CN115612192A - Bio-based antistatic agent master batch and preparation method thereof - Google Patents
Bio-based antistatic agent master batch and preparation method thereof Download PDFInfo
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- CN115612192A CN115612192A CN202211269505.9A CN202211269505A CN115612192A CN 115612192 A CN115612192 A CN 115612192A CN 202211269505 A CN202211269505 A CN 202211269505A CN 115612192 A CN115612192 A CN 115612192A
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- 239000002216 antistatic agent Substances 0.000 title claims abstract description 52
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 84
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000002028 Biomass Substances 0.000 claims abstract description 63
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 41
- 239000011347 resin Substances 0.000 claims abstract description 35
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 34
- 239000002699 waste material Substances 0.000 claims abstract description 30
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 26
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims abstract description 21
- 235000017491 Bambusa tulda Nutrition 0.000 claims abstract description 21
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims abstract description 21
- 239000011425 bamboo Substances 0.000 claims abstract description 21
- 239000000835 fiber Substances 0.000 claims abstract description 21
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 15
- 235000007164 Oryza sativa Nutrition 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 235000009566 rice Nutrition 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 240000007594 Oryza sativa Species 0.000 claims abstract 2
- 241001330002 Bambuseae Species 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000010335 hydrothermal treatment Methods 0.000 claims description 4
- ORAWFNKFUWGRJG-UHFFFAOYSA-N Docosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCC(N)=O ORAWFNKFUWGRJG-UHFFFAOYSA-N 0.000 claims description 3
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 3
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 3
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 3
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 3
- OXDXXMDEEFOVHR-CLFAGFIQSA-N (z)-n-[2-[[(z)-octadec-9-enoyl]amino]ethyl]octadec-9-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)NCCNC(=O)CCCCCCC\C=C/CCCCCCCC OXDXXMDEEFOVHR-CLFAGFIQSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011863 silicon-based powder Substances 0.000 claims description 2
- 230000003068 static effect Effects 0.000 abstract description 3
- 244000082204 Phyllostachys viridis Species 0.000 abstract 1
- 241000209094 Oryza Species 0.000 description 11
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000012748 slip agent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- 241000237502 Ostreidae Species 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 235000020636 oyster Nutrition 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- -1 alkyl phosphate Chemical compound 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000000035 biogenic effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- SWSBIGKFUOXRNJ-CVBJKYQLSA-N ethene;(z)-octadec-9-enamide Chemical group C=C.CCCCCCCC\C=C/CCCCCCCC(N)=O.CCCCCCCC\C=C/CCCCCCCC(N)=O SWSBIGKFUOXRNJ-CVBJKYQLSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 1
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
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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
- 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
-
- 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
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
-
- 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
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08K9/10—Encapsulated ingredients
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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)
Abstract
The invention relates to a bio-based antistatic agent master batch which comprises the following raw materials in parts by weight: 45-60 parts of carrier resin, 25-45 parts of maleic anhydride grafted resin, 25-40 parts of biomass antistatic agent and 1-5 parts of slipping agent. The biomass antistatic agent is formed by blending and coating biological calcium carbonate, biological silicon dioxide, biomass carbon points and a silane coupling agent. The maleic anhydride grafted resin, the biological calcium carbonate, the biological silicon dioxide and the biomass carbon dots are grafted to form a strong conductive network, so that the volume resistivity and the surface resistivity of the master batch are reduced, charge leakage is promoted, and the purpose of static resistance is achieved; according to the invention, the waste shells, the waste bamboo fibers and the rice hull ash are fully utilized to prepare the biomass antistatic agent, so that the antistatic performance of the master batch is improved, and the reutilization of waste resources is realized to the greatest extent.
Description
Technical Field
The invention relates to the technical field of plastic master batches, in particular to a bio-based antistatic agent master batch and a preparation method thereof.
Background
The electrostatic hazard is mainly caused by electrostatic adsorption and electrostatic discharge phenomena. The damage caused by static electricity is common in production and life, and the static electricity generated in the plastic film can adsorb dust and bacteria in the air, so that the film is polluted and the performance is reduced. During the production and processing of thin films, electrostatic discharge may cause electrical failure, and in severe cases, catastrophic damage such as explosion or fire may occur.
