CN115093607A - High-dispersity antistatic agent for plastic alloy and preparation method thereof - Google Patents
High-dispersity antistatic agent for plastic alloy and preparation method thereof Download PDFInfo
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- CN115093607A CN115093607A CN202210789114.3A CN202210789114A CN115093607A CN 115093607 A CN115093607 A CN 115093607A CN 202210789114 A CN202210789114 A CN 202210789114A CN 115093607 A CN115093607 A CN 115093607A
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- carbon black
- antistatic agent
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- 239000002216 antistatic agent Substances 0.000 title claims abstract description 141
- 239000004033 plastic Substances 0.000 title claims abstract description 86
- 229920003023 plastic Polymers 0.000 title claims abstract description 86
- 239000000956 alloy Substances 0.000 title claims abstract description 80
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 51
- 239000006229 carbon black Substances 0.000 claims abstract description 251
- 150000001721 carbon Chemical class 0.000 claims abstract description 79
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 65
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 24
- 239000000284 extract Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- 238000007747 plating Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- -1 dodecyl dimethyl quaternary ammonium hexanium salt Chemical class 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 43
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- 230000009286 beneficial effect Effects 0.000 abstract description 2
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- 239000000243 solution Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 24
- 150000001450 anions Chemical class 0.000 description 10
- 150000001768 cations Chemical class 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 241000872198 Serjania polyphylla Species 0.000 description 5
- 229910021485 fumed silica Inorganic materials 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 5
- 239000004299 sodium benzoate Substances 0.000 description 5
- 235000010234 sodium benzoate Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 4
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 4
- 229920006942 ABS/PC Polymers 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000008485 antagonism Effects 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 241000080590 Niso Species 0.000 description 3
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000003042 antagnostic effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
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- 239000002861 polymer material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000001215 fluorescent labelling Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/19—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/017—Additives being an antistatic agent
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The application relates to the field of high-dispersity antistatic agents, in particular to a high-dispersity antistatic agent for plastic alloys and a preparation method thereof, wherein the antistatic agent comprises the following components in parts by weight: 10-30 parts of an amphoteric antistatic agent; 5-20 parts of modified carbon black; 1-8 parts of white carbon black; 0.2-1 part of a dispersant; the modified carbon black is prepared from carbon black and 4,4' -biphenyl dicarboxylic acid in a weight ratio of 1: 1-1.2. The high-dispersity antistatic agent has the effect of enhancing the antistatic capacity of the plastic alloy, and is beneficial to reducing potential safety hazards caused by static electricity.
Description
Technical Field
The application relates to the field of high-dispersity antistatic agents, in particular to a high-dispersity antistatic agent for plastic alloys and a preparation method thereof.
Background
The plastic alloy is a new material with high performance, functionalization and specialization obtained by a physical blending or chemical grafting method. The plastic alloy product can be widely used in the fields of automobiles, electronics, precise instruments, office equipment, packaging materials, building materials and the like.
However, most of plastic alloys are good insulating materials, so that charges are easily generated and accumulated in the application process due to friction and stripping processes, spark discharge may be generated, serious safety accidents such as explosion and fire are caused, and hidden dangers are brought to production and application.
In order to reduce static electricity, the generation of plastic alloys in the market at present mainly adopts two types of methods, the first type is structural conductive plastic, and the second type is composite conductive plastic. The structural conductive plastic is a plastic which has conductivity or has conductivity after being chemically modified. The materials are all high molecular polymers with conjugated double bond structures. However, the synthesis process of the material is complex, the cost is high, the price is quite expensive at present, and the mass production is difficult. The composite conductive plastic is formed by compounding a conductive substance and a high polymer material, and carbon black as the conductive substance has the advantages of low price, good conductivity and the like, but the carbon black has poor dispersibility in the high polymer material, and the conditions of homopolymerization and precipitation are easy to occur, so the antistatic effect is still not ideal.
Disclosure of Invention
In order to reduce the accumulation of static charges on plastic alloys, the application provides a high-dispersity antistatic agent for plastic alloys and a preparation method thereof.
In a first aspect, the present application provides a highly dispersible antistatic agent for plastic alloys, which comprises the following components in parts by weight:
10-30 parts of an amphoteric antistatic agent;
5-20 parts of modified carbon black;
1-8 parts of white carbon black;
0.2-1 part of a dispersant;
the modified carbon black is prepared from carbon black and 4,4' -biphenyl dicarboxylic acid in a weight ratio of 1: 1-1.2.
The amphoteric antistatic agent is rich in anions and cations, and the surface of the common carbon black has a plurality of free radicals capable of being combined with the anions or the cations, so that the free anions or the cations of the amphoteric antistatic agent can be captured, the antistatic capability of the amphoteric antistatic agent is reduced, the surface activity of the reacted common carbon black is reduced, and the subsequent grafting difficulty with plastic alloy is improved. Therefore, the antistatic effect of the compounded antistatic agent obtained by compounding the amphoteric antistatic agent and the carbon black is poorer than that of a single antistatic agent.
