Antistatic master batch for plastic and preparation method of antistatic master batch

Abstract

The preparation method comprises the following steps: mixing a polyurethane prepolymer and a modified filler, adding the mixture into a twin-screw extruder, carrying out extrusion granulation to prepare the antistatic master batch, and carrying out melt extrusion on the polyurethane prepolymer and the modified filler in the melt extrusion process of the polyurethane prepolymer and the modified filler to prepare the antistatic master batch. When the polyurethane prepolymer reacts with hydroxyl on the surface of the modified filler, the modified filler can be uniformly dispersed among polyurethane molecular chain segments, the surface of the modified filler contains polyaniline chain segments and quaternary ammonium salt structures, a large number of conjugated pi electrons are contained on the main chain of polyaniline molecules, and the conjugated pi electrons can be dispersed among the polyurethane molecular chain segments. Pi electrons can freely move in a conjugated system to generate a delocalization effect, so that polyaniline has conductivity, a conductive path is further formed in the material, quaternary ammonium salt can neutralize charges carried by the polyurethane material, an antistatic effect is further achieved, and due to the addition of a polysiloxane chain segment, the antistatic property of the polyurethane material is improved. And the antistatic effect of the material is not reduced in a high-temperature environment.

Description

Technical Field

[0001] The invention relates to the technical field of antistatic material preparation, and in particular to an antistatic masterbatch for plastics and a preparation method thereof. Background Art

[0002] Polyurethane is a rapidly developing new type of polymer material. In just a few decades, it has become one of the most widely used polymer materials in the world. Scholars have studied PUE with different functions to meet the different needs of various industries. These PUE with good performance are widely used in many fields such as footwear, cables, clothing, automobiles, medicine and health, pipes, films and sheets. However, in actual use, polyurethane materials have poor antistatic properties, which makes it easy for the material to accumulate a large amount of charge. These large amounts of accumulated charges will cause great harm to electronic equipment, human health, production and life, and even cause fires or explosions in the presence of flammable and explosive substances. At this stage, the common antistatic method is to add antistatic agents, but in high temperature environments, the distribution and arrangement of antistatic agents may change, affecting the migration path of electrons, thereby causing a decrease in conductivity and affecting the normal use of materials. Summary of the invention

[0003] The purpose of the present invention is to provide an antistatic masterbatch for plastics and a preparation method thereof, so as to solve the problem that the antistatic effect of polyurethane plastics is poor at present.

[0004] The purpose of the present invention can be achieved through the following technical solutions:

[0005] A method for preparing antistatic masterbatch for plastics, specifically comprising the following steps:

[0006] Step A1: dispersing graphene oxide in ethanol, stirring and adding deionized water and 3-methacryloxypropyltriethoxysilane at a speed of 300-500 r / min and a temperature of 50-60° C., reacting for 3-5 hours to obtain functional graphene, mixing the functional graphene with hydrazine hydrate, reacting for 8-10 hours at a speed of 120-150 r / min and a temperature of 90-95° C., to obtain pretreated graphene;

[0007] Step A2: pretreated graphene, modified monomer, chloroplatinic acid and DMF are mixed uniformly, nitrogen is introduced for protection, and the reaction is carried out for 3-5 hours at a speed of 150-200 r / min and a temperature of 70-80° C. to obtain a precursor, the precursor is dispersed in tetrahydrofuran, trifluoroacetic acid is added, nitrogen is introduced for protection, and the reaction is carried out for 1-2 hours at a speed of 60-80 r / min and a temperature of 50-60° C. to obtain a modified precursor;

[0008] Step A3: dispersing the modified precursor in a hydrochloric acid solution, stirring and adding aniline and ammonium persulfate at a speed of 120-150 r / min and a temperature of 0-3° C., reacting for 5-7 hours, filtering and removing the filtrate, dispersing the substrate in acetone, adding propyl chloride, reacting for 20-24 hours at a speed of 300-500 r / min and a temperature of 40-45° C., and obtaining a modified filler;

[0009] Step A4: polyethylene glycol, 1,4-butanediol and dibutyltin dilaurate are uniformly mixed, and 4,4'-diphenylmethane diisocyanate is added under stirring at a rotation speed of 200-300 r / min and a temperature of 80-85°C to react for 6-8 hours to obtain a polyurethane prepolymer. The polyurethane prepolymer and the modified filler are mixed and added to a twin-screw extruder, and extruded into granules to obtain an antistatic masterbatch for plastics.

