CN117844167B - ABS antistatic plastic based on graphene modification and preparation process thereof - Google Patents

Abstract

The present invention relates to the technical field of antistatic plastics, in particular to graphene-modified ABS antistatic plastics and a preparation process thereof. The method comprises the following steps: step 1: using isocyanate-based ABS and pyridone acid to modify graphene oxide to prepare modified graphene; step 2: preparation of ABS antistatic plastic: drying ABS resin, polycarbonate, modified graphene, compatibilizer, crosslinking agent, and antioxidant and mixing them evenly to obtain raw materials; melt-extrude the raw materials in a screw extruder to obtain ABS antistatic plastic. The raw materials of the ABS antistatic plastic include the following components: by weight, 100 parts of ABS resin, 25-35 parts of polycarbonate, 6-8 parts of modified graphene, 6-9 parts of compatibilizer, 0.5-0.8 parts of crosslinking agent, and 0.2-0.5 parts of antioxidant. In the scheme, the prepared ABS antistatic plastic has excellent antistatic and impact resistance.

Description

ABS antistatic plastic based on graphene modification and its preparation process

Technical Field

The invention relates to the technical field of antistatic plastics, in particular to graphene-modified ABS antistatic plastics and a preparation process thereof.

Background technique

ABS (Acrylonitrile-Butadiene-Styrene) is a widely used engineering plastic with good processability and mechanical properties. It is widely used in many fields such as automobiles, electronic communications, aerospace, and national defense. However, ABS resin itself has some disadvantages: its surface resistivity is 4×10 ¹⁵ Ω, it has high insulation, and its antistatic performance is poor, which limits its application in some fields. On the other hand, it also has the problem of poor heat resistance, and its impact resistance needs to be further improved in some application fields.

In the prior art, antistatic agents such as graphene are usually introduced to improve the antistatic properties of ABS plastics. However, when the amount of inorganic filler introduced is less than 5wt%, the antistatic properties are limited. When the amount introduced exceeds 5wt%, the graphene has agglomeration problems, which makes its dispersion in ABS resin worse, resulting in a significant decrease in mechanical properties. On the other hand, amorphous thermoplastic resin polycarbonate is usually introduced to complement ABS resin, thereby improving the heat resistance and impact resistance of ABS plastics; however, there is a compatibility problem between the two, resulting in a decrease in mechanical properties.

In summary, it is of great significance to solve the above problems and prepare antistatic plastics based on graphene-modified ABS.

Summary of the invention

The purpose of the present invention is to provide an ABS antistatic plastic based on graphene modification and a preparation process thereof, so as to solve the problems raised in the above background technology.

In order to solve the above technical problems, the present invention provides the following technical solutions:

The preparation process of graphene-modified ABS antistatic plastic includes the following steps:

Step 1: Preparation of modified graphene:

S11: (1) Add 2,4-toluene diisocyanate to a reaction bottle, raise the temperature to 40°C~60°C under a nitrogen atmosphere, add hydroxyethyl acrylate dropwise, react for 4~6 hours, cool down, and obtain modified isocyanate; (2) Add ABS resin to toluene, raise the temperature to 120°C~125°C under a nitrogen atmosphere, add a toluene mixed solution containing modified isocyanate and diisopropylbenzene peroxide, react for 4~5 hours, precipitate with methanol, and purify to obtain isocyanate-based ABS;

S12: adding anhydrous citric acid and cysteine to deionized water in sequence to dissolve to obtain a mixed solution; placing the mixed solution in a forced air drying oven, drying at 130° C. to 140° C. for 12 to 24 hours, purifying, and obtaining pyridone acid;

S13: ultrasonically dispersing graphene oxide in chloroform, and under a nitrogen atmosphere, sequentially adding triethylamine, hexamethylene diisocyanate, and pyridine copper acid, and reacting at 40°C to 50°C for 2 to 4 hours; adding isocyanate ABS-chloroform solution, heating to 60°C to 65°C, reacting for 6 to 8 hours, cooling, and purifying to obtain modified graphene;

Step 2: Preparation of ABS antistatic plastic: ABS resin, polycarbonate, modified graphene, compatibilizer, crosslinking agent and antioxidant are dried and mixed evenly to obtain raw materials; the raw materials are melt-extruded in a screw extruder to obtain ABS antistatic plastic.

