Antistatic polyether-ether-ketone composite material for semiconductor device

Abstract

The invention relates to the field of high polymer materials, and discloses an antistatic polyether-ether-ketone composite material for semiconductor devices, the antistatic polyether-ether-ketone composite material comprises the following raw materials by weight: 60-70 parts of polyether-ether-ketone, 20-30 parts of polyetherimide, 3-5 parts of modified carbon nanotubes, 2-4 parts of nano core-shell particles, 0.5-1 part of a coupling agent, and 0.2-0.5 part of an antioxidant; the modified carbon nanotubes are obtained by acidizing carbon nanotubes and grafting imidazolyl quaternary ammonium salt on the surfaces of the acidized carbon nanotubes; according to the antistatic polyether-ether-ketone composite material, through blending of polyetherimide, the melt viscosity of a composite system can be reduced, the problems that polyether-ether-ketone is high in processing temperature and poor in flowability are solved, and the antistatic performance of the composite material is improved. Through the synergistic interaction of the added modified carbon nanotubes and nano core-shell particles, the material is endowed with excellent mechanical properties, wear resistance and antistatic properties.

Description

Technical Field

[0001] The present invention belongs to the field of polymer materials, and specifically relates to an antistatic polyetheretherketone composite material for semiconductor devices Background Art

[0002] Polyetheretherketone (PEEK) is a new type of thermoplastic engineering plastic with excellent physical and mechanical properties. PEEK is a semi-crystalline, thermoplastic aromatic polymer with a linear main chain containing chain links. It is the most important type in the polyaryletherketone series of polymers. Its molecular chain contains a large number of benzene rings, resulting in excellent physical and chemical properties such as excellent heat resistance, wear resistance, fatigue resistance, radiation resistance, peeling resistance, and creep resistance. Its two ether bonds and carbonyl groups provide flexibility and excellent processability, making it widely used as a special functional material in the petroleum, chemical, and machinery industries.

[0003] The semiconductor manufacturing industry has very high requirements for the antistatic properties of materials. Static electricity is easily generated during the packaging and transportation of electronic products. If the static electricity is not conducted away, it will cause great harm to electronic products. In order to give PEEK materials antistatic properties, they can usually be modified in the following ways: (1) Adding conductive fillers: such as carbon fiber, carbon black, metal powder, etc. These fillers can improve the conductivity of the material and effectively disperse static electricity. (2) Surface coating: Applying a conductive coating on the surface of the PEEK material can achieve an antistatic effect without changing the properties of the material itself. (3) Blending modification: Blending PEEK with other polymers with good conductivity to form a composite material, which can not only maintain the excellent properties of PEEK but also improve its antistatic ability. However, the addition of conductive fillers may cause the mechanical properties of PEEK materials to deteriorate, especially tensile strength, impact strength and fracture toughness. This is because the presence of conductive fillers may destroy the continuity of the PEEK matrix, forming stress concentration points, making the material more prone to crack propagation when subjected to stress. Therefore, there is an urgent need for a polyetheretherketone composite material that can improve the antistatic properties of the material without changing its mechanical properties, so as to expand the application of PEEK materials in semiconductor devices. Summary of the Invention

[0004] The purpose of the present invention is to provide an antistatic polyetheretherketone composite material for semiconductor devices. By blending with polyetherimide, the melt viscosity of the composite system can be reduced, solving the problems of high processing temperature and poor fluidity of polyetheretherketone. By adding modified carbon nanotubes and nano core-shell particles for synergistic enhancement, the material is given excellent mechanical properties, wear resistance and antistatic properties.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] An antistatic polyetheretherketone composite material for semiconductor devices, comprising the following raw materials in parts by weight: 60-70 parts of polyetheretherketone, 20-30 parts of polyetherimide, 3-5 parts of modified carbon nanotubes, 2-4 parts of nano core-shell particles, 0.5-1 part of a coupling agent, and 0.2-0.5 part of an antioxidant;

[0007] The modified carbon nanotubes are obtained by grafting imidazolyl quaternary ammonium salt onto the surface of carbon nanotubes after acid treatment.

[0008] The nano core-shell particles are a core-shell structure obtained by in-situ polymerization of nano TiO2 coated with sulfonated polyaniline.

