CN115558236A - Antistatic polyether-ether-ketone composite material and preparation method thereof - Google Patents
Antistatic polyether-ether-ketone composite material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The application relates to the technical field of polymer conductive materials, and provides a preparation method of an antistatic polyether-ether-ketone composite material, which comprises the following steps: mixing polyether-ether-ketone with the acidified carbon nanotubes to obtain a first mixture, and performing extrusion granulation on the first mixture to obtain carbon nanotube master batches; and mixing the carbon nanotube master batch and the polyether-ether-ketone to obtain a second mixture, performing extrusion molding on the second mixture, and performing ultrasonic treatment on the second mixture while performing extrusion molding to obtain the antistatic polyether-ether-ketone composite material. According to the preparation method of the antistatic polyether-ether-ketone composite material, the acidified carbon nano tubes are used as the conductive additive, and meanwhile, the molding process of firstly manufacturing the master batches and then mixing, melting and extruding and ultrasonic treatment are combined, so that the dispersibility of the carbon nano tubes in the polyether-ether-ketone base material is improved from multiple aspects, the surface resistivity of the obtained antistatic polyether-ether-ketone composite material is reduced, and the antistatic performance is improved.
Description
Technical Field
The application belongs to the technical field of high-molecular conductive materials, and particularly relates to an antistatic polyether-ether-ketone composite material and a preparation method thereof.
Background
Polyether-ether-ketone (PEEK) is a high polymer consisting of repeating units containing one ketone bond and two ether bonds in a main chain structure, belongs to a special high polymer material, has the characteristics of high heat resistance level, radiation resistance, high impact strength, good friction resistance and fatigue resistance, excellent flame retardance, excellent electrical property and the like, and has been widely applied to the fields of aerospace, automobiles, electronics and electrics, chemical industry, machinery, medical treatment and the like.
In recent years, with the growing market scale of semiconductor wafers and the increasing level of technical research and development, the demand for wafer carriers has been gradually increased, and traditional materials such as Polypropylene (PP) and soluble Polytetrafluoroethylene (PFA) have failed to meet the demand. The PEEK can be used as a wafer carrier due to the combination properties of excellent wear resistance, heat resistance and the like, but the antistatic grade of the common PEEK cannot meet the use requirement of the wafer carrier.
Disclosure of Invention
The application aims to provide an antistatic polyetheretherketone composite material and a preparation method thereof, and aims to solve the problem of how to improve the antistatic property of the polyetheretherketone material.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a method for preparing an antistatic polyetheretherketone composite, comprising:
mixing polyether-ether-ketone with acidified carbon nanotubes to obtain a first mixture, and performing extrusion granulation on the first mixture to obtain carbon nanotube master batches;
and mixing the carbon nanotube master batch and the polyether-ether-ketone to obtain a second mixture, performing extrusion molding on the second mixture, and performing ultrasonic treatment on the second mixture while performing the extrusion molding to obtain the antistatic polyether-ether-ketone composite material.
Optionally, the second mixture comprises, by mass, 90 to 105 parts of polyetheretherketone and 0.5 to 7 parts of acidified carbon nanotubes.
Optionally, the second mixture further comprises 1-5 parts of a lubricant, wherein the lubricant comprises polytetrafluoroethylene; and/or the second mixed material also comprises 5-30 parts of inorganic filler.
Optionally, when the second compound material comprises an inorganic filler: the inorganic filler comprises at least one of calcium carbonate, talcum powder, mica powder, sepiolite powder and attapulgite powder; and/or the granularity of the inorganic filler is 5000 meshes-10000 meshes; and/or the preparation of the second mixture comprises the steps of mixing polyether-ether-ketone and the inorganic filler to obtain a premix, and then mixing the premix and the carbon nanotube master batch to obtain the second mixture.
Optionally, the polyether-ether-ketone has a weight average molecular weight of 500000 to 1000000, and the melt viscosity of the polyether-ether-ketone is 100Pa.s to 150Pa.s.
Optionally, the mass ratio of the polyetheretherketone to the acidified carbon nanotubes in the first mixture is 1 (0.5-1);
optionally, the preparation method of the antistatic polyetheretherketone composite further comprises preparing the acidified carbon nanotubes: mixing concentrated nitric acid and concentrated sulfuric acid to obtain mixed acid; adding carbon nano tubes into the mixed acid and ultrasonically dispersing for a first time to obtain a carbon nano tube solution; diluting the carbon nano tube solution by using deionized water to obtain a diluted solution in which solid particles are uniformly dispersed in the solution; and separating the solid particles in the diluted solution to obtain the acidified carbon nano tube.
Optionally, the extrusion molding comprises: and melting the second mixture to obtain a melt, extruding the melt, and carrying out ultrasonic treatment on the melt while extruding.
Optionally, the ultrasonic power of the ultrasonic treatment is 400W-600W.
Optionally, the temperature of the extrusion is 340 ℃ to 410 ℃.
Optionally, in the extrusion molding process, the melt temperature of the melt is 390-400 ℃, and the melt pressure of the melt is 2.0-3.0 MPa.
