An antistatic polyolefin masterbatch and its production process

Abstract

The present invention relates to the technical field of polymer materials, and discloses an antistatic polyolefin masterbatch and its production process. The polyolefin masterbatch in the present invention comprises the following raw materials in parts by weight: 80 - 100 parts of polyolefin resin, 15 - 25 parts of composite antistatic agent, 5 - 10 parts of modified toughening agent, 1.5 - 3.5 parts of antioxidant, and 2 - 4 parts of lubricant; the masterbatch uses polyolefin resin as the matrix resin, adding a composite antistatic agent improves the antistatic performance of the masterbatch, and adding a modified toughening agent improves the mechanical properties of the masterbatch; among them, the composite antistatic agent adopts an organic-inorganic combination method, making the masterbatch have permanent antistatic performance; the modified toughening agent is obtained by modifying maleic anhydride grafted polyethylene, improving the mechanical properties of the masterbatch.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and particularly relates to an antistatic polyolefin masterbatch and its production process. Background Art

[0002] Polyolefins are the general term for all homopolymers, copolymers and their mixtures mainly composed of ethylene and propylene, and are widely used in industries such as electrical appliances, chemical engineering, food, machinery and transportation, and have become one of the indispensable chemical products in the national economy. Polyolefins themselves belong to high-insulation materials. Under the conditions of friction, extrusion, etc., static electricity is extremely easy to generate and accumulate, which often causes static induction, electric shock and production obstacles of products. In severe cases, it may even cause fire and explosion accidents, directly affecting the safety of production and use.

[0003] Therefore, when antistatic treatment is carried out on polyolefin materials, antistatic masterbatch is generally added to improve the antistatic performance of the materials, with the aim of reducing the surface resistance of plastic products and preventing various problems caused by static electricity accumulation, such as dust adsorption, static discharge, etc. And this kind of masterbatch usually consists of carrier resin, antistatic agent and other additives, and is made into particles through a specific production process for adding and using in the plastic processing process. In addition, considering that the antistatic masterbatch may be applied in materials with a certain toughness, it is necessary for researchers to develop a polyolefin masterbatch with excellent antistatic performance and mechanical properties to meet the actual needs. Summary of the Invention

[0004] In order to solve the above technical problems, the present invention provides an antistatic polyolefin masterbatch and its production process.

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

[0006] An antistatic polyolefin masterbatch, comprising the following raw materials in parts by weight: 80 - 100 parts of polyolefin resin, 15 - 25 parts of composite antistatic agent, 5 - 10 parts of modified toughening agent, 1.5 - 3.5 parts of antioxidant, and 2 - 4 parts of lubricant;

[0007] The polyolefin resin is polyethylene resin or polypropylene resin;

[0008] The composite antistatic agent is prepared by the following steps:

[0009] Step A1: Disperse nano-carbon black in 30wt% hydrogen peroxide solution, and perform ultrasonic treatment for 30 - 60 min, then reflux and stir at 60°C for 24 h, wash, dry, and collect the pretreated carbon black; add γ-aminopropyltriethoxysilane to ethanol solution and perform ultrasonic treatment for 15 min, then add the pretreated carbon black and perform ultrasonic treatment for 1.5 - 2.5 h, then reflux and stir at 65 - 75°C for 5 - 7 h, filter, wash, and dry to obtain modified carbon black;

[0010] Step A2: Add p-phenylenediamine, 2,5-diaminobenzoic acid, and triethylamine into N,N-dimethylformamide and disperse them evenly. Then add cyanuric chloride and modified carbon black, and ultrasonically disperse for 30 min. Then transfer to an autoclave and react at 100 - 120 °C for 10 - 16 h. Wash and dry to obtain the carbon black / COF composite material.

[0011] Step A3: Disperse the carbon black / COF composite material, propylene oxide, and tetrabutylammonium bromide in N,N-dimethylformamide, introduce nitrogen for 10 min, then react at 80 - 90 °C under nitrogen for 2 - 3 h. After cooling to room temperature, add ethylene oxide and potassium hydroxide, and then heat up to 60 - 80 °C and react for 4 - 5 h. Rotavapor, wash, and dry to obtain the composite antistatic agent.