[0010] Furthermore, the amount of 3-methacryloxypropyltriethoxysilane used in step A1 is 1% of the mass of graphene oxide, and the amount ratio of functional graphene to hydrazine hydrate is 1g:25mL.

[0011] Furthermore, the mass ratio of the pretreated graphene and the modified monomer described in step A2 is 1:5, the amount of chloroplatinic acid used is 1‰ of the mass of the modified monomer, and the amount ratio of the precursor, tetrahydrofuran and trifluoroacetic acid is 1g:80mL:6mL.

[0012] Furthermore, the dosage ratio of the modified precursor, hydrochloric acid solution, aniline and ammonium persulfate described in step A3 is 20 mg:40 mL:5 mmol:5 mmol, and the mass ratio of the substrate and propyl chloride is 1:8.

[0013] Furthermore, the molar ratio of polyethylene glycol, 1,4-butanediol and 4,4'-diphenylmethane diisocyanate in step A4 is 5:7:1, the amount of dibutyltin dilaurate is 2% of the mass of 4,4'-diphenylmethane diisocyanate, and the mass ratio of polyurethane prepolymer and modified filler is 40-50:2-4.

[0014] Further, the modified monomer is prepared by the following steps:

[0015] Step B1: octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide and 1,3-bis(aminopropyl)tetramethyldisiloxane are mixed, nitrogen is introduced for protection, and the reaction is carried out for 10-12 hours at a speed of 120-150 r / min and a temperature of 90-95° C. to obtain bisaminopolysiloxane;

[0016] Step B2: N, N-dimethylethanolamine, epichlorohydrin, boron trifluoride etherate and tetrahydrofuran are mixed evenly, reacted for 2-3 hours at a speed of 120-150 r / min and a temperature of 65-70° C., and then sodium hydroxide solution is added, the temperature is raised to 75-80° C., and the reaction is continued for 3-5 hours to obtain a modifier, and bisaminopolysiloxane, the modifier and DMF are mixed evenly, and reacted for 6-8 hours at a speed of 200-300 r / min, a temperature of 60-65° C. and a pH value of 11-12 to obtain a modified polysiloxane;

[0017] Step B3: 4-(BOC-amino)phenol, triethylamine and tetrahydrofuran are mixed evenly, stirred and acryloyl chloride is added at a speed of 200-300 r / min and a temperature of 0-3°C, the temperature is raised to 20-25°C, and the reaction is carried out for 3-5 hours to obtain an intermediate, and the modified polysiloxane, the intermediate, chloroplatinic acid and DMF are mixed evenly, nitrogen is introduced for protection, and the reaction is carried out at a speed of 150-200 r / min and a temperature of 70-80°C for 3-5 hours to obtain a modified monomer.

[0018] Furthermore, the molar ratio of octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide and 1,3-bis(aminopropyl)tetramethyldisiloxane described in step B1 is 1.8 mol:0.6 mol:2 mol:3 mol.

[0019] Furthermore, the dosage ratio of N,N-dimethylethanolamine, epichlorohydrin, boron trifluoride etherate, tetrahydrofuran and sodium hydroxide solution in step B2 is 35mmo l:35mmo l:1g:20mL:6mL, the mass fraction of the sodium hydroxide solution is 25%, and the molar ratio of bisaminopolysiloxane to the modifier is 1:4.

[0020] Furthermore, the molar ratio of 4-(BOC-amino)phenol, triethylamine and acryloyl chloride in step B3 is 1:1.1:1, the molar ratio of SiH bonds on the modified polysiloxane to the intermediate is 2:1, and the amount of chloroplatinic acid used is 1% by mass of the intermediate.

