CN115558236A - Antistatic polyether-ether-ketone composite material and preparation method thereof - Google Patents

Abstract

This application relates to the technical field of polymer conductive materials, and provides a method for preparing an antistatic polyetheretherketone composite material, including: mixing polyetheretherketone and acidified carbon nanotubes to obtain a first mixture, and preparing the first mixture Carry out extrusion granulation to obtain carbon nanotube masterbatch; mix carbon nanotube masterbatch and polyether ether ketone to obtain a second compound, carry out extrusion molding to the second compound, and mix the second The material was ultrasonically treated to obtain an antistatic polyether ether ketone composite material. The preparation method of the antistatic polyether ether ketone composite material provided by this application uses acidified carbon nanotubes as conductive additives, and at the same time combines the molding process of first making masterbatches and then mixing melt extrusion and ultrasonic treatment, and jointly improves carbon nanotubes from many aspects. The dispersibility of the tube in the polyether ether ketone base material reduces the surface resistivity of the obtained antistatic polyether ether ketone composite material and improves the antistatic performance.

Description

Antistatic polyether ether ketone composite material and preparation method thereof

technical field

The application belongs to the technical field of polymer conductive materials, and in particular relates to an antistatic polyether ether ketone composite material and a preparation method thereof.

Background technique

Poly(ether-ether-ketone), referred to as PEEK, is a high polymer composed of repeating units containing one ketone bond and two ether bonds in the main chain structure. It is a special polymer material with High heat resistance, radiation resistance, high impact strength, good friction and fatigue resistance, flame retardant, excellent electrical properties, etc., have been widely used in aerospace, automotive, electrical and electronic, chemical, mechanical and medical fields.

In recent years, as the market size of semiconductor wafers has grown and the level of technology research and development has continued to improve, the requirements for wafer carriers have also gradually increased. Polypropylene (PP) and soluble polytetrafluoroethylene (Polyfluoroalkoxy, PFA) And other traditional materials can no longer meet the demand. PEEK can be used as a wafer carrier due to its excellent comprehensive properties such as wear resistance and heat resistance, but the anti-static level of ordinary PEEK cannot meet the requirements for the use of wafer carriers.

Contents of the invention

The purpose of the present application is to provide an antistatic polyetheretherketone composite material and a preparation method thereof, aiming at solving the problem of how to improve the antistatic performance of the polyetheretherketone material.

In order to realize the above-mentioned application purpose, the technical scheme adopted in this application is as follows:

In a first aspect, the present application provides a method for preparing an antistatic polyether ether ketone composite material, comprising:

mixing polyetheretherketone and acidified carbon nanotubes to obtain a first mixture, and extruding and granulating the first mixture to obtain carbon nanotube masterbatch;

mixing the carbon nanotube masterbatch and polyether ether ketone to obtain a second compound, extruding the second compound, and performing ultrasonic treatment on the second compound while extruding , to obtain antistatic polyether ether ketone composites.

Optionally, in terms of parts by mass, the second mixture includes 90-105 parts of polyetheretherketone and 0.5-7 parts of acidified carbon nanotubes.

Optionally, the second mixture further includes 1-5 parts of lubricant, and the lubricant includes polytetrafluoroethylene; and/or, the second mixture further includes 5-30 parts of inorganic filler.

Optionally, when the second mixture includes an inorganic filler: the inorganic filler includes at least one of calcium carbonate, talc powder, mica powder, sepiolite powder and attapulgite powder; and/or, the inorganic The particle size of the filler is 5000 mesh to 10000 mesh; and/or, the preparation of the second mixture includes mixing polyether ether ketone and the inorganic filler to obtain a premix, and then mixing the premix with the carbon The nanotube masterbatches are mixed to obtain the second mixture.

Optionally, the weight average molecular weight of the polyetheretherketone is 500000-1000000, and the melt viscosity of the polyetheretherketone is 100Pa.s-150Pa.s.

Optionally, the mass ratio of the polyether ether ketone to the acidified carbon nanotubes in the first mixture is 1:(0.5-1);

Optionally, the preparation method of the antistatic polyether ether ketone composite material also includes preparing the acidified carbon nanotubes: mixing concentrated nitric acid and concentrated sulfuric acid to obtain a mixed acid; adding carbon nanotubes to the mixed acid and ultrasonically Dispersing for the first time to obtain a carbon nanotube solution; diluting the carbon nanotube solution with deionized water to obtain a diluted solution in which solid particles are uniformly dispersed in the solution; separating the solid particles in the diluted solution to obtain acidified carbon nanotubes.

Optionally, the extrusion molding includes: melting the second mixture to obtain a melt, extruding the melt, and performing ultrasonic treatment on the melt while extruding.

Optionally, the ultrasonic power of the ultrasonic treatment is 400W-600W.

Optionally, the extruding temperature is 340°C-410°C.

Optionally, during the extrusion molding process, the melt temperature of the melt is 390° C. to 400° C., and the melt pressure of the melt is 2.0 MPa to 3.0 MPa.

Optionally, a screw extruder is used to melt the second mixture to form a melt, and extrude the melt; along the direction from feeding to discharging, the extruder includes sequentially connected The first section, the second section, the third section, the fourth section, the fifth section and the extruder head, ultrasonic treatment is carried out at 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 respectively 340°C, 370°C~380°C, 370°C~ 380°C, 390°C~400°C, 400°C~410°C and 410°C.

