CN114957649A - Modified polyether-ether-ketone powder, modification method, polyether-ether-ketone product and preparation method - Google Patents
Modified polyether-ether-ketone powder, modification method, polyether-ether-ketone product and preparation method Download PDFInfo
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Abstract
The invention relates to a modification method of polyether-ether-ketone powder, modified polyether-ether-ketone powder, a polyether-ether-ketone product and a preparation method thereof. In the modification method of the polyether-ether-ketone powder, a sulfonating agent is mixed with a polar solvent to prepare a dispersing agent; mixing polyether ether ketone powder with a dispersing agent to prepare a dispersion liquid; heating the dispersion liquid to prepare a modified preform; mixing the prefabricated product with alkali liquor. The modified polyether-ether-ketone powder with good morphology can be obtained by mixing and matching the sulfonating agent, the polar solvent, the polyether-ether-ketone powder, heating treatment and alkali liquor, controlling the dosage of the sulfonating agent and the polyether-ether-ketone and controlling the heating treatment conditions, thereby effectively avoiding the agglomeration problem of the polyether-ether-ketone powder. Meanwhile, the modified polyether-ether-ketone powder has good formability, and is convenient for forming and preparing polyether-ether-ketone products. In the prepared polyether-ether-ketone product, the modified group is positioned in the whole product and is not easy to run off, so that the performance of the polyether-ether-ketone product is improved.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a modification method of polyether-ether-ketone powder, modified polyether-ether-ketone powder, a polyether-ether-ketone product and a preparation method thereof.
Background
Polyetheretherketone (PEEK) has good mechanical properties, wear resistance, corrosion resistance and other properties, but with the continuous expansion of the application scenes of PEEK, the expressed limitations of PEEK on the properties are more and more obvious, which also restricts the further development of PEEK to a certain extent. For example, polyetheretherketone has poor affinity for aqueous solutions, which results in poor lubricity due to poor ability of a friction pair made therefrom to form a fluid lubricating film under low speed conditions. For another example, the stability of polyetheretherketone itself also has certain limitations on its chemical modification. Therefore, the research on the modification method of the polyetheretherketone has very important significance for the popularization and the use of the polyetheretherketone.
When the polyetheretherketone is modified, in a traditional modification mode, on one hand, a polyetheretherketone product is subjected to surface modification, and the method can better improve the performance of the polyetheretherketone product, such as mechanical property, wear resistance, corrosion resistance and the like of the polyetheretherketone product, but when unavoidable or unpredictable wear occurs, modified groups on the surface of the polyetheretherketone product are easy to run off, so that modification failure is caused. On the other hand, when the conventional method of modifying polyetheretherketone by dissolution modification is used, although the grafting ratio can be high, it is difficult to obtain modified polyetheretherketone powder with good morphology, which causes difficulty in the preparation of polyetheretherketone products.
Disclosure of Invention
Accordingly, there is a need for a modified polyetheretherketone powder, a modification method, a polyetheretherketone product, and a method for producing the same. The modified polyether-ether-ketone powder with good form can be obtained by the modification method, so that a polyether-ether-ketone product with a modified group not easy to run off is prepared, and the performance of the polyether-ether-ketone product is improved.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a modification method of polyetheretherketone powder comprises the following steps:
mixing a sulfonating agent and a polar solvent to prepare a dispersing agent, wherein the sulfonating agent accounts for 2-15% of the polar solvent by volume;
mixing polyether-ether-ketone powder with the dispersing agent to prepare a dispersion liquid, wherein the polyether-ether-ketone powder accounts for 5-30% of the dispersing agent by mass;
heating the dispersion liquid at the temperature of 70-110 ℃ to prepare a modified pre-finished product;
and mixing the modified pre-product with alkali liquor.
In one embodiment, mixing the sulfonating agent with the polar solvent comprises the steps of:
and dropwise adding the sulfonating agent into the polar solvent at the dropping speed of 0.5-3 mL/min under the stirring condition.
In one embodiment, mixing the modified preform with a lye comprises the steps of:
and soaking the modified preform in the alkali liquor.
In one embodiment, the sulfonating agent comprises at least one of chlorosulfonic acid, concentrated sulfuric acid, and oleum.
In one embodiment, the polar solvent comprises at least one of acetone, pyridine, chloroform, dimethylformamide, and dimethylsulfoxide.
In one embodiment, the lye comprises at least one of a sodium hydroxide solution, a potassium hydroxide solution and a calcium hydroxide solution.
Modified polyetheretherketone powder, which is modified by the polyetheretherketone powder modification method described in any of the above embodiments.
A preparation method of a polyether-ether-ketone product comprises the following steps:
and carrying out hot press molding treatment on the modified polyether-ether-ketone powder.
In one embodiment, the pressure of the hot press molding treatment is 5MPa to 10 MPa.