[0021] Beneficial effects of the present invention: The present invention prepares an antistatic masterbatch for plastics, using graphene oxide as a raw material and treating it with 3-methacryloxypropyltriethoxysilane to graft double bonds on the surface to obtain functional graphene, reducing the functional graphene with hydrazine hydrate to obtain pretreated graphene, reacting the pretreated graphene with a modified monomer to react the double bonds on the surface of the pretreated graphene with the Si-H bonds on the modified monomer to obtain a precursor, and deprotecting the precursor with trifluoroacetic acid. The modified precursor is mixed with aniline to form polyaniline on the surface of the modified precursor under the action of ammonium persulfate, and then reacted with propyl chloride to form a quaternary ammonium salt structure on the surface to obtain a modified filler, polyethylene glycol, 1,4-butanediol and 4,4'-diphenylmethane diisocyanate are reacted to form a polyurethane prepolymer, and the polyurethane prepolymer and the modified filler are melt-extruded to obtain an antistatic masterbatch.

[0022] The modified monomer is prepared by ring-opening polymerization of octamethylcyclotetrasiloxane and tetramethylcyclotetrasiloxane as raw materials, and end-capping with 1,3-bis(aminopropyl)tetramethyldisiloxane to obtain bisaminopolysiloxane. N,N-dimethylethanolamine reacts with epichlorohydrin so that the hydroxyl group on the N,N-dimethylethanolamine reacts with the epoxy group on the epichlorohydrin, and then the ring is closed under the action of sodium hydroxide to form a new epoxy group to prepare the modifier. The bisaminopolysiloxane reacts with the modifier so that the amino group on the bisaminopolysiloxane reacts with the epoxy group on the modifier to obtain the modified polysiloxane. 4-(BOC-amino)phenol reacts with acryloyl chloride so that the phenolic hydroxyl group on the 4-(BOC-amino)phenol reacts with the acyl chloride on the acryloyl chloride to obtain the intermediate. The intermediate reacts with the modified polysiloxane so that the double bond on the intermediate reacts with the Si-H bond on the modified polysiloxane to obtain the modified monomer.

[0023] During the melt extrusion process of the polyurethane prepolymer and the modified filler, the isocyanate group in the polyurethane prepolymer will react with the hydroxyl group on the surface of the modified filler, so that the modified filler can be evenly dispersed between the polyurethane molecular segments. The surface of the modified filler contains polyaniline segments and quaternary ammonium salt structures. The main chain of the polyaniline molecule contains a large number of conjugated π electrons. These π electrons can move freely in the conjugated system, producing a delocalized effect, making the polyaniline conductive, thereby forming a conductive path inside the material, and the quaternary ammonium salt can neutralize the charge carried by the polyurethane material, thereby achieving an antistatic effect. The addition of the polysiloxane segment ensures that the antistatic effect of the material will not decrease even in a high temperature environment. DETAILED DESCRIPTION

[0024] 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.

[0025] Embodiment 1, a method for preparing antistatic masterbatch for plastics, specifically comprising the following steps:

[0026] Step A1: dispersing graphene oxide in ethanol, stirring and adding deionized water and 3-methacryloxypropyltriethoxysilane at a speed of 300 r / min and a temperature of 50° C., reacting for 3 hours to obtain functional graphene, mixing the functional graphene with hydrazine hydrate, reacting for 8 hours at a speed of 120 r / min and a temperature of 90° C., to obtain pretreated graphene;

[0027] Step A2: pretreated graphene, modified monomer, chloroplatinic acid and DMF were mixed evenly, nitrogen was introduced for protection, and the reaction was carried out for 3 hours at a speed of 150 r / min and a temperature of 70° C. to obtain a precursor, the precursor was dispersed in tetrahydrofuran, trifluoroacetic acid was added, nitrogen was introduced for protection, and the reaction was carried out for 1 hour at a speed of 60 r / min and a temperature of 50° C. to obtain a modified precursor;

[0028] Step A3: dispersing the modified precursor in a hydrochloric acid solution, stirring and adding aniline and ammonium persulfate at a speed of 120 r / min and a temperature of 0°C, reacting for 5 hours, filtering and removing the filtrate, dispersing the substrate in acetone, adding propyl chloride, and reacting for 20 hours at a speed of 300 r / min and a temperature of 40°C to obtain a modified filler;

[0029] Step A4: Polyethylene glycol, 1,4-butanediol and dibutyltin dilaurate are mixed evenly, and 4,4'-diphenylmethane diisocyanate is added under stirring at a rotation speed of 200 r / min and a temperature of 80°C to react for 6 hours to obtain a polyurethane prepolymer. The polyurethane prepolymer and the modified filler are mixed and added to a twin-screw extruder, and extruded into granules to obtain an antistatic masterbatch for plastics.