The carboxyl and hydroxyl on the surface of the carbon black have low reactivity, but can activate the carbon black by reacting with functional polymers with active end groups; the application relates to modified carbon black obtained by reacting 4,4' -biphenyldicarboxylic acid with carboxyl with hydroxyl on the surface of carbon black. The surface of the modified carbon black can be greatly reduced by combining with anions or cations, so that the antagonism between the carbon black and the amphoteric antistatic agent is reduced; meanwhile, polymer groups exist on the surface of the modified carbon black, so that the repulsion among particles can be enhanced, the space gap of the carbon black is enlarged, the homopolymerization of the carbon black is reduced, the specific surface area of the carbon black is improved, the surface activity of the carbon black is improved, and the subsequent grafting rate with resin is improved. Because the space gap on the surface of the carbon black is enlarged, the carbon black in unit volume can expose more active defects, and the active defects have stronger chemical adsorption force or physical adsorption force, so that more amphoteric antistatic agents can be adsorbed, the distribution of the antistatic agents in the plastic alloy is more uniform, and the antistatic property of the plastic alloy is improved.
Optionally, the amphoteric antistatic agent is dodecyl dimethyl quaternary ammonium hexyl inner salt.
By adopting the technical scheme, when dodecyl dimethyl quaternary ammonium hexyl inner salt is used as the amphoteric antistatic agent, the high-dispersity antistatic agent has better compatibility with resin.
Optionally, the dispersant is polyethylene glycol.
Hydroxyl in the polyethylene glycol can capture free radicals of the modified carbon black, so that the grafting rate of the modified carbon black is improved; the polyethylene glycol can improve the water absorption of the prepared plastic alloy and further improve the antistatic effect of the amphoteric antistatic agent.
Optionally, the particle size of the modified carbon black is 25-35 nm.
By adopting the technical scheme, the small-particle-size modified carbon black has larger specific surface area, so that the antistatic agent can be more uniformly dispersed in the plastic alloy, and the antistatic capability of the plastic alloy is improved; the transparency is better, and the influence on the color of the plastic alloy is reduced.
Optionally, the raw materials for preparing the modified carbon black further comprise a nickel-containing plating solution, and the weight ratio of the nickel-containing plating solution to the carbon black is 4.2-6.4: 1.
By introducing nickel, the terminal group monodentate of the biphenyldicarboxylic acid on the surface of the carbon black is coordinated with the nickel, so that the spatial structure of the surface of the carbon black grafted with the 4,4' -biphenyldicarboxylic acid is changed to form some spatial topological structures including kagoma, on one hand, the effect of fluorescent labeling is improved, and the modification degree of the modified carbon black can be detected more easily; on the other hand, the change of the space structure improves the adsorption and storage capacity of the carbon black, facilitates the carbon black to carry the amphoteric antistatic agent, ensures that the antistatic agent is more uniformly dispersed in the plastic alloy, and improves the antistatic capacity of the plastic alloy. By nickel plating, the modified carbon black has interaction force between the metal nano effect and antistatic agent molecules, so that the relative viscosity (Rv) of the plastic alloy is reduced, and the dispersibility of the antistatic agent in the plastic alloy is improved, so that the using amount of the antistatic agent is reduced on the premise of ensuring the antistatic effect.
Optionally, the preparation method of the modified carbon black comprises the following steps:
s1, blending carbon black and 4,4' -biphenyldicarboxylic acid in a rheometer to obtain a mixture A;
s2, adding an organic solvent into the mixture A, and repeatedly extracting for multiple times to obtain an extract B;
s3, vacuum drying the extract B to obtain 4,4' -biphenyldicarboxylic acid grafted solid carbon black;
s4, putting the solid carbon black obtained in the step S3 into a nickel-containing plating solution for mixing, filtering and drying to obtain the modified carbon black.
The carbon black is modified by blending it with 4,4' -biphenyldicarboxylic acid. The organic solvent is used for removing the free 4,4 '-biphenyldicarboxylic acid, so that the reaction of the free 4,4' -biphenyldicarboxylic acid in the subsequent nickel-containing plating solution can be prevented, some unnecessary impurities are formed, and the purity of the subsequent modified carbon black is improved.
Optionally, before the step S1, mixing and modifying the carbon black and the nitric acid to obtain a mixture, and then placing the mixture and the 4,4' -biphenyldicarboxylic acid into a rheometer to blend.
The carbon black is oxidized by nitric acid, so that on one hand, the agglomeration of the carbon black is inhibited, and meanwhile, the introduction amount of oxygen groups can be greatly increased as an introducing agent; on the other hand, the 4,4' -biphenyl dicarboxylic acid has higher grafting ratio with the modified carbon black under the acidic condition, thereby improving the dispersibility of the modified carbon black and improving the antistatic effect of the antistatic agent.