[0012] Further, in step A1, the dosage ratio of γ-aminopropyltriethoxysilane, ethanol solution, and pretreated carbon black is 1 - 2 mL : 100 mL : 0.1 - 0.5 g. The dosage ratio of nano-carbon black and hydrogen peroxide solution in the pretreated carbon black is 5 g : 100 mL, and the volume ratio of ethanol and deionized water in the ethanol solution is 9 : 1.

[0013] Further, in step A2, the dosage ratio of p-phenylenediamine, 2,5-diaminobenzoic acid, triethylamine, N,N-dimethylformamide, cyanuric chloride, and modified carbon black is 0.08 - 0.12 mol : 0.15 - 0.25 mol : 15 - 45 mL : 300 mL : 0.05 - 0.15 mol : 1 - 2 g.

[0014] Further, in step A3, the dosage ratio of the carbon black / COF composite material, propylene oxide, tetrabutylammonium bromide, N,N-dimethylformamide, ethylene oxide, and potassium hydroxide is 3 - 6 g : 5 - 9 g : 0.2 - 0.5 g : 100 mL : 8 - 12 g : 0.1 - 0.3 g.

[0015] The modified toughening agent is prepared by the following steps:

[0016] Step B1: Blend maleic anhydride-grafted polyethylene and 5-aminoisophthalic acid in a mixer for 10 - 20 min. The conditions of the mixer are: rotation speed 50 - 100 rpm, mixing temperature 120 - 140 °C, to obtain the graft-modified polyethylene.

[0017] Step B2: Disperse cellulose and sodium hydroxide in deionized water and stir at 50 - 70 °C for 3 - 5 h. Centrifuge, wash, and dry to collect the alkali-treated cellulose. Then add the alkali-treated cellulose and zinc chloride to the graft-modified polyethylene, and continue to blend under the conditions of step B1 for 15 - 25 min to obtain the modified toughening agent.

[0018] Further, the mass ratio of maleic anhydride grafted polyethylene to 5-aminoisophthalic acid in step B1 is 10:0.5 - 1.5;

[0019] Further, the mass ratio of alkali-treated cellulose, zinc chloride, and maleic anhydride grafted polyethylene in step B2 is 1 - 3:0.5 - 1.5:10, and the mass ratio of cellulose, sodium hydroxide, and deionized water in the alkali-treated cellulose is 5:0.5 - 1.5:30.

[0020] A production process of an antistatic polyolefin masterbatch includes the following steps:

[0021] Step S1: Weigh the raw materials by weight parts. Add polyolefin resin, composite antistatic agent, modified toughening agent, antioxidant, and lubricant into a high-speed kneader, knead for 25 - 35 min. When the temperature of the materials in the kneader rises to 100 - 120 °C, discharge the materials to obtain a mixed material;

[0022] Step S2: Put the mixed material into a twin-screw extruder. Under the conditions of a rotation speed of 150 - 300 rpm, a temperature of 70 - 90 °C in zone 1, a temperature of 120 - 130 °C in zone 2, a temperature of 135 - 145 °C in zone 3, and a temperature of 140 - 150 °C at the die head, extrude, cool, and pelletize to obtain the antistatic polyolefin masterbatch.

[0023] The beneficial effects of the present invention:

[0024] The polyolefin masterbatch in the present invention uses polyolefin resin as the matrix resin. Adding a composite antistatic agent improves the antistatic performance of the masterbatch, and adding a modified toughening agent improves the mechanical properties of the masterbatch; among them, the composite antistatic agent adopts an organic-inorganic combination method, making the masterbatch have permanent antistatic performance; the modified toughening agent improves the mechanical properties of the masterbatch by modifying maleic anhydride grafted polyethylene.