In one embodiment, the temperature program for hot press forming includes:
the temperature is preserved for 30min to 120min at 320 ℃ to 340 ℃ and then preserved for 20min to 60min at 230 ℃ to 270 ℃.
A polyetheretherketone article comprising the modified polyetheretherketone powder.
In one embodiment, the polyetheretherketone article comprises a friction pair, a bearing, or an artificial joint.
In the modification method of the polyether-ether-ketone powder, a sulfonating agent is mixed with a polar solvent, and the dosage of the sulfonating agent is controlled to prepare a dispersing agent; mixing polyether-ether-ketone powder with a dispersing agent, and controlling the using amount of the polyether-ether-ketone powder to prepare a dispersion liquid; heating the dispersion liquid, and carrying out grafting reaction of sulfonic acid groups in the heating process; mixing the prefabricated product with alkali liquor. In the modification method, the sulfonating agent, the polar solvent, the polyether-ether-ketone powder, the heating treatment and the alkali liquor are mixed and matched, the use amounts of the sulfonating agent and the polyether-ether-ketone are controlled, and the heating treatment condition is controlled, so that the agglomeration problem of the polyether-ether-ketone powder can be effectively avoided, and the modified polyether-ether-ketone powder with good form can be obtained. Meanwhile, the modified polyether-ether-ketone powder has good formability, and is convenient to form and prepare polyether-ether-ketone products. In the prepared polyether-ether-ketone product, the modification group is positioned in the whole product and is not easy to run off, so that the performance of the polyether-ether-ketone product is improved.
Drawings
FIG. 1 is a schematic illustration of a method of making an article of polyetheretherketone according to example 1 of the present invention;
FIG. 2 is a schematic diagram of the temperature program for spark plasma sintering in the method for preparing the PEEK article of example 1 according to the present invention;
FIG. 3 is a schematic representation of a PEEK article according to example 1 of the present invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
Unless defined otherwise, 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 belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
An embodiment of the invention provides a modification method of polyether-ether-ketone powder. The modification method of the polyetheretherketone powder comprises the following steps: mixing a sulfonating agent and a polar solvent to prepare a dispersing agent, wherein the sulfonating agent accounts for 2-15% of the polar solvent by volume; mixing polyether-ether-ketone powder with a dispersing agent to prepare a dispersion liquid, wherein the polyether-ether-ketone powder accounts for 5-30% of the dispersing agent by mass; heating the dispersion liquid at the temperature of 70-110 ℃ to prepare a modified pre-finished product; mixing the modified pre-product with alkali liquor. In the modification method of this embodiment, mainly through mixing and matching the sulfonating agent, the polar solvent, the polyetheretherketone powder, the heating treatment and the alkali solution, controlling the amounts of the sulfonating agent and the polyetheretherketone, and controlling the heating treatment conditions, the agglomeration problem of the polyetheretherketone powder can be effectively avoided, the advantages of the polyetheretherketone powder modification can be brought into play, and the modified polyetheretherketone powder with good morphology can be obtained. Meanwhile, the modified polyether-ether-ketone powder has good formability, and is convenient for forming and preparing polyether-ether-ketone products. In the prepared polyether-ether-ketone product, the modified group is positioned in the whole product and is not easy to run off, so that the performance of the polyether-ether-ketone product is improved.
As some specific examples of choices of sulfonating agents, sulfonating agents include chlorosulfonic acid (HSO) 3 Cl), concentrated sulfuric acid, and oleum. The volume percent of the sulfonating agent to the polar solvent can be, but is not limited to, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, or 15%. Preferably, the sulfonating agent is chlorosulfonic acid. It is understood that the volume percentage of the sulfonating agent in the polar solvent may be selected from a range of 2% to 15%.
As some specific selection examples of the polar solvent, the polar solvent includes at least one of acetone, pyridine, chloroform, Dimethylformamide (DMF), and Dimethylsulfoxide (DMSO).
In one particular example, mixing the sulfonating agent with the polar solvent comprises the steps of: under the condition of stirring, the sulfonating agent is dripped into the polar solvent at the dripping speed of 0.5-3 mL/min. When the sulfonating agent is mixed with the polar solvent, the sulfonating agent is slowly dripped into the polar solvent, so that the sulfonating agent and the polar solvent can be mixed more uniformly, the safety of the sulfonating agent and the polar solvent can be improved, and the sulfonating agent can be added into the polar solvent more safely. Optionally, the sulfonating agent is added dropwise at a rate of 0.5mL/min, 0.8mL/min, 1mL/min, 1.5mL/min, 1.8mL/min, 2mL/min, 2.2mL/min, 2.5mL/min, 2.8mL/min, or 3 mL/min. Of course, the dropping speed of the sulfonating agent can be selected from the range of 0.5mL/min to 3 mL/min.