Optionally, the white carbon black is modified white carbon black, and the modified white carbon black is prepared from a silane coupling agent and white carbon black in a weight ratio of 3.6-4.0: 1.
The preparation method of the modified white carbon black comprises the following steps:
a1, adding a silane coupling agent and white carbon black into toluene, and stirring while refluxing under the protection of nitrogen to obtain a solution C;
a2, solidifying the solution C at a high temperature of 111-120 ℃, adding an organic solvent, repeatedly extracting for multiple times to obtain an extract D, and filtering and drying the extract D to obtain the modified white carbon black.
By adopting the technical scheme, the white carbon black is grafted with the silane coupling agent, so that the fluidity of the white carbon black in an organic solvent is improved, and the homopolymerization phenomenon of the white carbon black is improved; the silane coupling agent can also react with the plastic alloy, so that the acting force between the white carbon black and the plastic alloy is enhanced, the compatibility of the modified white carbon black is improved, the dispersion stability of the modified white carbon black and the modified carbon black in the plastic alloy is improved, and the antistatic effect of the antistatic agent is improved.
In a second aspect, the present application provides a method for preparing a highly dispersible antistatic agent for plastic alloys, comprising the steps of:
b1, mixing and stirring the amphoteric antistatic agent and the modified carbon black, and uniformly stirring to obtain a premixed solution;
and B2, adding the white carbon black and the dispersing agent into the premixed solution, and uniformly stirring to obtain the antistatic agent.
By adopting the technical scheme, the adsorption and combination between the amphoteric antistatic agent and the modified carbon black are improved by mixing and stirring the amphoteric antistatic agent, and then the white carbon black and the dispersing agent are added to prepare the high-dispersity antistatic agent.
To sum up, the application comprises at least the following beneficial technical effects:
1. according to the application, an amphoteric antistatic agent, modified carbon black, white carbon black and a dispersing agent are prepared into an antistatic agent; the antistatic agent is prepared by modifying common carbon black, and the antistatic agent is added into plastic alloy, so that the obtained plastic alloy has excellent antistatic property;
2. the application also provides a preparation method of the modified carbon black, which comprises the steps of firstly blending the carbon black and the 4,4' -biphenyldicarboxylic acid by adopting a rheometer, then repeatedly extracting the mixture for many times by using an organic solvent, and drying the mixture in vacuum. And then putting the solid particles after vacuum drying into a nickel-containing plating solution, filtering and drying to obtain the modified carbon black. The modified carbon black obtained by the method has stronger surface activity and some special space topological structures, improves the storage and adsorption capacity of the carbon black, and improves the antistatic effect of the final antistatic agent.
Detailed Description
The present application is further described below with reference to the following specific contents:
preparation example:
preparation of modified carbon black:
preparation example 1-1, a modified carbon black, was prepared according to the following procedure:
s1, mixing and modifying 1kg of carbon black with the particle size of 25-35nm and 1L of 3mol/L dilute nitric acid to obtain a mixture, putting the mixture and 1.1kg of 4,4' -biphenyldicarboxylic acid into a rheometer, and blending for 1h by using toluene as a solvent to obtain a mixture A;
s2, adding acetone into the mixture A to repeatedly extract for 3 times to obtain an extract B;
s3, vacuum drying the extract B to obtain 4,4' -biphenyldicarboxylic acid grafted solid carbon black;
s4, putting the solid carbon black grafted by 4,4' -biphenyldicarboxylic acid into 5.3kg of NiSO 4.7H2O plating solution with the concentration of 1.5mol/L for mixing, filtering and drying to obtain the modified carbon black.
Preparation examples 1-2, a modified carbon black, was prepared according to the following steps:
s1, mixing and modifying 1kg of carbon black with the particle size of 25-35nm and 1L of 3mol/L dilute nitric acid to obtain a mixture, and then putting the mixture and 1.2kg of 4,4 '-biphenyldicarboxylic acid into a rheometer, and blending the mixture and the 1.2kg of 4,4' -biphenyldicarboxylic acid by using toluene as a solvent to obtain a mixture A;
s2, adding ethanol into the mixture A, and repeatedly extracting for 3 times to obtain an extract B;
s3, vacuum drying the extract B to obtain 4,4' -biphenyldicarboxylic acid grafted solid carbon black;
s4, 4.2kg of 1.5mol/L NiSO is added into the 4,4' -biphenyldicarboxylic acid grafted solid carbon black 4 ·7H 2 And mixing the solution in the plating solution O, filtering and drying to obtain the modified carbon black.