Optionally, melting the second mixture by using a screw extruder to form a melt, and extruding the melt; along the direction from feeding to discharging, the extruder comprises a first section, a second section, a third section, a fourth section, a fifth section and an extruder head which are sequentially connected, and ultrasonic treatment is carried out on the fourth section, the fifth section and the extruder head; the temperatures of the first section, the second section, the third section, the fourth section, the fifth section and the extruder head are 340 ℃, 370-380 ℃, 390-400 ℃, 400-410 ℃ and 410 ℃ respectively.
In a second aspect, the application provides an antistatic polyetheretherketone composite material, which is prepared by extrusion molding and ultrasonic processing of a mixture comprising acidified carbon nanotubes and polyetheretherketone.
Optionally, the antistatic polyetheretherketone composite material comprises, by mass, 90 to 105 parts of polyetheretherketone and 0.5 to 7 parts of acidified carbon nanotubes.
Optionally, the antistatic polyetheretherketone composite further comprises 1-5 parts of a lubricant, wherein the lubricant comprises polytetrafluoroethylene.
Optionally, the antistatic polyetheretherketone composite material further comprises 5-30 parts of an inorganic filler, wherein the inorganic filler comprises at least one of calcium carbonate, talcum powder, mica powder, sepiolite powder and attapulgite powder.
Optionally, the polyether ether ketone has a weight average molecular weight of 500000 to 1000000 and a melt viscosity of 100Pa.s to 150Pa.s.
According to the preparation method of the antistatic polyether-ether-ketone composite material, the acidified carbon nano tubes are used as the conductive additive, and meanwhile, the molding process of firstly manufacturing the master batches and then mixing, melting and extruding and ultrasonic treatment are combined, so that the dispersibility of the carbon nano tubes in the polyether-ether-ketone base material is improved from multiple aspects, the surface resistivity of the obtained antistatic polyether-ether-ketone composite material is reduced, and the antistatic performance is improved.
According to the antistatic polyether-ether-ketone composite material provided by the second aspect of the application, the acidified carbon nanotubes are used as a conductive agent and can be uniformly dispersed in the polyether-ether-ketone base material, so that the conductivity of the antistatic polyether-ether-ketone composite material is improved, the surface resistivity is reduced, and the antistatic performance is improved.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a flowchart of a preparation method of an antistatic polyetheretherketone composite material provided in an embodiment of the present application.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a alone, A and B together, and B alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the specification of the embodiments of the present application may not only refer to the specific content of each component, but also refer to the proportional relationship of the weight of each component, and therefore, the proportional enlargement or reduction of the content of the related components according to the specification of the embodiments of the present application is within the scope disclosed in the specification of the embodiments of the present application. Specifically, the mass described in the specification of the embodiments of the present application may be a mass unit known in the chemical industry field such as μ g, mg, g, kg, etc.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another and are not to be construed as indicating or implying relative importance or to implicitly indicate the number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
Aiming at the problem that the antistatic performance of a common polyether-ether-ketone material is not high, the first aspect of the embodiment of the application provides a preparation method of an antistatic polyether-ether-ketone composite material, which comprises the following steps:
s10: mixing polyether-ether-ketone with the acidified carbon nanotubes to obtain a first mixture, and performing extrusion granulation on the first mixture to obtain carbon nanotube master batches;
s20: and mixing the carbon nanotube master batch and the polyether-ether-ketone to obtain a second mixture, performing extrusion molding on the second mixture, and performing ultrasonic treatment on the second mixture during the extrusion molding to obtain the antistatic polyether-ether-ketone composite material.
Polyetheretherketone is a plastic with high volume resistivity and surface resistivity that can maintain good insulation properties over a wide temperature range. In order to improve the antistatic properties of plastics, it is common practice to add conductive additives to the plastic substrate. Common conductive additives include metal materials and Carbon-based conductive agents, and Carbon Nanotubes (CNTs) in the Carbon-based conductive agents have received great attention because of their small addition amount and good conductivity. However, carbon nanotubes have high specific surface area, specific surface energy and aspect ratio, and are easy to agglomerate and entangle with each other, which is disadvantageous to uniform dispersion of carbon nanotubes in polymers, so that they cannot exert their excellent properties.
According to the preparation method of the antistatic polyetheretherketone composite material provided by the first aspect of the application embodiment, the acidified carbon nanotubes are used as a conductive additive, and are obtained after acidification, so that the acidification not only can cause less damage to the structure of the carbon nanotubes and well keep the original appearance of the carbon nanotubes, but also can modify the surface of the carbon nanotubes, improve the interface compatibility of the carbon nanotubes and polyetheretherketone, and improve the dispersibility of the carbon nanotubes in a polyetheretherketone base material.
In addition, according to the preparation method of the antistatic polyetheretherketone composite material provided by the first aspect of the application embodiment, the acidified carbon nanotubes and polyetheretherketone are firstly prepared into the master batch, and then the master batch and the polyetheretherketone are mixed, melted and extruded, so that the miscibility of materials during processing is improved, ultrasonic treatment is added during extrusion molding, the carbon nanotubes are effectively prevented from agglomerating, and the dispersibility of the carbon nanotubes in a polyetheretherketone matrix is maintained.