[0009] Preferably, the coupling agent is one of silane coupling agent KH550, silane coupling agent KH560, titanate coupling agent NDZ101 and aluminate coupling agent DL411.

[0010] Preferably, the antioxidant is a mixture of antioxidant 168 and antioxidant 1076 in a mass ratio of 3-4:1.

[0011] Preferably, the method for preparing modified carbon nanotubes comprises the following steps:

[0012] (1) adding carbon nanotubes, concentrated nitric acid, and concentrated sulfuric acid into a reaction flask containing a reflux device, placing the reaction flask in a heating mantle, turning on the heating, heating to 100-110° C. for reflux reaction for 2-3 hours, and cooling naturally to room temperature after the reaction, washing with water, filtering, and drying to obtain functionalized modified carbon nanotubes;

[0013] (2) Weigh 1,4-di(1H-imidazol-1-yl)butane and add it to acetone to dissolve it. Place it in an ice bath and introduce nitrogen protection. Add 2-(2-bromoethoxy)ethanol dropwise while stirring. Stir the mixture in an ice bath overnight. Continue stirring at room temperature of 20-25°C for 2-3 hours. Place it in a water bath at 35-40°C and stir for 10-15 hours. After the reaction is completed, remove the solvent by distillation under reduced pressure. Wash the product with a mixture of petroleum ether and dichloromethane in a volume ratio of 3:1. After drying, obtain an imidazolyl quaternary ammonium salt grafted product.

[0014] (3) Weighing the functionalized modified carbon nanotubes and the imidazole quaternary ammonium salt grafted product, adding them to anhydrous DMF solution, adding p-toluenesulfonic acid, ultrasonically dispersing for 5-10 minutes, heating to 90-95°C, and stirring and reacting for 10-15 hours to obtain antistatic modified carbon nanotubes.

[0015] Preferably, in step (2), the mass ratio of 1,4-di(1H-imidazol-1-yl)butane to 2-(2-bromoethoxy)ethanol is 1.9-2.1:4.0-5.0.

[0016] Preferably, in step (3), the mass ratio of the functionalized modified carbon nanotubes, the imidazole quaternary ammonium salt graft, and the p-toluenesulfonic acid is 15-20:2-3:5-8.

[0017] Preferably, the preparation method of nano core-shell particles comprises the following steps:

[0018] A. Disperse nano-TiO2 in 1M HCl, ultrasonicate for 20-40 min, add aniline, and stir in an ice bath for 20-40 min;

[0019] B. Slowly add p-aminobenzenesulfonic acid solution dropwise to maintain pH < 2, add 0.1 M ammonium persulfate aqueous solution dropwise, react in an ice bath for 6-12 hours, add ethanol to terminate the reaction, wash by centrifugation until neutral, and dry in vacuo at 60°C to obtain nano core-shell particles.

[0020] Preferably, in step A, the mass ratio of aniline to nano-TiO2 is 1-3:1.

[0021] Preferably, the molar ratio of APS to aniline in step B is 1-1.2:1

[0022] Preferably, the preparation method of the antistatic polyetheretherketone composite material comprises the following steps:

[0023] S1. vacuum drying polyetheretherketone, polyetherimide, modified carbon nanotubes, and nano core-shell particles for 8-12 hours respectively;

[0024] S2, polyetheretherketone, polyetherimide, coupling agent and antioxidant are melt-blended in a twin-screw extruder at 360-380°C;

[0025] S3, adding modified carbon nanotubes and nano core-shell particles to the side feed of the twin-screw extruder and mixing them evenly, with the screw speed at 150 rpm, vacuum exhaust, and extrusion granulation;

[0026] S4. Place the composite pellets in a mold, hot-press at 385° C. and 15 MPa for 4-6 minutes, and quench with cold water to obtain an antistatic polyetheretherketone composite material.

[0027] Beneficial effects of the present invention:

[0028] The antistatic polyetheretherketone composite material of the present invention is obtained by blending polyetherimide with polyetheretherketone, which can reduce the melt viscosity of the composite system and solve the problems of high processing temperature and poor fluidity of polyetheretherketone. By adding modified carbon nanotubes and nano core-shell particles for synergistic enhancement, the material is given excellent mechanical properties, wear resistance and antistatic properties.

