Ion liquid and polyaniline modified carbon nanotube based permanent antistatic ABS composite material, preparation method and application thereof

Abstract

The application belongs to the field of antistatic materials, and discloses a permanent antistatic ABS composite material (PANI-A-CNT / IL / ABS) based on ionic liquid and polyaniline modified carbon nanotubes and a preparation method and application thereof. The method comprises the following steps: preparing an aminated carbon nanotube-polyaniline product and ionic liquid alkyl-3-methyl imidazolium bromide C n mimBr, blending the aminated carbon nanotube-polyaniline product, C n mimBr and ABS raw materials in a double-roller open mill, pressing the blended materials by using a flat vulcanization instrument, taking out the pressed materials and placing the pressed materials at room temperature to obtain the permanent antistatic ABS composite material based on ionic liquid and polyaniline modified carbon nanotubes. The obtained PANI-A-CNT / IL / ABS composite material can be well applied to the fields of antistatic packaging and automobile industry.

Description

Technical Field

[0001] This invention belongs to the field of antistatic materials, and specifically relates to a permanent antistatic ABS composite material based on ionic liquid and polyaniline modified carbon nanotubes, its preparation method and application. Background Technology

[0002] ABS is a terpolymer of acrylonitrile, butadiene, and styrene, a typical thermoplastic engineering plastic. ABS possesses excellent dimensional stability, low-temperature resistance, colorability, and processing flowability. However, due to the high insulation properties of ABS resin, static electricity generated within the material cannot be discharged promptly. When the static charge accumulates to a certain level, friction with other materials or objects may cause electric shocks or sparks, potentially leading to serious accidents such as fires or explosions. Therefore, we need to modify ABS to prepare an ABS material with antistatic properties.

[0003] Currently, there are three main types of antistatic agents added to ABS resin: surfactant-based antistatic agents, polymeric antistatic agents, and conductive filler-based antistatic agents. Surfactants have poor antistatic durability, while polymeric antistatic agents suffer from the drawback of decreased mechanical properties if added in excessive amounts. Therefore, current antistatic modification of ABS resin mainly utilizes carbon-based conductive materials. These materials primarily include carbon black, graphite, and carbon fiber.

[0004] In the prior art, carbon nanotubes are usually used as conductive fillers to improve the antistatic properties of ABS resin. For example, patent application CN102268171A discloses a new antistatic resin material and its preparation method. This invention utilizes the synergistic effect between carbon black, carbon nanotubes and polyaniline to prepare ABS composite materials by directly blending them, so that the material meets the antistatic requirements. However, due to the high content of carbon black added, the mechanical properties of the material are greatly lost.

[0005] Ionic liquids are compounds composed of cations and anions, characterized by a melting point below 100°C. They possess advantages such as good thermal stability and high electrical conductivity, making them suitable for antistatic applications. Introducing ionic liquids into polymers can reduce polymer viscosity, positively impacting processability. Furthermore, ionic liquids exhibit lubricity and can act as dispersants for conductive fillers, promoting uniform distribution within the polymer. However, due to poor compatibility between ionic liquids and polymers, existing technologies typically employ larger addition amounts of ionic liquids, or modify conductive materials with ionic liquids before adding them to the polymer. Patent application CN115975256A uses an antistatic agent formulated with inorganic ionic compounds and other raw materials, which is then blended with PVC resin to obtain an antistatic composite material. While achieving the same antistatic effect, this adds an extra processing step. Patent application CN115677930A uses a copolymerization of two ionic liquid monomers to obtain a polyionic liquid antistatic agent. Because it uses a quaternary ammonium salt type ionic liquid, the antistatic effect is not significant at low addition levels. To prevent excessive addition of ionic liquids, which could lead to their slow precipitation on the polymer surface and reduce the durability of the antistatic properties, patent CN115678140A adds inorganic nanomaterials as a carrier. However, since these inorganic nanomaterials themselves lack conductivity, they can actually increase the surface resistance of the composite material. Patent application CN110615953A discloses an antistatic ABS composite material and its preparation method. This invention introduces ionic liquids as a compatibilizer between ABS resin and carbon nanotubes, achieving a surface resistance of 10 Ω·cm. 5 However, the ionic liquid products used are purchased directly, which is relatively expensive. In addition, the carbon nanotubes used account for up to 5%, which increases the cost of material preparation. Summary of the Invention

[0006] In order to overcome the shortcomings and deficiencies of the existing technology, the primary objective of this invention is to provide a method for preparing a permanent antistatic ABS composite material based on ionic liquid and polyaniline modified carbon nanotubes. This method can effectively improve the antistatic properties and stability of the ABS composite material, while also improving its mechanical properties and processing performance.

