CN118085436B - Conductive carbon black master batch and preparation method thereof - Google Patents
Conductive carbon black master batch and preparation method thereof Download PDFInfo
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- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 34
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000006229 carbon black Substances 0.000 claims abstract description 87
- 150000001721 carbon Chemical class 0.000 claims abstract description 45
- 239000002131 composite material Substances 0.000 claims abstract description 34
- 239000002216 antistatic agent Substances 0.000 claims abstract description 33
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 14
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 6
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 6
- 239000000314 lubricant Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 56
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 30
- 239000002135 nanosheet Substances 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 20
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 20
- -1 allyl dimethyl malonate Chemical compound 0.000 claims description 19
- 239000005457 ice water Substances 0.000 claims description 16
- 238000002390 rotary evaporation Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000013067 intermediate product Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 229920000877 Melamine resin Polymers 0.000 claims description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 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
- 238000000034 method Methods 0.000 claims description 8
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000002064 nanoplatelet Substances 0.000 claims 2
- 229920003023 plastic Polymers 0.000 abstract description 17
- 239000004033 plastic Substances 0.000 abstract description 17
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003063 flame retardant Substances 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 239000004698 Polyethylene Substances 0.000 description 13
- 229920000573 polyethylene Polymers 0.000 description 13
- 239000011159 matrix material Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 7
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000011231 conductive filler Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000002055 nanoplate Substances 0.000 description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000001263 acyl chlorides Chemical group 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010096 film blowing Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- 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
- C08K3/10—Metal compounds
- C08K3/14—Carbides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- 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
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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
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- 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
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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Abstract
The invention relates to the technical field of carbon black master batches and discloses a conductive carbon black master batch and a preparation method thereof. The carbon black master batch comprises the following raw materials in parts by weight: 50-70 parts of low-density polyethylene resin, 15-25 parts of modified carbon black composite material, 5-10 parts of hyperbranched antistatic agent, 0.5-3 parts of lubricant and 1-2 parts of antioxidant; the modified carbon black composite material is prepared by taking low-density polyethylene resin as a base material and adding various auxiliary agents, wherein the modified carbon black composite material takes carbon black as a base material, and is subjected to oxidation and grafting modification, so that the conductivity of the composite material is improved, and the antistatic performance and the flame retardant performance of a plastic product prepared from a master batch are improved; the hyperbranched antistatic agent and the modified carbon black composite material act synergistically to further improve the antistatic property of the master batch. Therefore, the plastic product obtained by using the master batch prepared by the invention has excellent antistatic performance and flame retardant performance.
Description
Technical Field
The invention relates to the technical field of carbon black master batches, in particular to a conductive carbon black master batch and a preparation method thereof.
Background
The polyethylene resin material has excellent mechanical property, chemical stability, processability and higher cost performance, and is widely applied to the synthesis of plastic products. Most plastics are good insulators, however, and the surface is prone to static electricity during use, especially in dry environments. The generation of static electricity often has negative effects, such as uncomfortable feeling caused by simple human body contact, and easy damage to electronic components, ignition explosion of inflammable substances and the like. The surface resistivity of the plastic required to prevent static accumulation ranges from 10 6～1010 ohms, the lower the sheet resistance, the higher the antistatic level.
The antistatic mode of the traditional plastic is to spray antistatic liquid on the surface of the plastic or add antistatic agent (such as conductive filler or micromolecular antistatic agent) when producing plastic master batch, the antistatic plastic prepared by adopting the surface spraying mode does not have long-term antistatic effect, and the antistatic plastic prepared by adopting the conductive filler can realize long-term antistatic effect. The common conductive fillers include carbon black, graphene and the like, and compared with the conductive carbon black, the conductive carbon black is adopted as the filler, but the dispersibility of the carbon black in resin is poor, and meanwhile, the existence of a large number of hydroxyl groups on the surface of the carbon black reduces the conductivity of the carbon black, so that the antistatic performance of the carbon black in plastics is reduced. Therefore, it is required to improve the dispersibility and conductivity of the carbon black by modification, and an antistatic agent and a conductive filler may be added to exert a synergistic effect, thereby improving the antistatic performance of the plastic product.