In a second aspect, the present application provides an antistatic polyetheretherketone composite material, which is prepared from a mixture comprising acidified carbon nanotubes and polyetheretherketone through extrusion molding and ultrasonic treatment.

Optionally, in terms of parts by mass, the antistatic polyetheretherketone composite material includes 90-105 parts of polyetheretherketone and 0.5-7 parts of acidified carbon nanotubes.

Optionally, the antistatic polyether ether ketone composite material further includes 1-5 parts of lubricant, and the lubricant includes polytetrafluoroethylene.

Optionally, the antistatic polyetheretherketone composite material further includes 5-30 parts of inorganic fillers, and the inorganic fillers include at least one of calcium carbonate, talcum powder, mica powder, sepiolite powder and attapulgite powder.

Optionally, the weight average molecular weight of the polyetheretherketone is 500000-1000000, and the melt viscosity of the polyetheretherketone is 100Pa.s-150Pa.s.

The preparation method of the antistatic polyether ether ketone composite material provided by the first aspect of the present application uses acidified carbon nanotubes as conductive additives, and combines the molding process of first making masterbatches and then mixing melt extrusion and ultrasonic treatment, from many aspects. The dispersibility of the carbon nanotubes in the polyether ether ketone base material is improved, so that the surface resistivity of the obtained antistatic polyether ether ketone composite material is reduced, and the antistatic performance is improved.

The antistatic polyetheretherketone composite material provided by the second aspect of the present application uses acidified carbon nanotubes as the conductive agent, and the acidified carbon nanotubes can be uniformly dispersed in the polyetheretherketone substrate, so that the antistatic polyetheretherketone composite material The conductivity is improved, the surface resistivity is reduced, and the antistatic performance is improved.

Description of drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present application, the accompanying drawings that need to be used in the descriptions of the embodiments or the prior art will be briefly introduced below. Obviously, the accompanying drawings in the following description are only for the present application For some embodiments, those of ordinary skill in the art can also obtain other drawings based on these drawings without creative effort.

Fig. 1 is a flow chart of the preparation method of the antistatic polyether ether ketone composite material provided by the embodiment of the present application.

detailed description

In order to make the technical problems, technical solutions and beneficial effects to be solved in the present application clearer, the present application will be further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described here are only used to explain the present application, and are not intended to limit the present application.

In this application, the term "and/or" describes the association relationship of associated objects, indicating that there may be three relationships, for example, A and/or B may mean: A exists alone, A and B exist simultaneously, and B exists alone Condition. Among them, A and B can be singular or plural. The character "/" generally indicates that the contextual objects are an "or" relationship.

In this application, "at least one" means one or more, and "multiple" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or plural items. For example, "at least one item (unit) of a, b, or c", or "at least one item (unit) of a, b, and c" can mean: a, b, c, a-b( That is, a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple.

It should be understood that in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the order of execution, and some or all steps may be executed in parallel or sequentially, and the execution order of each process shall be based on its functions and The internal logic is determined and should not constitute any limitation to the implementation process of the embodiment of the present application.

Terms used in the embodiments of the present application are only for the purpose of describing specific embodiments, and are not intended to limit the present application. The singular forms "a", "said" and "the" used in the embodiments of this application and the appended claims are also intended to include plural forms unless the context clearly indicates otherwise.

The weight of the relevant components mentioned in the description of the embodiments of the present application can not only refer to the specific content of each component, but also represent the proportional relationship between the weights of the various components. The scaling up or down of the content of the fraction is within the scope disclosed in the description of the embodiments of the present application. Specifically, the mass described in the description of the embodiments of the present application may be μg, mg, g, kg and other well-known mass units in the chemical industry.

The terms "first" and "second" are only used for descriptive purposes to distinguish objects such as substances from each other, and cannot be understood as indicating or implying relative importance or implicitly specifying the quantity of indicated technical features. For example, without departing from the scope of the embodiments of the present application, the first XX can also be called the second XX, and similarly, the second XX can also be called the first XX. Thus, a feature defined as "first" and "second" may explicitly or implicitly include one or more of these features.

Aiming at the problem of low antistatic properties of ordinary polyether ether ketone materials, the first aspect of the embodiment of the present application provides a preparation method of antistatic polyether ether ketone composite materials, including:

S10: mixing polyetheretherketone and acidified carbon nanotubes to obtain a first mixture, and extruding and granulating the first mixture to obtain a carbon nanotube masterbatch;

S20: Mix the carbon nanotube masterbatch and polyether ether ketone to obtain a second mixture, extrude the second mixture, and perform ultrasonic treatment on the second mixture during extrusion molding to obtain an antistatic polyether Etherketone composites.

PEEK is a plastic with high volume resistivity and surface resistivity, which can maintain good insulating properties in 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. Commonly used conductive additives include metal materials and carbon-based conductive agents, and carbon nanotubes (CNTs) in carbon-based conductive agents have attracted great attention due to their small addition amount and good conductivity. However, due to the high specific surface area, specific surface energy and aspect ratio of carbon nanotubes, they are easy to agglomerate and entangle with each other. This property is not conducive to the uniform dispersion of carbon nanotubes in polymers, so that they cannot exert their excellent performance.

