Highly flame-retardant antistatic plastic master batch and preparation method thereof

Abstract

The application relates to the technical field of high polymer materials, and discloses a high-flame-retardant antistatic plastic master batch and a preparation method thereof. The plastic master batch prepared by the application is prepared by taking polypropylene as a main raw material and adding maleic anhydride grafted POE, organic-inorganic hybrid flame retardant, coupling agent KH550, conductive carbon black, graphene oxide and other additives; the plastic master batch is endowed with excellent antistatic performance by adding the conductive carbon black and the graphene oxide, and is endowed with excellent flame-retardant and smoke-suppressing performance by adopting the organic-inorganic hybrid flame retardant.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of high polymer materials, in particular to a high-flame-retardant and antistatic plastic master batch and a preparation method thereof. BACKGROUND

[0002] With the rapid development of the fields of electronic appliances, automobiles, aerospace, etc., the performance requirements for plastic materials are increasingly improved, and in particular, the flame retardancy and antistatic property become key indexes. Traditional plastics (such as polypropylene (PP), polyethylene (PE), ABS, etc.) are flammable and prone to static electricity accumulation, which poses a safety hazard in applications such as electronic packaging, mining equipment and medical devices. Therefore, it is of great industrial value to develop a plastic master batch with high flame retardancy and antistatic property.

[0003] At present, flame retardant and antistatic modification is usually achieved by physical blending, but there are the following technical bottlenecks: (1) poor compatibility of flame retardants with resins: traditional flame retardants (such as halogen-based, aluminum hydroxide, etc.) have a large addition amount, are prone to migration and precipitation, and affect the mechanical properties; (2) insufficient durability of antistatic agents: small-molecule antistatic agents (such as quaternary ammonium salts, esters) are prone to migration and loss, and the antistatic performance changes greatly with the environmental humidity; (3) poor processing stability: part of the flame retardants (such as intumescent flame retardants) decompose during high-temperature extrusion, affecting the processing performance of the master batch. Therefore, researchers need to develop a plastic master batch with both flame retardancy and antistatic property. SUMMARY

[0004] In order to solve the above technical problems, the application provides a high-flame-retardant and antistatic plastic master batch and a preparation method thereof.

[0005] The object of the application can be achieved by the following technical solutions.

[0006] A high-flame-retardant and antistatic plastic master batch comprises the following raw materials in parts by weight: 55-65 parts of polypropylene, 12-16 parts of maleic anhydride grafted POE, 6-10 parts of organic-inorganic hybrid flame retardant, 1-3 parts of coupling agent KH550, 3-6 parts of conductive carbon black, 2-4 parts of graphene oxide, 1-3 parts of antioxidant, 1.5-2.5 parts of ultraviolet absorber and 1-2 parts of lubricant.

[0007] Further, the antioxidant is one of antioxidant 168 or antioxidant 1010, the ultraviolet absorber is a benzophenone ultraviolet absorber, and the lubricant is polyethylene wax.

[0008] The organic-inorganic hybrid flame retardant is prepared by mixing, stirring, filtering and drying Ni-Co MOF@MoS2 NPs (MoS2 nanosheet loaded Ni-Co metal organic framework), an organic flame-retardant modifier and water at a mass ratio of 3-5:5-7:20 for 12 hours.

[0009] Further, the Ni-Co MOF@MoS2 NPs are prepared by the following steps:

[0010] Ultrasound-disperse the molybdenum disulfide nanosheet in ethanol for 1-3 h, and mark it as solution 1; mix DMF, 2,5-dihydroxyterephthalic acid, cobalt oxalate dihydrate and nickel oxalate dihydrate uniformly by stirring, and mark it as solution 2; add solution 1 to solution 2 and stir for 3-4 h, then transfer to an autoclave and react at 170℃ for 24 h; centrifuge, wash and dry, and the Ni-Co MOF@MoS2 NPs are obtained;

[0011] Further, the mass ratio of the molybdenum disulfide nanosheet and ethanol in solution 1 is 0.1-0.3:30;

[0012] Further, the mass ratio of DMF, 2,5-dihydroxyterephthalic acid, cobalt oxalate dihydrate and nickel oxalate dihydrate in solution 2 is 50:0.4-1.2:0.5-1.5:0.7-2.1.

