Heat-resistant corrosion-resistant strong and tough polyether ether ketone-based antistatic composite material and preparation method thereof

Abstract

The application provides a heat-resistant and corrosion-resistant tough polyether ether ketone-based antistatic composite material and a preparation method thereof. The preparation method of the polyether ether ketone-based antistatic composite material is as follows: a soluble polyether ether ketone precursor is prepared, the soluble polyether ether ketone precursor and uniformly dispersed fillers are mixed in a solution, a crystalline polyether ether ketone modified material is obtained after acid reduction, the crystalline polyether ether ketone modified filler is blended with a crystalline polyether ether ketone powder, and a polyether ether ketone-based antistatic composite material is obtained after melt extrusion. The antistatic composite material obtained by the application has the following advantages: the fillers and the modified crystalline polyether ether ketone produce good interaction through pi-pi bond interaction, the interface compatibility of the fillers and the resin is improved, and the problems of strength and toughness reduction, easy decomposition at high temperature and easy corrosion under the condition of improving the antistatic property of the material are effectively solved.

Description

Technical Field

[0001] This invention belongs to the field of antistatic material preparation technology, specifically relating to heat-resistant, corrosion-resistant, tough polyether ether ketone-based antistatic composite materials and their preparation methods. Background Technology

[0002] With the development of informatization and lightweighting, on the one hand, the speed of electronic integration has increased rapidly, and large-scale integrated circuits have been widely used, resulting in smaller component sizes and reduced electrostatic discharge (ESD) resistance. On the other hand, the widespread use of low-density, high-insulation polymer materials has greatly increased the chances of static electricity generation. How to eliminate static electricity in harsh service environments is particularly important for solving electronic equipment failures, spontaneous combustion, and explosion accidents caused by ESD in fields such as rail transportation and automobiles. Taking pipeline components in advanced aircraft as an example, these components, also known as "vascular" parts and life control lines, are key lightweight components that play an important role in fluid transmission and can meet various requirements of aircraft fuel, hydraulic, and environmental control systems. However, during aircraft service, pipeline components are often subjected to harsh environments such as high temperatures, oil and gas corrosion, vibration, and static electricity accumulation. Their performance directly affects the safety and airworthiness of the aircraft. Therefore, there is an urgent need for materials that can withstand extreme environments. Researchers are currently dedicated to developing heat-resistant, corrosion-resistant, tough, and antistatic composite materials to meet the requirements of harsh service environments.

[0003] Existing literature reports the use of silane coupling agents to modify graphene and carbon nanotubes respectively to solve filler dispersion and interface problems. However, silane coupling agents are prone to decomposition at high temperatures and have poor chemical corrosion resistance. The Spanish team AMDíez-Pascual (Carbon 2010, 48, 3500) added polyethersulfone to the PEEK / CNTs system to improve the conductivity of the composite material. However, in highly polar solvents, polyethersulfone will develop defects, which will affect the mechanical properties of the composite material.

[0004] Currently, antistatic composite materials have a wide range of applications, typically using polyethylene, polycarbonate, and polystyrene as the polymer matrix. However, the mechanical properties, corrosion resistance, and high-temperature resistance of these materials cannot meet the demands of high-end applications. Furthermore, adding conductive fillers to the polymer matrix easily leads to agglomeration, and the poor compatibility between the polymer matrix and the conductive filler makes it difficult for the conductive filler to disperse evenly within the polymer matrix. This prevents the simultaneous improvement of conductivity, mechanical properties, and thermal stability. Achieving higher conductivity comes at the expense of mechanical properties, thermal stability, and corrosion resistance; conversely, achieving better mechanical properties comes at the expense of conductivity, thermal stability, and corrosion resistance. Therefore, obtaining composite materials that possess heat resistance, corrosion resistance, toughness, and excellent antistatic capabilities is a pressing technical problem that needs to be solved. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention provides a heat-resistant, corrosion-resistant, tough, polyether ether ketone-based antistatic composite material, the preparation method of which includes the following steps:

[0006] (1) 4,4'-difluorobenzophenone, aluminum trichloride, and a solvent were mixed at room temperature. Then, aniline and triethylamine were added and stirred for 5–10 h. After mixing with sodium hydroxide solution, the mixture was filtered, recrystallized, and dried to obtain 1,1-bis(4-fluorophenyl)-N-phenylmethylimine. The solvent was one of chloroform, N,N-dimethylformamide, and N-methylpyrrolidone. The molar ratio of sodium hydroxide to aluminum trichloride was 1–1.5:1, the concentration of sodium hydroxide solution was 4–6 mol / L, and the molar ratio of 4,4'-difluorobenzophenone, aluminum trichloride, aniline, and triethylamine was 1:1.5–2:1.5–2:5–6. The solid content of 4,4'-difluorobenzophenone and aluminum trichloride in the solvent was 20–40%. The synthetic route of 1,1-bis(4-fluorophenyl)-N-phenylmethylimine is as follows:

[0007]

[0008] (2) The 1,1-bis(4-fluorophenyl)-N-phenylmethylimine, hydroquinone, and anhydrous potassium carbonate obtained in step (1) are added to a solvent and mixed. Under nitrogen or inert gas protection, the mixture is reacted at 130-200°C for 6-15 hours. After washing, drying, and pulverizing, a soluble crystalline polyether ether ketone precursor is obtained. The molar ratio of the 1,1-bis(4-fluorophenyl)-N-phenylmethylimine, hydroquinone, and anhydrous potassium carbonate is 1-1.1:1:1.2-1.5. The solid content of the 1,1-bis(4-fluorophenyl)-N-phenylmethylimine, hydroquinone, and anhydrous potassium carbonate in the solvent is 17-30%. The solvent is one of sulfolane, diphenyl sulfone, and N-methylpyrrolidone. The synthetic route of the soluble crystalline polyether ether ketone precursor is shown below:

[0009]

[0010] (3) The filler and solvent are mixed at a mass ratio of 1:50 to 150 and then ultrasonically stirred to disperse evenly. The soluble crystalline polyether ether ketone precursor obtained in step (2) is then mixed with the filler at a mass ratio of 1:50 to 120. After ultrasonic stirring for 3 to 7 hours, methanesulfonic acid is added and heated at 110 to 130°C for 5 to 8 hours. After washing and drying, crystalline polyether ether ketone modified material (PEEK@MWCNT) is obtained. The filler is one or any combination of carbon nanotubes, fullerenes, MXene, carbon black, graphene, sheet graphite, carbon fiber, etc. The solvent is one of N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF) or N-methylpyrrolidone (NMP). The concentration of methanesulfonic acid used is 50 to 98%.

[0011] (4) The crystalline polyether ether ketone modified material obtained in step (3) and the crystalline polyether ether ketone powder are vacuum dried at a mass ratio of 0.2% to 20%:1. The mixture is then premixed at a high speed of 25,000 to 30,000 r / min for 5 to 10 minutes. After high-speed extrusion at 350 to 380°C, a heat-resistant, corrosion-resistant, and tough polyether ether ketone-based antistatic composite material is obtained. The high-speed extrusion process is performed at a speed of 70 to 80 r / min. The melt index (MFI) of the crystalline polyether ether ketone powder is 10 to 140 g / 10 min. The volume resistivity of the heat-resistant, corrosion-resistant, and tough polyether ether ketone-based antistatic composite material is within 10... 3 ~10 8 Between Ω·cm, conductivity is between 10 -8 ~10 -3 With a tensile strength of 111–150 MPa, an elongation at break of 94–120%, and a 5% thermal weight loss temperature of 550–620℃, it can simultaneously meet the requirements of antistatic properties, high strength and toughness, as well as good heat resistance and corrosion resistance.

[0012] Furthermore, the heat-resistant, corrosion-resistant, tough, polyetheretherketone-based antistatic composite material has a volume resistivity of 2.3*10⁻⁶. 5 ~6.29*10 7 The conductivity is between Ω·cm and 1.59 × 10⁻⁶. -8 ~4.35*10 -6 S / cm, tensile strength is 118-130 MPa, elongation at break is 105-110%, and 5% thermal weight loss temperature is 560-600℃.