[0029] Among them, the modified carbon nanotubes are obtained by grafting imidazolyl quaternary ammonium salts on the surface of carbon nanotubes after acidification treatment. The high aspect ratio and high strength of the carbon nanotubes themselves can form a "skeleton" in the matrix, thereby improving the tensile strength, bending strength and wear resistance of the composite material. After acidification and grafting modification, the surface of the carbon nanotubes contains polar functional groups (such as carboxyl and imidazole), and hydrogen bonds or van der Waals forces exist between them and the polar groups (ether bonds, ketone groups, and imide groups) of PEEK and PEI, thereby improving the dispersibility and interfacial bonding strength. The imidazolyl quaternary ammonium salts grafted on the surface of the carbon nanotubes are cationic conductive groups. The high aspect ratio of the carbon nanotubes enables them to overlap with each other in the matrix to form charge transfer channels, reduce surface resistance, and inhibit static electricity accumulation, thereby improving antistatic properties.

[0030] Nano core-shell particles have a core-shell structure obtained by in-situ polymerization of nano-TiO2 and coating sulfonated polyaniline. The nano-TiO2 core has high hardness and light resistance, which can improve the material's wear resistance, scratch resistance and UV aging resistance; the sulfonated polyaniline shell contains sulfonic groups (-SO3H) and conjugated structures, which can assist in building a conductive network (synergistically enhancing antistatic properties with modified carbon nanotubes) on the one hand, and improve the dispersibility of nanoparticles on the other hand through the reaction of polar groups with the matrix (PEEK, PEI) and silane coupling agents; the core-shell structure reduces the tendency of nanoparticles to agglomerate, and its size effect (nanoscale) can improve the overall performance without significantly reducing the toughness of the material.

[0031] Furthermore, the carbon nanotubes provide rigid support, while the core-shell particles fill the gaps in the matrix, reducing stress concentration. Simultaneously, the interfacial interaction between the sulfonated polyaniline shell, the matrix, and the carbon nanotubes further optimizes stress transfer. The carbon nanotubes inhibit crack propagation, while the core-shell particles absorb impact energy. Together, they balance rigidity and toughness, synergistically enhancing the material's mechanical properties. Furthermore, with the modified carbon nanotubes as the primary conductive skeleton, the sulfonated polyaniline shell of the nanocore-shell particles forms "conductive nodes" with the carbon nanotubes, reducing defects in the conductive network and improving charge transfer efficiency. The modified carbon nanotubes are long-range conductive, while the nanocore-shell particles are short-range conductive. The two combine to form a dual-channel conductive network of "linear modified carbon nanotubes bridging point-like nanocore-shell particles," lowering the percolation threshold. The dual charge dissipation mechanism, proton conduction by the nanocore-shell particles and electron conduction by the modified carbon nanotubes, further enhances the material's antistatic properties.

[0032] Of course, any product implementing the present invention does not necessarily need to achieve all of the advantages described above at the same time. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0034] Figure 1 1 is a SEM image of carbon nanotubes before and after modification in Example 1 of the present invention;

[0035] Figure 2 TEM images of nano-TiO2 before and after modification in Example 2 of the present invention. DETAILED DESCRIPTION

[0036] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. 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 making any creative efforts shall fall within the scope of protection of the present invention.

[0037] Example 1

[0038] A modified carbon nanotube is obtained by grafting an imidazolyl quaternary ammonium salt onto the surface of a carbon nanotube after acidification treatment. The preparation method comprises the following steps:

[0039] (1) 1 g of carbon nanotubes, 30 ml of concentrated nitric acid, and 30 ml of concentrated sulfuric acid were added to a reaction flask containing a reflux device, and the reaction flask was placed in a heating mantle, and the heating was turned on and heated to 105° C. for reflux reaction for 2.5 h. After the reaction was completed, the reaction was naturally cooled to room temperature, washed with water, filtered, and dried to obtain functionalized modified carbon nanotubes;

[0040] (2) Weigh 2.0 g of 1,4-di(1H-imidazol-1-yl)butane and add it to 55 ml of acetone to dissolve it. Place it in an ice bath and purge it with nitrogen. Add 4.5 g of 2-(2-bromoethoxy)ethanol dropwise while stirring. Stir the mixture in an ice bath overnight. Then continue stirring at room temperature of 25°C for 2.5 hours. Place it in a water bath at 38°C and stir for 12 hours. After the reaction is completed, remove the solvent by distillation under reduced pressure. Wash the product with petroleum ether: dichloromethane = 3:1 and dry it to obtain an imidazolyl quaternary ammonium salt grafted product.