[0013] The organic flame-retardant modifier is prepared by the following steps:

[0014] Step A1, mix diethanolamine and 4-vinylphenylboronic acid in toluene and stir uniformly, and heat to 110℃, and reflux at constant temperature for 6-8 h; azeotrope and dry, and the phenyl borate ester is obtained;

[0015] Further, in step A1, the amount ratio of diethanolamine, 4-vinylphenylboronic acid and toluene is 0.02-0.04 mol:0.01-0.02 mol:50 mL;

[0016] Step A2, mix the phenyl borate ester and DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) in dichloromethane and stir uniformly, and heat to 60℃ and stir for 3.5-4.5 h; rotary evaporation and dry, and the DOPO-phenyl borate ester is obtained;

[0017] Further, in step A2, the amount ratio of the phenyl borate ester, DOPO and dichloromethane is 0.1-0.2 mol:0.1-0.2 mol:200 mL;

[0018] Step A3, mix the DOPO-phenyl borate ester in tetrahydrofuran uniformly, add triethylamine and stir for 10 min under nitrogen condition, then add phosphorus oxychloride tetrahydrofuran solution under ice water bath condition, react at room temperature for 2 h, then heat to 40℃ and reflux for 4-6 h; suction filtration, rotary evaporation, washing and drying, and the phosphate ester-DOPO-phenyl borate ester is obtained;

[0019] Further, in step A3, the amount ratio of DOPO-phenyl borate, tetrahydrofuran, triethylamine and phosphorus oxychloride tetrahydrofuran solution is 0.03-0.06 mol:100 mL:0.04-0.08 mol:50 mL;

[0020] Further, in step A3, the phosphorus oxychloride tetrahydrofuran solution is prepared by mixing and stirring 0.011-0.022 mol of phosphorus oxychloride and 50 mL of tetrahydrofuran;

[0021] Step A4, under the condition of nitrogen, 3-chloropropyl triethoxysilane, DMF and triethylamine are mixed and stirred uniformly, then phosphate-DOPO-phenyl borate is added, and the temperature is increased to 80-90 DEG C to reflux for 3.5-4.5 h, rotary evaporation, column chromatography purification, twice rotary evaporation, drying, to obtain the organic flame-retardant modifier;

[0022] Further, in step A4, the amount ratio of 3-chloropropyl triethoxysilane, DMF, triethylamine and phosphate-DOPO-phenyl borate is 3.6-7.2 mL:100 mL:2.2-4.4 mL:8.3-16.6 g.

[0023] A preparation method of a high flame-retardant antistatic plastic master batch comprises the following steps:

[0024] Step S1, the raw materials are weighed by weight parts, and polypropylene, maleic anhydride grafted POE, organic-inorganic hybrid flame retardant, coupling agent KH550, conductive carbon black, graphene oxide, antioxidant, ultraviolet absorber and lubricant are put into a mixing stirrer and mixed and stirred at a speed of 300-500 rpm / min for 40-60 min, to obtain a mixture;

[0025] Step S2, the mixture is transferred to a twin-screw extruder, and is melt extruded and granulated to obtain the high flame-retardant antistatic plastic master batch;

[0026] Further, the screw rotation speed of the twin-screw extruder is 200-300 rpm / min, and the temperature of each section is respectively: 190-200 DEG C for the first section, 210-220 DEG C for the second section, 235-245 DEG C for the third section, 220-230 DEG C for the fourth section, and 200-210 DEG C for the fifth section.

[0027] The present application has the following advantages:

[0028] The plastic master batch prepared by the present application is prepared by adding maleic anhydride grafted POE, organic-inorganic hybrid flame retardant, coupling agent KH550, conductive carbon black, graphene oxide and other additives to polypropylene as the main raw material; the plastic master batch is endowed with excellent antistatic performance by adding conductive carbon black and graphene oxide, and is endowed with excellent flame-retardant and smoke-suppressing performance by using organic-inorganic hybrid flame retardant.