Calcium carbonate plays a role in filling and reinforcing plastics, for example, CN103709627a, and calcium carbonate is used as inorganic filler particles, so that the cost is reduced, the heat resistance and processability of plastics are improved, the optical performance is improved, the effects on toughening of impact strength of plastics and the viscous flow property in a mixing process are obvious, and the tensile strength, bending strength, heat distortion temperature, hysteresis heat property and dimensional stability of plastics are improved. The organic matter in the biomass calcium carbonate is rich in carboxyl groups, (see New Material Perspective for water series by value function) but the use of calcium carbonate, especially biological calcium carbonate, as an antistatic agent is not seen, because the calcium carbonate itself does not have conductivity. Conventional antistatic agents are typically stearamide, alkyl phosphate diethanolammonium salt, glycerol monostearate, octylphenol polyoxyethylene ether, hydroxyethylalkylamine, and the like.
The silicon dioxide structure contains more silicon hydroxyl groups, so that the surface of the silicon dioxide structure shows stronger hydrophilic property, and the silicon hydroxyl groups are easily combined with water molecules in the environment, so that the surface of the silicon dioxide absorbs and is combined with more water molecules and polar substances. At present, the main function of the silicon dioxide is not as an antistatic agent, and the silicon dioxide is not conductive, but is used as an additive of master batches to improve the opening property and the adhesion resistance of the master batches.
In addition, the annual output of the national waste oyster shells is more than 1 million tons, but no effective treatment mode exists at present, and the waste oyster shells accumulate like a mountain on the wharf shore, so that serious environmental pollution is caused. The rice hull as a byproduct of the rice processing accounts for about 20% of the rice quality, the annual output is basically kept at 4000 ten thousand tons, and the rice hull as an agricultural waste causes great pressure on the environment. Therefore, the preparation and development of the bio-based antistatic master batch by using wastes such as biological calcium carbonate, rice husk and the like is of great significance to green industrial production.
Disclosure of Invention
In view of the defects of the prior art, the technical problem to be solved by the invention is to provide a bio-based antistatic master batch and a preparation method thereof, wherein waste shells, waste bamboo fibers and rice hull ash are used as raw material sources to prepare the green and environment-friendly antistatic master batch.
In order to achieve the purpose, the invention adopts the technical scheme that:
a bio-based antistatic agent master batch comprises the following raw materials in parts by weight: 45-60 parts of carrier resin, 25-45 parts of maleic anhydride grafted resin, 25-40 parts of biomass antistatic agent and 1-5 parts of slipping agent.
Further, the carrier resin is one of PE, PP, PET and NY.
Further, the maleic anhydride grafted resin is one of maleic anhydride grafted PE and maleic anhydride grafted PP.
Further, the slipping agent is one or more of erucamide, oleamide, behenamide, ethylene bis-oleamide, ethylene bis-stearamide and organic silicon powder.
Further, the biomass antistatic agent is formed by blending and coating biological calcium carbonate, biological silicon dioxide, a biomass carbon point and a silane coupling agent, wherein the mass ratio of the biological calcium carbonate to the biological silicon dioxide to the biomass carbon point is 10: 1-4.
Further, the silane coupling agent is KH560.
Further, the preparation method of the biomass antistatic agent comprises the following steps:
(1) Cleaning and drying shells, and then crushing and grinding the shells to obtain 2000-5000 meshes of biological calcium carbonate;
(2) Putting the rice hull ash into a calcining furnace, calcining for 3-8 h at 950-1200 ℃, and grinding to obtain 2000-5000 mesh biological silicon dioxide;
(3) Cleaning, drying and crushing waste bamboo fibers, mixing the waste bamboo fibers with ethanol, placing the mixture in a reaction kettle for hydrothermal treatment for 9-18 hours at the hydrothermal temperature of 160-230 ℃, and filtering, centrifuging and drying the mixture after the reaction is finished to obtain biomass carbon dots;
(4) And (2) carrying out microwave grinding on the biological calcium carbonate, the biological silicon dioxide and the biomass carbon dots according to the mass ratio of 10: 1-4, wherein the microwave power is 600W-1000W, the blending speed is 1200 rpm-1500 rpm, and then adding the silane coupling agent for microwave blending and coating for 3 min-5 min to obtain the biomass antistatic agent.
Furthermore, the mass ratio of the waste bamboo fibers to the ethanol is 1.
Further, the dosage of the silane coupling agent is 0.5-2% of the total mass of the biological calcium carbonate, the biological silicon dioxide and the biomass carbon dots.