[0025] In the composite antistatic agent, nano-carbon black is first treated with hydrogen peroxide, and then surface-treated with a silane coupling agent to obtain modified carbon black. Then, using p-phenylenediamine, 2,5-diaminobenzoic acid, and cyanuric chloride as organic ligands, COF is loaded on the surface of the modified carbon black to synthesize a carbon black / COF composite material. Finally, the carboxyl groups on the surface of the composite material react with propylene oxide and ethylene oxide to generate a composite antistatic agent containing hydrophilic polyether segments. The carbon black, COF, and polyether segments in the composite antistatic agent can work synergistically to improve the antistatic performance of the matrix. Among them, the composite material obtained by combining carbon black and COF acts as a conductive filler in the matrix, forming a conductive network in the matrix, thereby reducing the surface resistivity of the matrix, enabling the charges accumulated inside and on the surface of the matrix to be quickly released, and further improving the antistatic performance of the matrix. At the same time, the composite material has better dispersibility compared with traditional carbon black, can be evenly dispersed in the matrix, and further improves the antistatic performance of the matrix. The hydrophilic polyether segments in the composite antistatic agent can adsorb water molecules on the surface of the matrix to form a conductive water film, effectively reducing the surface resistivity of the matrix, reducing the possibility of static charge accumulation, thereby achieving the antistatic effect. At the same time, the polyether segments can migrate from the inside of the matrix to the surface of the matrix to make up for the loss of the surface antistatic agent, making the antistatic performance of the matrix more durable, ensuring the continuity and stability of the antistatic effect, avoiding the loss of the surface antistatic agent caused by washing or friction, and reducing the harm caused by static electricity.

[0026] In the modified toughening agent, the maleic anhydride in maleic anhydride-grafted polyethylene first reacts with the amino group in 5-aminoisophthalic acid to obtain graft-modified polyethylene. Then, alkali-treated cellulose and zinc chloride are added to the graft-modified polyethylene for blending to obtain the modified toughening agent. The addition of the modified toughening agent improves the mechanical properties of the masterbatch. Among them, the addition of zinc chloride enables Zn 2+ to have a certain coordination effect with the polar groups in the graft-modified polyethylene and cellulose, forming a metal coordination bond with Zn 2 + as the connection center, enhancing the interaction between the graft-modified polyethylene and cellulose, improving the toughness of the matrix, and thus increasing the toughness of the masterbatch. In addition, a hydrogen bond interaction can also be formed between the graft-modified polyethylene and cellulose, and the hydrogen bond interaction can cooperate with the metal coordination bond to dissipate the energy generated by external stretching, further improving the toughness of the masterbatch. Detailed implementation manners

[0027] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts shall fall within the protection scope of the present invention. Example

[0028] The composite antistatic agent is prepared by the following steps:

[0029] Step A1: Disperse 5 g of nano carbon black in 100 mL of 30 wt% hydrogen peroxide solution, and perform ultrasonic treatment for 30 min. Then, carry out reflux stirring reaction at 60 °C for 24 h, wash, dry, and collect the pretreated carbon black. Add 1 mL of γ-aminopropyltriethoxysilane to 100 mL of ethanol solution, perform ultrasonic treatment for 15 min, then add 0.1 g of pretreated carbon black and perform ultrasonic treatment for 1.5 h. Then, carry out reflux stirring at 65 °C for 5 h, perform suction filtration, wash, and dry to obtain modified carbon black. The volume ratio of ethanol to deionized water in the ethanol solution is 9:1;

[0030] Step A2: Disperse 0.08 mol of p-phenylenediamine, 0.15 mol of 2,5-diaminobenzoic acid, and 15 mL of triethylamine evenly in 300 mL of N,N-dimethylformamide. Then, add 0.05 mol of cyanuric chloride and 1 g of modified carbon black, perform ultrasonic dispersion for 30 min, and then transfer to an autoclave and react at 100 °C for 10 h. Wash and dry to obtain the carbon black / COF composite material;

[0031] Step A3: Disperse 3 g of carbon black / COF composite material, 5 g of propylene oxide, and 0.2 g of tetrabutylammonium bromide in 100 mL of N,N-dimethylformamide, introduce nitrogen for 10 min, and then react at 80 °C under nitrogen for 2 h. After cooling to room temperature, add 8 g of ethylene oxide and 0.1 g of potassium hydroxide, and then heat up to 60 °C and react for 4 h. Perform rotary evaporation, wash, and dry to obtain the composite antistatic agent.