[0007] Another objective of this invention is to provide a permanent antistatic ABS composite material based on ionic liquid and polyaniline-modified carbon nanotubes prepared by the above-described preparation method.

[0008] Another object of the present invention is to provide an application of the above-mentioned permanent antistatic ABS composite material based on ionic liquid and polyaniline modified carbon nanotubes.

[0009] The objective of this invention is achieved through the following technical solution:

[0010] A method for preparing a permanent antistatic ABS composite material based on ionic liquid and polyaniline-modified carbon nanotubes includes the following steps:

[0011] (1) Place carbon nanotubes in a mixture of concentrated nitric acid and concentrated sulfuric acid with a volume ratio of 1:3, sonicate at 60°C for 5-6 hours, pour the reaction solution into deionized water, cool, filter, wash the filter cake with distilled water, and dry to obtain acidified carbon nanotubes.

[0012] (2) Acidified carbon nanotubes were added to toluene, and then 1,2-ethylenediamine (EDA), 1-ethyl-(3-dimethylaminopropyl)carbodiimide (EDC) and 4-dimethylaminopyridine (DMAP) were added to the carbon nanotube suspension. The mixture was stirred at room temperature for 24 hours to obtain amination carbon nanotubes.

[0013] (3) 1-Methylimidazole and the alkyl bromide monomer were reacted at 60 °C for 72 h, and then recrystallized three times or more with ethyl acetate under ice-water bath conditions to obtain the ionic liquid alkyl-3-methylimidazole onium bromide C. n mimBr, where n is a natural number from 7 to 12;

[0014] (4) The amination carbon nanotubes and hexadecyltrimethylammonium bromide (CTAB) obtained in step (2) were added to toluene, and after ultrasonic treatment, aniline monomer and dodecylbenzenesulfonic acid were added, and then ultrasonic treatment was continued to obtain a mixed solution; ammonium persulfate (APS) was added to deionized water to prepare an ammonium persulfate solution; the ammonium persulfate solution was added to the above mixed solution, stirred evenly, and placed in a refrigerator for reaction for 24 hours. After the reaction was completed, the mixture was demulsified, washed, and filtered with methanol. The filter cake was washed with deionized water and dried to obtain the amination carbon nanotube-polyaniline product.

[0015] (5) The amination carbon nanotube-polyaniline product obtained in step (4) and the ionic liquid alkyl-3-methylimidazolium bromide C obtained in step (3) are combined. n After mimBr and ABS raw materials are blended in a two-roll mill, the mixture is pressed into plates using a flat vulcanizer, removed, and cold-pressed at room temperature to obtain a permanent antistatic ABS composite material based on ionic liquid and polyaniline-modified carbon nanotubes; the amount of the amination carbon nanotube-polyaniline product is 4% of the mass of the ABS raw material.

[0016] The drying process described in step (1) is carried out in a forced-air drying oven at 60-80°C.

[0017] The mass ratio of acidified carbon nanotubes, 1,2-ethylenediamine, 1-ethyl-(3-dimethylaminopropyl)carbodiimide and 4-dimethylaminopyridine in step (2) is 1:3:30:10.

[0018] The molar ratio of 1-methylimidazole and alkyl bromide monomer in step (3) is 1:1.

[0019] In step (4), the mass ratio of amination carbon nanotubes to aniline monomers is 1:10, and the molar ratio of aniline monomers, dodecylbenzenesulfonic acid and ammonium persulfate is 1:1:1.

[0020] The ionic liquid alkyl-3-methylimidazolium bromide C described in step (5) n The amount of mimBr used is 6-8% of the mass of the ABS raw material.

[0021] The mixing temperature in step (5) is 180°C and the time is 15 min; the temperature of the pressing plate is 180°C and the pressing time is 10-15 min; the cold pressing time is 0-10 min, and cooling circulating water is used for 0-5 min during the cold pressing.

[0022] A permanent antistatic ABS composite material based on ionic liquid and polyaniline-modified carbon nanotubes, prepared by the above-described method.

[0023] The above-mentioned permanent antistatic ABS composite material based on ionic liquid and polyaniline modified carbon nanotubes is used in antistatic packaging or automotive industries.