The invention also provides a preparation method of the biomass antistatic agent master batch, which is characterized by comprising the following steps of: weighing 20-40 parts of biomass antistatic agent and 25-45 parts of maleic anhydride grafted resin by weight, adding into an internal mixer, and banburying at 120-200 ℃ for 5-10 min; then adding 45-60 parts of carrier resin and 1-5 parts of slipping agent, banburying at 120-200 ℃ for 10-20 min; and extruding by using a double-screw extruder after banburying, and granulating after cooling.
Compared with the prior art, the invention has the following beneficial effects:
the biological calcium carbonate has excellent conductivity which is 5-10 times that of common calcium carbonate, the conductivity can reach 1700us/cm, the surface area is larger, the porosity is higher, and meanwhile, the organic matter contains carboxyl, so that the biological calcium carbonate is more beneficial to realizing conductivity and finishing graft modification; and the cost is low, the material source is wide, and the mildew resistance is better than that of the common calcium carbonate.
The maleic anhydride grafted resin can perform a grafting reaction with amino and hydroxyl in the biomass carbon points, the maleic anhydride grafted resin performs an esterification grafting reaction with hydroxyl in the biological silicon dioxide, and the biomass carbon points and the hydroxyl on the biological silicon dioxide and carboxyl in the biological calcium carbonate perform an esterification grafting reaction.
According to the invention, the biomass antistatic agent is prepared by fully utilizing the waste shells, the waste bamboo fibers and the rice hull ash, so that the antistatic property of the master batch is improved, and the reutilization of waste resources is realized to the greatest extent. Meanwhile, the carbon dots in the biomass antistatic agent also have the functions of antibiosis, anti-counterfeiting, ultraviolet shielding and the like, and the carbon dots are prepared from wastes, so that more possibilities are provided for high-value utilization of the plastic master batch.
Detailed Description
Example 1
The embodiment provides a bio-based antistatic agent master batch, which is characterized by comprising the following raw materials in parts by weight: 50 parts of carrier resin, 30 parts of maleic anhydride grafted resin, 25 parts of biomass antistatic agent and 1 part of slipping agent.
The preparation method of the biomass antistatic agent master batch comprises the following steps: weighing the biomass antistatic agent and the maleic anhydride grafted resin according to the weight, adding the mixture into an internal mixer, carrying out internal mixing at 165 ℃ for 5min and carrying out 50rpm; then adding carrier resin and slipping agent, banburying at 180 deg.C for 10min, and rotating at 50rpm; and extruding by using a double-screw extruder after banburying, and granulating after cooling.
In this embodiment, the carrier resin is PE, the maleic anhydride grafted resin is maleic anhydride grafted PE, and the slip agent is erucamide and oleamide mixed in equal proportion.
In the embodiment, the biomass antistatic agent is formed by blending and coating biological calcium carbonate, biological silica, biomass carbon dots and a silane coupling agent KH560, wherein the mass ratio of the biological calcium carbonate to the biological silica to the biomass carbon dots is 10: 1. The manufacturing method comprises the following steps: (1) Cleaning and drying shells, and then crushing and grinding the shells to obtain 2000-mesh biological calcium carbonate; (2) Putting the rice hull ash into a muffle furnace, setting the temperature at 1200 ℃, calcining for 4h, and grinding to obtain 2000-mesh biological silicon dioxide; (3) Cleaning, drying and crushing waste bamboo fibers, mixing the waste bamboo fibers with ethanol, placing the waste bamboo fibers and the ethanol in a mass ratio of 1:3 in a reaction kettle for hydrothermal for 9 hours at a hydrothermal temperature of 220 ℃, and filtering, centrifuging and drying the waste bamboo fibers after the reaction is finished to obtain biomass carbon dots; (4) And (2) carrying out microwave grinding on the biological calcium carbonate, the biological silicon dioxide and the biomass carbon dots according to the mass ratio, wherein the microwave power is 800W, the blending speed is 1500rpm, and then adding a silane coupling agent accounting for 1% of the total mass of the biological calcium carbonate, the biological silicon dioxide and the biomass carbon dots for microwave blending and coating for 5min to obtain the biomass antistatic agent.
Example 2
The embodiment provides a bio-based antistatic agent master batch, which is characterized by comprising the following raw materials in parts by weight: 55 parts of carrier resin, 40 parts of maleic anhydride grafted resin, 30 parts of biomass antistatic agent and 2.5 parts of slipping agent.