[0030] The amount of 3-methacryloxypropyltriethoxysilane used in step A1 is 1% of the mass of graphene oxide, and the amount ratio of functional graphene to hydrazine hydrate is 1g:25mL.

[0031] The mass ratio of the pretreated graphene and the modified monomer described in step A2 is 1:5, the amount of chloroplatinic acid used is 1‰ of the mass of the modified monomer, and the amount ratio of the precursor, tetrahydrofuran and trifluoroacetic acid is 1g:80mL:6mL.

[0032] The amount ratio of the modified precursor, hydrochloric acid solution, aniline and ammonium persulfate described in step A3 is 20 mg:40 mL:5 mmol:5 mmol, and the mass ratio of the substrate and propyl chloride is 1:8.

[0033] The molar ratio of polyethylene glycol, 1,4-butanediol and 4,4'-diphenylmethane diisocyanate described in step A4 is 5:7:1, the amount of dibutyltin dilaurate is 2% of the mass of 4,4'-diphenylmethane diisocyanate, the molecular weight of polyethylene glycol is 2000, and the mass ratio of polyurethane prepolymer and modified filler is 40:2.

[0034] The modified monomer is prepared by the following steps:

[0035] Step B1: octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide and 1,3-bis(aminopropyl)tetramethyldisiloxane are mixed, nitrogen is introduced for protection, and the reaction is carried out for 10 hours at a speed of 120 r / min and a temperature of 90° C. to obtain bisaminopolysiloxane;

[0036] Step B2: N, N-dimethylethanolamine, epichlorohydrin, boron trifluoride etherate and tetrahydrofuran were mixed evenly, reacted at a speed of 120 r / min and a temperature of 65°C for 2 hours, and then sodium hydroxide solution was added, the temperature was raised to 75°C, and the reaction was continued for 3 hours to obtain a modifier, and bisaminopolysiloxane, the modifier and DMF were mixed evenly, and reacted at a speed of 200 r / min, a temperature of 60°C and a pH value of 11 for 6 hours to obtain a modified polysiloxane;

[0037] Step B3: Evenly mix 4-(BOC-amino)phenol, triethylamine and tetrahydrofuran, stir and add acryloyl chloride at a speed of 200 r / min and a temperature of 0°C, raise the temperature to 20°C, and react for 3 hours to obtain an intermediate; evenly mix the modified polysiloxane, the intermediate, chloroplatinic acid and DMF, introduce nitrogen protection, and react for 3 hours at a speed of 150 r / min and a temperature of 70°C to obtain a modified monomer.

[0038] The molar ratio of octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide and 1,3-bis(aminopropyl)tetramethyldisiloxane described in step B1 is 1.8 mol:0.6 mol:2 mol:3 mol.

[0039] The amount ratio of N,N-dimethylethanolamine, epichlorohydrin, boron trifluoride etherate, tetrahydrofuran and sodium hydroxide solution in step B2 is 35mmo l:35mmo l:1g:20mL:6mL, the mass fraction of sodium hydroxide solution is 25%, and the molar ratio of bisaminopolysiloxane to modifier is 1:4.

[0040] The molar ratio of 4-(BOC-amino)phenol, triethylamine and acryloyl chloride in step B3 is 1:1.1:1, the molar ratio of SiH bonds on the modified polysiloxane and the intermediate is 2:1, and the amount of chloroplatinic acid used is 1% of the mass of the intermediate.