[0013] Compared with existing technologies, this invention achieves the following advantages in antistatic composite materials by synergistically controlling the types and ratios of raw materials, reaction conditions, and process parameters: It avoids reducing the electrical properties of the filler due to changes in filler structure and size; the filler interacts well with the modified crystalline polyether ether ketone through π-π bonds; furthermore, this invention effectively solves the problem of filler aggregation and the compatibility issue between the filler and the matrix resin interface, thereby achieving uniform dispersion of the filler in the matrix resin; and by constructing a three-dimensional conductive network, it effectively solves problems such as decreased material strength and toughness, easy decomposition at high temperatures, and susceptibility to chemical corrosion when improving the antistatic properties of the material. The obtained heat-resistant, corrosion-resistant, and tough polyether ether ketone-based antistatic composite material has a volume resistivity of 10... 3 ~10 8 Between Ω·cm, conductivity is between 10 -8 ~10 -3 With a tensile strength of 111–150 MPa, an elongation at break of 94–120%, and a 5% thermal weight loss temperature of 550–620℃, it can simultaneously meet the requirements of antistatic properties, high strength and toughness, as well as good heat resistance and corrosion resistance. Attached Figure Description

[0014] Figure 1 This is a cross-sectional scanning electron microscope image of the antistatic composite material prepared in Example 3. Detailed Implementation

[0015] The mechanical property testing instrument used in this invention is the Shimadzu AG-20KN electronic universal testing machine. The scanning electron microscope testing instrument is HITACHI-SU8020. In the resistivity test, the testing instruments used are Agilent 4339B and Keithley 2450. The chemical corrosion resistance test process is as follows: Apply the chemical reagent to the middle area of ​​the sample with a cotton swab to keep the sample surface moist for at least 1 minute. Then apply it every 1 hour. After 24 hours, check whether the sample shows any defects such as damage, cracking, expansion or softening. The following chemical reagents were used for corrosion resistance testing: (1) RP-3 (aviation kerosene); (2) No. 15 hydraulic oil; (3) methyl ethyl ketone; (4) toluene; (5) sodium hydroxide solution; (6) N-methylpyrrolidone.

[0016] Example 1

[0017] (1) Preparation of 1,1-bis(4-fluorophenyl)-N-phenylmethylimine

[0018] 4,4'-Diphenylmethyl ketone (65.46 g), aluminum trichloride (69.615 g), and 500 ml of chloroform were mixed and stirred at room temperature. Then, a mixed solution of aniline (43.7 ml) and triethylamine (213 ml) was added, and the mixture was stirred for 6–8 h. After stirring, 170 ml of sodium hydroxide solution (4 mol / L) was added, and the mixture was separated, washed, and dried to obtain 1,1-bis(4-fluorophenyl)-N-phenylmethylimine.

[0019] (2) Preparation of soluble crystalline polyether ether ketone precursor

[0020] The 1,1-bis(4-fluorophenyl)-N-phenylmethylimine (43.9965 g), hydroquinone (17.1772 g), anhydrous potassium carbonate catalyst (24.8778 g), sulfolane (234.29 ml), and toluene (117.15 ml) obtained in step (1) were mixed and kept at 130 °C for 4 h under nitrogen protection, and then heated to 210 °C for 5 h. After washing with water and ethanol and drying, a soluble crystalline polyether ether ketone precursor was obtained.

[0021] (3) Preparation of crystalline polyetheretherketone modified carbon nanotubes (PEEK@MWCNT)

[0022] Multi-walled carbon nanotubes (2g) and N,N-dimethylacetamide (DMAc) (300ml) were mixed and dispersed by ultrasonic stirring. Then, soluble crystalline polyether ether ketone precursor (0.02g) obtained in step (2) was added. After ultrasonic stirring, acetone was added and then 98% methanesulfonic acid (10ml) was added. The mixture was kept at 120℃ for 6h. After separation, washing and drying, crystalline polyether ether ketone modified carbon nanotubes (PEEK@MWCNT) were obtained. The crystalline polyether ether ketone was attached to the surface of the carbon nanotubes.