[0024] The principle of this invention:

[0025] This invention addresses the problems of carbon nanotube agglomeration and poor compatibility between ionic liquids and ABS resin in ABS resin composites, which reduce the overall performance of the composites. It employs emulsion polymerization to prepare an amination carbon nanotube-polyaniline antistatic agent (A-CNT-PANI), and uses a self-made ionic liquid C... 12 Blending mimBr and A-CNT-PANI with ABS yields a permanent antistatic ABS composite material (A-CNT-PANI / IL / ABS) based on ionic liquids and polyaniline-modified carbon nanotubes. This invention utilizes the π-π interaction between polyaniline and carbon nanotubes to encapsulate the polyaniline on the surface of the carbon nanotubes, thereby preventing carbon nanotube aggregation. Furthermore, the benzene rings on the polyaniline backbone of the A-CNT-PANI antistatic agent interact with the ionic liquid C... 12The strong π-cation interaction between mimBr can effectively improve the compatibility between ionic liquid and ABS resin. At the same time, the lubricity of ionic liquid promotes the dispersion of A-CNT-PANI in the ASB matrix during the blending process, helping A-CNT-PANI to be dispersed uniformly in the ABS matrix. This improves the antistatic effect, antistatic durability, mechanical properties, and processing properties of the A-CNT-PANI / IL / ABS composite material.

[0026] The present invention has the following advantages and beneficial effects compared with the prior art:

[0027] (1) The present invention prepares a permanent antistatic ABS composite material based on ionic liquid and polyaniline modified carbon nanotubes, which has a permanent antistatic effect.

[0028] (2) Although the PANI-A-CNT / ABS composite material prepared in CN202211018589.9 meets the requirements for antistatic performance, the mechanical properties and processing flow properties of the composite material are reduced to a certain extent due to the addition of carbon nanotubes, and there is still room for further improvement in the overall antistatic effect. This invention introduces an ionic liquid with good conductivity into the A-CNT-PANI / ABS composite system. The interaction between the A-CNT-PANI antistatic agent and the ionic liquid can effectively improve the compatibility between the ionic liquid and the ABS matrix. The lubricity of the ionic liquid promotes the uniform dispersion of the A-CNT-PANI filler in the ABS matrix, further improving the antistatic properties, mechanical properties, and processing flow properties of the ABS composite material. At the same time, the lubrication effect of the ionic liquid makes the A-CNT-PANI antistatic agent have a higher migration rate, improving the durability of the antistatic effect of the A-CNT-PANI / ABS composite material. Attached Figure Description

[0029] Figure 1 The graph shows the relationship between the surface resistivity of A-CNT-PANI / ABS and A-CNT-PANI / IL / ABS composites and the A-CNT-PANI content.

[0030] Figure 2 The surface resistivity of ABS composite material varies with C 12 Graph showing the relationship between changes in mimBr content.

[0031] Figure 3 The graph shows the relationship between the tensile strength of A-CNT-PANI / ABS and A-CNT-PANI / IL / ABS composites and the A-CNT-PANI content.

[0032] Figure 4The graph shows the relationship between the flexural strength of A-CNT-PANI / ABS and A-CNT-PANI / IL / ABS composites and the A-CNT-PANI content.

[0033] Figure 5 The graph shows the relationship between the surface resistivity of the A-CNT-PANI / IL / ABS composite material and the number of days of water washing.

[0034] Figure 6 The graph shows the relationship between the surface resistivity of the A-CNT-PANI / ABS composite material and the number of days of water washing.

[0035] Figure 7 The graph shows the relationship between the melt flow index of A-CNT-PANI / ABS and A-CNT-PANI / IL / ABS composites and the A-CNT-PANI content. Detailed Implementation

[0036] The present invention will be further described in detail below with reference to the embodiments and accompanying drawings, but the embodiments of the present invention are not limited thereto.

[0037] Example 1

[0038] Preparation of acidified carbon nanotubes: 0.01 g of carbon nanotubes were placed in a flask containing 75 ml of concentrated sulfuric acid. 25 ml of concentrated nitric acid was then added to the carbon nanotube mixture, and the mixture was reacted at 60 °C for 5 h. After the reaction was complete, the reaction solution was poured into deionized water, cooled, filtered, and the filter cake was washed with distilled water. The cake was then dried in a forced-air drying oven at 60 °C for 24 h to obtain acidified carbon nanotubes for later use.