[0041] Embodiment 2, a method for preparing antistatic masterbatch for plastics, specifically comprising the following steps:

[0042] Step A1: dispersing graphene oxide in ethanol, stirring and adding deionized water and 3-methacryloxypropyltriethoxysilane at a speed of 300 r / min and a temperature of 55° C., reacting for 4 hours to obtain functional graphene, mixing the functional graphene with hydrazine hydrate, reacting for 9 hours at a speed of 120 r / min and a temperature of 95° C., to obtain pretreated graphene;

[0043] Step A2: The pretreated graphene, the modified monomer, chloroplatinic acid and DMF were mixed uniformly, nitrogen was introduced for protection, and the reaction was carried out for 4 hours at a speed of 150 r / min and a temperature of 75° C. to obtain a precursor, and the precursor was dispersed in tetrahydrofuran, trifluoroacetic acid was added, nitrogen was introduced for protection, and the reaction was carried out for 1.5 hours at a speed of 60 r / min and a temperature of 55° C. to obtain a modified precursor;

[0044] Step A3: dispersing the modified precursor in a hydrochloric acid solution, stirring and adding aniline and ammonium persulfate at a speed of 120 r / min and a temperature of 3°C, reacting for 6 hours, filtering and removing the filtrate, dispersing the substrate in acetone, adding propyl chloride, and reacting for 22 hours at a speed of 300 r / min and a temperature of 45°C to obtain a modified filler;

[0045] Step A4: Polyethylene glycol, 1,4-butanediol and dibutyltin dilaurate are mixed evenly, and 4,4'-diphenylmethane diisocyanate is added under stirring at a rotation speed of 200 r / min and a temperature of 85°C to react for 7 hours to obtain a polyurethane prepolymer. The polyurethane prepolymer and the modified filler are mixed and added to a twin-screw extruder, and extruded into granules to obtain an antistatic masterbatch for plastics.

[0046] The amount of 3-methacryloxypropyltriethoxysilane used in step A1 is 1% of the mass of graphene oxide, and the amount ratio of functional graphene to hydrazine hydrate is 1g:25mL.

[0047] The mass ratio of the pretreated graphene and the modified monomer described in step A2 is 1:5, the amount of chloroplatinic acid used is 1‰ of the mass of the modified monomer, and the amount ratio of the precursor, tetrahydrofuran and trifluoroacetic acid is 1g:80mL:6mL.

[0048] The dosage ratio of the modified precursor, hydrochloric acid solution, aniline and ammonium persulfate described in step A3 is 20 mg:40 mL:5 mmol:5 mmol, and the mass ratio of the substrate and propyl chloride is 1:8.

[0049] The molar ratio of polyethylene glycol, 1,4-butanediol and 4,4'-diphenylmethane diisocyanate described in step A4 is 5:7:1, the amount of dibutyltin dilaurate is 2% of the mass of 4,4'-diphenylmethane diisocyanate, the molecular weight of polyethylene glycol is 2000, and the mass ratio of polyurethane prepolymer and modified filler is 45:3.

[0050] The modified monomer is prepared by the following steps:

[0051] Step B1: octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide and 1,3-bis(aminopropyl)tetramethyldisiloxane are mixed, nitrogen is introduced for protection, and the reaction is carried out for 11 hours at a speed of 120 r / min and a temperature of 95° C. to obtain bisaminopolysiloxane;

[0052] Step B2: N, N-dimethylethanolamine, epichlorohydrin, boron trifluoride etherate and tetrahydrofuran were mixed evenly, reacted at a speed of 120 r / min and a temperature of 70°C for 2 hours, and then sodium hydroxide solution was added, the temperature was raised to 80°C, and the reaction was continued for 4 hours to obtain a modifier, and bisaminopolysiloxane, the modifier and DMF were mixed evenly, and reacted at a speed of 200 r / min, a temperature of 65°C and a pH value of 11 for 7 hours to obtain a modified polysiloxane;

[0053] Step B3: Evenly mix 4-(BOC-amino)phenol, triethylamine and tetrahydrofuran, stir and add acryloyl chloride at a speed of 200 r / min and a temperature of 3°C, raise the temperature to 25°C, and react for 4 hours to obtain an intermediate; evenly mix the modified polysiloxane, the intermediate, chloroplatinic acid and DMF, introduce nitrogen protection, and react at a speed of 150 r / min and a temperature of 75°C for 4 hours to obtain a modified monomer.