The preparation method of the antistatic polyether ether ketone composite material provided in the first aspect of the application example uses acidified carbon nanotubes as conductive additives. The acidified carbon nanotubes refer to carbon nanotubes obtained after acidification treatment. The structure of the tube itself is less damaged, and the original shape of the carbon nanotubes can be well maintained, and the acidification can also modify the surface of the carbon nanotubes, improve the interfacial compatibility between the carbon nanotubes and polyether ether ketone, and improve the carbon nanotubes. Dispersion of nanotubes in polyether ether ketone substrates.

In addition, the preparation method of the antistatic polyether ether ketone composite material provided by the first aspect of the application example is to first make the acidified carbon nanotubes and polyether ether ketone into a masterbatch, and then mix the masterbatch and polyether ether ketone to melt extrude It improves the miscibility of materials during processing, and at the same time increases the ultrasonic treatment in the extrusion molding process, effectively prevents the aggregation of carbon nanotubes, and ensures the dispersibility of carbon nanotubes in the polyetheretherketone matrix. Compared with traditional plastics The processing method, the antistatic polyetheretherketone composite material processed by this process has a smoother surface and fewer bumps after being made into a plastic part.

In summary, the preparation method of the antistatic polyether ether ketone composite material provided by the first aspect of the application example adopts acidified carbon nanotubes as conductive additives, and combines the molding process of first making masterbatches and then mixing melt extrusion and ultrasonic The dispersibility of carbon nanotubes in the polyether ether ketone substrate is improved from various aspects, so that the surface resistivity of the obtained antistatic polyether ether ketone composite material is reduced and the antistatic performance is improved.

In some embodiments, in step S10, the preparation method of the antistatic polyether ether ketone composite material further includes preparing acidified carbon nanotubes. The preparation of acidified carbon nanotubes includes: mixing concentrated nitric acid and concentrated sulfuric acid to obtain a mixed acid, optionally, mixing concentrated nitric acid and concentrated sulfuric acid according to a volume ratio of 1:3 to obtain a mixed acid; adding carbon nanotubes to the mixed acid and ultrasonically Disperse for a first time to obtain a carbon nanotube solution. Optionally, the first time is 1h to 5h, for example, 1h, 2h, 3h, 4h or 5h; dilute the carbon nanotube solution with deionized water to obtain a solid The diluted solution in which the particles are uniformly dispersed in the solution, usually the diluted solution is no longer stratified, even if it is left to stand overnight, there is no stratification phenomenon, this is because the carbon nanotubes are uniformly dispersed after being successfully acidified; next, the diluted solution The solid particles in the solution are separated, that is, the acidified carbon nanotubes in the diluted solution are extracted, which specifically includes: pouring the diluted solution into a centrifuge tube, placing the centrifuge tube in a centrifuge, setting the speed of the centrifuge to 10000rpm, and carrying out Centrifuge for 20 minutes, then pour out the supernatant in the centrifuge tube, put the remaining sediment in the beaker, add deionized water to the beaker, test the acidity of the solution with pH test paper, and then centrifuge and cycle. , repeat about 3 times until the filtrate detected by the pH test paper is neutral, then use a funnel to filter the precipitate, put the filter cake in a vacuum drying oven for drying, the drying time is set to 24h, and the temperature is set to 60°C. The filter cake is ground for many times with a mortar to obtain acidified carbon nanotubes, namely CNTs-COOH.

In some embodiments, in step S10, the mass ratio of polyetheretherketone to acidified carbon nanotubes in the first mixture is 1: (0.5-1), that is, a part of polyetheretherketone and acidified carbon nanotubes are mixed according to 1:(0.5～1) mass ratio for mixing. Optionally, the mass ratio of polyether ether ketone to acidified carbon nanotubes in the first mixture is 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9 or 1:1.

In some embodiments, in steps S10 and S20, the weight average molecular weight of the polyether ether ketone is 500,000-1,000,000, for example, 500,000, 600,000, 700,000, 800,000, 900,000 or 1,000,000. The melt viscosity of polyetheretherketone is 100Pa.s˜150Pa.s, for example, it may be 100Pa.s, 110Pa.s, 120Pa.s, 130Pa.s, 140Pa.s or 150Pa.s.

In some embodiments, in step S20, in terms of parts by mass, the second mixture includes 90-105 parts of polyetheretherketone and 0.5-7 parts of acidified carbon nanotubes. Here, the amount of polyetheretherketone in the second mixture includes the amount of masterbatch made in S10 and the amount added later in S20. In the prior art, in order to ensure the antistatic properties of plastics, the amount of carbon nanotubes added to the plastics needs to be at least 4wt% to 8wt%. Ether ether ketone has good dispersion in the substrate, so even when the acidified carbon nanotubes are added in a small amount, the antistatic polyetheretherketone composite still has good antistatic properties. Optionally, the mass parts of polyetheretherketone in the second compounding material can be 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts, 98 parts, 99 parts, 100 parts parts, 101 parts, 102 parts, 103 parts, 104 parts or 105 parts. Optionally, the mass fraction 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 mixture further includes inorganic fillers. The addition of inorganic fillers can reduce processing difficulty and further improve the dispersion uniformity of materials. Optionally, high mesh inorganic fillers are used. It can 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 in the case of uniform dispersion. Optionally, the particle size of the inorganic filler is 5000 mesh to 10000 mesh, such as 5000 mesh, 6000 mesh, 7000 mesh, 8000 mesh, 9000 mesh and/or 10000 mesh. Optionally, the inorganic filler includes one or more of calcium carbonate, talc powder, mica powder, sepiolite powder and attapulgite powder.