In a further embodiment, the raw materials of the ABS antistatic plastic include the following components: by weight, 100 parts of ABS resin, 25 to 35 parts of polycarbonate, 6 to 8 parts of modified graphene, 6 to 9 parts of compatibilizer, 0.5 to 0.8 parts of cross-linking agent, and 0.2 to 0.5 parts of antioxidant.

In a further scheme, in S11 of step 1, in the modified isocyanate, the molar ratio of 2,4-toluene diisocyanate and hydroxyethyl acrylate is 1:(0.8~1); in the isocyanate-based ABS, the mass ratio of ABS resin, modified isocyanate, and diisopropylbenzene peroxide is 2.5:(0.4~0.45):(0.05~0.075).

In a further embodiment, in S12 of step 1, the molar ratio of anhydrous citric acid to cysteine in pyridine copper acid is 1:1.

In a further embodiment, in S13 of step 1, the raw materials for modifying graphene include the following components: by weight, 5 parts of graphene oxide, 4.5 to 5 parts of triethylamine, 3 to 4 parts of hexamethylene diisocyanate, 2 to 2.5 parts of pyridine copper acid, and 2.5 to 3.5 parts of isocyanate ABS.

In a further embodiment, the preparation process of the polycarbonate comprises the following steps:

S21: adding pyridine copper acid to tetrahydrofuran, setting the temperature to -10°C to -5°C, slowly adding H ₄ AlLi, stirring and reacting for 8 to 10 hours under a nitrogen atmosphere; adding 12 wt% to 15 wt% NaOH solution, continuing stirring for 30 to 40 minutes, extracting and purifying with ethyl acetate to obtain pyridine copper alcohol;

S22: At room temperature, diphenyl carbonate, isosorbide, copper pyridine alcohol, tetraethylene glycol, and double-terminated hydroxyl polybutadiene are added to a reaction kettle in sequence. Under a nitrogen atmosphere, a catalyst is added, and the mixture is reacted at 110-120°C for 2-3 hours. The temperature is gradually increased to 220-240°C while the pressure is reduced to 30 Pa-50 Pa. The reaction is continued for 25-35 minutes, and the temperature is reduced to obtain polycarbonate.

In a further embodiment, the raw materials of the polycarbonate include the following components: by weight, 18 to 20 parts of diphenyl carbonate, 6 to 8 parts of isosorbide, 1 to 2 parts of pyridine copper alcohol, 3 to 4 parts of tetraethylene glycol, and 0.4 to 0.6 parts of dihydroxy-terminated polybutadiene.

In a further scheme, in pyridine copper alcohol, the mass ratio of pyridine copper acid and H ₄ AlLi is 1:(0.5-0.6); the ratio of pyridine copper acid to NaOH solution is 1 mg:(0.6-0.8 mL).

In a further scheme, the speed of the screw extruder is 200rpm~250rpm, the temperature of each temperature zone is 200℃~210℃, 220℃~240℃, 240℃~250℃, 250℃~260℃, 260℃~270℃, and the feeding speed is 30rpm~60rpm.

In a further embodiment, an ABS antistatic plastic is prepared based on the preparation process of graphene-modified ABS antistatic plastic.

Compared with the prior art, the beneficial effects of this application are as follows:

(1) More than 5 wt% of modified graphene is introduced as an antistatic agent to ensure its dispersibility and compatibility in the raw materials of ABS antistatic plastic, thereby improving the antistatic properties and mechanical properties of ABS antistatic plastic.

In the scheme, the modified graphene is prepared by modifying the surface of graphene oxide with isocyanate-based ABS and pyridone acid based on the reaction between isocyanate and carboxyl. Among them, the isocyanate-based ABS is obtained by reacting an isocyanate group in 2,4-toluene diisocyanate with a hydroxyl group in hydroxyethyl acrylate to obtain a modified isocyanate containing an unsaturated bond, and then the unsaturated bond is used to graft ABS resin under the initiation of diisopropylbenzene peroxide. Due to its modification, its agglomeration is effectively suppressed, and the compatibility of the modified graphene with ABS resin is effectively increased, thereby effectively ensuring its uniform dispersion in ABS antistatic plastics and ensuring mechanical properties.