[0039] Preparation of amination-modified carbon nanotubes (A-CNTs): Acidified carbon nanotubes were added to toluene, followed by the addition of EDA, EDC, and DMAP to the carbon nanotube suspension. The reaction was carried out at room temperature for 24 hours to obtain amination-modified carbon nanotubes. The mass ratio of the reagents, namely acidified carbon nanotubes, EDA, EDC, and DMAP, was 1:3:30:10.

[0040] 1-Dodecyl-3-methylimidazolium bromide (C 12 Synthesis of 1-methylimidazole (CmBr): 0.1 mol of 1-methylimidazole and 0.1 mol of dodecyl bromide were reacted at 60 °C for 72 h. The mixture was recrystallized three times or more from ethyl acetate under ice-water bath conditions to obtain 1-dodecyl-3-methylimidazole onium bromide (CmBr). 12 mimBr).

[0041] The preparation of amination-carbon nanotube-polyaniline (A-CNT-PANI) is as follows: Amination-carbon nanotubes and hexadecyltrimethylammonium bromide (CTAB) were added to toluene and sonicated. Then, aniline monomer and dodecylbenzenesulfonic acid were added, and sonication was continued to obtain a mixed solution. Ammonium persulfate (APS) was added to deionized water to prepare an ammonium persulfate solution. The ammonium persulfate solution was added to the above mixed solution and stirred, then placed in a refrigerator for 24 hours. After the reaction was completed, the mixture was demulsified with methanol, washed, and filtered. The filter cake was washed with deionized water to obtain the product. The washed product was dried in a forced-air drying oven at 60°C for 24 hours to obtain amination-carbon nanotube-polyaniline. The mass ratio of amination-carbon nanotubes to aniline monomer was 1:10, and the molar ratio of aniline monomer, dodecylbenzenesulfonic acid, and ammonium persulfate was 1:1:1.

[0042] Preparation of A-CNT-PANI / ionic liquid / ABS composite material (A-CNT-PANI / IL / ABS): 4 parts by mass of the A-CNT-PANI obtained above, 6 parts by mass of the C-PNT-PANI obtained above... 12 90 parts by weight of ABS resin were added to a two-roll mill for blending at 180°C for 15 minutes. The mixture was then pressed in a flat vulcanizing apparatus at 180°C for 15 minutes. Afterward, the mixture was removed from the apparatus and cold-pressed at room temperature for 10 minutes to obtain a permanent antistatic ABS composite material (A-CNT-PANI / IL / ABS) based on ionic liquid and polyaniline-modified carbon nanotubes, ready for subsequent use. The sample prepared in this example was an A-CNT-PANI / IL / ABS composite material with an A-CNT-PANI content of 4 wt%. Its surface resistivity test results are as follows... Figure 1 As shown, its tensile strength test results are as follows: Figure 3 As shown, its bending strength test results are as follows: Figure 4 As shown, the water washing test results are as follows: Figure 5 As shown, the melt flow index test results are as follows: Figure 7 As shown.

[0043] Example 2

[0044] This embodiment is the same as Embodiment 1, except that the last step involves mixing 1 part by weight of A-CNT-PANI and 6 parts by weight of C. 12 93 parts by weight of ABS resin were added to a two-roll mill for blending at 180°C for 15 minutes. The sample prepared in this example is a permanent antistatic ABS composite material (A-CNT-PANI / IL / ABS) based on ionic liquid and polyaniline-modified carbon nanotubes, with an A-CNT-PANI content of 1 wt%. Its surface resistivity test results are as follows: Figure 1 As shown, its tensile strength test results are as follows: Figure 3 As shown, its bending strength test results are as follows: Figure 4 As shown, the water washing test results are as follows: Figure 5 As shown, the melt flow index test results are as follows: Figure 7 As shown.

[0045] Example 3

[0046] This embodiment is the same as Embodiment 1, except that the last step involves mixing 2 parts by weight of A-CNT-PANI and 6 parts by weight of C. 12 92 parts by weight of ABS resin were added to a two-roll mill for blending at 180°C for 15 minutes. The sample prepared in this example is a permanent antistatic ABS composite material (A-CNT-PANI / IL / ABS) based on ionic liquid and polyaniline-modified carbon nanotubes, with an A-CNT-PANI content of 2 wt%. Its surface resistivity test results are as follows: Figure 1 As shown, its tensile strength test results are as follows: Figure 3 As shown, its bending strength test results are as follows: Figure 4 As shown, the water washing test results are as follows: Figure 5 As shown, the melt flow index test results are as follows: Figure 7 As shown.