Disclosure of Invention
In order to solve the technical problems, the invention provides a conductive carbon black master batch and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
The conductive carbon black master batch comprises the following raw materials in parts by weight: 50-70 parts of low-density polyethylene resin, 15-25 parts of modified carbon black composite material, 5-10 parts of hyperbranched antistatic agent, 0.5-3 parts of lubricant and 1-2 parts of antioxidant 1010;
The modified carbon black composite material is prepared by the following steps:
Step A1, adding carbon black into a reactor containing 65wt% of nitric acid, stirring and mixing uniformly, raising the temperature of the system to 60-80 ℃, stirring and reacting for 10-20h, cooling, filtering, washing to be neutral after the reaction is finished, and vacuum drying at 70 ℃ for 12h to obtain pretreated carbon black;
Further, the ratio of carbon black to nitric acid is 1-3g:6-10mL.
Step A2, dispersing the pretreated carbon black in deionized water, stirring and mixing uniformly, adding melamine and dicyclohexylcarbodiimide, raising the temperature of the system to 100-120 ℃, reacting for 5-6 hours, washing, filtering, and drying at room temperature to obtain the grafted modified carbon black;
Further, the dosage ratio of the pretreated carbon black, deionized water, melamine and dicyclohexylcarbodiimide is 0.2-0.6g:200mL:0.7-2.4g:0.75-2.5g.
Step A3, dispersing the MXene nano-sheets in deionized water, performing ultrasonic dispersion for 3-6 hours, centrifuging, drying, adding the mixture into a flask containing toluene, adding thionyl chloride and triethylamine, stirring for 30min under an ice water bath, heating the system to 100-120 ℃, continuing to react for 30-60min, and performing rotary evaporation at 80 ℃ for 30-60min after the reaction is finished to obtain modified MXene nano-sheets;
further, the dosage ratio of the MXene nano-sheet to the deionized water to the thionyl chloride to the triethylamine to the toluene is 5-10g:100mL:1.25-2.5g:2-4mL:300mL.
Step A4, adding the grafted modified carbon black into a flask containing N, N-dimethylacetamide, stirring and mixing uniformly, reducing the temperature of a system to 0 ℃, adding triethylamine and stirring for 10-15min, slowly adding the modified MXene nano-sheet in a continuous stirring process, then raising the temperature of the system to 45-65 ℃, maintaining the temperature for reaction for 4h, and washing, suction filtering and drying after the reaction is finished to obtain a modified carbon black composite material;
Further, the dosage ratio of the grafted modified carbon black, the N, N-dimethylacetamide, the triethylamine and the modified MXene nano-sheets is 0.5-1.5g:100mL:10-20mL:0.3-0.9g.
The hyperbranched antistatic agent is prepared by the following steps:
Adding 2.71-5.42g of ethylenediamine and 100mL of methanol into a reactor, stirring and mixing uniformly under the conditions of ice-water bath and nitrogen, slowly dripping 38.52-77.04g of allyl dimethyl malonate by using a constant pressure dropping funnel, raising the temperature of the system to 30-40 ℃, continuously reacting for 24 hours, performing rotary evaporation to obtain an intermediate product, then re-dispersing the intermediate product into 100mL of methanol, adding 21.68-43.36g of ethanolamine, stirring and mixing uniformly under the conditions of ice-water bath and nitrogen, raising the temperature of the system to room temperature, continuously reacting for 24 hours, and performing rotary evaporation to obtain a hydroxyl-terminated hyperbranched precursor;
and B2, adding 3-5g of hydroxyl-terminated hyperbranched precursor into a reactor, dropwise adding 8-12g of phosphoric acid under the condition of stirring, after the dropwise adding is finished, raising the temperature of the system to 90-110 ℃, reacting for 5-7h under the condition of nitrogen, and obtaining the hyperbranched antistatic agent after the reaction is finished.
The preparation method of the conductive carbon black master batch comprises the following steps:
Weighing raw materials according to parts by weight, adding the low-density polyethylene resin, the modified carbon black composite material, the hyperbranched antistatic agent, the lubricant and the antioxidant into a stirrer, stirring and uniformly mixing at the speed of 200-300rpm, then putting the mixed materials into a screw extruder, and performing melt extrusion, cooling, granulating and drying to obtain the conductive carbon black master batch.