In some embodiments, in step S20, when the second mixture also includes inorganic fillers, the preparation of the second mixture includes: mixing polyether ether ketone and inorganic fillers to obtain a first premix, and then mixing the first The premixed material is mixed with the carbon nanotube masterbatch to obtain a second premixed material, and the second premixed material is also the second mixed material. Optionally, use a mixer to mix the materials. First, mix the polyether ether ketone and the inorganic filler in the mixer for 10 minutes to 15 minutes. The speed of the mixer is 100r/min to 300r/min; The carbon nanotube masterbatch is added into the machine, the speed of the mixer is 100r/min-300r/min, and the mixing is continued for 10min-15min to obtain the second mixture.

In some embodiments, in step S20, when the second mixture further includes inorganic fillers, in parts by mass, the second mixture includes 90-105 parts of polyetheretherketone, 5-30 parts of inorganic fillers and 0.5-7 parts of acidified carbon nanotubes. Optionally, the mass parts of polyetheretherketone in the second compounding material can be 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts, 98 parts, 99 parts, 100 parts parts, 101 parts, 102 parts, 103 parts, 104 parts or 105 parts. Optionally, the mass fraction 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. Optionally, the mass fraction of the inorganic filler in the second mixture can be 5 parts, 10 parts, 15 parts, 20 parts, 25 parts or 30 parts. Preferably, the mass fraction of the inorganic filler is 20, 25 or 30 parts, and increasing the content of the filler can significantly improve the processability.

In some embodiments, in step S20, the second mixture further includes a lubricant, and the lubricant includes polytetrafluoroethylene. Polytetrafluoroethylene with high molecular weight, in addition to its excellent lubrication resistance, is more important that it is arranged in fiber form under high temperature shearing, which can promote the arrangement of conductive carbon nanotubes along the radial direction. Cloth, and then form a more stable and continuous conductive network, which can greatly reduce the amount of conductive agent added, and achieve stable antistatic and conductive effects.

In some embodiments, in step S20, when the second mixture further includes a lubricant, in parts by mass, the second mixture includes 90-105 parts of polyetheretherketone, 1-5 parts of lubricant and 0.5-7 parts of acidified carbon nanotubes. Optionally, the mass parts of polyetheretherketone in the second compounding material can be 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts, 98 parts, 99 parts, 100 parts parts, 101 parts, 102 parts, 103 parts, 104 parts or 105 parts. Optionally, the mass fraction 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. Optionally, the mass parts of the lubricant in the second mixture can be 1 part, 2 parts, 3 parts, 4 parts, 4.5 parts or 5 parts.

In some embodiments, in step S20, when the second mixture further includes inorganic fillers and lubricants, in parts by mass, the second mixture includes 90-105 parts of polyether ether ketone, 5-30 parts Inorganic filler, 0.5-7 parts of acidified carbon nanotubes and 1-5 parts of lubricant. Optionally, the mass parts of polyetheretherketone in the second compounding material can be 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts, 98 parts, 99 parts, 100 parts parts, 101 parts, 102 parts, 103 parts, 104 parts or 105 parts. Optionally, the mass fraction 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. Optionally, the mass fraction of the inorganic filler in the second mixture can be 5 parts, 10 parts, 15 parts, 20 parts, 25 parts or 30 parts. Optionally, the mass parts of the lubricant in the second mixture can be 1 part, 2 parts, 3 parts, 4 parts or 5 parts.

In some embodiments, in step S20, when the second mixture further includes inorganic filler and lubricant, the preparation of the second mixture includes: mixing polyether ether ketone, inorganic filler and lubricant to obtain the first premixed The second premix is obtained by mixing the first premix with the carbon nanotube masterbatch, and the second premix is also the second mixture. Optionally, a mixer is used for mixing, and the polyetheretherketone, inorganic filler and lubricant are first stirred and mixed in the mixer for 10 minutes to 15 minutes, and the speed of the mixer is 100r/min to 300r/min; The carbon nanotube masterbatch is added into the mixer, the rotation speed of the mixer is 100r/min-300r/min, and the mixing is continued for 10min-15min to obtain the second mixture.

In some embodiments, in step S20, the extrusion molding includes: melting the second mixture to obtain a melt, extruding the melt, and performing ultrasonic treatment on the melt while extruding. In the embodiment of the present application, by creatively adding ultrasonic treatment in the process of extruding the melt, under the action of ultrasonic, it can effectively prevent the agglomeration of carbon nanotubes under the action of extrusion pressure and shear stress, thereby ensuring that the final obtained The carbon nanotubes in the material are still uniformly dispersed in the polyether ether ketone matrix.

In some embodiments, the ultrasonic power of the ultrasonic treatment is 400W-600W. The ultrasonic power is optimized by the inventor after long-term experimental research. If the power is less than 400W, the effect of improving the dispersion uniformity of carbon nanotubes in the extrusion process will be reduced. If the power is greater than 600W, it will affect the extrusion pressure and shear stress. Extrusion molding of resin materials. Optionally, the ultrasonic power is 400W, 450W, 500W, 550W or 600W.