[0032] The modified toughening agent is prepared by the following steps:

[0033] Step B1: Blend 10 g of maleic anhydride grafted polyethylene and 0.5 g of 5-aminoisophthalic acid in a mixer for 10 min. The conditions of the mixer are: rotation speed 50 rpm, mixing temperature 120 °C, to obtain graft-modified polyethylene;

[0034] Step B2: Disperse 5 g of cellulose and 0.5 g of sodium hydroxide in 30 g of deionized water, stir at 50 °C for 3 h, centrifuge, wash, and dry to collect the alkali-treated cellulose. Then, add 1 g of alkali-treated cellulose and 0.5 g of zinc chloride to the graft-modified polyethylene, and continue to blend under the conditions of Step B1 for 15 min to obtain the modified toughening agent. Example

[0035] The composite antistatic agent is prepared by the following steps:

[0036] Step A1: Disperse 5 g of nano carbon black in 100 mL of 30 wt% hydrogen peroxide solution, and ultrasonically treat for 45 min. Then, carry out a reflux stirring reaction at 60 °C for 24 h, wash, dry, and collect the pretreated carbon black. Add 1.5 mL of γ-aminopropyltriethoxysilane to 100 mL of ethanol solution, ultrasonically treat for 15 min, then add 0.3 g of the pretreated carbon black and ultrasonically treat for 2 h. Then, carry out a reflux stirring at 70 °C for 6 h, filter by suction, wash, and dry to obtain the modified carbon black. The volume ratio of ethanol to deionized water in the ethanol solution is 9:1;

[0037] Step A2: Add 0.1 mol of p-phenylenediamine, 0.2 mol of 2,5-diaminobenzoic acid, and 30 mL of triethylamine to 300 mL of N,N-dimethylformamide and disperse evenly. Then, add 0.1 mol of cyanuric chloride and 1.5 g of the modified carbon black, ultrasonically disperse for 30 min, then transfer to an autoclave and react at 110 °C for 13 h, wash, and dry to obtain the carbon black / COF composite material;

[0038] Step A3: Disperse 4.5 g of the carbon black / COF composite material, 7 g of propylene oxide, and 0.35 g of tetrabutylammonium bromide in 100 mL of N,N-dimethylformamide, introduce nitrogen for 10 min, then react at 85 °C under nitrogen for 2.5 h. Then, cool to room temperature, add 10 g of ethylene oxide and 0.2 g of potassium hydroxide, and then heat up to 70 °C and react for 4.5 h. Carry out rotary evaporation, wash, and dry to obtain the composite antistatic agent.

[0039] The modified toughening agent is prepared by the following steps:

[0040] Step B1: Add 10 g of maleic anhydride grafted polyethylene and 1 g of 5-aminoisophthalic acid to a mixer and blend for 15 min. The conditions of the mixer are: rotation speed 100 rpm, mixing temperature 130 °C, to obtain the graft-modified polyethylene;

[0041] Step B2: Add 5 g of cellulose and 1 g of sodium hydroxide to 30 g of deionized water and disperse, and stir at 60 °C for 4 h, centrifuge, wash, and dry to collect the alkali-treated cellulose. Then, add 2 g of the alkali-treated cellulose and 1 g of zinc chloride to the graft-modified polyethylene, and continue to blend under the conditions of Step B1 for 20 min to obtain the modified toughening agent. Example

[0042] The composite antistatic agent is prepared by the following steps:

[0043] Step A1: Disperse 5 g of nano carbon black in 100 mL of 30 wt% hydrogen peroxide solution, ultrasonically treat for 60 min, then reflux and stir at 60 °C for 24 h, wash, dry, and collect the pretreated carbon black; Add 2 mL of γ-aminopropyltriethoxysilane to 100 mL of ethanol solution, ultrasonically treat for 15 min, then add 0.5 g of pretreated carbon black and ultrasonically treat for 2.5 h, then reflux and stir at 75 °C for 7 h, filter by suction, wash, and dry to obtain the modified carbon black. The volume ratio of ethanol to deionized water in the ethanol solution is 9:1;