[0029] The organic-inorganic hybrid flame retardant in the application is prepared by mixing and stirring Ni-Co MOF@MoS2 NPs and organic flame-retardant modifiers in water, and the synergistic effect between the organic flame retardant and the inorganic flame retardant improves the flame-retardant and smoke-suppressing performance of the matrix; wherein, the Ni and Co elements in the Ni-Co MOF@MoS2 NPs serve as transition metal components and play a catalytic carbonization role in the matrix, can rapidly catalyze the formation of a carbon layer in the initial stage of combustion, and the barrier effect of the molybdenum disulfide nanosheet can hinder the flow and overflow of flammable gas and flammable substances, reduce the heat release of material combustion, and Ni / Co oxides are generated in the Ni-Co MOF@MoS2 NPs during the combustion process, thereby improving the oxidation resistance of the carbon layer, forming a dense carbon layer, and playing a physical barrier role to inhibit the transfer of heat and mass. The organic flame-retardant modifier introduces DOPO, phosphate, borate and siloxane structures, which can synergistically improve the flame-retardant performance of the matrix, DOPO and phosphate decompose to generate phosphorus-containing free radicals (such as PO· and HPO·) at high temperatures, which can capture H· and OH· free radicals in the combustion chain reaction, inhibit flame propagation, and promote PP dehydration and carbonization to form an expanded carbon layer to isolate heat and oxygen; borate melts to form a glassy borate layer at high temperatures, covering the surface of the material to block heat and oxygen and enhance the thermal stability and density of the carbon layer; in addition, the siloxane structure can also react with the hydroxyl groups on the surface of the Ni-Co MOF@MoS2 NPs to form an organic-inorganic hybrid flame retardant through chemical bonding. DETAILED DESCRIPTION

[0030] The technical solutions in the embodiments of the application will be described below in a clear and complete manner. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those of ordinary skill in the art without creative labor fall within the scope of protection of the application.

[0031] Example 1: The organic flame-retardant modifier is prepared by the following steps:

[0032] Step A1, 0.02 mol of diethanolamine and 0.01 mol of 4-vinylphenylboronic acid are mixed and stirred uniformly in 50 mL of toluene, heated to 110°C, and refluxed for 6 h, and then co-boiled and dried to obtain phenyl borate;

[0033] Step A2, 0.1 mol of phenyl borate and 0.1 mol of DOPO are mixed and stirred uniformly in 200 mL of dichloromethane, heated to 60°C, and stirred for 3.5 h, and then rotary evaporated and dried to obtain DOPO-phenyl borate;

[0034] Step A3, 0.03 mol of DOPO-phenyl borate was mixed uniformly in 100 mL of tetrahydrofuran, 0.04 mol of triethylamine was added, and stirred for 10 min under nitrogen, 50 mL of phosphorus oxychloride tetrahydrofuran solution was added under ice water bath, and reacted for 2 h at room temperature, and then the temperature was increased to 40℃ and reacted for 4 h under reflux, and then filtered, rotary evaporated, washed and dried to obtain the phosphate ester-DOPO-phenyl borate. The phosphorus oxychloride tetrahydrofuran solution was prepared by mixing 0.011 mol of phosphorus oxychloride and 50 mL of tetrahydrofuran;

[0035] Step A4, 3.6 mL of 3-chloropropyl triethoxysilane, 100 mL of DMF and 2.2 mL of triethylamine were mixed and stirred uniformly under nitrogen, 8.3 g of phosphate ester-DOPO-phenyl borate was added, and the temperature was increased to 80℃ and reacted for 3.5 h under reflux, and then rotary evaporated, purified by column chromatography, rotary evaporated twice, and dried to obtain the organic flame-retardant modifier.

[0036] The Ni-Co MOF@MoS2 NPs were prepared by the following steps:

[0037] 0.1 g of molybdenum disulfide nanosheets was ultrasonically dispersed in 30 g of ethanol for 1 h, and was recorded as solution 1; 50 g of DMF, 0.4 g of 2,5-dihydroxyterephthalic acid, 0.5 g of cobalt oxalate dihydrate and 0.7 g of nickel oxalate dihydrate were mixed and stirred uniformly, and was recorded as solution 2; solution 1 was added to solution 2 and stirred for 3 h, and then was transferred to an autoclave and reacted at 170℃ for 24 h, and then was centrifuged, washed and dried to obtain the Ni-Co MOF@MoS2 NPs.

[0038] The organic-inorganic hybrid flame retardant was prepared by mixing and stirring the above-mentioned Ni-Co MOF@MoS2 NPs, the above-mentioned organic flame-retardant modifier and water in a mass ratio of 3:7:20 for 12 h, and then filtering and drying.