Preparation examples 1 to 3, a modified carbon black, was prepared according to the following steps:
s1, mixing and modifying 1kg of carbon black with the particle size of 25-35nm and 1L of 3mol/L dilute nitric acid to obtain a mixture, and then putting the mixture and 1.0kg of 4,4 '-biphenyldicarboxylic acid into a rheometer, and blending the mixture and the 1.0kg of 4,4' -biphenyldicarboxylic acid by using toluene as a solvent to obtain a mixture A;
s2, adding ethanol into the mixture A, and repeatedly extracting for 3 times to obtain an extract B;
s3, vacuum drying the extract B to obtain 4,4' -biphenyldicarboxylic acid grafted solid carbon black;
s4, putting 4,4' -biphenyldicarboxylic acid grafted solid carbon black into 6.4kg of 1.5mol/L NiSO 4 ·7H 2 And mixing the solution in the plating solution O, filtering and drying to obtain the modified carbon black.
Preparation examples 1 to 4, modified carbon black, were different from preparation example 1 to 1 in that no nickel-containing bath was used in the preparation, i.e., the operation of step S4 was not performed.
Preparation examples 1-5, modified carbon black, differs from preparation example 1-1 in that 4,4' -biphenyldicarboxylic acid was replaced with an equal amount of nickel-containing plating solution.
Preparation examples 1-6, modified carbon blacks, differ from preparation example 1-1 in that the particle size of the carbon black is 40 to 50 nm.
Preparation examples 1 to 7, modified carbon blacks, differ from preparation example 1 to 1 in that the carbon black has a particle size of 5 to 15 nm.
Examples 1 to 8, modified carbon black, differ from preparation example 1 to 1 in that carbon black was not modified by mixing with 1L of 3mol/L nitric acid, and carbon black and 4,4' -biphenyldicarboxylic acid were directly put into a rheometer to be blended.
Preparing modified white carbon black:
preparation example 2-1
The preparation method of the modified white carbon black comprises the following steps:
a1: adding 3.6kg of 3-aminopropyl-triethoxysilane and 1kg of 20-30nm fumed silica into 1L of toluene, and stirring while refluxing for 2h under the protection of nitrogen to obtain a solution C;
a2: and (3) solidifying the solution C at a high temperature of 120 ℃, adding acetone, repeatedly extracting for 3 to obtain an extract D, and filtering and drying the extract D to obtain the modified white carbon black.
Preparation examples 2 to 2
The preparation method of the modified white carbon black comprises the following steps:
a1: adding 3.8kg of 3-aminopropyl-trimethoxy silane and 1kg of 20-30nm fumed silica into 1L of toluene, and stirring and refluxing for 2h under the protection of nitrogen to obtain a solution C;
a2: and (3) solidifying the solution C at a high temperature of 111 ℃, adding acetone, repeatedly extracting for 3 to obtain an extract D, and filtering and drying the extract D to obtain the modified white carbon black.
Preparation examples 2 to 3
The preparation method of the modified white carbon black comprises the following steps:
a1: adding 4kg of 3-aminopropyl-triethoxysilane and 1kg of 20-30nm fumed silica into 1L of toluene, and refluxing for 2 hours under the protection of nitrogen while stirring to obtain a solution C;
a2: and (3) solidifying the solution C at a high temperature of 115 ℃, adding acetone, repeatedly extracting for 3 to obtain an extract D, and filtering and drying the extract D to obtain the modified white carbon black.
Preparation example 2-4, the difference between the modified white carbon black and the preparation example 2-1 is that the fumed silica with the particle size of 40-50nm is used instead.
Preparation examples 2-5, modified white carbon black, different from preparation example 2-1, was fumed silica having a particle size of 5-15 nm.
Example (b):
the embodiment of the application discloses a high-dispersity antistatic agent for plastic alloy.
Example 1
A preparation method of a high-dispersity antistatic agent for plastic alloy comprises the following steps:
B1. mixing and stirring 20kg of amphoteric antistatic agent and 15kg of modified carbon black, and uniformly stirring and mixing for 2 hours to obtain a premixed solution;
B2. and adding 4kg of modified white carbon black and 0.6kg of PEG400 into the premixed solution, and stirring and uniformly mixing for 2 hours to obtain the high-dispersity antistatic agent. Modified carbon black was obtained from production example 1-1, and modified white carbon black was obtained from production example 2-1.
Example 2
A preparation method of a high-dispersity antistatic agent for plastic alloy comprises the following steps:
B1. mixing and stirring 30kg of amphoteric antistatic agent and 5kg of modified carbon black, and uniformly stirring and mixing for 2 hours to obtain a premixed solution;
B2. and adding 8kg of modified white carbon black and 1kg of PEG400 into the premixed solution, and uniformly stirring for 2 hours to obtain the high-dispersity antistatic agent. The modified carbon black is prepared from preparation examples 1-2, and the modified white carbon black is prepared from preparation examples 2-2.