[0041] (3) Weigh 0.18 g of functionalized modified carbon nanotubes and 25 mg of imidazole quaternary ammonium salt grafted product and add them to 25 ml of anhydrous DMF solution, add 65 mg of p-toluenesulfonic acid, ultrasonically disperse for 8 min, heat to 92 ° C, and stir and react for 12 h to obtain antistatic modified carbon nanotubes.

[0042] Figure 1 The SEM images of carbon nanotubes before and after modification are shown in Figure 2. Figure 1 A is the carbon nanotube before modification, Figure 1 B is functionalized modified carbon nanotubes, Figure 1 The carbon nanotubes in A have smooth, slender surfaces and are entangled with each other; Figure 1 The surface of the functionalized modified carbon nanotubes in B is smoother, which is because some impurities have been removed by acid treatment. However, the functionalized modified carbon nanotubes are uneven in thickness and are still cross-entangled and agglomerated. Figure 1 C is an antistatic modified carbon nanotube. It can be seen that the carbon nanotube is wrapped with an antistatic modified compound similar to a shadow. This wrapping can effectively improve the dispersion of the carbon nanotube in the composite material and make it have good compatibility with polyetheretherketone.

[0043] Example 2

[0044] A nano core-shell particle having a core-shell structure obtained by in-situ polymerization of nano-TiO2 coated with sulfonated polyaniline, wherein the preparation method comprises the following steps:

[0045] A. Disperse 0.5 g of nano-TiO2 in 100 mL of 1 M HCl, ultrasonicate for 30 min, add 0.93 g of aniline, and stir in an ice bath for 30 min;

[0046] B. Slowly dropwise add 20 mL of an aqueous solution containing 0.5 g of p-aminobenzenesulfonic acid to maintain pH < 2, then dropwise add 100 mL of a 0.1 M ammonium persulfate aqueous solution, react in an ice bath for 8 h, add ethanol to terminate the reaction, wash by centrifugation until neutral, and dry in a vacuum at 60°C to obtain nano core-shell particles.

[0047] Figure 2 TEM images of nano-TiO2 before and after modification. Figure 2 A is the nano-TiO2 before modification. The surface of the nano-TiO2 before modification is relatively rough, with uneven edges and jagged morphology and serious agglomeration. Figure 2 B is a nano core-shell particle. Nano TiO2 and sulfonated polyaniline form a core-shell structure with a smooth outer surface and clear edges.

[0048] Example 3

[0049] An antistatic polyetheretherketone composite material for semiconductor devices comprises the following raw materials in parts by weight: 70 parts of polyetheretherketone, 20 parts of polyetherimide, 5 parts of modified carbon nanotubes, 2 parts of nano core-shell particles, 1 part of silane coupling agent KH550, 1680.15 parts of antioxidant, and 10760.05 parts of antioxidant; the modified carbon nanotubes are prepared in Example 1; the nano core-shell particles are prepared in Example 2.

[0050] The preparation method of the antistatic polyetheretherketone composite material comprises the following steps:

[0051] S1, vacuum drying polyetheretherketone, polyetherimide, modified carbon nanotubes, and nano core-shell particles for 12 h respectively;

[0052] S2, polyetheretherketone, polyetherimide, silane coupling agent KH550, antioxidant 168 and antioxidant 1076 were melt-blended in a twin-screw extruder at 360-380°C;

[0053] S3, adding modified carbon nanotubes and nano core-shell particles to the side feed of the twin-screw extruder and mixing them evenly, with the screw speed at 150 rpm, vacuum exhaust, and extrusion granulation;

[0054] S4. Place the composite pellets in a mold, hot-press at 385° C. and 15 MPa for 6 min, and quench with cold water to obtain an antistatic polyetheretherketone composite material.