[0044] Step A2: Disperse 0.12 mol of p-phenylenediamine, 0.25 mol of 2,5-diaminobenzoic acid, and 45 mL of triethylamine in 300 mL of N,N-dimethylformamide evenly, then add 0.15 mol of cyanuric chloride and 2 g of modified carbon black, ultrasonically disperse for 30 min, then transfer to an autoclave and react at 120 °C for 16 h, wash, and dry to obtain the carbon black / COF composite material;

[0045] Step A3: Disperse 6 g of carbon black / COF composite material, 9 g of propylene oxide, and 0.5 g of tetrabutylammonium bromide in 100 mL of N,N-dimethylformamide, introduce nitrogen for 10 min, then react at 90 °C under nitrogen for 3 h, then lower the temperature to room temperature, add 12 g of ethylene oxide and 0.3 g of potassium hydroxide, then raise the temperature to 80 °C and react for 5 h, rotary evaporate, wash, and dry to obtain the composite antistatic agent.

[0046] The modified toughening agent is prepared by the following steps:

[0047] Step B1: Blend 10 g of maleic anhydride grafted polyethylene and 1.5 g of 5-aminoisophthalic acid in a mixer for 20 min. The conditions of the mixer are: rotation speed 100 rpm, mixing temperature 140 °C, to obtain the graft-modified polyethylene;

[0048] Step B2: Disperse 5 g of cellulose and 1.5 g of sodium hydroxide in 30 g of deionized water, stir at 70 °C for 5 h, centrifuge, wash, and dry to collect the alkali-treated cellulose; Then add 3 g of alkali-treated cellulose and 1.5 g of zinc chloride to the graft-modified polyethylene, and continue to blend for 25 min under the conditions of Step B1 to obtain the modified toughening agent. Example

[0049] A production process of an antistatic polyolefin masterbatch includes the following steps:

[0050] 80 parts of polyethylene resin, 15 parts of the composite antistatic agent prepared in Example 1, 5 parts of the modified toughening agent prepared in Example 1, 1.5 parts of antioxidant 1010, 2 parts of lubricant (polyethylene wax);

[0051] Step S1: Weigh the raw materials by parts by weight. Add polyethylene resin, the composite antistatic agent prepared in Example 1, the modified toughening agent prepared in Example 1, antioxidant 1010, and lubricant (polyethylene wax) into a high-speed kneader, knead for 25 minutes. When the temperature of the materials in the kneader rises to 100 °C, discharge the materials to obtain a mixed material.

[0052] Step S2: Put the mixed material into a twin-screw extruder. Under the conditions of a rotation speed of 150 rpm, a temperature of 70 °C in Zone 1, a temperature of 120 °C in Zone 2, a temperature of 135 °C in Zone 3, and a head temperature of 140 °C, carry out extrusion, cooling, and pelletizing to obtain the antistatic polyolefin masterbatch. Example

[0053] A production process of an antistatic polyolefin masterbatch includes the following steps:

[0054] 90 parts of polyethylene resin, 20 parts of the composite antistatic agent prepared in Example 2, 7 parts of the modified toughening agent prepared in Example 2, 2.5 parts of antioxidant 1010, 3 parts of lubricant (polyethylene wax);

[0055] Step S1: Weigh the raw materials by parts by weight. Add polyethylene resin, the composite antistatic agent prepared in Example 2, the modified toughening agent prepared in Example 2, antioxidant 1010, and lubricant (polyethylene wax) into a high-speed kneader, knead for 30 minutes. When the temperature of the materials in the kneader rises to 110 °C, discharge the materials to obtain a mixed material.