Example 3
A preparation method of a high-dispersity antistatic agent for plastic alloy comprises the following steps:
B1. mixing and stirring 10kg of amphoteric antistatic agent and 20kg of modified carbon black, and uniformly stirring and mixing for 2 hours to obtain a premixed solution;
B2. and adding 1kg of modified white carbon black and 0.2kg of PEG400 into the premixed solution, and stirring and uniformly mixing for 2 hours to obtain the high-dispersity antistatic agent. The modified carbon black is prepared from preparation examples 1-3, and the modified white carbon black is prepared from preparation examples 2-3.
Example 4, a highly dispersible antistatic agent for plastic alloys, differs from example 1 in that modified carbon black was prepared from preparation examples 1 to 4.
Example 5, a highly dispersible antistatic agent for plastic alloys, differs from example 1 in that modified carbon black was prepared from preparation examples 1 to 5.
Example 6, a highly dispersible antistatic agent for plastic alloys, differs from example 1 in that modified carbon black was prepared from preparation examples 1 to 6.
Example 7, a highly dispersible antistatic agent for plastic alloys, differs from example 1 in that modified carbon black was prepared from preparation examples 1 to 7.
Example 8, a highly dispersible antistatic agent for plastic alloys, differs from example 1 in that modified carbon black was prepared from preparation examples 1 to 8.
Example 9, a highly dispersible antistatic agent for plastic alloys, differs from example 1 in that modified white carbon black was prepared according to preparation examples 2 to 4.
Example 10, a highly dispersible antistatic agent for plastic alloys, differs from example 1 in that modified white carbon black was prepared according to preparation examples 2 to 5.
Example 11, a highly dispersible antistatic agent for plastic alloys, differs from example 1 in that the modified white carbon black is replaced with an equal amount of the above unmodified white carbon black.
Comparative example
Comparative example 1, a highly dispersible antistatic agent for plastic alloys, differs from example 1 in that the modified carbon black is replaced with an equal amount of the above-mentioned unmodified carbon black.
Comparative example 2, a highly dispersible antistatic agent for plastic alloys, differs from example 1 in that the modified carbon black is replaced with an equal amount of dodecyl dimethyl quaternary ammonium hexyl inner salt.
Comparative example 3, a highly dispersible antistatic agent for plastic alloys, differs from example 1 in that dodecyl dimethyl quaternary ammonium hexyl inner salt and modified carbon black are replaced with equal amounts of unmodified carbon black.
Comparative example 4, a highly dispersible antistatic agent for plastic alloys, differs from example 1 in that dodecyl dimethyl quaternary ammonium hexyl inner salt is replaced with an equal amount of modified carbon black.
Comparative example 5, a highly dispersible antistatic agent for plastic alloys, differs from example 1 in that 4,4' -biphenyldicarboxylic acid is replaced with an equal amount of sodium benzoate.
Comparative example 6, a highly dispersible antistatic agent for plastic alloys, differs from example 1 in that dodecyl dimethyl quaternary ammonium hexyl inner salt is replaced with an equal amount of sodium dodecyl sulfonate (anionic antistatic agent).
Comparative example 7, a highly dispersible antistatic agent for plastic alloy, was different from example 1 in that the highly dispersible antistatic agent was replaced with an equivalent amount of ASA-90 (conventional ABS/PC plastic alloy antistatic agent).
Performance test
Sample preparation:
the highly dispersible antistatic agents prepared in examples 1 to 11 and comparative examples 1 to 7 were applied to the preparation of ABS/PC plastic alloys, respectively, and the preparation methods were as follows:
PC was first dried at 120 ℃ for 10h and ABS at 90 ℃ for 8 h. Then PC and ABS are respectively added with additives and 3wt% of high-dispersity antistatic agent in advance according to the mass ratio of 60: 40 and then are subjected to extrusion experiment at 240 ℃ by adopting a BM65 double-screw extruder. After drying the pellets, they were produced on a 800T Haitian injection moulding machine into plastic plaques of 20cm X3 mm at an injection temperature of 200 ℃. And (5) balancing the sample for 20 hours after injection, and carrying out an antistatic performance test.
A blank control is set in the experiment, and the blank control is not added with the high-dispersity and high-antistatic agent.
And (3) detecting the antistatic performance of the prepared modified ABS/PC plastic alloy, wherein the detection method refers to GB/T1410-2006, and the environmental humidity during the test is 40% RH.