In summary, in the preparation method of the antistatic peek composite material provided in the first aspect of the application embodiment, the acidified carbon nanotubes are used as the conductive additive, and the molding process of firstly making the master batch and then mixing, melting and extruding and the ultrasonic treatment are combined, so that the dispersibility of the carbon nanotubes in the peek base material is improved from multiple aspects, the surface resistivity of the obtained antistatic peek composite material is reduced, and the antistatic performance is improved.
In some embodiments, in step S10, the method for preparing the antistatic peek composite further includes preparing acidified carbon nanotubes. The preparation of the acidified carbon nanotube comprises: mixing concentrated nitric acid and concentrated sulfuric acid to obtain mixed acid, and optionally mixing the concentrated nitric acid and the concentrated sulfuric acid according to a volume ratio of 1; adding carbon nanotubes into mixed acid and ultrasonically dispersing for a first time to obtain a carbon nanotube solution, wherein optionally, the first time is 1 h-5 h, for example, 1h, 2h, 3h, 4h or 5h; diluting the carbon nanotube solution by deionized water to obtain a diluted solution with uniformly dispersed solid particles in the solution, wherein the diluted solution is usually not layered any more, and the layering phenomenon does not occur even standing overnight, because the carbon nanotube is successfully acidified and then uniformly dispersed; next, separating solid particles in the diluted solution, namely extracting acidified carbon nanotubes in the diluted solution, specifically comprising: pouring the diluted solution into a centrifuge tube, placing the centrifuge tube into a centrifuge, setting the rotation speed of the centrifuge to 10000rpm, carrying out centrifugal treatment for 20min, pouring out supernatant in the centrifuge tube, placing the rest precipitate into a beaker, adding deionized water into the beaker, testing the acidity of the solution by using a pH test paper, centrifuging again, carrying out circulation operation, repeating for about 3 times until the filtrate detected by the pH test paper is neutral, then carrying out suction filtration on the precipitate by using a funnel, placing a filter cake into a vacuum drying box for drying, setting the drying time to 24h, setting the temperature to 60 ℃, and grinding the filter cake for multiple times by using a mortar to obtain an acidified carbon nanotube, namely CNTs-COOH.
In some embodiments, in step S10, the mass ratio of the polyetheretherketone to the acidified carbon nanotubes in the first mixture is 1 (0.5-1), i.e. a portion of the polyetheretherketone is mixed with the acidified carbon nanotubes in a mass ratio of 1 (0.5-1). Optionally, the mass ratio of the polyetheretherketone to the acidified carbon nanotubes in the first mixture is 1.
In some embodiments, in steps S10 and S20, the polyetheretherketone has a weight average molecular weight of 500000 to 1000000, which may be, for example, 500000, 600000, 700000, 800000, 900000 or 1000000. The melt viscosity of the polyether ether ketone is 100Pa.s to 150Pa.s, and may be, for example, 100Pa.s, 110Pa.s, 120Pa.s, 130Pa.s, 140Pa.s or 150Pa.s.
In some embodiments, in step S20, the second mixture includes 90 to 105 parts by mass of polyetheretherketone and 0.5 to 7 parts by mass of acidified carbon nanotubes. Here, the amount of polyether ether ketone in the second mixture includes the amount of the master batch prepared in S10 and the amount added later in S20. In the prior art, in order to ensure the antistatic performance of plastics, the addition amount of carbon nanotubes in the plastics needs to be at least 4wt% -8 wt%, and in the embodiment of the application, because acidified carbon nanotubes are adopted, the carbon nanotubes have good dispersibility in a polyetheretherketone base material, and therefore, even when the addition amount of the acidified carbon nanotubes is small, the antistatic polyetheretherketone composite material still has good antistatic performance. Alternatively, the mass parts of polyetheretherketone in the second blend may be 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, or 105 parts. Alternatively, the mass part of the acidified carbon nanotubes in the second mixture may be 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts or 7 parts.
In some embodiments, in step S20, the second mix further comprises an inorganic filler. The addition of the inorganic filler can reduce the processing difficulty and further improve the dispersion uniformity of the material. Optionally, a high mesh inorganic filler is employed. It is understood that the higher the mesh number, the smaller the particle size of the inorganic filler, and the better the mechanical properties of the plastic when uniformly dispersed. Alternatively, the inorganic filler has a particle size of 5000 mesh to 10000 mesh, and may be, for example, 5000 mesh, 6000 mesh, 7000 mesh, 8000 mesh, 9000 mesh and/or 10000 mesh. Optionally, the inorganic filler comprises one or more of calcium carbonate, talc powder, mica powder, sepiolite powder, and attapulgite powder.
In some embodiments, in step S20, when the second compound further comprises an inorganic filler, the preparing of the second compound comprises: mixing polyether-ether-ketone and an inorganic filler to obtain a first premix, and mixing the first premix with the carbon nanotube master batch to obtain a second premix, wherein the second premix is also the second premix. Optionally, mixing materials by using a mixer, stirring and mixing the polyether-ether-ketone and the inorganic filler in the mixer for 10-15 min, wherein the rotating speed of the mixer is 100-300 r/min; and adding the carbon nano tube master batch into a mixer at the rotating speed of 100-300 r/min, and continuously stirring and mixing for 10-15 min to obtain a second mixture.