In some embodiments, the extrusion temperature is 340°C-410°C, for example, 340°C, 350°C, 360°C, 370°C, 380°C, 390°C, 400°C or 410°C. Usually, the melting point of polyether ether ketone is about 340°C, and the extrusion temperature is higher than the melting point temperature, which is beneficial to ensure the extrusion effect.

In some embodiments, during the extrusion molding process, the melt temperature of the melt is 390°C to 400°C, such as 390°C, 392°C, 394°C, 396°C, 398°C or 400°C; The melt pressure is 2.0MPa-3.0MPa, for example, it can be 2.0MPa, 2.2MPa, 2.4MPa, 2.6MPa, 2.8MPa or 3.0MPa.

In some embodiments, the second mixture 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, venting performance, and extrusion stability. Of course, a single screw extruder may also be used in other embodiments. Under the action of the screw of the screw extruder, the second compound is first heated and melted at high temperature to form a melt, and then extruded through the screw. Optionally, along the direction from feeding to discharging, the extruder includes a first section, a second section, a third section, a fourth section, a fifth section and an extruder head connected in sequence, and in the fourth section, Sonication is performed at the fifth section and at 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 respectively 340°C, 370°C~380°C, 370°C~380°C, 390°C~ 400°C, 400°C～410°C and 410°C.

The second aspect of the embodiment of the present application provides an antistatic polyetheretherketone composite material, which is prepared from a mixture comprising acidified carbon nanotubes and polyetheretherketone through extrusion molding and ultrasonic treatment.

The antistatic polyether ether ketone composite material provided by the second aspect of the embodiment of the present application uses acidified carbon nanotubes as conductive additives, and the acidified carbon nanotubes can be uniformly dispersed in the polyetheretherketone substrate, so that the antistatic polyetheretherketone The conductivity of the composite material is improved, the surface resistivity is reduced, and the antistatic performance is improved.

In some embodiments, the antistatic polyetheretherketone composite material includes 90-105 parts of polyetheretherketone and 0.5-7 parts of acidified carbon nanotubes in terms of parts by mass. Since the embodiment of the present application uses acidified carbon nanotubes, the carbon nanotubes have good dispersion in the polyetheretherketone substrate. Has good antistatic properties. Optionally, the mass parts of polyetheretherketone in the antistatic polyetheretherketone composite material can be 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts, 98 parts, 99, 100, 101, 102, 103, 104 or 105 copies. Optionally, the mass fraction of acidified carbon nanotubes in the antistatic polyetheretherketone composite material may be 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts or 7 parts.

In some embodiments, the antistatic polyether ether ketone composite further includes a lubricant, and the lubricant includes polytetrafluoroethylene. Polytetrafluoroethylene with high molecular weight, in addition to its excellent lubrication resistance, is more important that it is arranged in fiber form under high temperature shearing, which can promote the arrangement of conductive carbon nanotubes along the radial direction. Cloth, and then form a more stable and continuous conductive network chain (network), which can greatly reduce the amount of conductive agent added, and achieve stable antistatic and conductive effects. Optionally, the mass fraction of the lubricant in the antistatic polyetheretherketone composite material is 1-5 parts, for example, 1 part, 2 parts, 3 parts, 4 parts, 4.5 parts or 5 parts.

In some embodiments, the antistatic polyetheretherketone composite material further includes inorganic fillers, which can further improve the dispersion uniformity of the materials. Optionally, high mesh inorganic fillers are used. It can 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 in the case of uniform dispersion. Optionally, the particle size of the inorganic filler is 5000 mesh to 10000 mesh, such as 5000 mesh, 6000 mesh, 7000 mesh, 8000 mesh, 9000 mesh and/or 10000 mesh. Optionally, the inorganic filler includes one or more of calcium carbonate, talc powder, mica powder, sepiolite powder and attapulgite powder. Optionally, the mass fraction of the inorganic filler in the antistatic polyether ether ketone composite material is 5-30 parts, such as 5 parts, 10 parts, 15 parts, 20 parts, 25 parts or 30 parts. Preferably, the mass fraction of the inorganic filler is 20, 25 or 30 parts, and increasing the content of the filler can significantly improve the processability.

In some embodiments, the weight average molecular weight of polyether ether ketone is 500,000-1,000,000, for example, 500,000, 600,000, 700,000, 800,000, 900,000 or 1,000,000. The melt viscosity of polyether ether ketone measured by rotational viscometer at room temperature is 100Pa.s-150Pa.s, for example, it may be 100Pa.s, 110Pa.s, 120Pa.s, 130Pa.s, 140Pa.s or 150Pa.s.

In some embodiments, the antistatic polyether ether ketone composite material is obtained by mixing polyetheretherketone and acidified carbon nanotubes and extruding and granulating to obtain carbon nanotube masterbatches, and then mixing the carbon nanotube masterbatches and polyetheretherketone and obtained by extrusion molding. By first making acidified carbon nanotubes and polyetheretherketone into a masterbatch, and then mixing and extruding the masterbatch and polyetheretherketone, it is beneficial to improve the miscibility of materials during processing. Compared with traditional plastic processing methods, this The surface of the antistatic polyether ether ketone composite material processed by the process is smoother and has fewer bumps after being made into plastic parts.