It will be appreciated that the stirring speed is selected to be between 50rpm and 1000rpm in order to more uniformly mix the sulfonating agent and the polar solvent. For example, the stirring speed may be, but is not limited to, 50rpm, 150rpm, 200rpm, 250rpm, 300rpm, 350rpm, 400rpm, 450rpm, 500rpm, 600rpm, 700rpm, 800rpm, 900rpm, 1000rpm, or the like. It will also be appreciated that the stirring speed may be suitably selected within the range of 50rpm to 1000 rpm.
As some specific examples of the amount of the peek powder, the peek powder may be, but is not limited to, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, or 30% by mass of the dispersant. It is understood that the polyether-ether-ketone powder can be selected from 5-30% by weight of the dispersant. It will also be appreciated that the polyetheretherketone powder is mixed with the dispersant under agitation. Specifically, the stirring speed is 50rpm to 1000 rpm. For example, the stirring speed may be, but is not limited to, 50rpm, 150rpm, 200rpm, 250rpm, 300rpm, 350rpm, 400rpm, 450rpm, 500rpm, 600rpm, 700rpm, 800rpm, 900rpm, 1000rpm, or the like. It will also be appreciated that the stirring speed may be suitably selected within the range of 50rpm to 1000 rpm.
In one particular example, mixing the polyetheretherketone powder with the dispersant comprises the step of adding the polyetheretherketone powder to the dispersant. Namely, polyether ether ketone powder is added to the dispersant under stirring. Specifically, the stirring speed may be appropriately selected from the range of 50rpm to 1000 rpm.
In a specific example, the dispersion is heat-treated at a temperature of 70 ℃ to 110 ℃ to prepare a modified preform. Wherein the heating temperature may be, but is not limited to, 70 deg.C, 75 deg.C, 80 deg.C, 85 deg.C, 90 deg.C, 95 deg.C, 100 deg.C, 105 deg.C, 110 deg.C. Of course, the temperature of the heat treatment can be selected from 70 ℃ to 110 ℃. In the process of heating treatment, a sulfonating agent and the polyetheretherketone powder are subjected to chemical grafting reaction so as to introduce modified groups on the polyetheretherketone powder. Specifically, when the sulfonating agent is selected from chlorosulfonic acid, chlorosulfonic acid undergoes a chemical grafting reaction with the polyetheretherketone powder as shown in the following formula to introduce sulfonic acid groups on the polyetheretherketone powder.
Further, the time of the heat treatment is 3 to 15 hours. For example, the time of the heat treatment may be 3 hours, 5 hours, 8 hours, 10 hours, 12 hours, 15 hours, or the like. It is understood that the time of the heat treatment can be selected from 3h to 15 h. Within the heating time range, the grafting ratio of the sulfonic acid group can be kept in a proper range, and the friction performance of the modified polyether-ether-ketone is further optimized.
In a specific example, when the modified preform is mixed with a lye, the lye includes at least one of a sodium hydroxide solution, a potassium hydroxide solution, and a calcium hydroxide solution. The sulfonic acid groups can be neutralized to sulfonate groups by treatment with alkali liquor, while the grafted groups are protected. In addition, the neutralized sulfonic acid group has better thermal stability, so that the modified polyether-ether-ketone powder can meet the molding process, and the moldability of the modified polyether-ether-ketone powder is improved.
In one specific example, mixing the modified preform with the lye comprises the steps of: and soaking the modified preform in alkali liquor. Optionally, the soaking time is 8-15 h. For example, the soaking time may be 8h, 9h, 10h, 11h, 12h, 13h, 14h, or 15 h. It is understood that the soaking time can be selected from 8h to 15 h.
In a specific example, before the modified preform is mixed with the alkali liquor, the method further comprises the following steps: and removing the residual sulfonating agent in the modified preform. Specifically, the step of removing the residual sulfonating agent in the modified preform comprises the following steps: and cleaning the modified preform by using ethanol. It will be appreciated that the washing step may be performed a plurality of times. In addition, in the cleaning process, the filtration can be performed after the cleaning, and then the solid phase obtained by the filtration can be cleaned again, and the operation is repeated, so as to obtain better effect of removing the residual sulfonating agent in the modified preform.
Further, after removing the residual sulfonating agent in the modified preform, the method also comprises the following steps: and removing the residual polar solvent in the modified preform. Specifically, the step of removing the residual polar solvent in the modified preform comprises the following steps: and cleaning the modified preform by using water. It will be appreciated that the washing step may be performed a plurality of times. In addition, in the cleaning process, the solid phase obtained by filtering after cleaning once can be cleaned again, and the operation is repeated, so as to obtain better effect of removing the residual polar solvent in the modified preform.
It is understood that after the modified preform is mixed with the alkali solution, the following steps are also included: and cleaning, filtering and drying the modified pre-formed product after alkali liquor mixing treatment. The washing may be performed with ethanol and/or water.