In some embodiments, in step S20, when the second mixture further includes an inorganic filler, the second mixture includes 90 to 105 parts by mass of polyetheretherketone, 5 to 30 parts by mass of the inorganic filler, and 0.5 to 7 parts by mass of the acidified carbon nanotubes. Alternatively, the mass parts of polyetheretherketone in the second blend may be 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, or 105 parts. Alternatively, the mass part of the acidified carbon nanotubes in the second mixture may be 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts or 7 parts. Alternatively, the mass part of the inorganic filler in the second mix may be 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, or 30 parts. The preferred mass portion of the inorganic filler is 20 parts, 25 parts or 30 parts, and the processing performance can be obviously improved by increasing the content of the filler.
In some embodiments, in step S20, the second blend material further comprises a lubricant comprising polytetrafluoroethylene. The polytetrafluoroethylene with high molecular weight is in fibrous arrangement under high-temperature shearing except that the polytetrafluoroethylene has excellent lubricating resistance, can promote the conductive carbon nanotubes to be radially arranged, further forms a more stable and continuous conductive network, can greatly reduce the addition of a conductive agent, and achieves stable antistatic and conductive effects.
In some embodiments, in step S20, when the second mixture further includes a lubricant, the second mixture includes 90 to 105 parts by mass of polyetheretherketone, 1 to 5 parts by mass of the lubricant, and 0.5 to 7 parts by mass of the acidified carbon nanotubes. Alternatively, the mass parts of polyetheretherketone in the second blend can be 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, or 105 parts. Alternatively, the mass part of the acidified carbon nanotubes in the second mixture may be 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts or 7 parts. Alternatively, the mass parts of the lubricant in the second mix may be 1 part, 2 parts, 3 parts, 4 parts, 4.5 parts, or 5 parts.
In some embodiments, in step S20, when the second mixed material further includes an inorganic filler and a lubricant, the second mixed material includes, in parts by mass, 90 to 105 parts of polyetheretherketone, 5 to 30 parts of the inorganic filler, 0.5 to 7 parts of acidified carbon nanotubes, and 1 to 5 parts of the lubricant. Alternatively, the mass parts of polyetheretherketone in the second blend can be 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, or 105 parts. Alternatively, the mass part of the acidified carbon nanotubes in the second mixture may be 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts or 7 parts. Alternatively, the mass parts of the inorganic filler in the second mix may be 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, or 30 parts. Alternatively, the mass part of the lubricant in the second mix may be 1 part, 2 parts, 3 parts, 4 parts, or 5 parts.
In some embodiments, in step S20, when the second compound further comprises an inorganic filler and a lubricant, the preparing of the second compound comprises: mixing polyether-ether-ketone, inorganic filler and lubricant to obtain a first premix, and mixing the first premix with the carbon nanotube master batch to obtain a second premix, wherein the second premix is also the second premix. Optionally, mixing materials by using a mixer, namely stirring and mixing the polyether-ether-ketone, the inorganic filler and the lubricant in the mixer for 10-15 min at the rotating speed of 100-300 r/min; and adding the carbon nano tube master batch into a mixer at the rotating speed of 100 r/min-300 r/min, and continuously stirring and mixing for 10 min-15 min to obtain a second mixture.
In some embodiments, in step S20, the extrusion molding comprises: and melting the second mixture to obtain a melt, extruding the melt, and carrying out ultrasonic treatment on the melt while extruding. According to the embodiment of the application, ultrasonic treatment is creatively added in the process of extruding the melt, and under the action of ultrasonic, the carbon nanotubes can be effectively prevented from agglomerating under the action of extrusion pressure and shearing stress, so that the carbon nanotubes in the finally obtained material can still be uniformly dispersed in the polyether-ether-ketone matrix.
In some embodiments, the ultrasonic power of the ultrasonic treatment is 400W to 600W. The ultrasonic power is obtained by optimization of the inventor after long-term experimental research, the power is less than 400W, the effect of improving the dispersion uniformity of the carbon nano tube in the extrusion process is reduced, the power is more than 600W, and the extrusion pressure and the shear stress are influenced, so that the extrusion molding of the resin material is influenced. Optionally, the ultrasonic power is 400W, 450W, 500W, 550W or 600W.
In some embodiments, the temperature of extrusion is 340 ℃ to 410 ℃, and may be, for example, 340 ℃, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃, 400 ℃ or 410 ℃. Usually, the melting point of the polyether-ether-ketone is about 340 ℃, and the extrusion temperature is higher than the melting point temperature, which is beneficial to ensuring the extrusion effect.
In some embodiments, the melt temperature of the melt during extrusion molding is 390 ℃ to 400 ℃, and may be 390 ℃, 392 ℃, 394 ℃, 396 ℃, 398 ℃ or 400 ℃, for example; the melt pressure of the melt is 2.0MPa to 3.0MPa, and may be, for example, 2.0MPa, 2.2MPa, 2.4MPa, 2.6MPa, 2.8MPa or 3.0MPa.