Among them, in the previous step of using isocyanate-based ABS for modification, the two isocyanate groups of hexamethylene diisocyanate and the π-π stacking between pyridone acid and graphene oxide are used to effectively insert pyridone acid into graphene oxide. Since pyridone acid contains π conjugation, it can produce π-π stacking interaction with graphene oxide, thereby improving the conductivity of graphene oxide; on the other hand, its structure contains sulfur atoms and has strong electrophilicity. Modifying graphene oxide with pyridone acid can increase the charge density on the graphene surface, thereby further improving its antistatic properties. In addition, the first grafting of small molecular pyridone acid is conducive to the intercalation of larger molecular weight isocyanate-based ABS.

(2) Polycarbonate containing pyridine copper alcohol and double-terminated hydroxyl polybutadiene was further introduced to further improve the antistatic and impact resistance of ABS antistatic plastics.

In the scheme, pyridone acid is converted into pyridone alcohol under the catalysis of H ₄ AlLi, and introduced into polycarbonate, which effectively promotes charge transfer, thereby improving antistatic performance. At the same time, the compatibility with modified graphene is increased, thereby utilizing the physical effect of modified graphene oxide to promote the compatible interface effect between polycarbonate and ABS resin and increase dispersibility. On the other hand, double-terminated hydroxyl polybutadiene is also introduced, and similar chain segments are utilized to promote similar compatibility with ABS resin, and at the same time, it has toughness that can increase the toughness of polycarbonate. In this way, compared with the introduction of common polycarbonate, the introduction of polycarbonate in this application has higher compatibility, antistatic performance, and impact resistance.

Detailed ways

The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

It should be noted that the following parts are by mass, and the purchase manufacturers of all raw materials involved in the present invention are not subject to any special restrictions, and exemplary examples include: CAS No. 584-84-9 of 2,4-toluene diisocyanate, CAS No. 818-61-1 of hydroxyethyl acrylate, CAS No. 77-92-9 of anhydrous citric acid, CAS No. 52-90-4 of cysteine, CAS No. 822-06-0 of hexamethylene diisocyanate, CAS No. 106-06-0 of tetraethylene glycol, CAS No. 11-11-1 of tantalum bis(ethylene glycol), ... The CAS number of alcohol is 112-60-7; the CAS number of tri(2-acryloxyethyl) isocyanurate is 40220-08-4; the average molecular weight of double-terminated hydroxyl polybutadiene is 5000, and the brand is Hongyuan New Materials; the antioxidant is antioxidant 1135, and the brand is Hengchang; the compatibilizer is SMA compatibilizer, and the brand is Xingyuan Chemical; the brand of graphene oxide is Aochuang, and the product number is 777676; the brand of ABS resin is PA-757, and the brand is Chimei.

Embodiment 1: The preparation process of graphene-modified ABS antistatic plastic comprises the following steps:

Step 1: S11: (1) Add 2,4-toluene diisocyanate to a reaction bottle, heat it to 55°C under a nitrogen atmosphere, drop hydroxyethyl acrylate, react for 6 hours, cool it down, and obtain modified isocyanate; the molar ratio of 2,4-toluene diisocyanate to hydroxyethyl acrylate is 1:1; (2) Add 2.5 parts of ABS resin to 50 parts of toluene, heat it to 120°C under a nitrogen atmosphere, add a toluene mixed solution containing modified isocyanate and diisopropylbenzene peroxide (0.42 parts of modified isocyanate, 0.06 parts of diisopropylbenzene peroxide, 30 parts of toluene), react for 5 hours, precipitate with methanol, and purify to obtain isocyanate-based ABS;

S12: adding anhydrous citric acid and cysteine to deionized water in sequence to dissolve, to obtain a mixed solution; placing the mixed solution in a forced air drying oven, drying at 130° C. for 18 hours, and purifying to obtain pyridone acid; the molar ratio of anhydrous citric acid to cysteine is 1:1;

S13: ultrasonically disperse 5 parts of graphene oxide in 50 parts of chloroform, and under a nitrogen atmosphere, sequentially add 5 parts of triethylamine, 3.5 parts of hexamethylene diisocyanate, and 2.5 parts of pyridine copper acid, and react at 50°C for 4 hours; add isocyanate ABS-chloroform solution (3 parts of isocyanate ABS and 10 parts of chloroform), raise the temperature to 60°C, react for 6 hours, cool down, and purify to obtain modified graphene;