Yet another embodiment of the present invention provides a modified polyetheretherketone powder. The modified polyetheretherketone powder is prepared by modifying polyetheretherketone powder by the polyetheretherketone powder modification method. The modified polyether-ether-ketone powder has good powder form and formability on the basis of keeping the excellent characteristics of polyether-ether-ketone, and is convenient to process into polyether-ether-ketone products.
In yet another embodiment of the present invention, an article of polyetheretherketone is provided. The polyether-ether-ketone product comprises the modified polyether-ether-ketone powder. Specifically, the polyetheretherketone article comprises a friction pair, a water lubricated bearing, or an artificial joint. Optionally, the bearing is a marine stern bearing. The polyether-ether-ketone product comprises the modified group, and has good abrasion resistance, excellent service life and good thermal stability. The polyetheretherketone product can realize an ultralow friction effect under the lubrication of a salt solution (such as a sodium chloride solution, a potassium chloride solution, seawater and the like), and has ultralow wear rate and certain water resistance.
In yet another embodiment of the present invention, a method of making a polyetheretherketone article is provided. The preparation method of the polyether-ether-ketone product comprises the following steps: and carrying out hot press molding treatment on the modified polyether-ether-ketone powder. The hot-press forming is more beneficial to improving the density of the product, the bonding strength between powders and regulating and controlling the microscopic morphology of the modified polyetheretherketone, so that the polyetheretherketone product with more excellent macroscopic properties is obtained. Compared with the traditional surface modification, in the polyether-ether-ketone product prepared by the embodiment, the modification group is positioned in the whole product and is not easy to run off, so that the performance of the polyether-ether-ketone product is effectively improved. The polyether-ether-ketone product prepared by the preparation method still has good thermal stability at 400 ℃, the friction coefficient is about 0.01, and the wear rate is 10 -7 mm 3 /(N·m)～10 -8 mm 3 Of the order of/(/ N · m).
Specifically, the hot press molding process is a hot press sintering process. Alternatively, the hot press forming process is performed in a vacuum sintering furnace or a spark plasma sintering furnace.
Optionally, the pressure of the hot press molding treatment is 5MPa to 15 MPa. For example, the pressure of the hot press molding treatment may be 5MPa, 6MPa, 7MPa, 8MPa, 9MPa, 10MPa or 15 MPa. It is understood that the pressure of the hot press molding treatment may be selected from a range of 5MPa to 15 MPa.
Optionally, the temperature program of the hot press forming includes: the temperature is preserved for 30min to 120min at 320 ℃ to 340 ℃ and then preserved for 20min to 60min at 230 ℃ to 270 ℃. In the hot-press molding process, the lower molding temperature is adopted, so that the modified groups can stably exist in the polyetheretherketone product, and the performance of the polyetheretherketone product is further improved. Specifically, the heat preservation is carried out for 30min to 120min at the temperature of 320 ℃ to 340 ℃, and the fusion stage (Powder formation) of the modified polyether-ether-ketone Powder can be used, and the modified polyether-ether-ketone Powder can be fully fused in the stage. Keeping the temperature at 230-270 ℃ for 20-60 min, and taking the crystal phase (Crystallizing) of the modified polyether-ether-ketone powder as the crystallization phase, wherein the crystallization phase can make the fused modified polyether-ether-ketone powder stably crystallized, and further form a stable polyether-ether-ketone product. Alternatively, the temperature may be 320 ℃, 322 ℃, 325 ℃, 330 ℃, 335 ℃, 338 ℃ or 400 ℃ during the fusion phase; the holding time can be 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min or 120 min. In the crystallization stage, the temperature may be 230 ℃, 235 ℃, 240 ℃, 245 ℃, 250 ℃, 255 ℃, 260 ℃, 265 ℃ or 270 ℃; the holding time can be 20min, 30min, 40min, 50min or 60 min. It will be appreciated that the temperatures and incubation times for the various stages may also be selected accordingly within the temperature ranges and incubation time ranges listed above.
In a specific example, the temperature program for hot press forming further includes: heating to 320-340 ℃ from the initial temperature at the speed of 4-8 ℃/min, preserving the heat, and then cooling to 230-270 ℃ at the speed of 3-5 ℃/min. Namely, during hot-press molding, the modified polyetheretherketone powder is heated to 320-340 ℃ from the initial temperature at the speed of 4-8 ℃/min and is kept at the temperature of 320-340 ℃ for 30-120 min, and then is cooled to 230-270 ℃ at the speed of 3-5 ℃/min and is kept at the temperature of 230-270 ℃ for 20-60 min. Optionally, in the temperature raising stage, the temperature raising rate can be 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, or the like. In the cooling stage, the cooling rate can be 3 ℃/min, 3.5 ℃/min, 4 ℃/min, 4.5 ℃/min, 5 ℃/min or the like.