[0047] Example 4

[0048] This embodiment is the same as Embodiment 1, except that the last step involves mixing 3 parts by weight of A-CNT-PANI and 6 parts by weight of C. 12 91 parts by weight of ABS resin were added to a two-roll mill for blending at 180°C for 15 minutes. The sample prepared in this example is a permanent antistatic ABS composite material (A-CNT-PANI / IL / ABS) based on ionic liquid and polyaniline-modified carbon nanotubes, with an A-CNT-PANI content of 3 wt%. Its surface resistivity test results are as follows: Figure 1 As shown, its tensile strength test results are as follows: Figure 3 As shown, its bending strength test results are as follows: Figure 4 As shown, the water washing test results are as follows: Figure 5 As shown, the melt flow index test results are as follows: Figure 7 As shown.

[0049] Example 5

[0050] This embodiment is the same as Embodiment 1, except that the last step involves mixing 4 parts by weight of A-CNT-PANI and 8 parts by weight of C. 1288 parts by weight of ABS resin and mimBr were added to a two-roll mill for blending at 180°C for 15 minutes. The sample prepared in this example had 4 wt% A-CNT-PANI and ionic liquid C. 12 The surface resistivity test results of a permanently antistatic ABS composite material (A-CNT-PANI / IL / ABS) based on ionic liquid and polyaniline-modified carbon nanotubes with a mimBr content of 8wt% are as follows: Figure 2 As shown.

[0051] Comparative Example 1

[0052] 1-Dodecyl-3-methylimidazolium bromide (C 12 Synthesis of 1-methylimidazole (MIMBr): 1-methylimidazole and dodecyl bromide were reacted at 60 °C for 72 h, and recrystallized three times or more with ethyl acetate under ice-water bath conditions to obtain 1-dodecyl-3-methylimidazole onium bromide (C10). 12 (mimBr). The molar ratio of 1-methylimidazole to dodecyl bromide is 1:1.

[0053] Preparation of ionic liquid / ABS composite material: 10 parts by mass of the above-obtained C 12 90 parts by weight of IMBr and ABS resin were added to a two-roll mill and blended at 180°C for 15 minutes. The mixture was then fed into a flat vulcanizing press and pressed at 180°C for 15 minutes. Afterward, the mixture was removed directly from the press and cold-pressed at room temperature for 10 minutes to obtain the ionic liquid / ABS composite material for subsequent use. The sample prepared in this example is an ionic liquid / ABS composite material with only 10 wt% ionic content. Its surface resistivity test results are as follows... Figure 2 As shown.

[0054] Comparative Example 2

[0055] Preparation of acidified carbon nanotubes: 0.01 g of carbon nanotubes were placed in a flask containing 75 ml of concentrated sulfuric acid. 25 ml of concentrated nitric acid was then added to the carbon nanotube mixture, and the mixture was reacted at 60 °C for 5 h. After the reaction was complete, the reaction solution was poured into deionized water, cooled, filtered, and the filter cake was washed with distilled water. The cake was then dried in a forced-air drying oven at 60 °C for 24 h to obtain acidified carbon nanotubes for later use.

[0056] Preparation of amination-modified carbon nanotubes (A-CNTs): Acidified carbon nanotubes were added to toluene, followed by the addition of EDA, EDC, and DMAP to the carbon nanotube suspension. The reaction was carried out at room temperature for 24 hours to obtain amination-modified carbon nanotubes. The mass ratio of the reagents, namely acidified carbon nanotubes, EDA, EDC, and DMAP, was 1:3:30:10.

[0057] The preparation of amination-carbon nanotube-polyaniline (A-CNT-PANI) is as follows: The obtained amination-carbon nanotubes and hexadecyltrimethylammonium bromide (CTAB) were added to 30 ml of toluene and sonicated. Then, aniline monomer and dodecylbenzenesulfonic acid were added, and sonication was continued to obtain a mixed solution. Ammonium persulfate (APS) was added to 10 ml of deionized water to prepare an ammonium persulfate solution. The ammonium persulfate solution was added to the above mixed solution and stirred, then placed in a refrigerator for 24 h. After the reaction was complete, the mixture was demulsified with methanol, washed, and filtered. The filter cake was washed with deionized water to obtain the product. The washed product was dried in a forced-air drying oven at 60 °C for 24 h to obtain amination-carbon nanotube-polyaniline. The mass ratio of amination-carbon nanotubes to aniline was 1:10, and the molar ratio of aniline, dodecylbenzenesulfonic acid, and ammonium persulfate was 1:1:1.