The invention has the beneficial effects that:
The carbon black master batch is prepared by taking low-density polyethylene resin as a base material and adding various auxiliary agents, wherein the modified carbon black composite material is prepared by taking carbon black as a base material and carrying out oxidation and grafting modification on the carbon black, so that the conductivity of the composite material is improved, and the antistatic performance and the flame retardant performance of a plastic product prepared by using the master batch are further improved; the hyperbranched antistatic agent and the modified carbon black composite material act synergistically to further improve the antistatic property of the master batch. Therefore, the plastic product obtained by using the master batch prepared by the invention has excellent antistatic performance and flame retardant performance.
The hyperbranched antistatic agent is prepared by taking ethylenediamine and allyl dimethyl malonate as raw materials, synthesizing an intermediate product, reacting amino in ethanolamine with ester groups in the intermediate product to generate a hydroxyl-terminated hyperbranched precursor, and reacting hydroxyl in the hydroxyl-terminated hyperbranched precursor with phosphoric acid to generate the hyperbranched antistatic agent containing a phosphate group structure. The hyperbranched antistatic agent is added into the matrix, can play a role in cooperation with the conductive modified carbon black composite material, and improves the antistatic performance of the matrix; the unique hyperbranched structure can improve the compatibility of the antistatic agent in the matrix, so that the antistatic agent has higher antistatic activity in the matrix; the phosphate group at the tail end can adsorb water molecules in the air, and a layer of water film is formed on the surface of the plastic product, so that the conductivity of the surface of the plastic product is improved, the antistatic performance of a matrix is further improved, and meanwhile, the phosphate group also has certain flame retardant performance, and the flame retardance of the plastic product can be improved.
In the modified carbon black composite material, firstly, nitric acid is adopted to oxidize carbon black to ensure that the surface of the carbon black has a large number of carboxyl groups, so as to generate pretreatment carbon black; secondly, utilizing carboxyl groups on the surface of the pretreated carbon black to react with amino groups in melamine to generate grafted modified carbon black; thirdly, synthesizing an improved MXene nano-sheet with acyl chloride groups on the surface by utilizing the reaction between carboxyl and hydroxyl contained on the surfaces of the thionyl chloride and MXene nano-sheet; and finally, compounding the grafted modified carbon black and the modified MXene nano-sheet by taking melamine as an intermediate to generate the modified carbon black composite material. The carbon black is used as a conductive substrate in the composite material, and is grafted on the surface of the MXene nano sheet to act cooperatively with the MXene nano sheet, so that the conductive performance of the matrix is improved, and the antistatic capability of the matrix is further improved, wherein after the carbon black is subjected to nitric acid oxidation treatment and melamine grafting modification, the dispersibility of the carbon black in the matrix is improved, and the conductive performance of the carbon black is further improved, and the reduction of the conductive performance caused by the damage of a carbon layer conjugated structure due to the existence of hydroxyl is avoided due to the reduction of the hydroxyl content existing on the surface of the modified carbon black; after the MXene nano-sheets are modified by thionyl chloride, the existence of acyl chloride groups on the surfaces of the MXene nano-sheets improves the dispersibility of the MXene nano-sheets, and meanwhile, the MXene nano-sheets have a graphene-like structure, so that the MXene nano-sheets have excellent conductivity; in addition, the composite material takes melamine as an intermediate, carbon black and MXene nano sheets are grafted together to form a three-dimensional structure, the three-dimensional structure is difficult to migrate in a matrix, the conductivity of the matrix is further improved, and the contained triazine group also has a certain flame-retardant effect.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
1) The modified carbon black composite material is prepared by the following steps:
Step A1, adding 1g of carbon black into a reactor containing 6mL of 65wt% nitric acid, stirring and mixing uniformly, raising the system temperature to 60 ℃, stirring and reacting for 10 hours, cooling, filtering, washing to neutrality after the reaction is finished, and vacuum drying at 70 ℃ for 12 hours to obtain pretreated carbon black;