Specifically, the initial temperature is 20 ℃ to 30 ℃. It is understood that room temperature may be used as the starting temperature during the hot press molding process. Alternatively, the starting temperature is 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃ or 30 ℃. Of course, the starting temperature may be selected from the range of 20 ℃ to 30 ℃ as appropriate.
It can be understood that before the hot press molding treatment is performed on the modified polyetheretherketone powder, the method further comprises the following steps: and drying the modified polyether-ether-ketone powder. Specifically, the temperature of the drying treatment is 110-150 ℃, and the time of the drying treatment is 2-5 h. For example, the temperature of the drying treatment may be 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃, and the time of the drying treatment may be 2 hours, 3 hours, 4 hours or 5 hours. And after drying, carrying out hot press molding treatment on the modified polyether-ether-ketone powder.
In one particular example, a method of making a polyetheretherketone article comprises the steps of:
s01: adding a polar solvent into a reaction container, and then dropwise adding a sulfonating agent into the polar solvent at a dropping speed of 0.5-3 mL/min at a stirring speed of 50-1000 rpm to prepare a dispersing agent. Wherein, the volume percentage of the sulfonating agent in the polar solvent is 2-15%.
S02: polyether ether ketone powder was added to the dispersant obtained in S01 at a stirring speed of 50rpm to 1000rpm to prepare a dispersion. Wherein, the polyether-ether-ketone powder accounts for 5 to 30 percent of the dispersant by mass percent.
S03: and (3) heating the dispersion liquid obtained in the step (S02) at the temperature of between 70 and 110 ℃ for 3 to 15 hours to prepare a modified preform.
S04: adding absolute ethyl alcohol into the modified preform obtained in the step S03 for cleaning, and removing the residual sulfonating agent in the modified preform; and then adding water for cleaning to remove the residual polar solvent in the modified preform.
S05: after S04 removing residual sulfonating agent and polar solvent, adding alkali liquor and soaking for 8-15 h. And after soaking, cleaning, filtering and drying to obtain modified polyether-ether-ketone powder.
S06: drying the modified polyether-ether-ketone powder obtained in the step S05 for 2 to 5 hours at the temperature of between 110 and 150 ℃.
S07: and (4) carrying out hot press molding treatment on the modified polyether-ether-ketone powder after drying the S06. Wherein the pressure of the hot-press molding treatment is 5MPa to 10 MPa; the temperature program is that the temperature is raised from the initial temperature to 320-340 ℃ at the speed of 4-8 ℃/min, and is preserved for 30-120 min at 320-340 ℃, then is reduced to 230-270 ℃ at the speed of 3-5 ℃/min, and is preserved for 20-60 min at 230-270 ℃. And (4) obtaining the polyether-ether-ketone product after hot press molding.
The following are specific examples.
In the following examples, the polyetheretherketone powder is commercially available from Wegener. Alternatively, the manufacturers of commercial polyetheretherketone powders may also be medium ground polymeric materials, threo, etc.
Example 1
The schematic diagram of the preparation method of the polyetheretherketone article in this example is shown in figure 1. In FIG. 1, (a) shows a polyether ether ketone powder, (b) shows a mixed system in which a modified preform is mixed with an alkali solution, (c) shows a modified polyether ether ketone powder after modification, and (d) shows spark plasma sintering.
S101: 100mL of Dimethylformamide (DMF) was added to a reaction vessel, and then 5mL of chlorosulfonic acid was added dropwise to the DMF at a dropping rate of 1mL/min with stirring at 100rpm to prepare a dispersant.
S102: 10g of polyether ether ketone powder was added to the dispersant obtained in S101 at a stirring speed of 100rpm to prepare a dispersion. The polyetheretherketone powder is shown in fig. 1 (a).
S103: the dispersion obtained in S102 was heat-treated at 80 ℃ for 5 hours to prepare a modified preform.
S104: adding absolute ethyl alcohol into the modified preform obtained in the step S103 for cleaning, and removing residual chlorosulfonic acid in the modified preform; and then adding water for cleaning to remove residual DMF in the modified preform.
S105: after removing the residual chlorosulfonic acid and DMF in S104, a sodium hydroxide solution was added and soaked for 10 hours to obtain a mixed system in which the modified preform is mixed with an alkali solution, which is shown in fig. 1 (b). And after soaking, cleaning, filtering and drying to obtain modified polyether-ether-ketone powder. The modified polyetheretherketone powder is shown in fig. 1 (c).
S106: the modified polyetheretherketone powder obtained in S105 was dried at 120 ℃ for 3 h.
