Antistatic masterbatch, PEEK composite material and preparation method

Abstract

The invention belongs to the field of new materials and discloses an antistatic masterbatch, comprising mesoporous black phosphorus, a conductive agent and PEEK; the content of the mesoporous black phosphorus is 1-20wt%. The antistatic masterbatch adopts the mesoporous black phosphorus and the conductive agent in combination, which can effectively improve the resistance uniformity of the PEEK composite material and maintain excellent mechanical properties. At the same time, the invention also provides a preparation method of the masterbatch and a PEEK composite material.

Description

Technical Field

[0001] The invention relates to the field of new materials, and in particular to an antistatic masterbatch, a PEEK composite material and a preparation method. Background Art

[0002] Polyetheretherketone (PEEK) is a linear aromatic polymer consisting of a repeating unit containing one ketone bond and two ether bonds in the main chain structure. It is a new type of semi-crystalline, thermoplastic special engineering plastic. Due to its excellent physical, chemical, mechanical and thermal properties, it has always been regarded as a strategic national defense military material. At the same time, due to its good weldability, recyclability, chemical corrosion resistance, especially the ability to be processed and formed in a short time, it has also rapidly emerged in the automotive, electronics, construction, aviation and other industrial fields in recent years.

[0003] With the development of semiconductor manufacturing technology, the width and spacing of interconnect wires are getting smaller and smaller, and the integration density of integrated circuits is getting higher and higher. At the same time, the problem is that the electrostatic breakdown voltage of the device is getting lower and lower. Therefore, the influence of static electricity must be taken seriously in the development and production of semiconductor devices. Polyetheretherketone does not deform in a wide temperature range, has high mechanical strength, high wear resistance, and strong resistance to chemical corrosion. The parts made of it can withstand the high temperature environment of heat welding treatment. Based on these characteristics, in the semiconductor industry, polyetheretherketone is widely used to manufacture wafer carriers, wafer control rods, wafer combs, wafer clamps, vacuum traceless suction cups and other operating tools.

[0004] However, the high wear rate and friction electrostatic charge accumulation of PEEK matrix limit its application in the field of friction and conductive materials. In order to improve the antistatic and wear properties of PEEK, it is necessary to add conductive fillers and reinforcing phases to the PEEK matrix to obtain antistatic PEEK-based composite materials. However, the antistatic PEEK prepared by the traditional method has uneven surface resistance of the composite material due to uneven dispersion of fillers, which also leads to uneven mechanical properties of the material.

[0005] The technical problem solved in this case is: how to prepare antistatic PEEK with uniform surface resistance and good mechanical properties. Summary of the invention

[0006] The object of the present invention is to provide an antistatic masterbatch, which is prepared by using mesoporous black phosphorus and a conductive agent in combination, and can effectively improve the resistance uniformity of a PEEK composite material and maintain excellent mechanical properties.

[0007] At the same time, the present invention also provides a preparation method of the masterbatch and a PEEK composite material.

[0008] To achieve the above object, the present invention provides the following technical solutions:

[0009] An antistatic masterbatch comprises mesoporous black phosphorus, a conductive agent and PEEK; the content of the mesoporous black phosphorus is 1-20wt%.

[0010] In the above antistatic masterbatch, the particle size of the mesoporous black phosphorus is 1 μm to 100 μm; the particle size of the conductive agent is 1 μm to 50 μm.

[0011] In the above antistatic masterbatch, the conductive agent is one or more combinations of graphite, carbon powder, and carbon nanotubes; the content of the conductive agent is 1 to 50 wt%.

[0012] In the above antistatic masterbatch, the PEEK is a low molecular weight PEEK; the weight average molecular weight of the low molecular weight PEEK is 4000-10000.

[0013] The antistatic masterbatch further comprises a silane coupling agent, wherein the silane coupling agent is at least one of KH560, KH550 and KH570; and the content of the silane coupling agent is 1 to 10 wt %.