Step A2, dispersing 0.2g of pretreatment carbon black in 200mL of deionized water, stirring and mixing uniformly, adding 0.7g of melamine and 0.75g of dicyclohexylcarbodiimide, raising the temperature of the system to 100 ℃, reacting for 5 hours, washing, filtering, and drying at room temperature to obtain grafted modified carbon black;
step A3, adding 5g of MXene nano-sheets, 1.25g of thionyl chloride and 2mL of triethylamine into a flask containing 300mL of toluene, stirring for 30min under ice-water bath, heating the system to 100 ℃, continuing to react for 30min, and performing rotary evaporation at 80 ℃ for 30min after the reaction is finished to obtain modified MXene nano-sheets;
Step A3, dispersing 5g of MXene nano-sheets in 100mL of deionized water, performing ultrasonic dispersion for 3h, centrifuging, drying, adding into a flask containing 300mL of toluene, adding 1.25g of thionyl chloride and 2mL of triethylamine, stirring for 30min in ice water bath, heating the system to 100 ℃, continuing to react for 30min, and performing rotary evaporation at 80 ℃ for 30min after the reaction is finished to obtain modified MXene nano-sheets;
And A4, adding 0.5g of grafted modified carbon black into a flask containing 100mLN and N-dimethylacetamide, stirring and mixing uniformly, reducing the temperature of the system to 0 ℃, adding 10mL of triethylamine and stirring for 10min, slowly adding 0.3g of modified MXene nano-plate in the continuous stirring process, then raising the temperature of the system to 45 ℃, maintaining the temperature for reaction for 4h, and washing, suction filtering and drying after the reaction is finished to obtain the modified carbon black composite material.
2) The hyperbranched antistatic agent is prepared by the following steps:
Step B1, adding 2.71g of ethylenediamine and 100mL of methanol into a reactor, stirring and mixing uniformly under the conditions of ice-water bath and nitrogen, slowly dripping 38.52g of allyl dimethyl malonate by using a constant-pressure dropping funnel, raising the temperature of the system to 30 ℃, continuously reacting for 24 hours, performing rotary evaporation to obtain an intermediate product, then redispersing the intermediate product in 100mL of methanol, adding 21.68g of ethanolamine, stirring and mixing uniformly under the conditions of ice-water bath and nitrogen, raising the temperature of the system to room temperature, continuously reacting for 24 hours, and performing rotary evaporation to obtain a hydroxyl-terminated hyperbranched precursor;
and B2, adding 3g of hydroxyl-terminated hyperbranched precursor into a reactor, dropwise adding 8g of phosphoric acid under the condition of stirring, after the dropwise adding is finished, raising the temperature of the system to 90 ℃, reacting for 5 hours under the condition of nitrogen, and obtaining the hyperbranched antistatic agent after the reaction is finished.
Example 2
1) The modified carbon black composite material is prepared by the following steps:
step A1, adding 2g of carbon black into a reactor containing 8mL of 65wt% nitric acid, stirring and mixing uniformly, raising the system temperature to 70 ℃, stirring and reacting for 15h, cooling, filtering, washing to neutrality after the reaction is finished, and vacuum drying at 70 ℃ for 12h to obtain pretreated carbon black;
Step A2, dispersing 0.4g of pretreatment carbon black in 200mL of deionized water, uniformly stirring and mixing, adding 1.4g of melamine and 1.5g of dicyclohexylcarbodiimide, raising the temperature of the system to 110 ℃, reacting for 5.5h, washing, suction filtering, and drying at room temperature to obtain grafted modified carbon black;
step A3, dispersing 7.5g of MXene nano-sheets in 100mL of deionized water, performing ultrasonic dispersion for 4.5h, centrifuging, drying, adding into a flask containing 300mL of toluene, adding 1.8g of thionyl chloride and 3mL of triethylamine, stirring for 30min under ice water bath, heating the system to 110 ℃, continuing to react for 45min, and performing rotary evaporation at 80 ℃ for 45min after the reaction is finished to obtain modified MXene nano-sheets;
And A4, adding 1g of grafted modified carbon black into a flask containing 100mLN and N-dimethylacetamide, stirring and mixing uniformly, reducing the temperature of the system to 0 ℃, adding 15mL of triethylamine and stirring for 10min, slowly adding 0.6g of modified MXene nano-plate in the continuous stirring process, then raising the temperature of the system to 55 ℃, maintaining the temperature and reacting for 4h, and washing, suction filtering and drying after the reaction is finished to obtain the modified carbon black composite material.