The detection results are shown in table 1:
TABLE 1 Performance test results
| Numbering | Volume resistivity/Ω · m | Numbering | Volume resistivity/Ω · m |
| Example 1 | 0.57*10 7 | Comparative example 1 | 4.37*10 11 |
| Example 2 | 0.76*10 7 | Comparative example 2 | 8.07*10 11 |
| Example 3 | 0.71*10 7 | Comparative example 3 | 7.51*10 10 |
| Example 4 | 2.52*10 8 | Comparative example 4 | 3.79*10 8 |
| Example 5 | 2.88*10 10 | Comparative example 5 | 7.61*10 9 |
| Example 6 | 2.77*10 7 | Comparative example 6 | 9.52*10 8 |
| Example 7 | 1.57*10 7 | Comparative example 7 | 7.07*10 10 |
| Example 8 | 0.91*10 7 | Blank control | 1.26*10 14 |
| Example 9 | 0.92*10 7 | ||
| Example 10 | 1.37*10 7 | ||
| Example 11 | 0.81*10 9 |
Combining example 1, example 2, example 3 and table 1, it can be seen that when the weight ratio of carbon black, 4 '-biphenyldicarboxylic acid and nickel-containing plating solution is 1:1 to 1.2:4.2 to 6.4, the prepared highly dispersible antistatic agent has excellent antistatic effect because the surface of the carbon black modified by 4,4' -biphenyldicarboxylic acid is greatly reduced in the amount of radicals capable of combining with anions or cations, thereby reducing the antagonistic effect between the carbon black and the amphoteric antistatic agent; meanwhile, polymer groups exist on the surface of the modified carbon black, so that the repulsion among particles can be enhanced, the space gap of the carbon black is enlarged, the homopolymerization of the carbon black is reduced, the specific surface area of the carbon black is improved, the surface activity of the carbon black is improved, and the subsequent grafting rate with resin is improved. Because the space gap on the surface of the carbon black is enlarged, more amphoteric antistatic agents can be adsorbed on the surface of the carbon black in unit volume, so that the antistatic agents are more uniformly distributed in the plastic alloy, and the antistatic property of the plastic alloy is improved.
By combining the example 1, the example 4 and the table 1, it can be found that the modified carbon black in the high-dispersibility antistatic agent is not subjected to a nickel plating step, and the obtained modified ABS/PC plastic alloy has slightly poor antistatic performance. The reason is that the nickel is plated on the surface of the carbon black, and the single tooth of the end group of the biphenyldicarboxylic acid on the surface of the carbon black is matched with the nickel, so that the spatial structure of the surface of the carbon black grafted with the 4,4' -biphenyldicarboxylic acid is changed, and a plurality of spatial topological structures including kagoma are formed, thereby improving the adsorption and storage capacities of the carbon black, facilitating the carbon black to carry the amphoteric antistatic agent, ensuring the dispersion of the antistatic agent to be more uniform and the antistatic capacity to be better. Through nickel plating, interaction force exists between the nanometer effect of the metal particles and the molecules of the antistatic agent, the relative viscosity (Rv) of the plastic alloy is reduced, the dispersity of the antistatic agent in the plastic alloy is improved, and the antistatic effect of the high-dispersity antistatic agent is improved.
Combining example 1, example 5 and table 1, it can be seen that the carboxyl groups and hydroxyl groups on the surface of carbon black have low reactivity, but can activate the carbon black by reacting with a functional polymer having a reactive terminal group; the application relates to modified carbon black obtained by reacting 4,4' -biphenyldicarboxylic acid with carboxyl with hydroxyl on the surface of carbon black. The surface of the modified carbon black can be greatly reduced by combining with anions or cations, so that the antagonism between the carbon black and the amphoteric antistatic agent is reduced; meanwhile, polymer groups exist on the surface of the modified carbon black, so that the repulsion among particles can be enhanced, the space gap of the carbon black is enlarged, the homopolymerization of the carbon black is reduced, the specific surface area of the carbon black is improved, the surface activity of the carbon black is improved, and the subsequent grafting rate with resin is improved. Because the space gap on the surface of the carbon black is enlarged, the carbon black in unit volume can expose more active defects, and the active defects have stronger chemical adsorption force or physical adsorption force, so that more amphoteric antistatic agents can be adsorbed, the distribution of the antistatic agents in the plastic alloy is more uniform, and the antistatic property of the plastic alloy is improved.
As can be seen from the combination of examples 1, 6, 7 and Table 1, the particle size of 25 to 35nm was used
The antistatic agent prepared by the carbon black particles has better antistatic effect, because when the particle size is larger than 35nm, the particle size of a homopolymer generated by homopolymerization of the carbon black is larger, and the dispersity of the antistatic agent in the plastic alloy is reduced; when the particle diameter is less than 25nm, the particle diameter of the carbon black is too small, and the ability to adsorb and carry an amphoteric antistatic agent is lowered, affecting the antistatic effect of the antistatic agent.