[0014] In the above antistatic masterbatch, the preparation method of the mesoporous black phosphorus is: using black phosphorus powder as raw material, soaking it in a dilute sulfuric acid solution with a concentration of 1-10wt%, performing oxidation reaction at 80-200°C for 24-72 hours, and drying.

[0015] In the above antistatic masterbatch, the black phosphorus powder is black phosphorus powder that has been pre-oxidized with hydrogen peroxide; the concentration of the hydrogen peroxide is 5-15wt%; the pre-oxidation operation is: immersing the black phosphorus powder in hydrogen peroxide and soaking it at room temperature for 12-24 hours.

[0016] At the same time, the present invention also discloses a method for preparing the antistatic masterbatch as described above, wherein the mesoporous black phosphorus and the conductive agent are premixed and a solution containing a silane coupling agent is added to obtain a mixed material, and the mixed material is mixed with the dried PEEK to form granules.

[0017] Finally, the present invention also discloses a PEEK composite material, comprising any of the above-mentioned antistatic masterbatch and PEEK; the content of the antistatic masterbatch in the PEEK composite material is 1 to 30 wt%.

[0018] In the above-mentioned PEEK composite material, the molecular weight of the PEEK is 10,000 to 500,000.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] In order to solve the problem of uneven surface resistance caused by uneven dispersion due to easy agglomeration of fillers, the present invention treats black phosphorus powder with dilute sulfuric acid to prepare mesoporous oxidized black phosphorus powder; on the one hand, the phosphorus element in black phosphorus itself is conducive to electron transmission, and on the other hand, the mesoporous structure helps carbon black adsorption and promotes uniform dispersion, and black phosphorus is easily oxidized to form an oxidized structure, which is easy to react chemically with the reactive groups in the silane coupling agent, thereby forming a good compatible interface with the low molecular weight PEEK resin. In addition, the low molecular weight PEEK resin has good fluidity and dispersibility, which also helps the uniform dispersion of the filler during melt kneading and twin-screw extrusion.

[0021] The composite material prepared by adopting the masterbatch of the invention has uniform surface resistance and good mechanical properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 Schematic diagram of the test points for surface resistance uniformity of PEEK composite material samples;

[0023] Figure 2 This is a SEM image of mesoporous black phosphorus 4 obtained after treatment with dilute sulfuric acid and hydrogen peroxide in Example A4;

[0024] Figure 3 is a SEM image of the PEEK composite resin prepared in Example C2;

[0025] Figure 4 This is an EDS image of the PEEK composite resin prepared in Example C2;

[0026] Figure 5 This is the stress-strain curve of the PEEK composite material prepared in Example C3. DETAILED DESCRIPTION

[0027] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0028] Preparation of black phosphorus powder

[0029] Currently, there is no stable and reliable black phosphorus on the market. The black phosphorus used in the present invention is donated by Shenzhen Kangxun New Materials Technology Co., Ltd.

[0030] Its preparation method is:

[0031] Industrial raw material red phosphorus powder, analytical pure tin and tin tetraiodide are mixed in a mass ratio of 1-6:40-50:1-2; they are loaded into a quartz tube, evacuated until the pressure in the quartz tube is less than 0.05 Pa, and the tube is sealed. The raw material end in the quartz tube is first heated to 200° C. and reacted for 2 hours; then the temperature is raised to 400° C. and reacted for another 2 hours; then the temperature is raised to 700° C. and reacted at a constant temperature for 10 hours; then the temperature is gradually lowered to 200° C. and kept warm for 3 days; finally the temperature is slowly lowered to room temperature to obtain black phosphorus powder.

[0032] The black phosphorus used in the subsequent embodiments of the present invention is this black phosphorus.

[0033] Part I Preparation of Mesoporous Black Phosphorus

[0034] Example A1

[0035] Black phosphorus powder with an average particle size of 4.8 μm was used as a raw material, immersed in a dilute sulfuric acid solution with a concentration of 5 wt%, oxidized at 100° C. for 36 hours, and dried to obtain mesoporous black phosphorus 1.

[0036] The volume ratio of black phosphorus to dilute sulfuric acid is 1:10.