2) The hyperbranched antistatic agent is prepared by the following steps:
Adding 4.06g of ethylenediamine and 100mL of methanol into a reactor, stirring and mixing uniformly under the conditions of ice-water bath and nitrogen, slowly dripping 57.78g of allyl dimethyl malonate by using a constant pressure dropping funnel, raising the temperature of the system to 35 ℃, continuously reacting for 24 hours, performing rotary evaporation to obtain an intermediate product, then redispersing the intermediate product in 100mL of methanol, adding 32.52g of ethanolamine, stirring and mixing uniformly under the conditions of ice-water bath and nitrogen, raising the temperature of the system to room temperature, continuously reacting for 24 hours, and performing rotary evaporation to obtain a hydroxyl-terminated hyperbranched precursor;
And B2, adding 4g of hydroxyl-terminated hyperbranched precursor into a reactor, dropwise adding 10g of phosphoric acid under the condition of stirring, after the dropwise adding is finished, raising the temperature of the system to 100 ℃, reacting under the condition of nitrogen for 6, and after the reaction is finished, obtaining the hyperbranched antistatic agent.
Example 3
1) The modified carbon black composite material is prepared by the following steps:
step A1, adding 3g of carbon black into a reactor containing 10mL of 65wt% nitric acid, stirring and mixing uniformly, raising the temperature of the system to 80 ℃, stirring and reacting for 20 hours, cooling, filtering, washing to neutrality after the reaction is finished, and vacuum drying at 70 ℃ for 12 hours to obtain pretreated carbon black;
Step A2, dispersing 0.6g of pretreatment carbon black in 200mL of deionized water, uniformly stirring and mixing, adding 2.4g of melamine and 2.5g of dicyclohexylcarbodiimide, raising the temperature of the system to 120 ℃, reacting for 6 hours, washing, filtering, and drying at room temperature to obtain grafted modified carbon black;
Step A3, dispersing 10g of MXene nano-sheets in 100mL of deionized water, performing ultrasonic dispersion for 6h, centrifuging, drying, adding into a flask containing 300mL of toluene, adding 2.5g of thionyl chloride and 4mL of triethylamine, stirring for 30min in an ice water bath, heating the system to 120 ℃, continuing to react for 60min, and performing rotary evaporation at 80 ℃ for 60min after the reaction is finished to obtain modified MXene nano-sheets;
And A4, adding 5g of grafted modified carbon black into a flask containing 100mLN and N-dimethylacetamide, stirring and mixing uniformly, reducing the temperature of the system to 0 ℃, adding 20mL of triethylamine and stirring for 15min, slowly adding 0.9g of modified MXene nano-plate in the continuous stirring process, then raising the temperature of the system to 65 ℃, maintaining the temperature for reaction for 4h, and washing, suction filtering and drying after the reaction is finished to obtain the modified carbon black composite material.
2) The hyperbranched antistatic agent is prepared by the following steps:
Step B1, adding 5.42g of ethylenediamine and 100mL of methanol into a reactor, stirring and mixing uniformly under the conditions of ice-water bath and nitrogen, slowly dripping 77.04g of allyl dimethyl malonate by using a constant-pressure dropping funnel, raising the temperature of the system to 40 ℃, continuously reacting for 24 hours, performing rotary evaporation to obtain an intermediate product, then redispersing the intermediate product in 100mL of methanol, adding 43.36g of ethanolamine, stirring and mixing uniformly under the conditions of ice-water bath and nitrogen, raising the temperature of the system to room temperature, continuously reacting for 24 hours, and performing rotary evaporation to obtain a hydroxyl-terminated hyperbranched precursor;
and B2, adding 5g of hydroxyl-terminated hyperbranched precursor into a reactor, dropwise adding 12g of phosphoric acid under the condition of stirring, after the dropwise adding is finished, raising the temperature of the system to 110 ℃, reacting for 7h under the condition of nitrogen, and obtaining the hyperbranched antistatic agent after the reaction is finished.