S107: and (3) carrying out hot press molding treatment on the modified polyether-ether-ketone powder after drying the S106 in a discharge plasma sintering furnace. The hot press molding process employs a spark plasma sintering process as shown in fig. 1 (d). Wherein the pressure of the hot-press molding treatment is 8 MPa. The temperature program is shown in FIG. 2, namely, the temperature is increased from 25 ℃ to 325 ℃ at the speed of 6 ℃/min, the temperature is kept at 325 ℃ for 60min, then the temperature is decreased to 250 ℃ at the speed of 3.75 ℃/min, and the temperature is kept at 250 ℃ for 30 min. And (4) obtaining the polyether-ether-ketone product after hot press molding. A polyetheretherketone article is shown in figure 3. The product still has good thermal stability (mass loss rate is lower than 0.5%) at 400 ℃, and the friction coefficient is as low as about 0.01, and the wear rate is 10 -7 mm 3 /(N·m)～10 -8 mm 3 Of the order of/(/ N · m). Specifically, the sliding speed was 12.5mm/s, the friction coefficient was about 0.020, and the wear rate was about 1.6 × 10 -7 mm 3 V (N · m); at a sliding speed of 25mm/s, the coefficient of friction was 0.015 and the wear rate was 8.2 x 10 -8 mm 3 V (N · m); at a sliding speed of 50mm/s, the coefficient of friction was about 0.012 and the wear rate was 4.7 x 10 -8 mm 3 /(N·m)。
Example 2
The schematic diagram of the preparation method of the polyetheretherketone article in this example is shown in figure 1. In FIG. 1, (a) shows a polyether ether ketone powder, (b) shows a mixed system in which a modified preform is mixed with an alkali solution, (c) shows a modified polyether ether ketone powder after modification, and (d) shows spark plasma sintering.
S101: 100mL of Dimethylformamide (DMF) was added to a reaction vessel, and then 15mL of chlorosulfonic acid was added dropwise to the DMF at a dropping rate of 1mL/min with stirring at 100rpm to prepare a dispersant.
S102: 10g of polyether ether ketone powder was added to the dispersant obtained in S101 at a stirring speed of 100rpm to prepare a dispersion. The polyetheretherketone powder is shown in fig. 1 (a).
S103: the dispersion obtained in S102 was heat-treated at 80 ℃ for 5 hours to prepare a modified preform.
S104: adding absolute ethyl alcohol into the modified preform obtained in the step S103 for cleaning, and removing residual chlorosulfonic acid in the modified preform; and then adding water for cleaning to remove residual DMF in the modified preform.
S105: after removing the residual chlorosulfonic acid and DMF in S104, a sodium hydroxide solution was added and soaked for 10 hours to obtain a mixed system in which the modified preform is mixed with an alkali solution, which is shown in fig. 1 (b). And after soaking, cleaning, filtering and drying to obtain modified polyether-ether-ketone powder.
S106: the modified polyetheretherketone powder obtained in S105 was dried at 120 ℃ for 3 h.
S107: and (3) carrying out hot press molding treatment on the modified polyether-ether-ketone powder after drying the S106 in a discharge plasma sintering furnace. The hot press molding process employs a spark plasma sintering process as shown in fig. 1 (d). Wherein the pressure of the hot-press molding treatment is 8 MPa. The temperature program is shown in FIG. 2, namely, the temperature is increased from 25 ℃ to 325 ℃ at the speed of 6 ℃/min, the temperature is kept at 325 ℃ for 60min, then the temperature is decreased to 250 ℃ at the speed of 3.75 ℃/min, and the temperature is kept at 250 ℃ for 30 min. And (4) obtaining the polyether-ether-ketone product after hot press molding. The product still has good thermal stability (mass loss rate is lower than 0.5%) at 400 ℃, and the friction coefficient can be as low as about 0.02, and the wear rate is 10 -7 mm 3 /(N·m)～10 -8 mm 3 Of the order of/(/ N · m). Specifically, the sliding speed was 12.5mm/s, the friction coefficient was about 0.030, and the wear rate was about 9.1 × 10 -7 mm 3 V (N · m); at a sliding speed of 25mm/s, the coefficient of friction was 0.026 and the wear rate was 3.7 x 10 -7 mm 3 V (N · m); at a sliding speed of 50mm/s, the coefficient of friction was about 0.021 and the wear rate was 8.6 x 10 -8 mm 3 /(N·m)。
Example 3
The schematic diagram of the preparation method of the polyetheretherketone article in this example is shown in figure 1. In FIG. 1, (a) shows a polyether ether ketone powder, (b) shows a mixed system in which a modified preform is mixed with an alkali solution, (c) shows a modified polyether ether ketone powder after modification, and (d) shows spark plasma sintering.
S101: 100mL of Dimethylformamide (DMF) was added to a reaction vessel, and then 15mL of chlorosulfonic acid was added dropwise to the DMF at a dropping rate of 1mL/min with stirring at 100rpm to prepare a dispersant.
S102: 10g of polyether ether ketone powder was added to the dispersant obtained in S101 at a stirring speed of 100rpm to prepare a dispersion. The polyetheretherketone powder is shown in fig. 1 (a).