[0023] (4) Preparation of polyether ether ketone (PEEK@MWCNT / PEEK) antistatic composite material: The crystalline polyether ether ketone modified carbon nanotubes (PEEK@MWCNT) prepared in step (3) and the crystalline polyether ether ketone powder (MFI = 10 g / 10 min) were premixed in a high-speed mixer at a stirring rate of 20000 r / min for 8 min according to a mass ratio of 0.8:99.2. Then, the mixture was extruded by a twin-screw extruder at 375°C and a rotation speed of 80 r / min and granulated to obtain polyether ether ketone antistatic composite material 1.

[0024] Antistatic composite material 1 was molded into sheets, and then heat-treated at 200℃ for 2 hours. The resistivity of the molded sheets was tested, and corrosion resistance tests were conducted using chemical reagents including RP-3 (aviation kerosene), No. 15 hydraulic oil, methyl ethyl ketone, toluene, sodium hydroxide solution, and N-methylpyrrolidone. No damage, cracking, expansion, or softening was observed in the corrosion resistance tests; the volume resistivity was 6.24 × 10⁻⁶. 7 Ω·cm, conductivity 1.6×10 -8 S / cm. The tensile strength of polyether ether ketone-based antistatic composite material 1 after heat treatment at 200℃ for 2h is 111MPa, the elongation at break is 106%, and the 5% thermal weight loss temperature is 563℃.

[0025] Example 2

[0026] (1) Preparation of 1,1-bis(4-fluorophenyl)-N-phenylmethylimine

[0027] The preparation of 1,1-bis(4-fluorophenyl)-N-phenylmethylimine was performed as described in step (1) of Example 1;

[0028] (2) Preparation of soluble crystalline polyether ether ketone precursor

[0029] The 1,1-bis(4-fluorophenyl)-N-phenylmethylimine (43.9965 g), hydroquinone (16.8468 g), anhydrous potassium carbonate catalyst (24.8778 g), sulfolane (234.29 ml), and toluene (117.15 ml) obtained in step (1) were mixed and kept at 130 °C for 4 h under nitrogen protection, and then kept at 210 °C for 9 h. After washing with water and ethanol and drying, a soluble crystalline polyether ether ketone precursor was obtained.

[0030] (3) Preparation of crystalline polyetheretherketone physically modified carbon nanotubes (PEEK@MWCNT)

[0031] Multi-walled carbon nanotubes (2g) and N,N-dimethylacetamide (DMAc) (300ml) were mixed and dispersed by ultrasonic stirring. Then, soluble crystalline polyether ether ketone precursor (0.025g) obtained in step (2) was added. After ultrasonic stirring, acetone was added, followed by 98% methanesulfonic acid (10ml). The mixture was kept at 120℃ for 6h. After separation, washing and drying, crystalline polyether ether ketone modified carbon nanotubes (PEEK@MWCNT) were obtained. The crystalline polyether ether ketone was attached to the surface of the carbon nanotubes.

[0032] (4) Preparation of polyetheretherketone (PEEK@MWCNT / PEEK) antistatic composite material

[0033] The crystalline polyether ether ketone modified carbon nanotubes (PEEK@MWCNT) prepared in step (3) were premixed with crystalline polyether ether ketone powder (MFI = 10 g / 10 min) in a high-speed mixer at a stirring rate of 20,000 r / min for 8 min at a mass ratio of 1:99. Then, the mixture was extruded through a twin-screw extruder at 375°C and a rotation speed of 80 r / min and granulated to obtain polyether ether ketone-based antistatic composite material 2.

[0034] The granules of antistatic composite material 2 were molded into sheets, and then heat-treated at 200℃ for 2 hours. The resistivity of the molded sheets was tested, and corrosion resistance tests were conducted using chemical reagents such as RP-3 (aviation kerosene), No. 15 hydraulic oil, methyl ethyl ketone, toluene, sodium hydroxide solution, and N-methylpyrrolidone. No damage, cracking, expansion, or softening was observed in the corrosion resistance tests; the volume resistivity was 8.56 × 10⁻⁶. 6 Ω·cm, conductivity 1.2×10 -7 S / cm. The tensile strength of polyether ether ketone-based antistatic composite material 2 after heat treatment at 200℃ for 2h is 112MPa, the elongation at break is 94%, and the 5% thermal weight loss temperature is 565℃.