In some embodiments, the second compound is extruded using a screw extruder. Optionally, the screw extruder is a twin-screw extruder, and the twin-screw extruder has the advantages of good feeding performance, mixing and plasticizing performance, exhaust performance, extrusion stability and the like. Of course, a single screw extruder may be used in other embodiments. Under the action of a screw extruder, the second mixture is heated and melted at high temperature to form a melt, and then the melt is extruded by the screw. Optionally, the extruder comprises a first section, a second section, a third section, a fourth section, a fifth section and an extruder head which are connected in sequence along the direction from the feeding to the discharging, and the ultrasonic treatment is performed at the fourth section, the fifth section and the extruder head. Optionally, the temperatures of the first section, the second section, the third section, the fourth section, the fifth section and the extruder head are 340 ℃, 370-380 ℃, 390-400 ℃, 400-410 ℃ and 410 ℃ respectively.
The second aspect of the embodiment of the application provides an antistatic polyetheretherketone composite material, which is prepared by extrusion molding and ultrasonic processing of a mixture comprising acidified carbon nanotubes and polyetheretherketone.
According to the antistatic polyetheretherketone composite material provided by the second aspect of the embodiment of the application, the acidified carbon nanotubes are used as a conductive additive, and can be uniformly dispersed in the polyetheretherketone base material, so that the conductivity of the antistatic polyetheretherketone composite material is improved, the surface resistivity is reduced, and the antistatic performance is improved.
In some embodiments, the antistatic polyetheretherketone composite comprises, in parts by mass, 90 to 105 parts polyetheretherketone and 0.5 to 7 parts acidified carbon nanotubes. Because the acidified carbon nanotubes are adopted in the embodiment of the application, the carbon nanotubes have good dispersibility in the polyetheretherketone base material, and even when the addition amount of the acidified carbon nanotubes is small, the antistatic polyetheretherketone composite material still has good antistatic property. Alternatively, the mass parts of polyetheretherketone in the antistatic polyetheretherketone composite may be 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104 or 105 parts. Alternatively, the mass parts of the acidified carbon nanotubes in the antistatic polyetheretherketone composite material may be 0.5, 1, 2, 3, 4, 5, 6 or 7 parts.
In some embodiments, the antistatic polyetheretherketone composite further comprises a lubricant, the lubricant comprising polytetrafluoroethylene. Besides excellent lubricity, the polytetrafluoroethylene with high molecular weight is more mainly in fibrous arrangement under high-temperature shearing, so that conductive carbon nanotubes can be promoted to be radially arranged, a more stable and continuous conductive network chain (network) is further formed, the addition amount of a conductive agent can be greatly reduced, and stable antistatic and conductive effects are achieved. Optionally, the mass part of the lubricant in the antistatic polyetheretherketone composite material is 1 to 5 parts, and may be, for example, 1 part, 2 parts, 3 parts, 4 parts, 4.5 parts, or 5 parts.
In some embodiments, the antistatic polyetheretherketone composite further comprises an inorganic filler, which can further improve the dispersion uniformity of the material. Optionally, a high mesh number of inorganic fillers is employed. It will be understood that the higher the mesh number, the smaller the particle size of the inorganic filler, and the better the mechanical properties of the plastic when dispersed uniformly. Alternatively, the inorganic filler has a particle size of 5000 mesh to 10000 mesh, and may be, for example, 5000 mesh, 6000 mesh, 7000 mesh, 8000 mesh, 9000 mesh and/or 10000 mesh. Optionally, the inorganic filler comprises one or more of calcium carbonate, talc, mica powder, sepiolite powder, and attapulgite powder. Optionally, the mass part of the inorganic filler in the antistatic polyetheretherketone composite material is 5 to 30 parts, for example, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts or 30 parts. The preferable mass portion of the inorganic filler is 20 parts, 25 parts or 30 parts, and the processing performance can be obviously improved by increasing the content of the filler.
In some embodiments, the polyetheretherketone has a weight average molecular weight of 500000 to 1000000, which may be, for example, 500000, 600000, 700000, 800000, 900000 or 1000000. The melt viscosity of the polyetheretherketone at room temperature as measured by a rotational viscometer is from 100Pa.s to 150Pa.s and may be, for example, 100Pa.s, 110Pa.s, 120Pa.s, 130Pa.s, 140Pa.s or 150Pa.s.
In some embodiments, the antistatic polyetheretherketone composite material is prepared by mixing polyetheretherketone with acidified carbon nanotubes, extruding and granulating to obtain carbon nanotube master batches, and then mixing the carbon nanotube master batches with polyetheretherketone, and extruding and molding. The antistatic polyether-ether-ketone composite material is prepared by preparing the acidified carbon nanotubes and polyether-ether-ketone into master batches, mixing the master batches with the polyether-ether-ketone, melting and extruding, so that the miscibility of materials during processing is improved.
In some embodiments, extrusion molding comprises melting the mixture to obtain a melt, extruding the melt, and sonicating the melt while extruding. According to the embodiment of the application, ultrasonic treatment is creatively added in the process of extruding the melt, and under the action of ultrasonic, the carbon nano tubes can be effectively prevented from agglomerating under the action of extrusion pressure and shearing stress, so that the carbon nano tubes in the finally obtained antistatic polyether-ether-ketone composite material still keep uniform dispersion in a polyether-ether-ketone matrix.
The following description will be given with reference to specific examples.
Example 1
S1, preparing master batch
And (3) mixing the dried PEEK with the prepared acidified carbon nano tube according to the mass ratio of 1:1, then melt extrusion granulation is carried out to prepare the carbon nano tube master batch.