[0037] Example A2

[0038] Black phosphorus powder with an average particle size of 27.2 μm was used as a raw material, immersed in a dilute sulfuric acid solution with a concentration of 10 wt%, oxidized at 100° C. for 72 hours, and dried to obtain mesoporous black phosphorus 2.

[0039] The volume ratio of black phosphorus to dilute sulfuric acid is 1:10.

[0040] Example A3

[0041] Black phosphorus powder with an average particle size of 41.8 μm was used as a raw material, immersed in a dilute sulfuric acid solution with a concentration of 10 wt%, oxidized at 100° C. for 24 hours, and dried to obtain mesoporous black phosphorus 3.

[0042] The volume ratio of black phosphorus to dilute sulfuric acid is 1:10.

[0043] Example A4

[0044] Black phosphorus powder with an average particle size of 27.2 μm was used as raw material. It was first soaked in 15wt% hydrogen peroxide at room temperature for 24 hours, dried, and then soaked in 10wt% dilute sulfuric acid solution. An oxidation reaction was carried out at 100°C for 72 hours and dried to obtain mesoporous black phosphorus 4.

[0045] The volume ratio of black phosphorus, hydrogen peroxide and dilute sulfuric acid is 1:10:10.

[0046] Example A5

[0047] Black phosphorus powder with an average particle size of 27.2 μm was used as raw material. It was first soaked in 10wt% hydrogen peroxide at room temperature for 12 hours, dried, and then soaked in 10wt% dilute sulfuric acid solution. An oxidation reaction was carried out at 100°C for 72 hours and dried to obtain mesoporous black phosphorus 5.

[0048] The volume ratio of black phosphorus, hydrogen peroxide and dilute sulfuric acid is 1:10:10.

[0049] Example A6

[0050] Black phosphorus powder with an average particle size of 27.2 μm was used as raw material. It was first soaked in 5wt% hydrogen peroxide at room temperature for 24 hours, dried, and then soaked in 10wt% dilute sulfuric acid solution. An oxidation reaction was carried out at 100°C for 72 hours and dried to obtain mesoporous black phosphorus 6.

[0051] The volume ratio of black phosphorus, hydrogen peroxide and dilute sulfuric acid is 1:10:10.

[0052] Part 2 Preparation of Antistatic Masterbatch

[0053] Example B1 to Example B6

[0054] Mesoporous black phosphorus and carbon black with an average particle size of 5 μm were premixed to obtain a mixed powder, and the mixed powder was added to a solution containing a silane coupling agent to obtain a mixed material, and the mixed material was dried and mixed with PEEK for granulation. The volume ratio of the mixed powder to the solution was 1:10; the solution was composed of a silane coupling agent and ethanol; Table 1 shows the dosage ratio of mesoporous black phosphorus, carbon black, and silane coupling agent.

[0055] Table 1 Recipe

[0056]

[0057] Part III Preparation of PEEK composites

[0058] The molecular weight of PEEK used in this section is 200,000.

[0059] Example C1

[0060] 95 parts by weight of polyetheretherketone (PEEK) resin and 5 parts by weight of antistatic masterbatch 1 were weighed and uniformly mixed; and melt-granulated at 300° C. using a twin-screw extruder to prepare an antistatic polyetheretherketone (PEEK) composite material.

[0061] Example C2

[0062] 80 parts by weight of polyetheretherketone (PEEK) resin and 20 parts by weight of antistatic masterbatch 2 were weighed and uniformly mixed; the mixture was melt-granulated at 280° C. using a twin-screw extruder to prepare an antistatic polyetheretherketone (PEEK) composite material.

[0063] Example C3

[0064] 70 parts by weight of polyetheretherketone (PEEK) resin and 30 parts by weight of antistatic masterbatch 3 were weighed and uniformly mixed; the mixture was melt-granulated at 280° C. using a twin-screw extruder to prepare an antistatic polyetheretherketone (PEEK) composite material.