[0058] Preparation of A-CNT-PANI / ABS composite material: 4 parts by weight of the A-CNT-PANI obtained above and 96 parts by weight of ABS resin were added to a two-roll mill for blending at 180℃ for 15 minutes. Then, the mixture was placed in a flat vulcanizing apparatus for pressing at 180℃ for 15 minutes. Afterward, it was removed directly from the apparatus and cold-pressed at room temperature for 10 minutes to obtain the A-CNT-PANI / ABS composite material for subsequent use. The sample prepared in this example is an A-CNT-PANI / ABS composite material with only 4 wt% A-CNT-PANI added. Its surface resistivity test results are as follows: Figure 1 As shown. Its tensile strength test results are as follows. Figure 3 As shown, its bending strength test results are as follows: Figure 4 As shown, the water washing test results are as follows: Figure 6 As shown, the melt flow index test results are as follows: Figure 7 As shown.

[0059] Comparative Example 3

[0060] Comparative Example 3 is the same as Comparative Example 2, except that in the final step, 1 part by weight of A-CNT-PANI and 99 parts by weight of ABS resin are added to a two-roll mill for blending at 180°C for 15 minutes. The sample prepared in this example is an A-CNT-PANI / ABS composite material with only 1 wt% A-CNT-PANI added. Its surface resistivity test results are as follows... Figure 1 As shown. Its tensile strength test results are as follows. Figure 3 As shown, its bending strength test results are as follows: Figure 4 The results of its water washing experiment are shown below. Figure 6 As shown, the melt flow index test results are as follows: Figure 7As shown.

[0061] Comparative Example 4

[0062] Comparative Example 4 is the same as Comparative Example 2, except that in the final step, 2 parts by weight of A-CNT-PANI and 98 parts by weight of ABS resin are added to a two-roll mill for blending at 180°C for 15 minutes. The sample prepared in this example is an A-CNT-PANI / ABS composite material with only 2 wt% A-CNT-PANI added. Its surface resistivity test results are as follows... Figure 1 As shown. Its tensile strength test results are as follows. Figure 3 As shown, its bending strength test results are as follows: Figure 4 As shown in the figure, the water washing test results are as follows: Figure 6 As shown, the melt flow index test results are as follows: Figure 7 As shown.

[0063] Comparative Example 5

[0064] Comparative Example 5 is the same as Comparative Example 2, except that in the final step, 3 parts by weight of A-CNT-PANI and 97 parts by weight of ABS resin are added to a two-roll mill for blending at 180°C for 15 minutes. The sample prepared in this example is an A-CNT-PANI / ABS composite material with only 3 wt% A-CNT-PANI added. Its surface resistivity test results are as follows... Figure 1 As shown. Its tensile strength test results are as follows. Figure 3 As shown, its bending strength test results are as follows: Figure 4 As shown, the water washing test results are as follows: Figure 6 As shown, the melt flow index test results are as follows: Figure 7 As shown.

[0065] Comparative Example 6

[0066] 100 parts by weight of ABS resin were added to a two-roll mill for blending at 180°C for 15 minutes. Then, the mixture was placed in a flat vulcanizing press at 180°C for 15 minutes. Afterward, the resin was removed from the press and cold-pressed at room temperature for 10 minutes to obtain the final ABS resin for subsequent use. The sample prepared in this example is pure ABS resin, and its surface resistivity test results are as follows. Figure 1 As shown. Its tensile strength test results are as follows. Figure 3 As shown, its bending strength test results are as follows: Figure 4 As shown, the melt flow index test results are as follows: Figure 7 As shown.

[0067] The comprehensive performance of the ABS composite materials prepared in Examples 1-5 and Comparative Examples 1-5 was tested, and the results are as follows: Figure 1-4 As shown:

[0068] The antistatic properties of the samples were tested according to the national standard GB / T 31838.3-2019;

[0069] The tensile properties of the samples were tested according to the national standard GB / T 1040.2-2022;

[0070] Bending performance was tested according to the bending strength test method in national standard GB / T 9341-2008; impact resistance was tested according to national standard GB / T 1043.1-2008.