S2, mixing
A first premix: pouring 87Kg of dried PEEK coarse powder into a mixer, weighing 20Kg of inorganic filler and 1Kg of polytetrafluoroethylene serving as a lubricant according to a proportion, pouring into the mixer, treating for 15min at the rotating speed of the mixer of 100r/min, and stirring and mixing uniformly;
a second premix: then 6Kg of carbon nano tube master batch is added, the mixture is processed for 10min at the rotating speed of 300r/min, and the mixture is stirred and mixed evenly.
S3, extrusion molding
And (3) putting the second premix into a feed opening of a main feed of the double-screw extruder, and then melting and mixing the materials in the double-screw extruder. Along the direction of feeding to discharging, the extruder comprises a first section, a second section, a third section, a fourth section, a fifth section and an extruder head which are sequentially connected, the corresponding extrusion temperature is 340 ℃/375 ℃/375 ℃/390 ℃/400 ℃/410 ℃, the feeding speed is 20Hz, the melt temperature is 395 ℃, and the melt pressure is 3.0MPa. And (4) carrying out ultrasonic treatment on the melts of the fourth section, the fifth section and the extruder head, wherein the ultrasonic power is 400W. The twin-screw extruder uses medium-strength screws. And drawing out the melt obtained by melting and mixing at a constant moving speed through a shaping neck mold, cooling by a water tank, and air-drying and granulating to obtain the antistatic PEEK particles, wherein the particle diameter is 2-3 mm.
Example 2
S1, preparing master batch
And (3) mixing the dried PEEK with the prepared acidified carbon nano tube according to the mass ratio of 1:1, then melt extrusion granulation is carried out to prepare the carbon nano tube master batch.
S2, mixing
A first premix: pouring 91Kg of dried PEEK coarse powder into a mixer, weighing 25Kg of inorganic filler according to a proportion, pouring the inorganic filler into the mixer, treating for 10min at the rotating speed of the mixer of 300r/min, and stirring and mixing uniformly;
a second premix: adding 8Kg of carbon nanotube master batch, processing for 15min at the rotating speed of 100r/min of a mixer, and stirring and mixing uniformly.
S3, extrusion molding
And (3) putting the second premix into a feed opening of a main feed of the double-screw extruder, and then melting and mixing the materials in the double-screw extruder. Along the direction from feeding to discharging, the extruder comprises a first section, a second section, a third section, a fourth section, a fifth section and an extruder head which are sequentially connected, the corresponding extrusion temperature is 340 ℃/380 ℃/380 ℃/400 ℃/400 ℃/410 ℃, the feeding speed is 15Hz, the melt temperature is 390 ℃, and the melt pressure is 2.50MPa. And (4) carrying out ultrasonic treatment on the melts of the fourth section, the fifth section and the extruder head, wherein the ultrasonic power is 400W. The twin-screw extruder uses medium-strength screws. And drawing out the melt obtained by melting and mixing at a constant moving speed through a shaping neck mold, cooling by a water tank, and air-drying and granulating to obtain the antistatic PEEK particles, wherein the particle diameter is 2-3 mm.
Example 3
S1, preparing master batch
Mixing the dried PEEK with prepared acidified carbon nanotubes in a mass ratio of 1:1, and then melting, extruding and granulating to prepare the carbon nano tube master batch.
S2, mixing
A first premix: pouring 98Kg of dried PEEK coarse powder into a mixer, weighing 30Kg of inorganic filler according to the proportion, pouring the inorganic filler into the mixer, treating for 15min at the rotating speed of the mixer of 200r/min, and stirring and mixing uniformly;
a second premix: then 8Kg of carbon nanotube master batch is added, the mixture is processed for 10min at the rotating speed of 200r/min, and the mixture is stirred and mixed evenly.
S3, extrusion molding
And (3) putting the second premix into a feed opening of a main feed of the double-screw extruder, and then melting and mixing the materials in the double-screw extruder. Along the direction of feeding to discharging, the extruder comprises a first section, a second section, a third section, a fourth section, a fifth section and an extruder head which are sequentially connected, the corresponding extrusion temperature is 340 ℃/380 ℃/380 ℃/390 ℃/400 ℃/410 ℃, the feeding speed is 18Hz, the melt temperature is 390 ℃, and the melt pressure is 2.50MPa. And (4) carrying out ultrasonic treatment on the melts of the fourth section, the fifth section and the extruder head, wherein the ultrasonic power is 400W. And drawing out the melt obtained by melting and mixing at a constant moving speed through a shaping neck mold, cooling by a water tank, and air-drying and granulating to obtain the antistatic PEEK particles, wherein the particle diameter is 2-3 mm.
Comparative example 1
S1, preparing master batch
And (3) mixing the dried PEEK with the prepared carbon nano tube according to the mass ratio of 1:1, and then melting, extruding and granulating to prepare the carbon nano tube master batch.
S2, mixing
A first premix: pouring 87Kg of dried PEEK coarse powder into a mixer, weighing 20Kg of inorganic filler and 1Kg of polytetrafluoroethylene serving as a lubricant according to a proportion, pouring into the mixer, treating for 15min at the rotating speed of the mixer of 100r/min, and stirring and mixing uniformly;
a second premix: then 6Kg of carbon nanotube master batch is added, the mixture is processed for 10min at the rotating speed of 300r/min, and the mixture is stirred and mixed evenly.