[0065] Example C4

[0066] 80 parts by weight of polyetheretherketone (PEEK) resin and 20 parts by weight of antistatic masterbatch 4 were weighed and uniformly mixed; the mixture was melt-granulated at 280° C. using a twin-screw extruder to prepare an antistatic polyetheretherketone (PEEK) composite material.

[0067] Example C5

[0068] 80 parts by weight of polyetheretherketone (PEEK) resin and 20 parts by weight of antistatic masterbatch 5 were weighed and uniformly mixed; the mixture was melt-granulated at 280° C. using a twin-screw extruder to prepare an antistatic polyetheretherketone (PEEK) composite material.

[0069] Example C6

[0070] 80 parts by weight of polyetheretherketone (PEEK) resin and 20 parts by weight of antistatic masterbatch 6 were weighed and uniformly mixed; the mixture was melt-granulated at 280° C. using a twin-screw extruder to prepare an antistatic polyetheretherketone (PEEK) composite material.

[0071] Comparative Example C1

[0072] 80 parts by weight of polyetheretherketone (PEEK) resin and 20 parts by weight of antistatic masterbatch 7 were weighed and uniformly mixed; the mixture was melt-granulated at 280° C. using a twin-screw extruder to prepare an antistatic polyetheretherketone (PEEK) composite material.

[0073] The preparation method of antistatic masterbatch 7 is:

[0074] Black phosphorus powder with an average particle size of 27.2 μm and carbon black with an average particle size of 5 μm are premixed to obtain a mixed powder, and the mixed powder is added to a solution containing a silane coupling agent to obtain a mixed material, and the mixed material is dried and mixed with PEEK for granulation. The volume ratio of the mixed powder to the solution is 1:10; the solution is composed of a silane coupling agent and ethanol.

[0075] The weight ratio of black phosphorus powder, carbon black, silane coupling agent and PEEK is 10:30:5:55. The molecular weight of PEEK is 7000; the silane coupling agent is KH550.

[0076] Comparative Example C2

[0077] 80 parts by weight of polyetheretherketone (PEEK) resin and 20 parts by weight of antistatic masterbatch 8 were weighed and uniformly mixed; the mixture was melt-granulated at 280° C. using a twin-screw extruder to prepare an antistatic polyetheretherketone (PEEK) composite material.

[0078] The preparation method of antistatic masterbatch 8 is:

[0079] Carbon black with an average particle size of 5 μm is added to a solution containing a silane coupling agent to obtain a mixed material, and the mixed material is dried and then mixed with PEEK to form granules. The volume ratio of the mixed powder to the solution is 1:10; and the solution is composed of a silane coupling agent and ethanol.

[0080] The weight ratio of carbon black, silane coupling agent and PEEK is 40:5:55. The molecular weight of PEEK is 7000; the silane coupling agent is KH550.

[0081] Comparative Example C3

[0082] 80 parts by weight of polyetheretherketone (PEEK) resin and 20 parts by weight of antistatic masterbatch 9 were weighed and uniformly mixed; the mixture was melt-granulated at 280° C. using a twin-screw extruder to prepare an antistatic polyetheretherketone (PEEK) composite material.

[0083] The preparation method of antistatic masterbatch 9 is:

[0084] The hydrophobic mesoporous silica with an average particle size of 10 μm and the carbon black with an average particle size of 5 μm are pre-mixed to obtain a mixed powder, and the mixed powder is added to a solution containing a silane coupling agent to obtain a mixed material, and the mixed material is dried and mixed with PEEK for granulation. The volume ratio of the mixed powder to the solution is 1:10; the solution is composed of a silane coupling agent and ethanol.

[0085] The weight ratio of mesoporous silica, carbon black, silane coupling agent and PEEK is 20:30:5:55. The molecular weight of PEEK is 7000; the silane coupling agent is KH550; the model of mesoporous silica is Brofos-SiO2-JC10, which is hydrophobically modified with polymethylsiloxane, spherical and mesoporous solid.

[0086] Performance Testing

[0087] The composite materials obtained in the above-mentioned Examples C1 to C6 and Comparative Examples C1 to C3 were prepared into boards, and the performance of the boards was tested.