[0039] Example 2: The organic flame-retardant modifier was prepared by the following steps:

[0040] Step A1, 0.03 mol of diethanolamine and 0.015 mol of 4-vinylphenyl borate were mixed and stirred uniformly in 50 mL of toluene, and heated to 110℃, and reacted for 7 h under reflux, and then co-evaporated and dried to obtain the phenyl borate;

[0041] Step A2, 0.15 mol of phenyl borate and 0.15 mol of DOPO were mixed and stirred uniformly in 200 mL of dichloromethane, and the temperature was increased to 60℃ and reacted for 4 h, and then rotary evaporated and dried to obtain the DOPO-phenyl borate;

[0042] Step A3, 0.045 mol of DOPO-phenyl borate was mixed uniformly in 100 mL of tetrahydrofuran, 0.06 mol of triethylamine was added, and stirred for 10 min under nitrogen, 50 mL of phosphorus oxychloride tetrahydrofuran solution was added under ice water bath, and reacted for 2 h at room temperature, and then the temperature was increased to 40℃ and reacted for 5 h under reflux, and then filtered, rotary evaporated, washed and dried to obtain the phosphate ester-DOPO-phenyl borate. The phosphorus oxychloride tetrahydrofuran solution was prepared by mixing 0.016 mol of phosphorus oxychloride and 50 mL of tetrahydrofuran;

[0043] Step A4, 4.8 mL of 3-chloropropyl triethoxysilane, 100 mL of DMF and 3.3 mL of triethylamine were mixed and stirred uniformly under nitrogen, and then 12.5 g of phosphate ester-DOPO-phenyl borate was added, and the temperature was increased to 85℃ and reacted for 4 h under reflux, and then rotary evaporated, purified by column chromatography, rotary evaporated twice, and dried to obtain the organic flame retardant modifier.

[0044] The Ni-Co MOF@MoS2 NPs were prepared by the following steps:

[0045] 0.2 g of molybdenum disulfide nanosheets was ultrasonically dispersed in 30 g of ethanol for 12 h, and was recorded as solution 1; 50 g of DMF, 0.8 g of 2,5-dihydroxyterephthalic acid, 1 g of cobalt oxalate dihydrate and 1.4 g of nickel oxalate dihydrate were mixed and stirred uniformly, and was recorded as solution 2; solution 1 was added to solution 2 and stirred for 3.5 h, and then was transferred to an autoclave and reacted at 170℃ for 24 h, and then was centrifuged, washed and dried to obtain the Ni-Co MOF@MoS2 NPs.

[0046] The organic-inorganic hybrid flame retardant was prepared by mixing and stirring the above-mentioned Ni-Co MOF@MoS2 NPs, the above-mentioned organic flame retardant modifier and water in a mass ratio of 5:5:20 for 12 h, and then filtering and drying.

[0047] Example 3: The organic flame retardant modifier was prepared by the following steps:

[0048] Step A1, 0.04 mol of diethanolamine and 0.02 mol of 4-vinylphenyl borate were mixed and stirred uniformly in 50 mL of toluene, and heated to 110℃, and reacted for 8 h under reflux, and then co-evaporated and dried to obtain the phenyl borate;

[0049] Step A2, 0.2 mol of phenyl borate and 0.2 mol of DOPO were mixed and stirred uniformly in 200 mL of dichloromethane, and the temperature was increased to 60℃ and reacted for 4.5 h, and then rotary evaporated and dried to obtain the DOPO-phenyl borate;

[0050] Step A3, 0.06 mol of DOPO-phenylborate is uniformly mixed in 100 mL of tetrahydrofuran, 0.08 mol of triethylamine is added, and stirred for 10 min under nitrogen, 50 mL of phosphorus oxychloride tetrahydrofuran solution is added under ice water bath, and stirred for 2 h at room temperature, and then heated to 40℃ for 6 h, filtered, rotary evaporated, washed and dried to obtain the phosphate-DOPO-phenylborate, the phosphorus oxychloride tetrahydrofuran solution is prepared by mixing 0.022 mol of phosphorus oxychloride and 50 mL of tetrahydrofuran;

[0051] Step A4, 7.2 mL of 3-chloropropyl triethoxysilane, 100 mL of DMF and 4.4 mL of triethylamine are uniformly mixed and stirred under nitrogen, 16.6 g of phosphate-DOPO-phenylborate is added, and heated to 90℃ for 4.5 h, rotary evaporated, purified by column chromatography, twice rotary evaporated and dried to obtain the organic flame-retardant modifier.