S3, extrusion molding
And (3) putting the second premix into a feed opening of a main feed of the double-screw extruder, and then melting and mixing the materials in the double-screw extruder. Along the direction of feeding to discharging, the extruder comprises a first section, a second section, a third section, a fourth section, a fifth section and an extruder head which are sequentially connected, the corresponding extrusion temperature is 340 ℃/375 ℃/375 ℃/390 ℃/400 ℃/410 ℃, the feeding speed is 20Hz, the melt temperature is 395 ℃, and the melt pressure is 3.0MPa. And (4) carrying out ultrasonic treatment on the melts of the fourth section, the fifth section and the extruder head, wherein the ultrasonic power is 400W. The twin-screw extruder uses medium-strength screws. And drawing out the melt obtained by melting and mixing at a constant moving speed through a shaping neck mold, cooling by a water tank, and air-drying and granulating to obtain the antistatic PEEK particles, wherein the particle diameter is 2-3 mm.
Comparative example 2
S1, preparing master batch
And (3) mixing the dried PEEK with the prepared acidified carbon nano tube according to the mass ratio of 1:1, then melt extrusion granulation is carried out to prepare the carbon nano tube master batch.
S2, mixing
A first premix: pouring 87Kg of dried PEEK coarse powder into a mixer, weighing 20Kg of inorganic filler and 1Kg of polytetrafluoroethylene serving as a lubricant according to a proportion, pouring into the mixer, treating for 15min at the rotating speed of the mixer of 100r/min, and stirring and mixing uniformly;
a second premix: then 6Kg of carbon nanotube master batch is added, the mixture is processed for 10min at the rotating speed of 300r/min, and the mixture is stirred and mixed evenly.
S3, extrusion molding
And (3) putting the second premix into a feed opening of a main feed of the double-screw extruder, and then melting and mixing the materials in the double-screw extruder. Along the direction of feeding to discharging, the extruder comprises a first section, a second section, a third section, a fourth section, a fifth section and an extruder head which are sequentially connected, the corresponding extrusion temperature is 340 ℃/375 ℃/375 ℃/390 ℃/400 ℃/410 ℃, the feeding speed is 20Hz, the melt temperature is 395 ℃, and the melt pressure is 3.0MPa. The twin-screw extruder uses medium-strength screws. And drawing out the melt obtained by melting and mixing at a constant moving speed through a shaping neck mold, cooling by a water tank, and air-drying and granulating to obtain the antistatic PEEK particles, wherein the particle diameter is 2-3 mm.
To verify the progress of the examples of the present application, the following tests were performed on the samples of examples and comparative examples, respectively:
the antistatic PEEK particles prepared in examples 1-3 and comparative examples 1 and 2 were baked in an oven at 150-180 ℃ for 2-4 h, and the moisture in the antistatic PEEK particles was removed to control the moisture to within 0.02 wt%. And (3) carrying out injection molding on the baked antistatic PEEK particles in an injection molding machine, wherein the injection molding temperature is 410-420 ℃, the front mold temperature is 150-200 ℃, the rear mold temperature is 180-200 ℃, the speed is 50-90 g/s, and the pressure is 50-90 bar, and carrying out injection molding to obtain the wafer box.
The surface resistivity of the wafer case made of the antistatic PEEK particles of examples 1 to 3 was (1 × 10) 5 ～1*10 8 ) omega/Sq, high surface flatness (flatness)<0.004mm, degree of tilt<0.2 mm), high surface cleanliness (no dust precipitation, no decarburization, etc.) and no micropores (such as fine bumps, pits and fine pits). The wafer boxes of comparative examples 1 and 2 had rough surfaces and bumps.
In addition, the antistatic PEEK particles prepared in examples 1 to 3 and comparative examples 1 and 2 were injection molded into a standard part to be subjected to the performance test as shown in table 1.
TABLE 1
With reference to table 1, examples 1 to 3 and comparative example 1 are all antistatic peek composite materials prepared by using a molding process of first making master batches and then mixing, melting and extruding, and ultrasonic treatment, except that the antistatic peek composite materials are prepared by using common carbon nanotubes and peek in comparative example 1, and the antistatic peek composite materials are prepared by using acidified carbon nanotubes and peek in examples 1 to 3, wherein the amount of acidified carbon nanotubes in example 2 is the highest, and the amount of acidified carbon nanotubes in example 1 is the lowest. Compared with comparative example 1, the surface resistivity of examples 1 to 3 is lower than that of comparative example 1, wherein example 2 is the lowest, and then example 3 is the lowest, and example 3 is the highest in the three examples, and it can be seen that the surface resistivity of the antistatic polyetheretherketone composite decreases as the amount of acidified carbon nanotubes increases. In addition, as can be seen from table 1, the addition of the acidified carbon nanotubes can improve the tensile strength, bending strength and molding shrinkage of the antistatic peek composite material to some extent, but the izod impact strength is slightly reduced.