[0035] Example 3

[0036] (1) Preparation of 1,1-bis(4-fluorophenyl)-N-phenylmethylimine

[0037] The preparation of 1,1-bis(4-fluorophenyl)-N-phenylmethylimine was performed as described in step (1) of Example 1;

[0038] (2) Preparation of soluble crystalline polyether ether ketone precursor

[0039] The preparation of the soluble crystalline polyether ether ketone precursor is as described in step (2) of Example 1;

[0040] (3) Preparation of crystalline polyetheretherketone modified carbon nanotubes (PEEK@MWCNT)

[0041] The preparation of crystalline polyether ether ketone modified carbon nanotubes (PEEK@MWCNT) is as described in step (3) of Example 1, except that the mass of the soluble crystalline polyether ether ketone precursor is 0.025 g.

[0042] (4) Preparation of polyetheretherketone (PEEK@MWCNT / PEEK) antistatic composite material

[0043] The preparation of polyether ether ketone (PEEK@MWCNT / PEEK) antistatic composite material is as described in step (4) of Example 1, except that the mass ratio of crystalline polyether ether ketone modified carbon nanotubes to crystalline polyether ether ketone powder (MFI = 22 g / 10 min) is 0.8:99.2. Then, it is premixed in a high-speed mixer at a stirring rate of 20000 r / min for 8 min, and then extruded by a twin-screw extruder at 375°C and a speed of 80 r / min and granulated to obtain polyether ether ketone antistatic composite material 3.

[0044] Antistatic composite material 3 was molded into sheets, and then heat-treated at 200℃ for 2 hours. The resistivity of the molded sheets was tested, and corrosion resistance tests were conducted using chemical reagents including RP-3 (aviation kerosene), No. 15 hydraulic oil, methyl ethyl ketone, toluene, sodium hydroxide solution, and N-methylpyrrolidone. No damage, cracking, expansion, or softening was observed in the corrosion resistance tests, and the volume resistivity was 2.3 × 10⁻⁶. 5 Ω·cm, conductivity 4.35×10 -6 The tensile strength of the polyetheretherketone-based antistatic composite material 3 after heat treatment at 200℃ for 2 hours was 118 MPa, the elongation at break was 108%, and the 5% thermogravimetric temperature was 565℃. To further verify its corrosion resistance, the resistivity and mechanical properties of the composite material 3 were tested after immersion in a 4M NaOH solution for 15 days. Its volume resistivity was 9.6 × 10⁻⁶. 5 Ω·cm, conductivity 1.04×10 -6 The tensile strength of the polyetheretherketone (PEEK)-based antistatic composite material 3 after soaking and heat treatment at 200℃ for 2 hours was 116 MPa, and the elongation at break was 106%. Scanning electron microscopy analysis of the cross-section of the PEEK-based antistatic composite material 3 showed that... Figure 1 It can be seen that after crystalline polyether ether ketone is coated onto the surface of carbon nanotubes, it promotes the uniform dispersion of carbon nanotubes in polyether ether ketone resin. The white dashed box represents the uniformly dispersed carbon nanotubes, and no agglomeration of carbon nanotubes is observed.

[0045] Example 4

[0046] (1) Preparation of 1,1-bis(4-fluorophenyl)-N-phenylmethylimine

[0047] The preparation of 1,1-bis(4-fluorophenyl)-N-phenylmethylimine was performed as described in step (1) of Example 1;

[0048] (2) Preparation of soluble crystalline polyether ether ketone precursor

[0049] 1,1-Bis(4-fluorophenyl)-N-phenylmethylimine (43.9965 g), hydroquinone (17.5075 g), anhydrous potassium carbonate catalyst (24.8778 g), sulfolane (234.29 ml), and toluene (117.15 ml) were sequentially added to a reaction vessel. Under nitrogen protection, the mixture was kept at 130 °C for 4 h, then heated to 210 °C and kept at 210 °C for 4 h. After washing with water and ethanol and drying, a soluble crystalline polyether ether ketone precursor was obtained.