[0055] Example 4

[0056] An antistatic polyetheretherketone composite material for semiconductor devices comprises the following raw materials in parts by weight: 60 parts of polyetheretherketone, 30 parts of polyetherimide, 3 parts of modified carbon nanotubes, 4 parts of nano core-shell particles, 0.5 parts of silane coupling agent KH560, 1680.4 parts of antioxidant, and 10760.1 parts of antioxidant; the modified carbon nanotubes are prepared in Example 1; and the nano core-shell particles are prepared in Example 2.

[0057] The preparation method of the antistatic polyetheretherketone composite material comprises the following steps:

[0058] S1, vacuum drying polyetheretherketone, polyetherimide, modified carbon nanotubes, and nano core-shell particles for 8 h respectively;

[0059] S2, polyetheretherketone, polyetherimide, silane coupling agent KH560, antioxidant 168 and antioxidant 1076 were melt-blended in a twin-screw extruder at 360-380°C;

[0060] S3, adding modified carbon nanotubes and nano core-shell particles to the side feed of the twin-screw extruder and mixing them evenly, with the screw speed at 150 rpm, vacuum exhaust, and extrusion granulation;

[0061] S4. Place the composite pellets in a mold, hot-press at 385° C. and 15 MPa for 6 min, and quench with cold water to obtain an antistatic polyetheretherketone composite material.

[0062] Example 5

[0063] An antistatic polyetheretherketone composite material for semiconductor devices comprises the following raw materials in parts by weight: 65 parts of polyetheretherketone, 25 parts of polyetherimide, 4 parts of modified carbon nanotubes, 3 parts of nano core-shell particles, 10.8 parts of titanate coupling agent NDZ101, 1680.3 parts of antioxidant, and 10760.1 parts of antioxidant; the modified carbon nanotubes are prepared in Example 1; the nano core-shell particles are prepared in Example 2.

[0064] The preparation method of the antistatic polyetheretherketone composite material comprises the following steps:

[0065] S1, vacuum drying polyetheretherketone, polyetherimide, modified carbon nanotubes, and nano core-shell particles for 10 h respectively;

[0066] S2, polyetheretherketone, polyetherimide, titanate coupling agent NDZ101, antioxidant 168 and antioxidant 1076 were melt-blended in a twin-screw extruder at 360-380°C;

[0067] S3, adding modified carbon nanotubes and nano core-shell particles to the side feed of the twin-screw extruder and mixing them evenly, with the screw speed at 150 rpm, vacuum exhaust, and extrusion granulation;

[0068] S4. Place the composite pellets in a mold, hot-press at 385° C. and 15 MPa for 5 min, and quench with cold water to obtain an antistatic polyetheretherketone composite material.

[0069] Comparative Example 1

[0070] An antistatic polyetheretherketone composite material for semiconductor devices, the antistatic polyetheretherketone composite material comprises the following raw materials in parts by weight: 65 parts of polyetheretherketone, 25 parts of polyetherimide, 3 parts of nano core-shell particles, 10.8 parts of titanate coupling agent NDZ101, 1680.3 parts of antioxidant, and 10760.1 parts of antioxidant; the nano core-shell particles are prepared in Example 2.

[0071] The preparation method of the antistatic polyetheretherketone composite material comprises the following steps:

[0072] S1, vacuum drying polyetheretherketone, polyetherimide, modified carbon nanotubes, and nano core-shell particles for 10 h respectively;

[0073] S2, polyetheretherketone, polyetherimide, titanate coupling agent NDZ101, antioxidant 168 and antioxidant 1076 were melt-blended in a twin-screw extruder at 360-380°C;

[0074] S3, adding nano core-shell particles to the side feed of the twin-screw extruder and mixing evenly, the screw speed is 150 rpm, vacuum exhaust is performed, and extrusion granulation is performed;

[0075] S4. Place the composite pellets in a mold, hot-press at 385° C. and 15 MPa for 5 min, and quench with cold water to obtain an antistatic polyetheretherketone composite material.

[0076] Comparative Example 2

[0077] An antistatic polyetheretherketone composite material for semiconductor devices includes the following raw materials in parts by weight: 65 parts of polyetheretherketone, 25 parts of polyetherimide, 4 parts of modified carbon nanotubes, 10.8 parts of titanate coupling agent NDZ101, 1680.3 parts of antioxidant, and 10760.1 parts of antioxidant; the modified carbon nanotubes are prepared in Example 1.