[0056] Step S2: Put the mixed material into a twin-screw extruder. Under the conditions of a rotation speed of 200 rpm, a temperature of 80 °C in Zone 1, a temperature of 125 °C in Zone 2, a temperature of 140 in Zone 3, and a head temperature of 145 °C, carry out extrusion, cooling, and pelletizing to obtain the antistatic polyolefin masterbatch. Example

[0057] A production process of an antistatic polyolefin masterbatch includes the following steps:

[0058] 100 parts of polyethylene resin, 25 parts of the composite antistatic agent prepared in Example 3, 10 parts of the modified toughening agent prepared in Example 3, 3.5 parts of antioxidant 1010, 4 parts of lubricant (polyethylene wax);

[0059] Step S1: Weigh the raw materials by parts by weight. Add polyethylene resin, the composite antistatic agent prepared in Example 3, the modified toughening agent prepared in Example 3, antioxidant 1010, and lubricant (polyethylene wax) into a high-speed kneader, knead for 35 minutes. When the temperature of the materials in the kneader rises to 120 °C, discharge the materials to obtain a mixed material.

[0060] Step S2: Put the mixture into a twin-screw extruder. Under the conditions of a rotation speed of 300 rpm, a temperature of 90 °C in Zone 1, a temperature of 130 °C in Zone 2, a temperature of 145 °C in Zone 3, and a head temperature of 150 °C, through extrusion, cooling, and pelletizing, the antistatic polyolefin masterbatch is obtained.

[0061] Comparative Example 1

[0062] This comparative example is a kind of polyolefin masterbatch. The difference from Example 6 is that a commercially available antistatic agent carbon black is used instead of the composite antistatic agent prepared in Example 3, and the rest are the same.

[0063] Comparative Example 2

[0064] This comparative example is a kind of polyolefin masterbatch. The difference from Example 6 is that a commercially available toughening agent POE is used instead of the modified toughening agent prepared in Example 3, and the rest are the same.

[0065] Mix the polyolefin masterbatches prepared in Examples 4 - 6 and Comparative Examples 1 - 2 with polyethylene resin at a mass ratio of 1:8 to prepare test specimens. The injection molding process is adopted during the specimen preparation process, and a twin-screw injection molding machine is used. The process parameters of the injection molding machine are: 100 °C in the feeding section, 170 °C in the compression section, 190 °C in the homogenization section, 185 °C at the injection mold opening, and an injection pressure of 7 MPa for performance testing:

[0066] Notched impact strength test: Test the notched impact strength of the specimens according to "GB / T 1043 - 1993 Test Method for Izod Impact Strength of Rigid Plastics";

[0067] Tensile strength test: Test the tensile strength of the specimens according to "GB / T 1040 - 1992 Test Method for Tensile Properties of Plastics";

[0068] Surface resistivity test: Test the surface resistivity of the material according to the GB / T 31838.3 - 2019 standard;

[0069] The test results are shown in the following table:

[0070]

[0071] As can be seen from the above table, after the mechanical property test of the polyolefin masterbatch prepared by the present invention, the notched impact strength is between 37 KJ / m 2 - 40 KJ / m 2 , and the tensile strength is between 26 MPa - 31 MPa, indicating that the polyolefin masterbatch has excellent mechanical properties; after the surface resistivity test, the surface resistivity is between 9.2×10 7 Ω - 5.4×10 8 Ω, indicating that the polyolefin masterbatch has excellent antistatic properties.

[0072] The above content is only an example and illustration of the concept of the present invention. Those skilled in the art of this technology can make various modifications, supplements, or use similar methods of substitution to the specific embodiments described. As long as they do not deviate from the scope defined by the concept of the invention, they should all fall within the protection scope of the present invention.