[0050] (3) Preparation of crystalline polyetheretherketone modified carbon nanotubes (PEEK@MWCNT)

[0051] The preparation of crystalline polyether ether ketone modified carbon nanotubes (PEEK@MWCNT) is as described in step (3) of Example 1, except that the mass of the crystalline polyether ether ketone precursor is 0.0166 g.

[0052] (4) Preparation of polyetheretherketone (PEEK@MWCNT / PEEK) antistatic composite material

[0053] The preparation of polyether ether ketone (PEEK@MWCNT / PEEK) antistatic composite material is as described in step (4) of Example 1, and the polyether ether ketone antistatic composite material 4 is obtained.

[0054] Antistatic composite material 4 was molded into sheets, and then heat-treated at 200℃ for 2 hours. The resistivity of the molded sheets was tested, and corrosion resistance tests were conducted using chemical reagents including RP-3 (aviation kerosene), No. 15 hydraulic oil, methyl ethyl ketone, toluene, sodium hydroxide solution, and N-methylpyrrolidone. No damage, cracking, expansion, or softening was observed in the corrosion resistance tests; the volume resistivity was 6.29 × 10⁻⁶. 7 Ω·cm, conductivity 1.59×10 -8 S / cm. The tensile strength of polyether ether ketone-based antistatic composite material 4 after heat treatment at 200℃ for 2h is 111MPa, the elongation at break is 105%, and the 5% thermal weight loss temperature is 564℃.

[0055] Table 1. Comprehensive performance of composite materials obtained in Examples 1-4

[0056]

[0057] Comparative Example 1

[0058] In their paper "Preparation of antistatic high-density polyethylene composites based on synergistic effect of graphene nanoplatelets and multi-walled carbon nanotubes" (Polymers for Advanced Technologies, 2017), Ting Wei's team incorporated GNPs and MWCNTs into a material. Through synergistic effects, they increased filler dispersion. This composite material, then mixed with high-density polyethylene, achieved a volume resistivity of 1.55 × 10⁻⁶ when the mass fractions of MWCNTs and GNPs were 1 wt% and 0.5 wt%, respectively. 11 Ω·cm, tensile strength is 22.93MPa.

[0059] Comparative Example 2

[0060] In their paper "Enhancing flame retardant and antistatic properties of polyamide 6 by a grafted multiwall carbon nanotubes" (Journal of Applied Polymer Science, 2021, 138(11a12)), Zhiyuan Zhang's team prepared an antistatic composite material by grafting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) onto MWCNTs to increase their dispersion. This composite material was then melt-blended with PA6, resulting in a volume resistivity of 2 × 10⁻⁶. 8 The tensile strength and elongation at break can reach 59.1 MPa and 7.8% respectively, and its T... 5％ It occurs between 400-500℃.

[0061] Existing technologies, through chemical modification of MWCNTs or the addition of different fillers to the matrix material, achieve some dispersion but still exhibit a certain degree of agglomeration. Furthermore, the volume resistivity, tensile strength, elongation at break, and thermal stability of the composite materials reported in the comparative literature are all weaker than those obtained in the embodiments of this invention. It is difficult to simultaneously improve the comprehensive properties of the composite material, thus limiting its application in extreme environments.

[0062] According to existing technology reports, composite materials, while achieving good antistatic properties, cannot simultaneously maintain high strength and toughness, as well as good heat resistance and corrosion resistance. Compared with existing technologies, the composite material obtained by this invention exhibits significantly superior conductivity, strength, toughness, heat resistance, and corrosion resistance. Furthermore, in all embodiments of this invention, different raw material ratios and process parameters were used. Among them, the composite material obtained in Example 3 showed the highest conductivity, strength, toughness, corrosion resistance, and thermal stability, achieving a simultaneous improvement in all properties required for antistatic materials. This demonstrates that the superior performance of the composite material obtained by this invention is the result of the synergistic effect of raw materials, ratios, processes, and parameters. Only raw materials, raw material ratios, processes, and parameters within the scope of protection of the claims of this invention can achieve the superior effects of this invention.