[0078] The preparation method of the antistatic polyetheretherketone composite material comprises the following steps:

[0079] S1, vacuum drying polyetheretherketone, polyetherimide, modified carbon nanotubes, and nano core-shell particles for 10 h respectively;

[0080] S2, polyetheretherketone, polyetherimide, titanate coupling agent NDZ101, antioxidant 168 and antioxidant 1076 were melt-blended in a twin-screw extruder at 360-380°C;

[0081] S3, adding modified carbon nanotubes to the side feed of the twin-screw extruder and mixing evenly, the screw speed is 150 rpm, vacuum exhaust is performed, and extrusion granulation is performed;

[0082] S4. Place the composite pellets in a mold, hot-press at 385° C. and 15 MPa for 5 min, and quench with cold water to obtain an antistatic polyetheretherketone composite material.

[0083] Comparative Example 3

[0084] An antistatic polyetheretherketone composite material for semiconductor devices comprises the following raw materials in parts by weight: 65 parts of polyetheretherketone, 25 parts of polyetherimide, 10.8 parts of titanate coupling agent NDZ101, 1680.3 parts of antioxidant, and 10760.1 parts of antioxidant.

[0085] The preparation method of the antistatic polyetheretherketone composite material comprises the following steps:

[0086] S1, vacuum drying polyetheretherketone, polyetherimide, modified carbon nanotubes, and nano core-shell particles for 10 h respectively;

[0087] S2, polyetheretherketone, polyetherimide, titanate coupling agent NDZ101, antioxidant 168 and antioxidant 1076 were melt-blended in a twin-screw extruder at 360-380°C, with a screw speed of 150 rpm and vacuum degassing, and extruded into pellets;

[0088] S3. Place the composite pellets in a mold, hot-press at 385° C. and 15 MPa for 5 min, and quench with cold water to obtain an antistatic polyetheretherketone composite material.

[0089] Performance testing

[0090] The antistatic polyetheretherketone composite materials prepared in Example 5 and Comparative Examples 1-3 were subjected to performance testing, including tensile strength testing according to GB / T1040.1-2018, flexural strength testing according to GB / T9341-2008, impact strength testing according to GB / T1843-2021, antistatic performance testing according to GB / T1410-2006, heat resistance testing according to GB / T1634.2-2021, and wear resistance testing according to GB / T3960-2016. The obtained data are shown in Table 1 below.

[0091] Table 1

[0092]

[0093]

[0094] From the data in Table 1, it can be seen that the surface resistance of Comparative Example 3 is as high as 1.8×10 14 Ω, which is a typical insulating material (PEEK / PEI matrix itself is not conductive) and cannot be antistatic. Comparative Example 2 contains only modified carbon nanotubes, and the surface resistance is reduced to 3.1×10 9 Ω, reaching the entry-level standard of "antistatic material" (usually <10 11 Ω), indicating that the modified carbon nanotubes can independently construct a conductive network. The imidazolyl quaternary ammonium salt grafted on its surface is a cationic conductive group. The high aspect ratio of the carbon nanotubes enables them to overlap with each other in the matrix, forming a charge transfer channel and reducing the surface resistance. Comparative Example 1 contains only nano core-shell particles, and the surface resistance is 8.6×10 12 Ω, which is still at the insulating level, indicating that the core-shell particles alone cannot effectively construct a conductive network, but the conjugated structure of the sulfonated polyaniline shell can conduct electricity weakly, so the resistance is slightly lower than that of Comparative Example 3. The surface resistance of Example 5 is further reduced to 5.2×10 7 Ω, significantly improving antistatic performance, demonstrating a synergistic effect: the modified carbon nanotubes serve as the primary conductive backbone, while the sulfonated polyaniline shell of the nanocore-shell particles forms "conductive nodes" with the carbon nanotubes, reducing defects in the conductive network and improving charge transfer efficiency. This demonstrates that the modified carbon nanotubes are the core contributor to antistatic performance, while the core-shell particles provide a complementary synergistic effect.