In some embodiments, extrusion molding includes melting the mixture to obtain a melt, extruding the melt, and performing ultrasonic treatment on the melt while extruding. In the embodiment of the present application, by creatively adding ultrasonic treatment in the process of extruding the melt, under the action of ultrasonic, it can effectively prevent the agglomeration of carbon nanotubes under the action of extrusion pressure and shear stress, so that the final anti- The carbon nanotubes in the electrostatic polyetheretherketone composites are still uniformly dispersed in the polyetheretherketone matrix.

The following will be described in conjunction with specific embodiments.

Example 1

S1. Preparation of masterbatch

Mix the dried PEEK with the prepared acidified carbon nanotubes in a mass ratio of 1:1, and then melt extrusion and granulate to prepare carbon nanotube masterbatches.

S2, mixing

The first premix: Pour 87Kg of dried PEEK coarse powder into the mixer, then weigh 20Kg of inorganic filler and 1Kg of lubricant polytetrafluoroethylene into the mixer according to the proportion, and pour it into the mixer at the speed of the mixer. Treat at 100r/min for 15min, stir and mix evenly;

The second premix: add 6Kg of carbon nanotube masterbatch, process it for 10min at the speed of the mixer at 300r/min, stir and mix evenly.

S3, extrusion molding

The second premixed material is put into the feed opening of the main feed of the twin-screw extruder, and then the materials are melted and mixed through the twin-screw extruder. Along the direction from feeding to discharging, the extruder includes the first section, the second section, the third section, the fourth section, the fifth section and the extruder head connected in sequence, and the corresponding extrusion temperature is 340°C/375°C ℃/375℃/390℃/400℃/410℃, the feeding speed is 20Hz, the melt temperature is 395℃, and the melt pressure is 3.0MPa. Ultrasonic treatment is performed on the melt of the fourth section, the fifth section and the extruder head, and the ultrasonic power is 400W. The twin-screw extruder uses a medium-strength screw. The melt obtained by melting and mixing is drawn out at a constant moving speed through a shaping die, then cooled in a water tank, air-dried and pelletized to obtain antistatic PEEK particles, wherein the diameter of the particles is 2mm to 3mm.

Example 2

S1. Preparation of masterbatch

Mix the dried PEEK with the prepared acidified carbon nanotubes in a mass ratio of 1:1, and then melt extrusion and granulate to prepare carbon nanotube masterbatches.

S2, mixing

The first premix: Pour 91Kg of dried PEEK coarse powder into the mixer, then weigh 25Kg of inorganic fillers according to the proportion and pour them into the mixer, and process it for 10 minutes at the speed of the mixer at 300r/min. Stir to mix well;

The second premixed material: add 8Kg of carbon nanotube masterbatch, process it for 15min at the speed of the mixer at 100r/min, stir and mix evenly.

S3, extrusion molding

The second premixed material is put into the feed opening of the main feed of the twin-screw extruder, and then the materials are melted and mixed through the twin-screw extruder. Along the direction from feed to discharge, the extruder includes the first section, the second section, the third section, the fourth section, the fifth section and the extruder head connected in sequence, and the corresponding extrusion temperature is 340°C/380°C ℃/380℃/400℃/400℃/410℃, the feeding speed is 15Hz, the melt temperature is 390℃, and the melt pressure is 2.50MPa. Ultrasonic treatment is performed on the melt of the fourth section, the fifth section and the extruder head, and the ultrasonic power is 400W. The twin-screw extruder uses a medium-strength screw. The melt obtained by melting and mixing is drawn out at a constant moving speed through a shaping die, then cooled in a water tank, air-dried and pelletized to obtain antistatic PEEK particles, wherein the diameter of the particles is 2mm to 3mm.

Example 3

S1. Preparation of masterbatch

Mix the dried PEEK with the prepared acidified carbon nanotubes in a mass ratio of 1:1, and then melt extrusion and granulate to prepare carbon nanotube masterbatches.

S2, mixing

The first premix: Pour 98Kg of dried PEEK coarse powder into the mixer, then weigh 30Kg of inorganic fillers according to the proportion and pour them into the mixer, and process it for 15min at the speed of the mixer at 200r/min. Stir to mix well;

The second premix: add 8Kg of carbon nanotube masterbatch, process it for 10min at the speed of the mixer at 200r/min, stir and mix evenly.

S3, extrusion molding

The second premixed material is put into the feed opening of the main feed of the twin-screw extruder, and then the materials are melted and mixed through the twin-screw extruder. Along the direction from feed to discharge, the extruder includes the first section, the second section, the third section, the fourth section, the fifth section and the extruder head connected in sequence, and the corresponding extrusion temperature is 340°C/380°C ℃/380℃/390℃/400℃/410℃, the feeding speed is 18Hz, the melt temperature is 390℃, and the melt pressure is 2.50MPa. Ultrasonic treatment is performed on the melt of the fourth section, the fifth section and the extruder head, and the ultrasonic power is 400W. The melt obtained by melting and mixing is drawn out at a constant moving speed through a shaping die, then cooled in a water tank, air-dried and pelletized to obtain antistatic PEEK particles, wherein the diameter of the particles is 2mm to 3mm.

Comparative example 1

S1. Preparation of masterbatch

The dried PEEK is mixed with the prepared carbon nanotubes in a mass ratio of 1:1, and then melt-extruded and granulated to prepare carbon nanotube masterbatches.