[0052] The Ni-Co MOF@MoS2 NPs are prepared by the following steps:

[0053] 0.3 g of molybdenum disulfide nanosheet is ultrasonically dispersed in 30 g of ethanol for 3 h, and is recorded as solution 1; 50 g of DMF, 1.2 g of 2,5-dihydroxyterephthalic acid, 1.5 g of cobalt oxalate dihydrate and 2.1 g of nickel oxalate dihydrate are uniformly mixed and stirred, and are recorded as solution 2; solution 1 is added to solution 2 and stirred for 4 h, and then is transferred to an autoclave for constant temperature reaction at 170℃ for 24 h, and is centrifuged, washed and dried to obtain the Ni-Co MOF@MoS2 NPs.

[0054] The organic-inorganic hybrid flame retardant is prepared by mixing and stirring the above-mentioned Ni-Co MOF@MoS2 NPs, the above-mentioned organic flame-retardant modifier and water in a mass ratio of 4:6:20 for 12 h, and then filtering and drying.

[0055] Example 4: A preparation method of a high flame-retardant antistatic plastic master batch comprises the following steps:

[0056] Polypropylene 55 parts, maleic anhydride grafted POE 12 parts, organic-inorganic hybrid flame retardant prepared in example 1 6 parts, coupling agent KH550 1, conductive carbon black 3 parts, graphene oxide 2 parts, antioxidant 168 1 part, ultraviolet absorber UV-1009 1.5 parts, polyethylene wax 1 part;

[0057] Step S1, the raw materials were weighed by weight parts, polypropylene, maleic anhydride grafted POE, the organic-inorganic hybrid flame retardant prepared in example 1, coupling agent KH550, conductive carbon black, graphene oxide, antioxidant 168, ultraviolet absorber UV-1009 and polyethylene wax were put into a mixing stirrer, mixed and stirred at a speed of 300 rpm / min for 40 min, and the mixture was obtained.

[0058] Step S2, the mixture was transferred to a twin-screw extruder, melt extruded and granulated, and a high flame-retardant antistatic plastic master batch was obtained, the screw speed of the twin-screw extruder was 200 rpm / min, and the temperature of each section was 190℃, 210℃, 235℃, 220℃ and 200℃ respectively.

[0059] Example 5: a preparation method of a high flame-retardant antistatic plastic master batch comprises the following steps:

[0060] Polypropylene 55 parts, maleic anhydride grafted POE 14 parts, organic-inorganic hybrid flame retardant prepared in example 2 8 parts, coupling agent KH550 2 parts, conductive carbon black 4.5 parts, graphene oxide 3 parts, antioxidant 1010 2 parts, ultraviolet absorber UV-1009 2 parts, and polyethylene wax 1.5 parts.

[0061] Step S1, the raw materials were weighed by weight parts, polypropylene, maleic anhydride grafted POE, the organic-inorganic hybrid flame retardant prepared in example 2, coupling agent KH550, conductive carbon black, graphene oxide, antioxidant 1010, ultraviolet absorber UV-1009 and polyethylene wax were put into a mixing stirrer, mixed and stirred at a speed of 400 rpm / min for 50 min, and the mixture was obtained.

[0062] Step S2, the mixture was transferred to a twin-screw extruder, melt extruded and granulated, and a high flame-retardant antistatic plastic master batch was obtained, the screw speed of the twin-screw extruder was 250 rpm / min, and the temperature of each section was 195℃, 215℃, 240℃, 225℃ and 205℃ respectively.

[0063] Example 6: a preparation method of a high flame-retardant antistatic plastic master batch comprises the following steps:

[0064] Polypropylene 65 parts, maleic anhydride grafted POE 16 parts, organic-inorganic hybrid flame retardant prepared in example 3 10 parts, coupling agent KH550 3 parts, conductive carbon black 6 parts, graphene oxide 4 parts, antioxidant 1010 3 parts, ultraviolet absorber UV-1009 2.5 parts, and polyethylene wax 2 parts.