[0095] The tensile / bending strength of comparative example 3 is the lowest because the pure matrix has no reinforcing filler; the tensile / bending strength of comparative example 2 is increased to 102 / 140 MPa, indicating that the modified carbon nanotubes improve the rigidity through the "fiber reinforcement effect", and their high tensile strength and aspect ratio form a "skeleton" in the matrix to share the external force, and the surface functional groups form hydrogen bonds with the polar groups of the matrix (ether bonds, ketone groups), the interface bonding force is strong, and the stress is effectively transferred; the strength of comparative example 1 is slightly lower than that of comparative example 2, indicating that the core-shell particles are weaker than carbon nanotubes in enhancing the rigidity, but the high hardness of the TiO2 core can still help improve the strength; Example 5 has the highest strength, reflecting synergistic enhancement, carbon nanotubes provide the main rigid support, core-shell particles fill the gaps in the matrix, reduce stress concentration, and at the same time, the interface between the sulfonated polyaniline shell and the matrix / carbon nanotubes further optimizes stress transfer.

[0096] Comparative Example 3 has the worst toughness, and the PEEK / PEI matrix is ​​more brittle; the impact strength of Comparative Example 1 is increased to 22kJ / m 2 , which shows that nano core-shell particles are the key to improving toughness: the "soft-hard" composite of the core-shell structure (TiO2 hard core + sulfonated polyaniline soft shell) can absorb impact energy through shell deformation, and the nano size effect reduces agglomeration and disperses stress concentration; the impact strength of comparative example 2 is slightly lower than that of comparative example 1, because carbon nanotubes are rigid but easy to agglomerate (if there is no core-shell particle to assist in dispersion, local stress concentration may occur); Example 5 has the best toughness, carbon nanotubes inhibit crack propagation, and core-shell particles absorb impact energy, and the two together balance rigidity and toughness.

[0097] Comparative Example 3 has the lowest heat deformation temperature, and the heat resistance of the pure matrix is ​​limited by the movement of the molecular chain; the HDT of Comparative Example 1 is increased to 220°C, indicating that the "thermal barrier effect" of the nano-TiO2 core is the core of the improved heat resistance. Nano-TiO2 has a low thermal conductivity, which can inhibit the movement of the matrix molecular chain at high temperature and delay deformation; the HDT of Comparative Example 2 is slightly higher than that of Comparative Example 1, because the high thermal conductivity of carbon nanotubes can evenly disperse heat and reduce local overheating; Example 5 has the highest HDT, the TiO2 core hinders the movement of the molecular chain, and the carbon nanotubes quickly dissipate heat, which together improve the high-temperature stability of the material.

[0098] The wear amount of comparative example 3 is the largest, and the wear resistance of the pure matrix is ​​poor; the wear amount of comparative example 1 is reduced to 12.0 mg, indicating that the TiO2 hard core can effectively improve the wear resistance, and the nano-TiO2 has a high hardness (Mohs hardness 6-7), which can form a "wear-resistant protective layer" on the surface of the material to reduce the matrix loss during friction; the wear amount of comparative example 2 is 10.2 mg, and the high aspect ratio of carbon nanotubes can enhance the surface strength of the matrix and reduce scratches, but the effect is weaker than that of core-shell particles; the wear amount of embodiment 5 is the lowest, the TiO2 core provides hard support for wear resistance, and the carbon nanotubes enhance the surface integrity, reduce the shedding of wear chips, and jointly improve the wear resistance life.

[0099] The above content is merely an example and explanation of the concept of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. An antistatic polyetheretherketone composite material for semiconductor devices, characterized in that: The antistatic polyetheretherketone composite material comprises the following raw materials in parts by weight: 60-70 parts of polyetheretherketone, 20-30 parts of polyetherimide, 3-5 parts of modified carbon nanotubes, 2-4 parts of nano core-shell particles, 0.5-1 part of coupling agent, and 0.2-0.5 part of antioxidant; The modified carbon nanotubes are obtained by grafting imidazolyl quaternary ammonium salt onto the surface of carbon nanotubes after acidification treatment; The nano core-shell particles have a core-shell structure obtained by in-situ polymerization of nano TiO2 and coating sulfonated polyaniline.

2. The antistatic polyetheretherketone composite material for semiconductor devices according to claim 1, characterized in that: The coupling agent is one of silane coupling agent KH550, silane coupling agent KH560, titanate coupling agent NDZ101 and aluminate coupling agent DL411.