With reference to table 1, examples 1 to 3 and comparative example 2 all used an antistatic peek composite material obtained by extrusion molding of acidified carbon nanotubes and peek, except that example 1 to 3 were subjected to ultrasonic treatment simultaneously with extrusion molding, while comparative example 2 was not subjected to ultrasonic treatment during extrusion molding. Compared with the comparative example 2, the surface resistivity of the antistatic polyetheretherketone composite material is lower than that of the comparative example 2 in the examples 1 to 3, and it can be seen that the carbon nanotubes can be prevented from agglomerating under the action of extrusion pressure and shear stress in the extrusion molding process by simultaneously assisting ultrasonic treatment in the extrusion molding process, so that the carbon nanotubes in the finally obtained material can still be uniformly dispersed in the polyetheretherketone matrix, and the surface resistivity of the antistatic polyetheretherketone composite material is reduced.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The preparation method of the antistatic polyether-ether-ketone composite material is characterized by comprising the following steps:
mixing polyether-ether-ketone with acidified carbon nanotubes to obtain a first mixture, and performing extrusion granulation on the first mixture to obtain carbon nanotube master batches;
and mixing the carbon nanotube master batch and the polyether-ether-ketone to obtain a second mixture, performing extrusion molding on the second mixture, and performing ultrasonic treatment on the second mixture while performing the extrusion molding to obtain the antistatic polyether-ether-ketone composite material.
2. The method for preparing the antistatic PEEK composite material of claim 1, wherein the second mixture comprises 90-105 parts by mass of PEEK and 0.5-7 parts by mass of acidified carbon nanotubes.
3. The method of claim 2, wherein the second blend material further comprises 1 to 5 parts of a lubricant, the lubricant comprising polytetrafluoroethylene;
and/or the second mixed material also comprises 5-30 parts of inorganic filler.
4. The method of preparing an antistatic polyetheretherketone composite according to claim 3 wherein when the second compound comprises an inorganic filler: the inorganic filler comprises at least one of calcium carbonate, talcum powder, mica powder, sepiolite powder and attapulgite powder;
and/or the granularity of the inorganic filler is 5000 meshes-10000 meshes;
and/or the preparation of the second mixture comprises the steps of mixing polyether-ether-ketone and the inorganic filler to obtain a premix, and then mixing the premix and the carbon nanotube master batch to obtain the second mixture.
5. The method for preparing an antistatic polyetheretherketone composite material according to claim 1 wherein the polyetheretherketone has a weight average molecular weight of 500000 to 1000000 and a melt viscosity of 100pa.s to 150pa.s;
and/or the mass ratio of the polyether-ether-ketone to the acidified carbon nano tube in the first mixture is 1 (0.5-1);
and/or, the preparation method of the antistatic polyetheretherketone composite material further comprises the following steps: mixing concentrated nitric acid and concentrated sulfuric acid to obtain mixed acid; adding carbon nano tubes into the mixed acid and ultrasonically dispersing for a first time to obtain a carbon nano tube solution; diluting the carbon nano tube solution by using deionized water to obtain a diluted solution in which solid particles are uniformly dispersed in the solution; and separating the solid particles in the diluted solution to obtain the acidified carbon nano tube.
6. The method of preparing an antistatic polyetheretherketone composite according to any of claims 1 to 5, wherein the extrusion molding comprises: and melting the second mixture to obtain a melt, extruding the melt, and carrying out ultrasonic treatment on the melt while extruding.
7. The preparation method of the antistatic polyetheretherketone composite material of claim 6, wherein the ultrasonic power of the ultrasonic treatment is 400W to 600W;
and/or the temperature of the extrusion is 340-410 ℃;
and/or, in the extrusion molding process, the melt temperature of the melt is 390-400 ℃, and the melt pressure of the melt is 2.0-3.0 MPa;
and/or, melting the second mixture by adopting a screw extruder to form a melt, and extruding the melt; along the direction from feeding to discharging, the extruder comprises a first section, a second section, a third section, a fourth section, a fifth section and an extruder head which are sequentially connected, and ultrasonic treatment is carried out on the fourth section, the fifth section and the extruder head; the temperatures of the first section, the second section, the third section, the fourth section, the fifth section and the extruder head are 340 ℃, 370-380 ℃, 390-400 ℃, 400-410 ℃ and 410 ℃ respectively.
8. The antistatic polyetheretherketone composite material is characterized by being prepared by extrusion molding and ultrasonic treatment of a mixture comprising acidified carbon nanotubes and polyetheretherketone.
9. The antistatic polyetheretherketone composite of claim 8, wherein the antistatic polyetheretherketone composite comprises 90 to 105 parts by mass of polyetheretherketone and 0.5 to 7 parts of acidified carbon nanotubes.
10. The antistatic polyetheretherketone composite of claim 9 further comprising 1 to 5 parts of a lubricant comprising polytetrafluoroethylene;
and/or the antistatic polyetheretherketone composite material also comprises 5 to 30 parts of inorganic filler, wherein the inorganic filler comprises at least one of calcium carbonate, talcum powder, mica powder, sepiolite powder and attapulgite powder;
and/or the weight-average molecular weight of the polyether-ether-ketone is 500000-1000000, and the melt viscosity of the polyether-ether-ketone is 100Pa.s-150Pa.s.
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| WO2024066693A1 (en) * | 2022-09-28 | 2024-04-04 | 烯湾科城(广州)新材料有限公司 | Antistatic polyether-ether-ketone composite material and preparation method therefor |
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