[0065] Step S1, the raw materials were weighed by weight parts, polypropylene, maleic anhydride grafted POE, the organic-inorganic hybrid flame retardant prepared in Example 3, coupling agent KH550, conductive carbon black, graphene oxide, antioxidant 1010, ultraviolet absorber UV-1009 and polyethylene wax were put into a mixing stirrer and mixed and stirred at a speed of 500 rpm / min for 60 min to obtain a mixture;

[0066] Step S2, the mixture was transferred to a twin-screw extruder, and melt extruded and granulated to obtain a high flame-retardant antistatic plastic master batch. The screw rotation speed of the twin-screw extruder was 300 rpm / min, and the temperature of each section was 200°C, 220°C, 245°C, 230°C and 210°C, respectively.

[0067] Comparative Example 1: This comparative example is a plastic master batch, which is different from Example 6 in that magnesium hydroxide is used instead of the organic-inorganic hybrid flame retardant prepared in Example 3, and the rest are the same.

[0068] Comparative Example 2: This comparative example is a plastic master batch, which is different from Example 6 in that is used instead of the organic-inorganic hybrid flame retardant prepared in Example 3, and the rest are the same.

[0069] Comparative Example 3: This comparative example is a plastic master batch, which is different from Example 6 in that is used instead of the organic-inorganic hybrid flame retardant prepared in Example 3, and the rest are the same.

[0070] The plastic master batches prepared in Examples 4-6 and Comparative Examples 1-3 were tested for performance:

[0071] Flame retardant performance test: (1) The vertical burning test was carried out on the samples according to the UL-94 flame retardant grade standard to test the flame retardant performance; (2) The oxygen index test was carried out according to the method of GB / T 2406.2-2009; (3) The smoke density was tested according to the standard of GB / T 8323.2-2008;

[0072] Antistatic performance test: The volume resistivity of the plastic master batches prepared in the examples and comparative examples was tested, and the smaller the volume resistivity, the better the conductivity, i.e. the better the antistatic property, and the reference standard was GB / T 156621995;

[0073] The test results are shown in Table 1:

[0074] Table 1: Performance test results

[0075]

[0076] As shown in Table 1, the plastic master batch prepared by the application has a flame-retardant grade of V0, an oxygen index greater than 32%, and a smoke density less than 50, indicating that the plastic master batch has excellent flame-retardant and smoke-suppressing properties; the antistatic performance test shows that the volume resistivity is in the range of (1.8×10 8 -6.5×10 8 ) Ω·cm, indicating that the plastic master batch also has excellent antistatic properties.

[0077] The above content is merely an example and description of the concept of the application, and those skilled in the art can make various modifications or supplements to the described specific embodiments or replace them with similar ways without departing from the scope defined by the concept of the application, which shall fall within the protection scope of the application.

Claims

1. A high flame retardant antistatic plastic masterbatch, characterized in that, The raw materials include the following components by weight: polypropylene 55-65 parts, maleic anhydride grafted POE 12-16 parts, organic-inorganic hybrid flame retardant 6-10 parts, coupling agent KH550 1-3 parts, conductive carbon black 3-6 parts, graphene oxide 2-4 parts, antioxidant 1-3 parts, ultraviolet absorber 1.5-2.5 parts, and lubricant 1-2 parts; The organic-inorganic hybrid flame retardant is prepared by mixing and stirring Ni / Co-MOF@MoS2 nanosheets, an organic flame-retardant modifier, and water at a mass ratio of 3-5:5-7:20 for 12 hours, and then filtering and drying; The organic flame-retardant modifier is prepared by refluxing phosphonate-DOPO-phenyl borate and 3-chloropropyl triethoxysilane at 80-90°C for 3.5-4.5 hours, wherein the phosphonate-DOPO-phenyl borate is prepared by reacting DOPO-phenyl borate and phosphorus oxychloride at room temperature for 2 hours and then refluxing at 40°C for 4-6 hours, the DOPO-phenyl borate is prepared by reacting phenyl borate and DOPO at 60°C for 3.5-4.5 hours, and the phenyl borate is prepared by refluxing diethanolamine and 4-vinylphenylboronic acid at 110°C for 6-8 hours; The Ni / Co-MOF@MoS2 nanosheets are prepared by the following steps: The molybdenum disulfide nanosheets are ultrasonically dispersed in ethanol for 1-3 hours to obtain solution 1; DMF, 2,5-dihydroxyterephthalic acid, cobalt oxalate dihydrate, and nickel oxalate dihydrate are uniformly mixed and stirred to obtain solution 2; solution 1 is added to solution 2 and stirred for 3-4 hours, and then transferred to an autoclave for constant-temperature reaction at 170°C for 24 hours; centrifugation, washing, and drying are performed to obtain the Ni / Co-MOF@MoS2 nanosheets.