[0054] The molar ratio of octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide and 1,3-bis(aminopropyl)tetramethyldisiloxane described in step B1 is 1.8 mol:0.6 mol:2 mol:3 mol.

[0055] The amount ratio of N,N-dimethylethanolamine, epichlorohydrin, boron trifluoride etherate, tetrahydrofuran and sodium hydroxide solution in step B2 is 35mmo l:35mmo l:1g:20mL:6mL, the mass fraction of sodium hydroxide solution is 25%, and the molar ratio of bisaminopolysiloxane to modifier is 1:4.

[0056] The molar ratio of 4-(BOC-amino)phenol, triethylamine and acryloyl chloride in step B3 is 1:1.1:1, the molar ratio of SiH bonds on the modified polysiloxane and the intermediate is 2:1, and the amount of chloroplatinic acid used is 1% of the mass of the intermediate.

[0057] Embodiment 3, a method for preparing an antistatic masterbatch for plastics, specifically comprising the following steps:

[0058] Step A1: dispersing graphene oxide in ethanol, stirring and adding deionized water and 3-methacryloxypropyltriethoxysilane at a speed of 500 r / min and a temperature of 60° C., reacting for 5 hours to obtain functional graphene, mixing the functional graphene with hydrazine hydrate, reacting for 10 hours at a speed of 150 r / min and a temperature of 95° C., and obtaining pretreated graphene;

[0059] Step A2: The pretreated graphene, the modified monomer, chloroplatinic acid and DMF were mixed evenly, nitrogen was introduced for protection, and the reaction was carried out for 5 hours at a speed of 200 r / min and a temperature of 80° C. to obtain a precursor, and the precursor was dispersed in tetrahydrofuran, trifluoroacetic acid was added, nitrogen was introduced for protection, and the reaction was carried out for 2 hours at a speed of 80 r / min and a temperature of 60° C. to obtain a modified precursor;

[0060] Step A3: Disperse the modified precursor in a hydrochloric acid solution, stir and add aniline and ammonium persulfate at a speed of 150 r / min and a temperature of 3°C, react for 7 hours, filter and remove the filtrate, disperse the substrate in acetone, add propyl chloride, and react for 24 hours at a speed of 500 r / min and a temperature of 45°C to obtain a modified filler;

[0061] Step A4: Polyethylene glycol, 1,4-butanediol and dibutyltin dilaurate are mixed evenly, and 4,4'-diphenylmethane diisocyanate is added under stirring at a rotation speed of 300 r / min and a temperature of 85°C to react for 8 hours to obtain a polyurethane prepolymer. The polyurethane prepolymer and the modified filler are mixed and added to a twin-screw extruder, and extruded into granules to obtain an antistatic masterbatch for plastics.

[0062] The amount of 3-methacryloxypropyltriethoxysilane used in step A1 is 1% of the mass of graphene oxide, and the amount ratio of functional graphene to hydrazine hydrate is 1g:25mL.

[0063] The mass ratio of the pretreated graphene and the modified monomer described in step A2 is 1:5, the amount of chloroplatinic acid used is 1‰ of the mass of the modified monomer, and the amount ratio of the precursor, tetrahydrofuran and trifluoroacetic acid is 1g:80mL:6mL.

[0064] The dosage ratio of the modified precursor, hydrochloric acid solution, aniline and ammonium persulfate described in step A3 is 20 mg:40 mL:5 mmol:5 mmol, and the mass ratio of the substrate and propyl chloride is 1:8.

[0065] The molar ratio of polyethylene glycol, 1,4-butanediol and 4,4'-diphenylmethane diisocyanate described in step A4 is 5:7:1, the amount of dibutyltin dilaurate is 2% of the mass of 4,4'-diphenylmethane diisocyanate, the molecular weight of polyethylene glycol is 2000, and the mass ratio of polyurethane prepolymer and modified filler is 50:4.