[0088] Testing items include: surface resistance, tensile strength, elongation at break, elastic modulus

[0089] Surface resistance: The surface resistance tester Quick 499D produced by Quick Intelligent Equipment Co., Ltd. was used for testing. Six different areas were taken for testing of each test sample, such as Figure 1 shown.

[0090] Mechanical properties, including tensile strength, elongation at break and elastic modulus, were tested according to GB / T 1040-2006 (150*10*4mm) standard, and the tensile rate was set at 10mm / min;

[0091] The test results refer to Table 2 and Table 3;

[0092] Table 2. Surface resistance uniformity test (unit: Ω)

[0093]

[0094]

[0095] Note: PEEK sheet refers to PEEK sheet without any masterbatch. The molecular weight of polyetheretherketone (PEEK) resin used in PEEK sheet is 200,000.

[0096] Table 3 Mechanical properties test results

[0097] Tensile strength(MPa) Elongation at break (%) Elastic modulus (MPa) Example C1 85.59 15.31 875.23 Example C2 84.87 13.25 869.25 Example C3 85.48 14.53 845.53 Example C4 86.64 16.25 924.61 Example C5 84.36 14.58 884.52 Example C6 83.96 13.10 856.15 Comparative Example C1 82.31 12.09 828.81 Comparative Example C2 80.12 10.54 856.24 Comparative Example C3 85.12 18.79 881.23 PEEK Sheet 88.59 35.21 895.54

[0098] Result analysis:

[0099] 1. By Figure 2 It can be seen that during the preparation of mesoporous black phosphorus, some mesoporous structures were formed in black phosphorus after being immersed in dilute sulfuric acid solution. The higher the concentration, the more obvious the mesopores. In particular, there were more mesoporous structures after being treated with hydrogen peroxide. At the same time, EDS test showed that the oxygen content increased, such as Figure 2 As shown, fine particles and various mesopores are formed on the surface of black phosphorus.

[0100] After the prepared mesoporous black phosphorus is mixed with carbon black, a silicon molten coupling agent and low molecular weight PEEK are added and kneaded into granules, and then melt-compounded with PEEK resin, a PEEK composite material with uniform surface distribution can be prepared, such as Figure 3 shown. Figure 3 : is a SEM image of the PEEK composite resin prepared in Example C2. There is no obvious filling aggregation on the surface of the material, indicating that the conductive particles such as carbon black are evenly dispersed. In addition, in the EDS image, as shown in FIG. Figure 4 As shown in the figure, the uniform element distribution of C and O can also be seen. Figure 5 As shown, the stress-strain curve of the PEEK composite material prepared in Example C3.

[0101] It can be seen from the above figures and experimental data that, through the treatment of the present invention, the mesoporous structure of black phosphorus can be achieved, the surface resistance can be reduced, and at the same time, it is as close to the PEEK sheet as possible.

[0102] 2. It can be seen from Examples C1 to C3 and Comparative Example C1 that the surface resistances of Examples C1, C3 and Comparative Example C1 are similar. The main reason is that there is too much carbon black in Example C1 and too little carbon black in Example C3. Although both use mesoporous black phosphorus, due to the difference in the amount of carbon black and the size of black phosphorus, there is no obvious advantage between Example C1 and Example C3 over Comparative Example 1; however, compared with the PEEK sheet, Example C1 and Example C3 have obvious advantages in surface resistance; more specifically, Example C1 uses more carbon black, and its conductivity is improved, but because the amount of mesoporous black phosphorus is insufficient and the homogenization treatment is not perfect, it is inferior to Example C2. In Example C3, 30 parts of antistatic masterbatch 3 are selected, but the antistatic masterbatch 3 contains less carbon black, only 1wt%. Therefore, although the uniformity has improved, the surface resistance in Example C3 cannot exceed that of Example C2.

[0103] The surface resistance of Example C2 is significantly lower than that of Comparative Example C1.