[0071] The melt flow index of the test sample was determined according to the national standard GB / T 3682.1-2018.

[0072] The water wash resistance of the ABS composite materials prepared in Examples 1-4 and Comparative Examples 2-5 was tested.

[0073] The sample was placed in 1L of deionized water and wiped 100 times with degreased cotton. After drying in a 60℃ oven for 24 hours, its surface resistivity was measured. This process was repeated for five days to obtain the material's water wash resistance curve, as shown below. Figure 5 and Figure 6 As shown.

[0074] The test results of the antistatic and mechanical properties of the composite materials obtained in Examples 1-5 and Comparative Examples 1-6 are shown in Table 1:

[0075] Table 1. Test results of surface resistivity and mechanical properties of composite materials in Examples 1-5 and Comparative Examples 1-6.

[0076]

[0077] Note: "-" in the table indicates that the sample did not undergo this test.

[0078] From Table 1 and Figure 2 As can be seen, the surface resistance data of Example 5 is significantly better than that of Comparative Example 1, while the surface resistance data of Example 1 is similar to that of Example 5. It can be concluded that the antistatic effect of simultaneously adding modified carbon nanotubes and ionic liquid to ABS resin is far superior to that of adding only ionic liquid, and the antistatic performance is excellent when the contents of modified carbon nanotubes and ionic liquid are 4wt% and 6wt%, respectively. The surface resistance data of Example 2 is better than that of Comparative Example 2, indicating that the excellent conductivity of the ionic liquid itself can work synergistically with the modified carbon nanotubes to jointly reduce the surface resistance of ABS resin.

[0079] From Table 1 and Figure 1As can be seen, the tensile strength data of Examples 1, 2, 3, and 4 are all higher than those of Comparative Examples 2, 3, 4, and 5, indicating that when C is added... 12 When mimBr is incorporated into the A-CNT-PANI / ABS composite system, the tensile strength of the A-CNT-PANI / IL / ABS composite does not decrease significantly with increasing A-CNT-PANI content; the decrease is much smaller than that of the A-CNT-PANI / ABS composite. This may be due to the fact that C 12 mimBr plays a role in uniformly dispersing and lubricating the A-CNT-PANI filler, resulting in minimal change in the tensile strength of the A-CNT-PANI / IL / ABS composite material. Therefore, the A-CNT-PANI / IL / ABS composite material is more advantageous for the practical application of ABS resin. Table 1 also shows that the impact strength data of Example 1 is higher than that of Comparative Example 2. This can be attributed to C... 12 The imidazole ring structure in mimBr can interact with PANI via π-cationic interactions, thereby improving the compatibility of PANI with ABS resin. When a 4wt% A-CNT-PANI / ABS system is supplemented with 6wt% C... 12 At mimBr, the impact strength of the A-CNT-PANI / IL / ABS composite material is 10.66 KJ / m. 2 The reduction was significantly reduced, and the impact performance of the composite material was improved. Meanwhile, C 12 The introduction of mimBr can also effectively improve the stress-weak areas caused by nanoparticle aggregation, further enhancing the impact resistance of the composite material.

[0080] from Figure 5 , Figure 6 As can be seen from Table 2, the water washing results of Examples 1, 2, 3 and 4 are better than those of Comparative Examples 2, 3, 4 and 5. This is because the lubricating effect of the ionic liquid gives the A-CNT-PANI filler a higher migration rate. Therefore, the surface resistance of the composite material does not change significantly after water washing. This shows that the addition of ionic liquid is beneficial to improving the durability of the antistatic effect of the A-CNT-PANI / IL / ABS composite material.

[0081] Table 2. Relationship between surface resistivity of ABS composite material and number of washing days.

[0082]

[0083]

[0084] from Figure 7It can be seen that the melt flow index (MFR) of Examples 1, 2, 3, and 4 is higher than that of Comparative Examples 2, 3, 4, and 5. This is because PANI-A-CNT forms a network structure in the ABS resin matrix, which to some extent hinders the relative movement between chain segments, thus leading to a decrease in MFR. Meanwhile, C... 12 The addition of mimBr acts as a lubricant, promoting the dispersion of PANI-A-CNT in ABS resin. This increases the molecular distance in the PANI-A-CNT / IL / ABS composite material, ultimately improving its melt flow index. Therefore, the introduction of C12mimBr can increase the melt flow rate of ABS composite materials and enhance their processing flow properties.