Claims

1. An antistatic polyolefin masterbatch, characterized in that: The invention comprises the following raw materials in parts by weight: 80-100 parts of polyolefin resin, 15-25 parts of composite antistatic agent, 5-10 parts of modified toughening agent, 1.5-3.5 parts of antioxidant and 2-4 parts of lubricant; The polyolefin resin is polyethylene resin or polypropylene resin; The composite antistatic agent is prepared by the following steps: Step A1, dispersing nano carbon black in a 30wt% hydrogen peroxide solution, and ultrasonically treating it for 30-60min, then refluxing and stirring at 60°C for 24h, washing, drying, and collecting the pre-treated carbon black; adding γ-aminopropyltriethoxysilane to an ethanol solution and ultrasonically treating it for 15min, then adding the pre-treated carbon black and ultrasonically treating it for 1.5-2.5h, then refluxing and stirring it at 65-75°C for 5-7h, filtering, washing, and drying to obtain modified carbon black; Step A2, adding p-phenylenediamine, 2,5-diaminobenzoic acid and triethylamine to N,N-dimethylformamide and dispersing them uniformly, then adding cyanuric chloride and modified carbon black and ultrasonically dispersing them for 30 minutes, then transferring them to an autoclave and reacting them at 100-120° C. for 10-16 hours, washing and drying, to obtain a carbon black / COF composite material; Step A3, dispersing the carbon black / COF composite material, propylene oxide and tetrabutylammonium bromide in N,N-dimethylformamide, introducing nitrogen for 10 minutes, reacting under nitrogen at 80-90° C. for 2-3 hours, then cooling to room temperature, adding ethylene oxide and potassium hydroxide, and then heating to 60-80° C. to react for 4-5 hours, rotary evaporation, washing and drying to obtain a composite antistatic agent; The modified toughening agent is prepared by the following steps: Step B1, adding maleic anhydride grafted polyethylene and 5-aminoisophthalic acid into an internal mixer and mixing for 10-20 minutes, the conditions of the internal mixer are: a speed of 50-100 rpm, a mixing temperature of 120-140° C., to obtain grafted modified polyethylene; Step B2, adding cellulose and sodium hydroxide to deionized water for dispersion, stirring at 50-70°C for 3-5h, centrifuging, washing, drying, and collecting the alkali-treated cellulose; then adding the alkali-treated cellulose and zinc chloride to the grafted modified polyethylene, maintaining the conditions of step B1 and continuing to blend for 15-25min to obtain a modified toughening agent.

2. The antistatic polyolefin masterbatch according to claim 1, characterized in that: In step A1, the usage ratio of γ-aminopropyltriethoxysilane, ethanol solution and pre-treated carbon black is 1-2mL:100mL:0.1-0.5g, the usage ratio of nano carbon black and hydrogen peroxide solution in the pre-treated carbon black is 5g:100mL, and the volume ratio of ethanol and deionized water in the ethanol solution is 9:

1.

3. The antistatic polyolefin masterbatch according to claim 1, characterized in that: In step A2, the dosage ratio of p-phenylenediamine, 2,5-diaminobenzoic acid, triethylamine, N,N-dimethylformamide, cyanuric chloride and modified carbon black is 0.08-0.12 mol: 0.15-0.25 mol: 15-45 mL: 300 mL: 0.05-0.15 mol: 1-2 g.

4. The antistatic polyolefin masterbatch according to claim 1, characterized in that: In step A3, the usage ratio of carbon black / COF composite material, propylene oxide, tetrabutylammonium bromide, N,N-dimethylformamide, ethylene oxide and potassium hydroxide is 3-6g:5-9g:0.2-0.5g:100mL:8-12g:0.1-0.3g.

5. The antistatic polyolefin masterbatch according to claim 1, characterized in that: In step B1, the mass ratio of maleic anhydride grafted polyethylene to 5-aminoisophthalic acid is 10:0.5-1.

5.

6. The antistatic polyolefin masterbatch according to claim 1, characterized in that: In step B2, the mass ratio of alkali-treated cellulose, zinc chloride and maleic anhydride grafted polyethylene is 1-3:0.5-1.5:10, and the mass ratio of cellulose, sodium hydroxide and deionized water in the alkali-treated cellulose is 5:0.5-1.5:

30.

7. The production process of the antistatic polyolefin masterbatch according to any one of claims 1 to 6, characterized in that: The following steps are involved: Step S1, weighing raw materials by weight, adding polyolefin resin, composite antistatic agent, modified toughening agent, antioxidant and lubricant into a high-speed kneader, kneading for 25-35 minutes, and when the material temperature in the kneader rises to 100-120° C., discharging the material to obtain a mixed material; Step S2, putting the mixed material into a twin-screw extruder, extruding, cooling and pelletizing at a rotation speed of 150-300 rpm, a temperature of 70-90°C in zone 1, a temperature of 120-130°C in zone 2, a temperature of 135-145°C in zone 3 and a head temperature of 140-150°C, to obtain an antistatic polyolefin masterbatch.

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