[0066] The modified monomer is prepared by the following steps:

[0067] Step B1: octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide and 1,3-bis(aminopropyl)tetramethyldisiloxane are mixed, nitrogen is introduced for protection, and the reaction is carried out for 12 hours at a speed of 150 r / min and a temperature of 95° C. to obtain bisaminopolysiloxane;

[0068] Step B2: N, N-dimethylethanolamine, epichlorohydrin, boron trifluoride etherate and tetrahydrofuran were mixed evenly, reacted at a speed of 150 r / min and a temperature of 70°C for 3 hours, and then sodium hydroxide solution was added, the temperature was raised to 80°C, and the reaction was continued for 5 hours to obtain a modifier, and bisaminopolysiloxane, the modifier and DMF were mixed evenly, and reacted at a speed of 300 r / min, a temperature of 65°C and a pH value of 12 for 8 hours to obtain a modified polysiloxane;

[0069] Step B3: Evenly mix 4-(BOC-amino)phenol, triethylamine and tetrahydrofuran, stir and add acryloyl chloride at a speed of 300 r / min and a temperature of 3°C, raise the temperature to 25°C, and react for 5 hours to obtain an intermediate; evenly mix the modified polysiloxane, the intermediate, chloroplatinic acid and DMF, introduce nitrogen protection, and react for 5 hours at a speed of 200 r / min and a temperature of 80°C to obtain a modified monomer.

[0070] The molar ratio of octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide and 1,3-bis(aminopropyl)tetramethyldisiloxane described in step B1 is 1.8 mol:0.6 mol:2 mol:3 mol.

[0071] The amount ratio of N,N-dimethylethanolamine, epichlorohydrin, boron trifluoride etherate, tetrahydrofuran and sodium hydroxide solution in step B2 is 35mmo l:35mmo l:1g:20mL:6mL, the mass fraction of sodium hydroxide solution is 25%, and the molar ratio of bisaminopolysiloxane to modifier is 1:4.

[0072] The molar ratio of 4-(BOC-amino)phenol, triethylamine and acryloyl chloride in step B3 is 1:1.1:1, the molar ratio of SiH bonds on the modified polysiloxane and the intermediate is 2:1, and the amount of chloroplatinic acid used is 1% of the mass of the intermediate.

[0073] Comparative Example 1: Compared with Example 1, the precursor is replaced by a modified monomer, and the remaining steps are the same.

[0074] Comparative Example 2: Compared with Example 1, no propyl chloride was added in this comparative example, and the remaining steps were the same.

[0075] Comparative Example 3. Compared with Example 1, octamethylcyclotetrasiloxane, tetramethylammonium hydroxide and 1,3-bis(aminopropyl)tetramethyldisiloxane were mixed, nitrogen was introduced for protection, and the reaction was carried out for 10 hours at a speed of 120 r / min and a temperature of 90°C. The obtained product 1 replaced the bisaminopolysiloxane, and the product 1, the modifier and DMF were evenly mixed. The reaction was carried out for 6 hours at a speed of 200 r / min, a temperature of 60°C and a pH value of 11, and the obtained product 2 replaced the modified monomer.

[0076] Comparative Example 4. Compared with Example 1, methylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide and hexamethyldisiloxane are mixed, nitrogen is introduced for protection, and the reaction is carried out for 10 hours at a speed of 120 r / min and a temperature of 90°C. The obtained product 3 replaces the modified polysiloxane, and the remaining steps are the same.

[0077] The antistatic masterbatches obtained in Examples 1-3 and Comparative Examples 1-3 were made into sheets with a diameter of 100 mm and a thickness of 2 mm. The surface resistance was tested at temperatures of 25° C., 50° C. and 80° C. and a humidity of 33%. The test results are described in Table 1 below.

[0078] Table 1

[0079]

[0080] It can be seen from Table 1 above that the present invention has a very good antistatic effect, and the antistatic effect is still maintained in a high temperature environment.