S2, mixing

The first premix: Pour 87Kg of dried PEEK coarse powder into the mixer, then weigh 20Kg of inorganic filler and 1Kg of lubricant polytetrafluoroethylene into the mixer according to the proportion, and pour it into the mixer at the speed of the mixer. Treat at 100r/min for 15min, stir and mix evenly;

The second premix: add 6Kg of carbon nanotube masterbatch, process it for 10min at the speed of the mixer at 300r/min, stir and mix evenly.

S3, extrusion molding

The second premixed material is put into the feed opening of the main feed of the twin-screw extruder, and then the materials are melted and mixed through the twin-screw extruder. Along the direction from feeding to discharging, the extruder includes the first section, the second section, the third section, the fourth section, the fifth section and the extruder head connected in sequence, and the corresponding extrusion temperature is 340°C/375°C ℃/375℃/390℃/400℃/410℃, the feeding speed is 20Hz, the melt temperature is 395℃, and the melt pressure is 3.0MPa. Ultrasonic treatment is carried out on the melt of the fourth section, the fifth section and the extruder head, and the ultrasonic power is 400W. The twin-screw extruder uses a medium-strength screw. The melt obtained by melting and mixing is pulled out at a constant moving speed through a shaping die, then cooled in a water tank, air-dried and pelletized to obtain antistatic PEEK particles, wherein the diameter of the particles is 2 mm to 3 mm.

Comparative example 2

S1. Masterbatch preparation

Mix the dried PEEK with the prepared acidified carbon nanotubes in a mass ratio of 1:1, and then melt extrusion and granulate to prepare carbon nanotube masterbatches.

S2, mixing

The first premix: Pour 87Kg of dried PEEK coarse powder into the mixer, then weigh 20Kg of inorganic filler and 1Kg of lubricant polytetrafluoroethylene into the mixer according to the proportion, and pour it into the mixer at the speed of the mixer. Treat at 100r/min for 15min, stir and mix evenly;

The second premix: add 6Kg of carbon nanotube masterbatch, process it for 10min at the speed of the mixer at 300r/min, stir and mix evenly.

S3, extrusion molding

The second premixed material is put into the feed opening of the main feed of the twin-screw extruder, and then the materials are melted and mixed through the twin-screw extruder. Along the direction from feeding to discharging, the extruder includes the first section, the second section, the third section, the fourth section, the fifth section and the extruder head connected in sequence, and the corresponding extrusion temperature is 340°C/375°C ℃/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 a medium-strength screw. The melt obtained by melting and mixing is drawn out at a constant moving speed through a shaping die, then cooled in a water tank, air-dried and pelletized to obtain antistatic PEEK particles, wherein the diameter of the particles is 2mm to 3mm.

In order to verify the progressiveness of the embodiment of the present application, the samples of embodiment and comparative example have been tested respectively as follows:

Bake the antistatic PEEK particles prepared in Examples 1 to 3 and Comparative Examples 1 and 2 in an oven at 150°C to 180°C for 2h-4h to remove the moisture in the antistatic PEEK particles, and control the moisture to 0.02wt % within. The baked antistatic PEEK particles are injected into the injection molding machine, the injection temperature is 410°C-420°C, the mold temperature of the front mold is 150°C-200°C, the mold temperature of the rear film is 180°C-200°C, and the speed is 50g/s ～90g/s, pressure 50bar～90bar, injection molded into a wafer box.

The surface resistivity of the wafer box made of the antistatic PEEK particles of Examples 1 to 3 is (1*10 ⁵ ～1*10 ⁸ )Ω/Sq, and its surface flatness is high (flatness<0.004mm, Warping degree <0.2mm), high surface cleanliness (no dust precipitation, no decarburization, etc.) and no micro-pores (such as tiny protrusions, pits, and tiny pits). The surfaces of the wafer cassettes of Comparative Examples 1 and 2 were not smooth and had bumps.

In addition, the antistatic PEEK particles prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were injection molded into standard parts for performance tests as shown in Table 1.

Table 1

In combination with Table 1, Examples 1 to 3 and Comparative Example 1 all use the molding process of first making masterbatches and then mixing melt extrusion and ultrasonic treatment to prepare antistatic polyetheretherketone composite materials. The difference is that Comparative Example 1 Common carbon nanotubes and polyether ether ketone were used to prepare antistatic polyetheretherketone composite materials. Examples 1 to 3 used acidified carbon nanotubes and polyether ether ketone to prepare antistatic polyetheretherketone Composite materials, wherein the amount of acidified carbon nanotubes in embodiment 2 is the highest, and the amount of acidified carbon nanotubes in embodiment 1 is the lowest. Compared with comparative example 1, the surface resistivity of embodiment 1 to embodiment 3 is all lower than comparative example 1, wherein embodiment 2 is the lowest, followed by embodiment 3, and embodiment 3 is the highest in three embodiments, as seen, The surface resistivity of antistatic polyetheretherketone composites decreased with the increase of acidified carbon nanotubes content. In addition, it can also be seen from Table 1 that the addition of acidified carbon nanotubes can improve the tensile strength, bending strength and molding shrinkage of antistatic PEEK composites to a certain extent, but the Izod impact strength will be slightly reduced. reduce.