Example 4
The preparation method of the conductive carbon black master batch comprises the following steps:
50 parts of low-density polyethylene resin, 15 parts of modified carbon black composite material prepared in example 1, 5 parts of hyperbranched antistatic agent prepared in example 1, 0.5 part of polyethylene wax and 1010 parts of antioxidant;
Weighing raw materials according to parts by weight, adding the low-density polyethylene resin, the modified carbon black composite material prepared in the example 1, the hyperbranched antistatic agent prepared in the example 1, the polyethylene wax and the antioxidant 1010 into a stirrer, stirring and mixing uniformly at a speed of 200rpm, and then putting the mixed materials into a screw extruder, and carrying out melt extrusion, cooling, granulating and drying to obtain the conductive carbon black master batch.
Example 5
The preparation method of the conductive carbon black master batch comprises the following steps:
60 parts of low-density polyethylene resin, 20 parts of modified carbon black composite material prepared in example 2, 8 parts of hyperbranched antistatic agent prepared in example 2, 1.5 parts of polyethylene wax and 1.5 parts of antioxidant 1010;
Weighing raw materials according to parts by weight, adding the low-density polyethylene resin, the modified carbon black composite material prepared in the example 2, the hyperbranched antistatic agent prepared in the example 2, the polyethylene wax and the antioxidant 1010 into a stirrer, stirring and mixing uniformly at the speed of 250rpm, and then putting the mixed materials into a screw extruder, and carrying out melt extrusion, cooling, granulating and drying to obtain the conductive carbon black master batch.
Example 6
The preparation method of the conductive carbon black master batch comprises the following steps:
70 parts of low-density polyethylene resin, 25 parts of modified carbon black composite material prepared in example 3, 10 parts of hyperbranched antistatic agent prepared in example 3, 3 parts of polyethylene wax and 1010 2 parts of antioxidant;
Weighing raw materials according to parts by weight, adding the low-density polyethylene resin, the modified carbon black composite material prepared in the example 3, the hyperbranched antistatic agent prepared in the example 3, the polyethylene wax and the antioxidant 1010 into a stirrer, stirring and mixing uniformly at the speed of 300rpm, and then adding the mixed materials into a screw extruder, and carrying out melt extrusion, cooling, granulating and drying to obtain the conductive carbon black master batch.
Comparative example 1
This comparative example is a conductive masterbatch, and differs from example 6 in that the modified carbon black composite prepared in example 3 is replaced with an equal amount of carbon black, the remainder being the same.
Comparative example 2
This comparative example is a conductive masterbatch, which differs from example 6 in that the hyperbranched antistatic agent prepared in example 3 is replaced by an equal amount of antistatic agent B-2, the remainder being identical.
Performance test: 9.7kg of LDPE with the model number of 2426K is taken, 0.3kg of the conductive master batch prepared in examples 4-6 and comparative examples 1-2 is added, the mixture is uniformly mixed and then put into a film blowing machine, a polyethylene film with the thickness of 50 mu m is obtained by blowing through a conventional process, the polyethylene film is sequentially recorded as a sample 1-5, and the obtained polyethylene film is subjected to performance test according to the following method:
surface resistivity: according to GB/T1410-2006 test method of volume resistivity and surface resistivity of solid insulating material, the surface resistivity of the polyethylene film is tested in 7 days, 30 days, 90 days and 180 days respectively; the ambient temperature is 25 ℃ and the relative humidity is 65%;
Flame retardancy test: the test was performed according to the UL94 VTM film vertical burn test. The test results are shown in the following table:
after the conductive master batch prepared by the invention is formed into a polyethylene film by blow molding, flame retardance and surface resistivity tests are carried out on the polyethylene film, and the polyethylene film has excellent flame retardance and antistatic property as can be seen from the table.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar alternatives may be made by those skilled in the art, without departing from the scope of the invention as defined by the principles of the invention.