[0085] In summary, this invention prepares A-CNT-PANI / IL / ABS composite materials by blending imidazole ionic liquids into a polyaniline-modified carbon nanotube / ABS composite system. The ionic liquids and polyaniline can effectively regulate the dispersion of carbon nanotubes in the A-CNT-PANI / IL / ABS composite material, enabling the A-CNT-PANI / IL / ABS composite material to achieve excellent antistatic properties with a relatively small amount of carbon nanotubes added. At the same time, it plays a positive role in the mechanical and processing properties of the A-CNT-PANI / IL / ABS composite material, ensuring the practical application value of the antistatic A-CNT-PANI / IL / ABS composite material.

[0086] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A method for preparing a permanent antistatic ABS composite material based on ionic liquid and polyaniline-modified carbon nanotubes, characterized in that... The following steps are included: (1) Place carbon nanotubes in a mixture of concentrated nitric acid and concentrated sulfuric acid with a volume ratio of 1:3, sonicate at 60°C for 5-6 hours, pour the reaction solution into deionized water, cool, filter, wash the filter cake with distilled water, and dry to obtain acidified carbon nanotubes. (2) Add acidified carbon nanotubes to toluene, then add 1,2-ethylenediamine, 1-ethyl-(3-dimethylaminopropyl)carbodiimide and 4-dimethylaminopyridine to the carbon nanotube suspension, stir at room temperature for 24 h to obtain amination carbon nanotubes; (3) 1-Methylimidazole and the alkyl bromide monomer were reacted at 60°C for 72 h, and then recrystallized three times or more with ethyl acetate under ice-water bath conditions to obtain the ionic liquid alkyl-3-methylimidazole onium bromide C. n mimBr, where n is a natural number from 7 to 12; (4) The amination carbon nanotubes and hexadecyltrimethylammonium bromide obtained in step (2) are added to toluene, and after ultrasonic treatment, aniline monomer and dodecylbenzenesulfonic acid are added, and then ultrasonic treatment is continued to obtain a mixed solution; ammonium persulfate is added to deionized water to prepare an ammonium persulfate solution; the ammonium persulfate solution is added to the above mixed solution, stirred evenly, and placed in a refrigerator for reaction for 24 hours. After the reaction is completed, methanol is used for demulsification, washing, and filtration. The filter cake is washed with deionized water and dried to obtain the amination carbon nanotube-polyaniline product; the mass ratio of amination carbon nanotubes to aniline monomer is 1:10, and the molar ratio of aniline monomer, dodecylbenzenesulfonic acid and ammonium persulfate is 1:1:1; (5) The amination carbon nanotube-polyaniline product obtained in step (4) and the ionic liquid alkyl-3-methylimidazolium bromide C obtained in step (3) are combined. n After mimBr and ABS raw materials are blended in a two-roll mill, the mixture is pressed into plates using a flat vulcanizer, removed, and cold-pressed at room temperature to obtain a permanent antistatic ABS composite material based on ionic liquid and polyaniline-modified carbon nanotubes; the amount of the amination carbon nanotube-polyaniline product is 4% of the mass of the ABS raw material; the ionic liquid alkyl-3-methylimidazolium bromide C n The amount of mimBr used is 6-8% of the mass of the ABS raw material.

2. The preparation method according to claim 1, characterized in that: The drying process described in step (1) is carried out in a forced-air drying oven at 60~80℃.

3. The preparation method according to claim 1, characterized in that: The mass ratio of acidified carbon nanotubes, 1,2-ethylenediamine, 1-ethyl-(3-dimethylaminopropyl)carbodiimide and 4-dimethylaminopyridine in step (2) is 1:3:30:

10.

4. The preparation method according to claim 1, characterized in that: The molar ratio of 1-methylimidazole and alkyl bromide monomer in step (3) is 1:

1.

5. The preparation method according to claim 1, characterized in that: The mixing temperature in step (5) is 180°C and the time is 15 min; the temperature of the pressing plate is 180°C and the pressing time is 10-15 min; the cold pressing time is 0-10 min, and cooling circulating water is used for 0-5 min during the cold pressing.

6. A permanent antistatic ABS composite material based on ionic liquid and polyaniline-modified carbon nanotubes, prepared by the preparation method according to any one of claims 1 to 5.

7. The application of the permanent antistatic ABS composite material based on ionic liquid and polyaniline modified carbon nanotubes according to claim 6 in the fields of antistatic packaging or automotive industry.

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