The preparation method of the biomass antistatic agent master batch comprises the following steps: weighing the biomass antistatic agent and the maleic anhydride grafted resin according to the weight, adding the mixture into an internal mixer, and internally mixing the mixture for 10min at the temperature of 145 ℃ at the rotating speed of 60rpm; then adding carrier resin and slipping agent, banburying at 200 deg.C for 15min, at 40rpm; and extruding by using a double-screw extruder after banburying, and granulating after cooling.
In this embodiment, the carrier resin is PP, the maleic anhydride grafted resin is maleic anhydride grafted PP, and the slip agent is ethylene bis-oleic acid amide.
In the embodiment, the biomass antistatic agent is formed by blending and coating biological calcium carbonate, biological silica, a biomass carbon point and a silane coupling agent KH560, wherein the mass ratio of the biological calcium carbonate to the biological silica to the biomass carbon point is 10: 2: 3. The manufacturing method comprises the following steps: (1) Cleaning and drying shells, and then crushing and grinding the shells to obtain 3000-mesh biological calcium carbonate; (2) Putting the rice hull ash into a muffle furnace, setting the temperature at 1000 ℃, calcining for 8 hours, and grinding to obtain 3000-mesh biological silicon dioxide; (3) Cleaning, drying and crushing waste bamboo fibers, mixing the waste bamboo fibers with ethanol, placing the waste bamboo fibers and ethanol in a mass ratio of 1:5 in a reaction kettle, performing hydrothermal treatment for 12 hours at the hydrothermal temperature of 200 ℃, and filtering, centrifuging and drying the waste bamboo fibers after the reaction is finished to obtain biomass carbon dots; (4) And (2) carrying out microwave grinding on the biological calcium carbonate, the biological silicon dioxide and the biomass carbon dots according to the mass ratio, wherein the microwave power is 800W, the blending speed is 1500rpm, and then adding a silane coupling agent accounting for 1% of the total mass of the biological calcium carbonate, the biological silicon dioxide and the biomass carbon dots for microwave blending and coating for 4min to obtain the biomass antistatic agent.
Example 3
The embodiment provides a bio-based antistatic agent master batch, which is characterized by comprising the following raw materials in parts by weight: 60 parts of carrier resin, 45 parts of maleic anhydride grafted resin, 40 parts of biomass antistatic agent and 3 parts of slipping agent.
The preparation method of the biomass antistatic agent master batch comprises the following steps: weighing the biomass antistatic agent and the maleic anhydride grafted resin according to the weight, adding the mixture into an internal mixer, carrying out internal mixing at 180 ℃ for 5min, and carrying out the rotation speed of 80rpm; then adding carrier resin and slipping agent, banburying at 165 deg.C for 20min, at 50rpm; and extruding by using a double-screw extruder after banburying, and granulating after cooling.
In this embodiment, the carrier resin is PE, the maleic anhydride grafted resin is maleic anhydride grafted PE, and the slip agent is behenamide.
In the embodiment, the biomass antistatic agent is formed by blending and coating biological calcium carbonate, biological silica, a biomass carbon point and a silane coupling agent KH560, wherein the mass ratio of the biological calcium carbonate to the biological silica to the biomass carbon point is 10: 1: 2. The manufacturing method comprises the following steps: (1) Cleaning and drying shells, and then crushing and grinding the shells to obtain 2500-mesh biological calcium carbonate; (2) Placing the rice hull ash into a muffle furnace, setting the temperature to be 1100 ℃, calcining for 5 hours, and grinding to obtain 2500-mesh biological silicon dioxide; (3) Cleaning, drying and crushing waste bamboo fibers, mixing the waste bamboo fibers with ethanol, placing the waste bamboo fibers and ethanol in a mass ratio of 1:4 in a reaction kettle, performing hydrothermal treatment for 18 hours at the hydrothermal temperature of 210 ℃, and filtering, centrifuging and drying the waste bamboo fibers after the reaction is finished to obtain biomass carbon dots; (4) And (2) carrying out microwave grinding on the biological calcium carbonate, the biological silicon dioxide and the biomass carbon dots according to the mass ratio, wherein the microwave power is 1000W, the blending speed is 1200rpm, and then adding a silane coupling agent accounting for 1% of the total mass of the biological calcium carbonate, the biological silicon dioxide and the biomass carbon dots for microwave blending and coating for 5min to obtain the biomass antistatic agent.
Comparative example 1
Except that the biological calcium carbonate in example 1 was replaced with the same parts by mass of ordinary calcium carbonate as in example 1.
Comparative example 2
Except for replacing the biogenic silica in example 1 with the same parts by mass of ordinary silica as in example 1.