As can be seen from the combination of examples 1 and 8 and table 1, the carbon black is pretreated by nitric acid and then modified, and the antistatic effect of the high-dispersibility antistatic agent is better, because the carbon black is oxidized by nitric acid, on one hand, the agglomeration of the carbon black is inhibited, and meanwhile, the introduction amount of oxygen groups can be greatly increased as an introducing agent; on the other hand, in the subsequent modification stage, the grafting ratio of the 4,4' -biphenyldicarboxylic acid and the modified carbon black is higher under the acidic condition, the dispersibility of the modified carbon black is further improved, and the antistatic effect of the antistatic agent is improved.
By combining the examples 1, 9, 10 and table 1, it can be seen that the antistatic effect of the finally prepared antistatic agent is best when the modified white carbon black with the particle size of 20-30nm is used. The reason may be that when the particle size is larger than 30nm, the particle size of the homopolymer generated by homopolymerization of the modified white carbon black, the carbon black and the modified white carbon black is larger, so that the dispersity of the antistatic agent in the plastic alloy is reduced; when the particle size is less than 20nm, the modified white carbon black with too small particle size has too strong surface activity and is easy to react with the amphoteric antistatic agent, so that the antistatic effect of the amphoteric antistatic agent is reduced, and the antistatic effect of the antistatic agent is reduced.
By combining example 1, example 11 and table 1, it can be seen that the antistatic agent prepared by adding the modified white carbon black has better effect than the antistatic agent prepared by adding the unmodified white carbon black. The reason is that: the white carbon black can improve the water absorption of the plastic alloy, so that the antistatic effect of the antistatic agent is improved. However, the white carbon black is the same as the carbon black, and is easy to homopolymerize and separate out, and the white carbon black is grafted with 3-aminopropyl-triethoxysilane, so that the fluidity of the white carbon black in an organic solvent is improved, and the agglomeration phenomenon of the white carbon black is improved; the 3-aminopropyl-triethoxysilane can also react with the plastic alloy, so that the acting force between the white carbon black and the plastic alloy is enhanced, the compatibility of the modified white carbon black is improved, the dispersion stability of the modified white carbon black and the modified carbon black in the plastic alloy is improved, and the antistatic effect of the antistatic agent is improved.
It can be concluded from the combination of comparative example 1, comparative example 2, comparative example 3 and table 1 that the antistatic effect is worse than that of the highly dispersible antistatic agent in which no carbon black or amphoteric antistatic agent is added, and that the highly dispersible antistatic agent to which carbon black and an amphoteric antistatic agent are added simultaneously demonstrates the antagonistic action between carbon black and antistatic agent. The reason may be that many free radicals capable of combining with anions or cations exist on the surface of the common carbon black, and can capture free anions or cations of the amphoteric antistatic agent, so that the antistatic capability of the amphoteric antistatic agent is reduced, the surface activity of the common carbon black after reaction is reduced, and the difficulty of subsequent grafting with plastic alloy is improved, so that the antistatic effect of the compound antistatic agent obtained by compounding the amphoteric antistatic agent and the carbon black is poorer than that of a single antistatic agent.
It can be seen by combining example 1, comparative example 2, comparative example 4 and table 1 that the antistatic effect of the antistatic agent added with the modified carbon black and dodecyl dimethyl quaternary ammonium hexanium salt is better than that of the antistatic agent added with the modified carbon black and dodecyl dimethyl quaternary ammonium hexanium salt alone. The modified carbon black and dodecyl show synergistic effect on antistatic effect, because: the carbon black modified by 4,4' -biphenyldicarboxylic acid greatly reduces free radicals of which the surfaces can be combined with anions or cations, so that the antagonism between the carbon black and an amphoteric antistatic agent is reduced; meanwhile, polymer groups exist on the surface of the modified carbon black, so that the repulsion among particles can be enhanced, the space gap of the carbon black is enlarged, the homopolymerization of the carbon black is reduced, the specific surface area of the carbon black is improved, the surface activity of the carbon black is improved, and the subsequent grafting rate with resin is improved. Because the space gap on the surface of the carbon black is enlarged, more amphoteric antistatic agents can be adsorbed on the surface of the carbon black in unit volume, so that the antistatic agents are more uniformly distributed in the plastic alloy, and the antistatic property of the plastic alloy is improved.
It can be seen from the combination of examples 1 and 5, comparative example 5 and Table 1 that the carbon black was modified with an equal amount of sodium benzoate instead of 4,4 '-biphenyldicarboxylic acid, and the highly dispersible antistatic agent obtained from the carbon black modified with sodium benzoate was not as effective as the highly dispersible antistatic agent obtained from the carbon black modified with 4,4' -biphenyldicarboxylic acid. The reason is that: the surface activity of the carbon black modified by the sodium benzoate is not improved a lot, and a space structure for improving the antistatic effect cannot be formed on the surface of the carbon black in the subsequent nickel plating process, so that compared with the conventional modifier sodium benzoate of the carbon black, the modified carbon black prepared by modifying the carbon black by adopting the 4,4' -biphenyldicarboxylic acid has a more excellent antistatic effect.