[0081] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

Claims

1. A method for preparing antistatic masterbatch for plastics, characterized in that: The specific steps include: Step A1: dispersing graphene oxide in ethanol, stirring and adding deionized water and 3-methacryloxypropyltriethoxysilane to react to obtain functional graphene, mixing the functional graphene and hydrazine hydrate to react to obtain pretreated graphene; Step A2: pretreated graphene, modified monomer, chloroplatinic acid and DMF are uniformly mixed, nitrogen is introduced for protection, and a reaction is carried out to obtain a precursor; the precursor is dispersed in tetrahydrofuran, trifluoroacetic acid is added, nitrogen is introduced for protection, and a reaction is carried out to obtain a modified precursor; Step A3: dispersing the modified precursor in a hydrochloric acid solution, stirring and adding aniline and ammonium persulfate, reacting, filtering and removing the filtrate, dispersing the substrate in acetone, adding propyl chloride, reacting, and obtaining a modified filler; Step A4: Mix polyethylene glycol, 1,4-butanediol and dibutyltin dilaurate and add 4,4'-diphenylmethane diisocyanate to react to obtain a polyurethane prepolymer. Mix the polyurethane prepolymer and modified filler and add them to a twin-screw extruder to extrude and granulate to obtain an antistatic masterbatch for plastics.

2. The method for preparing an antistatic masterbatch for plastics according to claim 1, characterized in that: The amount of 3-methacryloxypropyltriethoxysilane used in step A1 is 1% of the mass of graphene oxide, and the amount ratio of functional graphene to hydrazine hydrate is 1g:25mL.

3. The method for preparing an antistatic masterbatch for plastics according to claim 1, characterized in that: The mass ratio of the pretreated graphene and the modified monomer described in step A2 is 1:5, and the amount ratio of the precursor, tetrahydrofuran and trifluoroacetic acid is 1g:80mL:6mL.

4. The method for preparing an antistatic masterbatch for plastics according to claim 1, characterized in that: The amount ratio of the modified precursor, hydrochloric acid solution, aniline and ammonium persulfate described in step A3 is 20 mg:40 mL:5 mmol:5 mmol, and the mass ratio of the substrate and propyl chloride is 1:

8.

5. The method for preparing an antistatic masterbatch for plastics according to claim 1, characterized in that: The molar ratio of polyethylene glycol, 1,4-butanediol and 4,4'-diphenylmethane diisocyanate described in step A4 is 5:7:1, and the mass ratio of the polyurethane prepolymer and the modified filler is 40-50:2-4.

6. The method for preparing an antistatic masterbatch for plastics according to claim 1, characterized in that: The modified monomer is prepared by the following steps: Step B1: octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide and 1,3-bis(aminopropyl)tetramethyldisiloxane are mixed, nitrogen is introduced for protection, and the mixture is reacted to obtain bisaminopolysiloxane; Step B2: After N,N-dimethylethanolamine, epichlorohydrin, boron trifluoride etherate and tetrahydrofuran are mixed and reacted, sodium hydroxide solution is added and the reaction is continued to obtain a modifier, and bisaminopolysiloxane, the modifier and DMF are mixed and reacted to obtain a modified polysiloxane; Step B3: 4-(BOC-amino)phenol, triethylamine and tetrahydrofuran are mixed and stirred, and acryloyl chloride is added to react to obtain an intermediate. The modified polysiloxane, the intermediate, chloroplatinic acid and DMF are evenly mixed, and nitrogen is introduced for protection to react to obtain a modified monomer.

7. The method for preparing an antistatic masterbatch for plastics according to claim 6, characterized in that: The molar ratio of octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetramethylammonium hydroxide and 1,3-bis(aminopropyl)tetramethyldisiloxane described in step B1 is 1.8 mol:0.6 mol:2 mol:3 mol.

8. The method for preparing an antistatic masterbatch for plastics according to claim 6, characterized in that: The amount ratio of N,N-dimethylethanolamine, epichlorohydrin, boron trifluoride etherate, tetrahydrofuran and sodium hydroxide solution described in step B2 is 35mmol:35mmol:1g:20mL:6mL, and the molar ratio of bisaminopolysiloxane to modifier is 1:

4.

9. The method for preparing an antistatic masterbatch for plastics according to claim 6, characterized in that: The molar ratio of 4-(BOC-amino)phenol, triethylamine and acryloyl chloride in step B3 is 1:1.1:1, and the molar ratio of Si-H bonds on the modified polysiloxane to the intermediate is 2:

1. 10.An antistatic masterbatch for plastics, characterized in that: Prepared according to any one of claims 1 to 9.

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