2. A high flame retardant antistatic plastic masterbatch as claimed in claim 1, wherein, The mass ratio of the molybdenum disulfide nanosheets to ethanol in the solution 1 is 0.1-0.3:30, and the mass ratio of DMF, 2,5-dihydroxyterephthalic acid, cobalt oxalate dihydrate, and nickel oxalate dihydrate in the solution 2 is 50:0.4-1.2:0.5-1.5:0.7-2.

1.

3. The high flame-retardant and antistatic plastic masterbatch according to claim 1, characterized in that, The organic flame-retardant modifier is prepared by the following steps: Step A1, diethanolamine and 4-vinylphenylboronic acid are uniformly mixed and stirred in toluene, heated to 110°C, and constant-temperature refluxed for 6-8 hours; azeotroping and drying are performed to obtain phenyl borate; Step A2, phenyl borate and DOPO are uniformly mixed and stirred in dichloromethane, heated to 60°C, and stirred for 3.5-4.5 hours; rotary evaporation and drying are performed to obtain DOPO-phenyl borate; Step A3, DOPO-phenyl borate is uniformly mixed in tetrahydrofuran, triethylamine is added, and stirred under nitrogen for 10 minutes; a solution of phosphorus oxychloride in tetrahydrofuran is added under ice water bath conditions, reacted at room temperature for 2 hours, and then heated to 40°C for refluxing for 4-6 hours; suction filtration, rotary evaporation, washing, and drying are performed to obtain phosphonate-DOPO-phenyl borate; Step A4, under the condition of nitrogen, 3-chloropropyl triethoxysilane, DMF and triethylamine were mixed and stirred uniformly, then phosphate-DOPO-phenyl borate was added, and the temperature was increased to 80-90℃ to reflux for 3.5-4.5h, rotary evaporation, column chromatography purification, twice rotary evaporation, drying, to obtain the organic flame retardant modifier.

4. A high flame retardant antistatic plastic masterbatch as claimed in claim 3, wherein, In step A1, the amount ratio of diethanolamine, 4-vinylphenyl boronic acid and toluene was 0.02-0.04mol:0.01-0.02mol:50mL.

5. The high flame-retardant and antistatic plastic masterbatch according to claim 3, characterized in that, In step A2, the amount ratio of phenyl borate, DOPO and dichloromethane was 0.1-0.2mol:0.1-0.2mol:200mL.

6. The high flame-retardant and antistatic plastic masterbatch according to claim 3, characterized in that, In step A3, the amount ratio of DOPO-phenyl borate, tetrahydrofuran, triethylamine and phosphorus oxychloride tetrahydrofuran solution was 0.03-0.06mol:100mL:0.04-0.08mol:50mL, and the phosphorus oxychloride tetrahydrofuran solution was prepared by mixing and stirring 0.011-0.022mol of phosphorus oxychloride and 50mL of tetrahydrofuran.

7. The high flame-retardant and antistatic plastic masterbatch according to claim 3, characterized in that, In step A4, the amount ratio of 3-chloropropyl triethoxysilane, DMF, triethylamine and phosphate-DOPO-phenyl borate was 3.6-7.2mL:100mL:2.2-4.4mL:8.3-16.6g.

8. A process for the preparation of the high flame retardant antistatic plastic masterbatch as claimed in any one of claims 1 to 7, characterized in that, The following steps are included: Step S1, the raw materials were weighed by weight parts, and polypropylene, maleic anhydride grafted POE, organic-inorganic hybrid flame retardant, coupling agent KH550, conductive carbon black, graphene oxide, antioxidant, ultraviolet absorber and lubricant were put into a mixing stirrer and mixed and stirred at a speed of 300-500rpm / min for 40-60min to obtain a mixture; Step S2, the mixture was transferred to a twin-screw extruder, and melt extruded and granulated to obtain a high flame-retardant antistatic plastic master batch.

9. The process for the preparation of a high flame retardant antistatic plastic masterbatch as claimed in claim 8, wherein, The screw rotation speed of the twin-screw extruder was 200-300rpm / min, and the temperature of each section was: zone 1 190-200℃, zone 2 210-220℃, zone 3 235-245℃, zone 4 220-230℃, and zone 5 200-210℃.

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