In combination with Table 1, in Example 1 to Example 3 and Comparative Example 2, acidified carbon nanotubes and polyether ether ketone are extruded to obtain antistatic polyetheretherketone composite materials, the difference is that in Example 1 to Example 2 In 3, ultrasonic treatment was carried out during extrusion molding, while comparative example 2 was not subjected to ultrasonic treatment during extrusion molding. Compared with comparative example 2, the surface resistivity of embodiment 1 to embodiment 3 is all lower than comparative example 2, it can be seen that in the extrusion molding process, auxiliary ultrasonic treatment can prevent the extrusion pressure and Under the action of shear stress, the carbon nanotubes are agglomerated, so as to ensure that the carbon nanotubes in the final material are still uniformly dispersed in the polyetheretherketone matrix, so that the surface resistivity of the antistatic polyetheretherketone composite material is reduced.

The above descriptions are only preferred embodiments of the application, and are not intended to limit the application. Any modifications, equivalent replacements and improvements made within the spirit and principles of the application should be included in the protection of the application. within range.

Claims (10)

1. A preparation method of antistatic polyether ether ketone composite material, characterized in that, comprising: mixing polyetheretherketone and acidified carbon nanotubes to obtain a first mixture, and extruding and granulating the first mixture to obtain carbon nanotube masterbatch; mixing the carbon nanotube masterbatch and polyether ether ketone to obtain a second compound, extruding the second compound, and performing ultrasonic treatment on the second compound while extruding , to obtain antistatic polyetheretherketone composite materials. 2. The preparation method of antistatic polyether ether ketone composite material according to claim 1, characterized in that, in terms of parts by mass, the second mixture comprises 90-105 parts of polyether ether ketone and 0.5- 7 parts acidified carbon nanotubes. 3. The preparation method of the antistatic polyetheretherketone composite material according to claim 2, wherein the second mixture further comprises 1 to 5 parts of lubricant, and the lubricant comprises polytetrafluoroethylene; And/or, the second mixture further includes 5-30 parts of inorganic filler. 4. the preparation method of antistatic polyether ether ketone composite material as claimed in claim 3, is characterized in that, when described second mixture comprises inorganic filler: described inorganic filler comprises calcium carbonate, talcum powder, mica powder , at least one of sepiolite powder and attapulgite powder; And/or, the particle size of the inorganic filler is 5000 mesh to 10000 mesh; And/or, the preparation of the second mixture includes mixing polyether ether ketone and the inorganic filler to obtain a premix, and then mixing the premix with the carbon nanotube masterbatch to obtain a second mixture . 5. The preparation method of antistatic polyetheretherketone composite material according to claim 1, characterized in that, the weight average molecular weight of the polyetheretherketone is 500000-1000000, and the melt viscosity of the polyetheretherketone 100Pa.s～150Pa.s; And/or, the mass ratio of the polyether ether ketone to the acidified carbon nanotubes in the first mixture is 1:(0.5-1); And/or, the preparation method of the antistatic polyether ether ketone composite material also includes preparing the acidified carbon nanotubes: mixing concentrated nitric acid and concentrated sulfuric acid to obtain a mixed acid; adding carbon nanotubes to the mixed acid and ultrasonically Dispersing for the first time to obtain a carbon nanotube solution; diluting the carbon nanotube solution with deionized water to obtain a diluted solution in which solid particles are uniformly dispersed in the solution; separating the solid particles in the diluted solution to obtain acidified carbon nanotubes. 6. The preparation method of the antistatic polyether ether ketone composite material according to any one of claims 1 to 5, wherein the extrusion molding comprises: melting the second compound to obtain a melt, The melt was extruded, and the melt was sonicated while extruding. 7. The preparation method of antistatic polyether ether ketone composite material as claimed in claim 6, characterized in that, the ultrasonic power of the ultrasonic treatment is 400W-600W; And/or, the extruding temperature is 340°C-410°C; And/or, during the extrusion molding process, the melt temperature of the melt is 390°C-400°C, and the melt pressure of the melt is 2.0MPa-3.0MPa; And/or, using a screw extruder to melt the second mixture to form a melt, and extrude the melt; along the direction from feeding to discharging, the extruder includes sequentially connected The first section, the second section, the third section, the fourth section, the fifth section and the extruder head, ultrasonic treatment is carried out at 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 respectively 340°C, 370°C~380°C, 370°C~ 380°C, 390°C~400°C, 400°C~410°C and 410°C. 8. An antistatic polyether ether ketone composite material, characterized in that it is prepared from a mixture comprising acidified carbon nanotubes and polyetherether ketone through extrusion molding combined with ultrasonic treatment. 9. The antistatic polyether ether ketone composite material according to claim 8, characterized in that, in terms of parts by mass, the antistatic polyether ether ketone composite material comprises 90 to 105 parts of polyether ether ketone and 0.5 -7 parts acidified carbon nanotubes. 10. The antistatic polyether ether ketone composite material according to claim 9, characterized in that, the antistatic polyether ether ketone composite material further comprises 1 to 5 parts of lubricant, and the lubricant comprises polytetrafluoroethylene ; And/or the antistatic polyetheretherketone composite material further includes 5 to 30 parts of inorganic fillers, and the inorganic fillers include at least one of calcium carbonate, talcum powder, mica powder, sepiolite powder and attapulgite powder; And/or, the weight average molecular weight of the polyetheretherketone is 500000-1000000, and the melt viscosity of the polyetheretherketone is 100Pa.s-150Pa.s.

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