Step 2: S21: add 10 parts of pyridine copper acid to 50 parts of tetrahydrofuran, set the temperature to -10°C, slowly add 5 parts of H ₄ AlLi, stir and react for 10 hours under nitrogen atmosphere; add 14 wt % NaOH solution (the ratio of NaOH solution to pyridine copper acid is 1 mg: 0.6 mL), continue stirring for 30 minutes, extract and purify with ethyl acetate to obtain pyridine copper alcohol;

S22: At room temperature, 20 parts of diphenyl carbonate, 7 parts of isosorbide, 1.5 parts of pyridine copper alcohol, 3 parts of tetraethylene glycol, and 0.5 parts of double-terminated hydroxyl polybutadiene are added to a reaction kettle in sequence, and 1-butyl-3-methylimidazole lactate (accounting for 0.005 mol% of diphenyl carbonate) is added under a nitrogen atmosphere, and the reaction is carried out at 120° C. for 2 hours, and the temperature is gradually increased to 220° C. while the pressure is reduced to 50 Pa, and the reaction is continued for 30 minutes, and the temperature is reduced to obtain polycarbonate;

Step 3: 100 parts of ABS resin, 30 parts of polycarbonate, 8 parts of modified graphene, 8 parts of SMA compatibilizer, 0.5 parts of tri(2-acryloxyethyl)isocyanurate, and 0.5 parts of antioxidant 1135 are dried and mixed evenly to obtain raw materials; the raw materials are placed in a screw extruder, the speed of the screw extruder is set to 250 rpm, the temperatures in each temperature zone are 200°C, 220°C, 240°C, 250°C, and 260°C, the feeding speed is 50 rpm, and melt-extruded to obtain ABS antistatic plastic.

Embodiment 2: The preparation process of graphene-modified ABS antistatic plastic comprises the following steps:

Step 1: S11: (1) Add 2,4-toluene diisocyanate to a reaction bottle, heat it to 55°C under a nitrogen atmosphere, drop hydroxyethyl acrylate, react for 6 hours, cool it down, and obtain modified isocyanate; the molar ratio of 2,4-toluene diisocyanate to hydroxyethyl acrylate is 1:1; (2) Add 2.5 parts of ABS resin to 50 parts of toluene, heat it to 120°C under a nitrogen atmosphere, add a toluene mixed solution containing modified isocyanate and diisopropylbenzene peroxide (0.42 parts of modified isocyanate, 0.06 parts of diisopropylbenzene peroxide, 30 parts of toluene), react for 5 hours, precipitate with methanol, and purify to obtain isocyanate-based ABS;

S12: adding anhydrous citric acid and cysteine to deionized water in sequence to dissolve, to obtain a mixed solution; placing the mixed solution in a forced air drying oven, drying at 130° C. for 18 hours, and purifying to obtain pyridone acid; the molar ratio of anhydrous citric acid to cysteine is 1:1;

S13: ultrasonically disperse 5 parts of graphene oxide in 50 parts of chloroform, and add 5 parts of triethylamine, 3 parts of hexamethylene diisocyanate, and 2 parts of pyridine copper acid in sequence under a nitrogen atmosphere, and react at 50°C for 4 hours; add isocyanate ABS-chloroform solution (3.5 parts of isocyanate ABS and 10 parts of chloroform), heat to 60°C, react for 6 hours, cool, and purify to obtain modified graphene;

Step 2: S21: add 10 parts of pyridine copper acid to 50 parts of tetrahydrofuran, set the temperature to -10°C, slowly add 5 parts of H ₄ AlLi, stir and react for 10 hours under nitrogen atmosphere; add 14 wt % NaOH solution (the ratio of NaOH solution to pyridine copper acid is 1 mg: 0.6 mL), continue stirring for 30 minutes, extract and purify with ethyl acetate to obtain pyridine copper alcohol;