Combining example 1, comparative example 6, and table 1, it can be seen that the antistatic agent made with an equal amount of sodium dodecyl sulfate instead of dodecyl dimethyl quat hexane salt had a reduced effect because: the compatibility of the anionic antistatic agent and resin is poor, the modified carbon black has the phenomena of homopolymerization and precipitation, and the problems of uneven dispersion in the plastic alloy exist in the modified carbon black and the modified carbon black, so that the antistatic effect of the antistatic property is reduced.
Combining example 1, comparative example 7 and the blank control and table 1, it can be concluded that the highly dispersible antistatic agent prepared herein has better antistatic effect than the conventional antistatic agent because the antagonism between the carbon black and the amphoteric antistatic agent is reduced by the carbon black modified with 4,4' -biphenyldicarboxylic acid due to the large reduction of the number of radicals whose surface can be combined with anions or cations; meanwhile, polymer groups exist on the surface of the modified carbon black, so that the repulsion among particles can be enhanced, the space gap of the carbon black is enlarged, the homopolymerization of the carbon black is reduced, the specific surface area of the carbon black is improved, the surface activity of the carbon black is improved, and the subsequent grafting rate with resin is improved. Because the space gap on the surface of the carbon black is enlarged, more amphoteric antistatic agents can be adsorbed on the surface of the carbon black in unit volume, so that the antistatic agents are more uniformly distributed in the plastic alloy, and the antistatic property of the plastic alloy is improved.
The above embodiments are preferred embodiments of the present application, and the protection scope of the present application is not limited by the above embodiments, so: all equivalent changes made according to the structure, shape and principle of the present application shall be covered by the protection scope of the present application.
Claims (10)
1. The high-dispersity antistatic agent for the plastic alloy is characterized by comprising the following components in parts by weight:
10-30 parts of an amphoteric antistatic agent;
5-20 parts of modified carbon black;
1-8 parts of white carbon black;
0.1-1 part of a dispersant;
the modified carbon black is prepared from carbon black and 4,4' -biphenyl dicarboxylic acid in a weight ratio of 1: 1-1.2.
2. The high-dispersity antistatic agent for the plastic alloy as claimed in claim 1, wherein the amphoteric antistatic agent is dodecyl dimethyl quaternary ammonium hexanium salt.
3. The high-dispersity antistatic agent for plastic alloys according to claim 1, wherein the dispersing agent is polyethylene glycol.
4. The highly dispersible antistatic agent for plastic alloy as claimed in claim 1, wherein the particle size of the modified carbon black is 25-35 nm.
5. The high-dispersity antistatic agent for plastic alloy as claimed in claim 1, wherein the modified carbon black is prepared from raw materials comprising a nickel-containing plating solution, and the weight ratio of the nickel-containing plating solution to the carbon black is 4.2-6.4: 1.
6. The method for preparing the high-dispersity antistatic agent for the plastic alloy as claimed in claim 1, wherein the modified carbon black is prepared by the following steps:
s1, putting the carbon black and the 4,4' -biphenyldicarboxylic acid into a rheometer, and blending to obtain a mixture A;
s2, adding an organic solvent into the mixture A, and repeatedly extracting for multiple times to obtain an extract B;
s3, vacuum drying the extract B to obtain 4,4' -biphenyldicarboxylic acid grafted solid carbon black;
s4, putting the solid carbon black of the step S3 into a nickel-containing plating solution for mixing, filtering and drying to obtain the modified carbon black.
7. The high-dispersity antistatic agent for plastic alloys according to claim 6, wherein before the step S1, the carbon black and the nitric acid are mixed and modified to obtain a mixture, and the mixture and the 4,4' -biphenyldicarboxylic acid are placed into a rheometer to be blended.
8. The high-dispersity antistatic agent for plastic alloy as claimed in claim 1, wherein the white carbon black is modified white carbon black, and the modified white carbon black is prepared from 3.6-4.0: 1 by weight of silane coupling agent and white carbon black.
9. The highly dispersible antistatic agent for plastic alloys according to claim 8, characterized in that: the preparation method of the modified white carbon black comprises the following steps:
a1, adding a silane coupling agent and white carbon black into toluene, and stirring while refluxing under the protection of nitrogen to obtain a solution C;
a2, curing the solution C at a high temperature of 111-120 ℃, then adding an organic solvent for repeated extraction to obtain an extract D, and filtering and drying the extract D to obtain the modified white carbon black.
10. The method for preparing the high-dispersity antistatic agent for the plastic alloy as claimed in any one of claims 1 to 9, wherein the method comprises the following steps:
b1, mixing and stirring the amphoteric antistatic agent and the modified carbon black, and uniformly stirring to obtain a premix;
and B2, adding the white carbon black and the dispersing agent into the premixed solution, and uniformly stirring to obtain the antistatic agent.
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