Comparative example 3
Except that the biomass carbon dots in example 1 were replaced with the same parts by mass of conductive carbon black as in example 1.
The volume resistivity of each of the antistatic masterbatches prepared in examples 1 to 3 and comparative examples 1 to 3 was measured according to the test method of IEC60093, and the results are shown in table 1.
Table 1: volume resistivity of the antistatic master batches of examples 1 to 3 of the invention and comparative examples 1 to 3
While there have been shown and described what are at present considered the fundamental principles and essential features of the invention and its advantages, it will be understood by those skilled in the art that the invention is not limited by the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.
Claims (10)
1. The bio-based antistatic agent master batch is characterized by comprising the following raw materials in parts by weight: 45-60 parts of carrier resin, 25-45 parts of maleic anhydride grafted resin, 25-40 parts of biomass antistatic agent and 1-5 parts of slipping agent.
2. The bio-based antistatic agent masterbatch according to claim 1, characterized in that: the carrier resin is one of PE, PP, PET and NY.
3. The bio-based antistatic agent masterbatch according to claim 1, characterized in that: the maleic anhydride grafted resin is one of maleic anhydride grafted PE and maleic anhydride grafted PP.
4. The bio-based antistatic agent masterbatch according to claim 1, characterized in that: the slipping agent is one or more of erucamide, oleamide, behenamide, ethylene bisoleamide, ethylene bisstearamide and organic silicon powder.
5. The bio-based antistatic agent masterbatch according to claim 1, characterized in that: the biomass antistatic agent is formed by blending and coating biological calcium carbonate, biological silicon dioxide, biomass carbon points and a silane coupling agent, wherein the mass ratio of the biological calcium carbonate to the biological silicon dioxide to the biomass carbon points is 10: 1-4.
6. The bio-based antistatic agent masterbatch according to claim 5, characterized in that: the silane coupling agent is KH560.
7. The bio-based antistatic agent masterbatch according to claim 5, wherein: the preparation method of the biomass antistatic agent comprises the following steps:
(1) Cleaning and drying shells, and then crushing and grinding the shells to obtain 2000-5000 meshes of biological calcium carbonate;
(2) Putting the rice hull ash into a calcining furnace, calcining for 3-8 h at 950-1200 ℃, and grinding to obtain 2000-5000 mesh biological silicon dioxide;
(3) Cleaning, drying and crushing waste bamboo fibers, mixing the waste bamboo fibers with ethanol, placing the mixture in a reaction kettle for hydrothermal treatment for 9-18 hours at the hydrothermal temperature of 160-230 ℃, and filtering, centrifuging and drying the mixture after the reaction is finished to obtain biomass carbon dots;
(4) And (2) carrying out microwave grinding on the biological calcium carbonate, the biological silicon dioxide and the biomass carbon dots according to the mass ratio of 10: 1-4, wherein the microwave power is 600W-1000W, the blending speed is 1200 rpm-1500 rpm, and then adding the silane coupling agent for microwave blending and coating for 3 min-5 min to obtain the biomass antistatic agent.
8. The bio-based antistatic agent masterbatch according to claim 7, characterized in that: the mass ratio of the waste bamboo fibers to the ethanol is 1.5-5.
9. The bio-based antistatic agent masterbatch according to claim 7, characterized in that: the dosage of the silane coupling agent is 0.5-2% of the total mass of the biological calcium carbonate, the biological silicon dioxide and the biomass carbon dots.
10. The preparation method of the biomass antistatic agent masterbatch according to any one of claims 1 to 9, characterized by comprising the following steps: weighing 20-40 parts of biomass antistatic agent and 25-45 parts of maleic anhydride grafted resin by weight, adding into an internal mixer, and mixing for 5-10 min at 120-200 ℃; then adding 45-60 parts of carrier resin and 1-5 parts of slipping agent, banburying at 120-200 ℃ for 10-20 min; and (3) extruding by using a double-screw extruder after banburying, and granulating after cooling.
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| CN120737494A (en) * | 2025-07-25 | 2025-10-03 | 长沙赫发新材料有限公司 | Smooth antistatic composite master batch and preparation method thereof |
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| Title |
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| 《化工百科全书》编辑委员会: "《化工百科全书（第9卷）》", vol. 1, 广西师范大学出版社, pages: 683 * |
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| CN120737494A (en) * | 2025-07-25 | 2025-10-03 | 长沙赫发新材料有限公司 | Smooth antistatic composite master batch and preparation method thereof |
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