S22: At room temperature, 20 parts of diphenyl carbonate, 7 parts of isosorbide, 1.5 parts of pyridine copper alcohol, 3 parts of tetraethylene glycol, and 0.5 parts of double-terminated hydroxyl polybutadiene are added to a reaction kettle in sequence, and 1-butyl-3-methylimidazole lactate (accounting for 0.005 mol% of diphenyl carbonate) is added under a nitrogen atmosphere, and the reaction is carried out at 120° C. for 2 hours, and the temperature is gradually increased to 220° C. while the pressure is reduced to 50 Pa, and the reaction is continued for 30 minutes, and the temperature is reduced to obtain polycarbonate;

Step 3: 100 parts of ABS resin, 25 parts of polycarbonate, 8 parts of modified graphene, 6 parts of SMA compatibilizer, 0.5 parts of tri(2-acryloxyethyl)isocyanurate, and 0.2 parts of antioxidant 1135 are dried and mixed evenly to obtain raw materials; the raw materials are placed in a screw extruder, the speed of the screw extruder is set to 250 rpm, the temperatures in each temperature zone are 200°C, 220°C, 240°C, 250°C, and 260°C, the feeding speed is 50 rpm, and melt-extruded to obtain ABS antistatic plastic.

Embodiment 3: The preparation process of graphene-modified ABS antistatic plastic comprises the following steps:

Step 1: S11: (1) Add 2,4-toluene diisocyanate to a reaction bottle, heat it to 55°C under a nitrogen atmosphere, drop hydroxyethyl acrylate, react for 6 hours, cool it down, and obtain modified isocyanate; the molar ratio of 2,4-toluene diisocyanate to hydroxyethyl acrylate is 1:1; (2) Add 2.5 parts of ABS resin to 50 parts of toluene, heat it to 120°C under a nitrogen atmosphere, add a toluene mixed solution containing modified isocyanate and diisopropylbenzene peroxide (0.42 parts of modified isocyanate, 0.06 parts of diisopropylbenzene peroxide, 30 parts of toluene), react for 5 hours, precipitate with methanol, and purify to obtain isocyanate-based ABS;

S12: adding anhydrous citric acid and cysteine to deionized water in sequence to dissolve, to obtain a mixed solution; placing the mixed solution in a forced air drying oven, drying at 130° C. for 18 hours, and purifying to obtain pyridone acid; the molar ratio of anhydrous citric acid to cysteine is 1:1;

S13: ultrasonically disperse 5 parts of graphene oxide in 50 parts of chloroform, and add 4.5 parts of triethylamine, 4 parts of hexamethylene diisocyanate, and 2.5 parts of pyridine copper acid in sequence under a nitrogen atmosphere, and react at 50°C for 4 hours; add isocyanate ABS-chloroform solution (2.5 parts of isocyanate ABS and 10 parts of chloroform), heat to 60°C, react for 6 hours, cool, and purify to obtain modified graphene;

Step 2: S21: add 10 parts of pyridine copper acid to 50 parts of tetrahydrofuran, set the temperature to -10°C, slowly add 5 parts of H ₄ AlLi, stir and react for 10 hours under nitrogen atmosphere; add 14 wt % NaOH solution (the ratio of NaOH solution to pyridine copper acid is 1 mg: 0.6 mL), continue stirring for 30 minutes, extract and purify with ethyl acetate to obtain pyridine copper alcohol;

S22: At room temperature, 20 parts of diphenyl carbonate, 7 parts of isosorbide, 1.5 parts of pyridine copper alcohol, 3 parts of tetraethylene glycol, and 0.5 parts of double-terminated hydroxyl polybutadiene are added to a reaction kettle in sequence, and 1-butyl-3-methylimidazole lactate (accounting for 0.005 mol% of diphenyl carbonate) is added under a nitrogen atmosphere, and the reaction is carried out at 120° C. for 2 hours, and the temperature is gradually increased to 220° C. while the pressure is reduced to 50 Pa, and the reaction is continued for 30 minutes, and the temperature is reduced to obtain polycarbonate;

Step 3: 100 parts of ABS resin, 35 parts of polycarbonate, 6 parts of modified graphene, 9 parts of SMA compatibilizer, 0.8 parts of tri(2-acryloxyethyl)isocyanurate, and 0.5 parts of antioxidant 1135 are dried and mixed evenly to obtain raw materials; the raw materials are placed in a screw extruder, the speed of the screw extruder is set to 250 rpm, the temperatures in each temperature zone are 200°C, 220°C, 240°C, 250°C, and 260°C, the feeding speed is 50 rpm, and melt-extruded to obtain ABS antistatic plastic.