Claims (6)
1. The conductive carbon black master batch is characterized by comprising the following raw materials in parts by weight: 50-70 parts of low-density polyethylene resin, 15-25 parts of modified carbon black composite material, 5-10 parts of hyperbranched antistatic agent, 0.5-3 parts of lubricant and 1-2 parts of antioxidant;
The modified carbon black composite material is prepared by the following steps:
Step A1, adding carbon black into a reactor containing 65wt% of nitric acid, stirring and mixing uniformly, raising the temperature of the system to 60-80 ℃, stirring and reacting for 10-20h, cooling, filtering, washing to be neutral after the reaction is finished, and vacuum drying at 70 ℃ for 12h to obtain pretreated carbon black;
step A2, dispersing the pretreated carbon black in deionized water, stirring and mixing uniformly, adding melamine and dicyclohexylcarbodiimide, raising the temperature of the system to 100-120 ℃, reacting for 5-6 hours, washing, filtering, and drying at room temperature to obtain the grafted modified carbon black;
Step A3, dispersing the MXene nano-sheets in deionized water, performing ultrasonic dispersion for 3-6 hours, centrifuging, drying, adding the mixture into a flask containing toluene, adding thionyl chloride and triethylamine, stirring for 30min under an ice water bath, heating the system to 100-120 ℃, continuing to react for 30-60min, and performing rotary evaporation at 80 ℃ for 30-60min after the reaction is finished to obtain modified MXene nano-sheets;
Step A4, adding the grafted modified carbon black into a flask containing N, N-dimethylacetamide, stirring and mixing uniformly, reducing the temperature of a system to 0 ℃, adding triethylamine and stirring for 10-15min, slowly adding the modified MXene nano-sheet in a continuous stirring process, then raising the temperature of the system to 45-65 ℃, maintaining the temperature for reaction for 4h, and washing, suction filtering and drying after the reaction is finished to obtain a modified carbon black composite material;
The hyperbranched antistatic agent is prepared by the following steps:
Adding 2.71-5.42g of ethylenediamine and 100mL of methanol into a reactor, stirring and mixing uniformly under the conditions of ice-water bath and nitrogen, slowly dripping 38.52-77.04g of allyl dimethyl malonate by using a constant pressure dropping funnel, raising the temperature of the system to 30-40 ℃, continuously reacting for 24 hours, performing rotary evaporation to obtain an intermediate product, then re-dispersing the intermediate product into 100mL of methanol, adding 21.68-43.36g of ethanolamine, stirring and mixing uniformly under the conditions of ice-water bath and nitrogen, raising the temperature of the system to room temperature, continuously reacting for 24 hours, and performing rotary evaporation to obtain a hydroxyl-terminated hyperbranched precursor;
and B2, adding 3-5g of hydroxyl-terminated hyperbranched precursor into a reactor, dropwise adding 8-12g of phosphoric acid under the condition of stirring, after the dropwise adding is finished, raising the temperature of the system to 90-110 ℃, reacting for 5-7h under the condition of nitrogen, and obtaining the hyperbranched antistatic agent after the reaction is finished.
2. A conductive carbon black masterbatch according to claim 1 wherein the ratio of carbon black to nitric acid used in step A1 is 1-3g:6-10mL.
3. A conductive carbon black masterbatch according to claim 1 characterized in that the ratio of pre-treated carbon black, deionized water, melamine and dicyclohexylcarbodiimide in step A2 is 0.2-0.6g:200mL:0.7-2.4g:0.75-2.5g.
4. The conductive carbon black masterbatch according to claim 1, wherein the amount ratio of MXene nanoplatelets, deionized water, thionyl chloride, triethylamine and toluene in step A3 is 5-10g:100mL:1.25-2.5g:2-4mL:300mL.
5. The conductive carbon black masterbatch according to claim 1, characterized in that the amount ratio of grafted modified carbon black, N-dimethylacetamide, triethylamine, modified MXene nanoplatelets in step A4 is 0.5-1.5g:100mL:10-20mL:0.3-0.9g.
6. The method for preparing a conductive carbon black masterbatch according to claim 1, characterized by comprising the steps of:
Weighing raw materials according to parts by weight, adding the low-density polyethylene resin, the modified carbon black composite material, the hyperbranched antistatic agent, the lubricant and the antioxidant into a stirrer, stirring and uniformly mixing at the speed of 200-300rpm, then putting the mixed materials into a screw extruder, and performing melt extrusion, cooling, granulating and drying to obtain the conductive carbon black master batch.
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