S103: the dispersion obtained in S102 was heat-treated at 100 ℃ for 5 hours to prepare a modified preform.
S104: adding absolute ethyl alcohol into the modified preform obtained in the step S103 for cleaning, and removing residual chlorosulfonic acid in the modified preform; and then adding water for cleaning to remove residual DMF in the modified preform.
S105: after removing the residual chlorosulfonic acid and DMF in S104, a sodium hydroxide solution was added and soaked for 10 hours to obtain a mixed system in which the modified preform is mixed with an alkali solution, which is shown in fig. 1 (b). And after soaking, cleaning, filtering and drying to obtain modified polyether-ether-ketone powder.
S106: the modified polyetheretherketone powder obtained in S105 was dried at 120 ℃ for 3 h.
S107: and (3) carrying out hot press molding treatment on the modified polyether-ether-ketone powder after drying the S106 in a discharge plasma sintering furnace. The hot press molding process employs a spark plasma sintering process as shown in fig. 1 (d). Wherein the pressure of the hot-press molding treatment is 8 MPa. The temperature program is shown in FIG. 2, namely, the temperature is increased from 25 ℃ to 325 ℃ at the speed of 6 ℃/min, the temperature is kept at 325 ℃ for 60min, then the temperature is decreased to 250 ℃ at the speed of 3.75 ℃/min, and the temperature is kept at 250 ℃ for 30 min. And (4) obtaining the polyether-ether-ketone product after hot press molding. The product still has good thermal stability (mass loss rate is lower than 0.5%) at 400 ℃, and the friction coefficient can be as low as about 0.01, and the wear rate is 10 -7 mm 3 /(N·m)～10 -8 mm 3 Of the order of/(N m). In particular, a slideAt a dynamic speed of 12.5mm/s, the coefficient of friction was about 0.026 and the wear rate was about 2.2 x 10 -7 mm 3 V (N · m); at a sliding speed of 25mm/s, the coefficient of friction was 0.017 and the wear rate was 7.3 × 10 -8 mm 3 V (N · m); at a sliding speed of 50mm/s, the coefficient of friction was about 0.015 and the wear rate was 5.4 x 10 -8 mm 3 /(N·m)。
Example 4
The schematic diagram of the preparation method of the polyetheretherketone article in this example is shown in figure 1. In FIG. 1, (a) shows a polyether ether ketone powder, (b) shows a mixed system in which a modified preform is mixed with an alkali solution, (c) shows a modified polyether ether ketone powder after modification, and (d) shows spark plasma sintering.
S101: 100mL of dimethyl sulfoxide (DMSO) was added to the reaction vessel, and then 5mL of chlorosulfonic acid was added dropwise to the DMSO at a dropping rate of 1mL/min with stirring at 100rpm, to prepare a dispersant.
S102: 10g of polyether ether ketone powder was added to the dispersant obtained in S101 at a stirring speed of 100rpm to prepare a dispersion. The polyetheretherketone powder is shown in fig. 1 (a).
S103: the dispersion obtained in S102 was heat-treated at 80 ℃ for 5 hours to prepare a modified preform.
S104: adding absolute ethyl alcohol into the modified preform obtained in the step S103 for cleaning, and removing residual chlorosulfonic acid in the modified preform; and then adding water for cleaning to remove residual DMF in the modified preform.
S105: after removing the residual chlorosulfonic acid and DMF in S104, a sodium hydroxide solution was added and soaked for 10 hours to obtain a mixed system in which the modified preform is mixed with an alkali solution, which is shown in fig. 1 (b). And after soaking, cleaning, filtering and drying to obtain modified polyether-ether-ketone powder.
S106: the modified polyetheretherketone powder obtained in S105 was dried at 120 ℃ for 3 h.
S107: and (3) carrying out hot press molding treatment on the modified polyether-ether-ketone powder after drying the S106 in a discharge plasma sintering furnace. The hot press forming process employs a spark plasma sintering process as shown in fig. 1 (d). Wherein the press of the hot press forming processThe force was 8 MPa. The temperature program is shown in FIG. 2, namely, the temperature is increased from 25 ℃ to 325 ℃ at the speed of 6 ℃/min, the temperature is kept at 325 ℃ for 60min, then the temperature is decreased to 250 ℃ at the speed of 3.75 ℃/min, and the temperature is kept at 250 ℃ for 30 min. And (4) obtaining the polyether-ether-ketone product after hot press molding. The product still has good thermal stability (mass loss rate is lower than 0.5%) at 400 ℃, and the friction coefficient can be as low as about 0.04, and the wear rate is 10 -7 mm 3 Of the order of/(/ N · m). Specifically, the sliding speed was 12.5mm/s, the friction coefficient was about 0.049, and the wear rate was about 9.7 × 10 -7 mm 3 V (N · m); at a sliding speed of 25mm/s, the coefficient of friction was 0.043 and the wear rate was 7.2 x 10 -7 mm 3 V (N · m); at a sliding speed of 50mm/s, the coefficient of friction was about 0.042 and the wear rate was 5.6 x 10 -7 mm 3 /(N·m)。
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the patent of the present invention should be subject to the appended claims, and the description and the drawings can be used for explaining the contents of the claims.