Comparative Example 1: Based on Example 1, graphene oxide was modified using 3-isocyanate propylene, and the specific changes were as follows: S13: 5 parts of graphene oxide were ultrasonically dispersed in 50 parts of chloroform, and under a nitrogen atmosphere, 5 parts of triethylamine and 5.5 parts of 3-isocyanate propylene were added in sequence, the temperature was raised to 60°C, the reaction was carried out for 6 hours, the temperature was lowered, and the modified graphene was obtained. The rest was the same as in Example 1.

Comparative Example 2: Based on Example 1, graphene oxide is modified using pyridine copper acid alone, and the specific changes are as follows: S13: 5 parts of graphene oxide are ultrasonically dispersed in 50 parts of chloroform, and under a nitrogen atmosphere, 5 parts of triethylamine, 3.5 parts of hexamethylene diisocyanate, and 5.5 parts of pyridine copper acid are added in sequence, the temperature is raised to 60°C, the reaction is carried out for 6 hours, the temperature is lowered, and the modified graphene is obtained. The rest is the same as Example 1.

Comparative Example 3: Based on Example 1, graphene oxide is modified using only isocyanate ABS, and the specific changes are as follows: S13: 5 parts of graphene oxide are ultrasonically dispersed in 50 parts of chloroform, and under a nitrogen atmosphere, 5 parts of triethylamine and a mixed solution of 5.5 parts of isocyanate ABS-10 parts of chloroform are added in sequence, the temperature is raised to 60°C, the reaction is carried out for 6 hours, the temperature is lowered, and the modified graphene is obtained. The rest is the same as in Example 1.

Comparative Example 4: The polycarbonate was replaced with polycarbonate-CD402, the brand of which is Bayer from Germany, and the rest was the same as Example 1.

Experiment 1: The ABS antistatic plastics prepared in Examples 1 to 3 and Comparative Examples 1 to 4 were subjected to performance tests;

(1) According to the standard method of GB/T1040.1, the tensile strength is tested at a tensile rate of 10 mm/min;

(2) According to the standard method of GB/T1410, a sample with a size of 10 cm × 10 cm × 1 mm was placed at 23°C and a humidity of 33% for a period of time, and its volume resistivity was measured using a volume surface resistivity meter; the obtained data are as follows:

Conclusion: The data of Examples 1 to 3 show that the scheme effectively enhances the dispersibility of graphene in ABS antistatic plastic by modifying it, and effectively enhances the antistatic performance while ensuring the mechanical properties. Comparing the data of Example 1 with Comparative Examples 1 to 4, the data show that when the graphene oxide in Comparative Example 1 is modified with 3-isocyanate propylene, although the propylene group can produce reactive crosslinking, there is still a dispersibility problem, resulting in a decrease in mechanical properties. At the same time, due to the absence of conjugated pyridine keto acid, the antistatic performance is also significantly reduced; in Comparative Example 2, due to the single use of pyridine copper acid to modify graphene, the dispersibility is reduced, resulting in a decrease in mechanical properties; in Comparative Example 3, due to the single use of isocyanate ABS modification, the antistatic performance is reduced; at the same time, due to the weakening of the interaction with polycarbonate, the mechanical properties are reduced; in Comparative Example 4, due to the use of polycarbonate-CD402, the compatibility is reduced, resulting in a decrease in mechanical properties.

Finally, it should be noted that the above is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims (6)