[0104] Through the performance comparison of the above-mentioned Examples C1 to C3 and Comparative Example C1 and PEEK plate, the use of mesoporous black phosphorus in the present invention can effectively reduce the surface resistance;

[0105] According to the mechanical properties of Example C1 to Example C3 and Comparative Example C1 and PEEK plate, the mechanical properties of Example C1 to Example C3 of the present invention are better than Comparative Example C1. Except that the elongation at break is significantly worse than that of PEEK plate, the tensile strength and elastic modulus are close to those of PEEK plate.

[0106] 3. It can be seen from Examples C2 and C4 to C6 that after the black phosphorus is further treated with hydrogen peroxide of different concentrations by antistatic masterbatch, due to the oxidation effect and mesoporous effect on the surface of black phosphorus, Example C4 shows a lower surface resistance value and is evenly distributed, about 2.1-3.8×10 7 However, as the concentration of hydrogen peroxide decreases, the oxidation effect of the mesoporous black phosphorus decreases, resulting in a decrease in the distribution uniformity of the carbon black filler, and an increase in the surface resistance in Examples C5 and C6, and a decrease in uniformity.

[0107] However, no matter how the hydrogen peroxide concentration and treatment process are selected, the surface resistance performance is significantly improved compared with Example C2, and the mechanical properties are also improved.

[0108] 4. Comparative Example C2 shows that if black phosphorus powder is not used at all and carbon black is used directly to prepare the antistatic masterbatch, although it has a higher content of carbon black, the filling distribution is more uneven and it cannot further reduce the surface resistance.

[0109] It can be seen from comparative example C3 that its mesoporous effect also promotes the dispersion effect of carbon black, resulting in a certain degree of improvement in mechanical properties compared to example C2, but the surface resistance is not as good as that of example C2. The reason is that the phosphorus element of mesoporous black phosphorus itself is conducive to the electron transmission property and the charge transmission channel it constructs, which can further reduce the surface resistance compared to mesoporous silica.

Claims

1. An antistatic masterbatch, characterized in that: It includes mesoporous black phosphorus, a conductive agent, and PEEK; the content of the mesoporous black phosphorus is 1 to 20wt%, the particle size of the mesoporous black phosphorus is 1μm to 100μm; the particle size of the conductive agent is 1μm to 50μm; the PEEK is a small molecular weight PEEK; the weight average molecular weight of the small molecular weight PEEK is 4000 to 10000; the preparation method of the mesoporous black phosphorus is: using black phosphorus powder as a raw material, soaking it in a dilute sulfuric acid solution with a concentration of 1 to 10wt%, performing an oxidation reaction at 80 to 200°C for 24 to 72 hours, and drying.

2. The antistatic masterbatch according to claim 1, characterized in that: The conductive agent is one or more combinations of graphite, carbon powder, and carbon nanotubes; the content of the conductive agent is 1 to 50 wt %.

3. The antistatic masterbatch according to claim 1, characterized in that: It also includes a silane coupling agent, which is at least one of KH560, KH550, and KH570; the content of the silane coupling agent is 1 to 10 wt%.

4. The antistatic masterbatch according to claim 1, characterized in that: The black phosphorus powder is black phosphorus powder that has been pre-oxidized with hydrogen peroxide; the concentration of the hydrogen peroxide is 5 to 15 wt %; the pre-oxidation operation is: immersing the black phosphorus powder in hydrogen peroxide and soaking it at room temperature for 12 to 24 hours.

5. A method for preparing the antistatic masterbatch according to claim 3, characterized in that: The mesoporous black phosphorus and the conductive agent are premixed and a solution containing a silane coupling agent is added to obtain a mixed material, and the mixed material and the dried PEEK are mixed and granulated.

6. A PEEK composite material, characterized in that: Contains the antistatic masterbatch according to any one of claims 1 to 4 and PEEK; the content of the antistatic masterbatch in the PEEK composite material is 1 to 30wt%.

7. The PEEK composite material according to claim 6, characterized in that: The molecular weight of the PEEK is 10,000 to 500,000.

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