Claims (10)
1. A modification method of polyether-ether-ketone powder is characterized by comprising the following steps:
mixing a sulfonating agent and a polar solvent to prepare a dispersing agent, wherein the sulfonating agent accounts for 2-15% of the polar solvent by volume;
mixing polyether-ether-ketone powder with the dispersing agent to prepare a dispersion liquid, wherein the polyether-ether-ketone powder accounts for 5-30% of the dispersing agent by mass;
heating the dispersion liquid at the temperature of 70-110 ℃ to prepare a modified pre-finished product;
mixing the modified preform with an alkali solution.
2. The method for modifying polyetheretherketone powder of claim 1, wherein mixing the sulfonating agent with a polar solvent comprises the steps of:
and dropwise adding the sulfonating agent into the polar solvent at a dropwise adding speed of 0.5-3 mL/min under the stirring condition.
3. The method for modifying polyetheretherketone powder according to claim 1, wherein mixing the modified preform with a lye comprises the steps of:
and soaking the modified preform in the alkali liquor.
4. The method for modifying polyetheretherketone powder according to any one of claims 1 to 3, wherein the sulfonating agent comprises at least one of chlorosulfonic acid, concentrated sulfuric acid, and oleum; and/or the presence of a gas in the gas,
the polar solvent comprises at least one of acetone, pyridine, chloroform, dimethylformamide and dimethyl sulfoxide; and/or the presence of a gas in the gas,
the alkali liquor comprises at least one of a sodium hydroxide solution, a potassium hydroxide solution and a calcium hydroxide solution.
5. A modified polyetheretherketone powder, which is obtained by modifying a polyetheretherketone powder by the method according to any one of claims 1 to 4.
6. A preparation method of a polyether-ether-ketone product is characterized by comprising the following steps:
the modified polyetheretherketone powder of claim 5 subjected to a hot press forming process.
7. The method of claim 6, wherein the hot press forming process is performed at a pressure of 5MPa to 15 MPa.
8. The method of any one of claims 6 to 7, wherein the thermoforming temperature profile comprises:
the temperature is preserved for 30min to 120min at 320 ℃ to 340 ℃ and then preserved for 20min to 60min at 230 ℃ to 270 ℃.
9. An article of polyetheretherketone comprising the modified polyetheretherketone powder of claim 5.
10. The article of claim 9, comprising a friction pair, a water lubricated bearing, or an artificial joint.
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| CN115737933A (en) * | 2022-11-29 | 2023-03-07 | 华南理工大学 | Radial gradient hydroxyapatite/polyether-ether-ketone composite material bracket with large-surface-through-hole structure and preparation method and application thereof |
| CN117327238A (en) * | 2023-11-30 | 2024-01-02 | 季华实验室 | Porous sulfonated polyether-ether-ketone water lubrication bearing material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004123971A (en) * | 2002-10-04 | 2004-04-22 | Kanegafuchi Chem Ind Co Ltd | Method for producing sulfonated polymer film |
| CN109988278A (en) * | 2019-04-03 | 2019-07-09 | 山东星火科学技术研究院 | A method of improving polyether-ether-ketone sulfonation degree |
| CN111184913A (en) * | 2020-01-13 | 2020-05-22 | 吉林大学 | Artificial bone composite material based on polyether-ether-ketone and preparation method thereof |
-
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- 2022-06-07 CN CN202210634284.4A patent/CN114957649B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004123971A (en) * | 2002-10-04 | 2004-04-22 | Kanegafuchi Chem Ind Co Ltd | Method for producing sulfonated polymer film |
| CN109988278A (en) * | 2019-04-03 | 2019-07-09 | 山东星火科学技术研究院 | A method of improving polyether-ether-ketone sulfonation degree |
| CN111184913A (en) * | 2020-01-13 | 2020-05-22 | 吉林大学 | Artificial bone composite material based on polyether-ether-ketone and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115737933A (en) * | 2022-11-29 | 2023-03-07 | 华南理工大学 | Radial gradient hydroxyapatite/polyether-ether-ketone composite material bracket with large-surface-through-hole structure and preparation method and application thereof |
| CN117327238A (en) * | 2023-11-30 | 2024-01-02 | 季华实验室 | Porous sulfonated polyether-ether-ketone water lubrication bearing material and preparation method thereof |
| CN117327238B (en) * | 2023-11-30 | 2024-03-08 | 季华实验室 | Porous sulfonated polyether-ether-ketone water lubrication bearing material and preparation method thereof |
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