1. A preparation process of graphene-modified ABS antistatic plastic, characterized in that it comprises the following steps: Step 1: Preparation of modified graphene: S11: (1) Add 2,4-toluene diisocyanate to a reaction bottle, raise the temperature to 40°C~60°C under a nitrogen atmosphere, add hydroxyethyl acrylate dropwise, react for 4~6 hours, cool down, and obtain modified isocyanate; (2) Add ABS resin to toluene, raise the temperature to 120°C~125°C under a nitrogen atmosphere, add a toluene mixed solution containing modified isocyanate and diisopropylbenzene peroxide, react for 4~5 hours, precipitate with methanol, and purify to obtain isocyanate-based ABS; S12: adding anhydrous citric acid and cysteine to deionized water in sequence to dissolve to obtain a mixed solution; placing the mixed solution in a forced air drying oven, drying at 130° C. to 140° C. for 12 to 24 hours, purifying, and obtaining pyridone acid; S13: ultrasonically dispersing graphene oxide in chloroform, and under a nitrogen atmosphere, sequentially adding triethylamine, hexamethylene diisocyanate, and pyridone acid, and reacting at 40°C to 50°C for 2 to 4 hours; adding isocyanate ABS-chloroform solution, heating to 60°C to 65°C, reacting for 6 to 8 hours, cooling, and purifying to obtain modified graphene; Step 2: Preparation of polycarbonate: S21: adding pyridone acid to tetrahydrofuran, setting the temperature to -10°C~-5°C, slowly adding H ₄ AlLi, stirring and reacting for 8~10 hours under nitrogen atmosphere; adding 12wt%~15wt% NaOH solution, continuing stirring for 30~40 minutes, extracting and purifying with ethyl acetate to obtain pyridone alcohol; S22: At room temperature, diphenyl carbonate, isosorbide, pyridone alcohol, tetraethylene glycol, and dihydroxy-terminated polybutadiene are added to a reaction kettle in sequence, and a catalyst is added under a nitrogen atmosphere, and the mixture is reacted at 110-120° C. for 2-3 hours, and the temperature is gradually increased to 220-240° C. while the pressure is reduced to 30 Pa-50 Pa, and the reaction is continued for 25-35 minutes, and the temperature is reduced to obtain polycarbonate; Step 3: Preparation of ABS antistatic plastic: drying ABS resin, polycarbonate, modified graphene, compatibilizer, crosslinking agent, and antioxidant and mixing them evenly to obtain raw materials; melt-extrude the raw materials in a screw extruder to obtain ABS antistatic plastic; The raw materials of the ABS antistatic plastic include the following components: by weight, 100 parts of ABS resin, 25-35 parts of polycarbonate, 6-8 parts of modified graphene, 6-9 parts of compatibilizer, 0.5-0.8 parts of cross-linking agent, and 0.2-0.5 parts of antioxidant; The raw materials of the modified graphene include the following components: by weight, 5 parts of graphene oxide, 4.5-5 parts of triethylamine, 3-4 parts of hexamethylene diisocyanate, 2-2.5 parts of pyridone acid, and 2.5-3.5 parts of isocyanate-based ABS; The raw materials of the polycarbonate include the following components: by weight, 18-20 parts of diphenyl carbonate, 6-8 parts of isosorbide, 1-2 parts of pyridone alcohol, 3-4 parts of tetraethylene glycol, and 0.4-0.6 parts of double-terminated hydroxyl polybutadiene. 2. The preparation process of graphene-modified ABS antistatic plastic according to claim 1, characterized in that: in S11 of step 1, in the modified isocyanate, the molar ratio of 2,4-toluene diisocyanate and hydroxyethyl acrylate is 1:(0.8~1); in the isocyanate-based ABS, the mass ratio of ABS resin, modified isocyanate, and diisopropylbenzene peroxide is 2.5:(0.4~0.45):(0.05~0.075). 3. The preparation process of graphene-modified ABS antistatic plastic according to claim 1, characterized in that: in S12 of step 1, the molar ratio of anhydrous citric acid to cysteine in pyridone acid is 1:1. 4. The preparation process of graphene-modified ABS antistatic plastic according to claim 1, characterized in that: in pyridone alcohol, the mass ratio of pyridone acid to H ₄ AlLi is 1:(0.5-0.6); the ratio of pyridone acid to NaOH solution is 1 mg:(0.6-0.8 mL). 5. The preparation process of graphene-modified ABS antistatic plastic according to claim 1 is characterized in that the speed of the screw extruder is 200rpm~250rpm, the temperature of each temperature zone is 200℃~210℃, 220℃~240℃, 240℃~250℃, 250℃~260℃, 260℃~270℃, and the feeding speed is 30rpm~60rpm. 6. The ABS antistatic plastic prepared according to the preparation process of the graphene-modified ABS antistatic plastic according to any one of claims 1 to 5.