3. The antistatic polyetheretherketone composite material for semiconductor devices according to claim 1, characterized in that: The antioxidant is a mixture of antioxidant 168 and antioxidant 1076 in a mass ratio of 3-4:

1.

4. The antistatic polyetheretherketone composite material for semiconductor devices according to claim 1, characterized in that: The preparation method of the modified carbon nanotubes comprises the following steps: (1) adding carbon nanotubes, concentrated nitric acid, and concentrated sulfuric acid into a reaction flask containing a reflux device, placing the reaction flask in a heating mantle, turning on the heating, heating to 100-110° C. for reflux reaction for 2-3 hours, and cooling naturally to room temperature after the reaction, washing with water, filtering, and drying to obtain functionalized modified carbon nanotubes; (2) Weigh 1,4-di(1H-imidazol-1-yl)butane and add it to acetone to dissolve it. Place it in an ice bath and introduce nitrogen protection. Add 2-(2-bromoethoxy)ethanol dropwise while stirring. Stir the mixture in an ice bath overnight. Continue stirring at room temperature of 20-25°C for 2-3 hours. Place it in a water bath at 35-40°C and stir for 10-15 hours. After the reaction is completed, remove the solvent by distillation under reduced pressure. Wash the product with a mixture of petroleum ether and dichloromethane in a volume ratio of 3:

1. After drying, obtain an imidazolyl quaternary ammonium salt grafted product. (3) Weighing the functionalized modified carbon nanotubes and the imidazole quaternary ammonium salt grafted product, adding them to anhydrous DMF solution, adding p-toluenesulfonic acid, ultrasonically dispersing for 5-10 minutes, heating to 90-95°C, and stirring and reacting for 10-15 hours to obtain antistatic modified carbon nanotubes.

5. The antistatic polyetheretherketone composite material for semiconductor devices according to claim 3, characterized in that: In the step (2), the mass ratio of 1,4-di(1H-imidazol-1-yl)butane to 2-(2-bromoethoxy)ethanol is 1.9-2.1:4.0-5.

0.

6. The antistatic polyetheretherketone composite material for semiconductor devices according to claim 3, characterized in that: In the step (3), the mass ratio of the functionalized modified carbon nanotubes, the imidazole quaternary ammonium salt grafted product, and the p-toluenesulfonic acid is 15-20:2-3:5-8.

7. The antistatic polyetheretherketone composite material for semiconductor devices according to claim 1, characterized in that: The preparation method of the nano core-shell particles comprises the following steps: A. Disperse nano-TiO2 in 1M HCl, ultrasonicate for 20-40 min, add aniline, and stir in an ice bath for 20-40 min; B. Slowly add p-aminobenzenesulfonic acid solution dropwise to maintain pH < 2, add 0.1 M ammonium persulfate aqueous solution dropwise, react in an ice bath for 6-12 hours, add ethanol to terminate the reaction, wash by centrifugation until neutral, and dry in vacuo at 60°C to obtain nano core-shell particles.

8. The antistatic polyetheretherketone composite material for semiconductor devices according to claim 7, characterized in that: In step A, the mass ratio of aniline to nano-TiO2 is 1-3:

1.

9. The antistatic polyetheretherketone composite material for semiconductor devices according to claim 1, characterized in that: The molar ratio of APS to aniline in step B is 1-1.2:

1.

10. The antistatic polyetheretherketone composite material for semiconductor devices according to claim 1, characterized in that: The preparation method of the antistatic polyetheretherketone composite material comprises the following steps: S1. vacuum drying polyetheretherketone, polyetherimide, modified carbon nanotubes, and nano core-shell particles for 8-12 hours respectively; S2, polyetheretherketone, polyetherimide, coupling agent and antioxidant are melt-blended in a twin-screw extruder at 360-380°C; S3, adding modified carbon nanotubes and nano core-shell particles to the side feed of the twin-screw extruder and mixing them evenly, with the screw speed at 150 rpm, vacuum exhaust, and extrusion granulation; S4. Placing the composite pellets in a mold, hot pressing at 385° C. and 15 MPa for 4-6 minutes, and quenching with cold water to obtain the antistatic polyetheretherketone composite material.

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