The temperature program for hot pressing includes: first holding at 320℃~340℃ for 30min~120min, and then holding at 230℃~270℃ for 20min~60min.

9. A sulfonated polyetheretherketone product, characterized in that, Prepared using the sulfonated polyether ether ketone powder according to claim 5.

10. The sulfonated polyether ether ketone product according to claim 9, characterized in that, The sulfonated polyether ether ketone products include friction pairs, water-lubricated bearings, artificial joints, ion exchange membranes, or flocculants.

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