Claims

1. A heat-resistant, corrosion-resistant, tough, polyetheretherketone-based antistatic composite material, the preparation method of which includes the following steps: (1) 4,4'-difluorobenzophenone, aluminum trichloride, and a solvent were mixed at room temperature. Aniline and triethylamine were then added and stirred for 5–10 h. The mixture was then mixed with a sodium hydroxide solution, filtered, recrystallized, and dried to obtain 1,1-bis(4-fluorophenyl)-N-phenylmethylimine. The solvent was one of chloroform, N,N-dimethylformamide, and N-methylpyrrolidone. The molar ratio of sodium hydroxide to aluminum trichloride was 1–1.5:1, with a sodium hydroxide solution concentration of 4–6 mol / L. The molar ratio of 4,4'-difluorobenzophenone, aluminum trichloride, aniline, and triethylamine was 1:1.5–2:1.5–2:5–6. The solid content of 4,4'-difluorobenzophenone and aluminum trichloride in the solvent was 20–40%. The synthetic route for 1,1-bis(4-fluorophenyl)-N-phenylmethylimine is as follows: (2) The 1,1-bis(4-fluorophenyl)-N-phenylmethylimine, hydroquinone, and anhydrous potassium carbonate obtained in step (1) are added to a solvent and mixed. Under nitrogen or inert gas protection, the mixture is reacted at 130-200°C for 6-15 hours. After washing, drying, and pulverizing, a soluble crystalline polyether ether ketone precursor is obtained. The molar ratio of the 1,1-bis(4-fluorophenyl)-N-phenylmethylimine, hydroquinone, and anhydrous potassium carbonate is 1-1.1:1:1.2-1.

5. The solid content of the 1,1-bis(4-fluorophenyl)-N-phenylmethylimine, hydroquinone, and anhydrous potassium carbonate in the solvent is 17-30%. The solvent is one of sulfolane, diphenyl sulfone, and N-methylpyrrolidone. The synthetic route of the soluble crystalline polyether ether ketone precursor is shown below: (3) The filler and solvent are mixed at a mass ratio of 1:50-150 and then ultrasonically stirred to disperse evenly. The soluble crystalline polyether ether ketone precursor obtained in step (2) is then mixed with the filler at a mass ratio of 1:50-120. After ultrasonic stirring for 3-7 hours, methanesulfonic acid is added and heated at 110-130℃ for 5-8 hours. After washing and drying, a crystalline polyether ether ketone modified material is obtained. The filler is carbon nanotubes, and the solvent is one of N,N-dimethylacetamide, N,N-dimethylformamide, or N-methylpyrrolidone. The concentration of methanesulfonic acid used is 50-98%. The crystalline polyether ether ketone modified material obtained in step (3) and the crystalline polyether ether ketone powder are vacuum dried and then premixed at a high speed of 25,000 to 30,000 r / min for 5 to 10 min. The mixture is then subjected to high-speed extrusion at 350 to 380 °C to obtain a heat-resistant, corrosion-resistant, tough, and antistatic polyether ether ketone-based composite material. The high-speed extrusion process is performed at a speed of 70 to 80 r / min. The melt index of the crystalline polyether ether ketone powder is 10 to 140 g / 10 min. The volume resistivity of the heat-resistant, corrosion-resistant, tough, and antistatic polyether ether ketone-based composite material is within 10 ohms. 3 ~10 8 Between Ω·cm, conductivity is between 10 -8 ~10 -3 S / cm, tensile strength is 111-150 MPa, elongation at break is 94-120%, and 5% thermal weight loss temperature is 550-620℃.

2. The heat-resistant, corrosion-resistant, tough, polyetheretherketone-based antistatic composite material according to claim 1, characterized in that, The heat-resistant, corrosion-resistant, tough, and antistatic polyether ether ketone-based composite material has a volume resistivity of 2.3 x 10⁻⁶. 5 ~6.29x10 7 The conductivity is between Ω·cm and 1.59 x 10⁻⁶. -8 ~4.35x10 -6 S / cm, tensile strength is 118-130 MPa, elongation at break is 105-110%, and 5% thermal weight loss temperature is 560-600℃.

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