CN115975424B - Conductive filler and preparation method and application thereof - Google Patents
Conductive filler and preparation method and application thereof Download PDFInfo
- Publication number
- CN115975424B CN115975424B CN202211594774.2A CN202211594774A CN115975424B CN 115975424 B CN115975424 B CN 115975424B CN 202211594774 A CN202211594774 A CN 202211594774A CN 115975424 B CN115975424 B CN 115975424B
- Authority
- CN
- China
- Prior art keywords
- conductive filler
- stirring
- graphene oxide
- agent
- deionized water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011231 conductive filler Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 49
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000000576 coating method Methods 0.000 claims abstract description 41
- 239000011248 coating agent Substances 0.000 claims abstract description 40
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- 238000003756 stirring Methods 0.000 claims description 50
- 239000008367 deionised water Substances 0.000 claims description 35
- 229910021641 deionized water Inorganic materials 0.000 claims description 35
- 238000005406 washing Methods 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 239000007822 coupling agent Substances 0.000 claims description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 238000005303 weighing Methods 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 230000007935 neutral effect Effects 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 239000012286 potassium permanganate Substances 0.000 claims description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 239000004925 Acrylic resin Substances 0.000 claims description 8
- 229920000178 Acrylic resin Polymers 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 8
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 7
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- WYPBVHPKMJYUEO-NBTZWHCOSA-M sodium;(9z,12z)-octadeca-9,12-dienoate Chemical compound [Na+].CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O WYPBVHPKMJYUEO-NBTZWHCOSA-M 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000002518 antifoaming agent Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 3
- 230000007797 corrosion Effects 0.000 abstract description 15
- 238000005260 corrosion Methods 0.000 abstract description 15
- 239000000945 filler Substances 0.000 abstract description 5
- 239000003973 paint Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000725 suspension Substances 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 6
- 238000009825 accumulation Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000002216 antistatic agent Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000013530 defoamer Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000006866 deterioration 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
- 239000003792 electrolyte Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- -1 uniformly mixing Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The invention belongs to the technical field of paint, and particularly relates to a conductive filler, and a preparation method and application thereof. The preparation method of the conductive filler comprises the following steps: s1, preparing graphene oxide; s2, preparing reduced graphene oxide; s3, preparing functionalized silica; s4, preparing modified graphene; s5, preparing conductive filler. The conductive filler prepared by the invention can effectively overcome the problems of poor weather resistance, corrosion resistance and conductivity of the existing filler after being added into the coating, and realizes good weather resistance, corrosion resistance and conductivity.
Description
Technical Field
The invention belongs to the technical field of paint, and particularly relates to a conductive filler, and a preparation method and application thereof.
Background
The antistatic coating can prevent static accumulation on the surface of a substance and prevent dust collection, electric shock and other phenomena caused by the static accumulation by utilizing the electrostatic discharge effect. The common conductive filler comprises metal powder, carbon-based filler, antistatic agent and the like, and the conductive filler is added, so that a charge channel is formed on the surface of the paint on the premise of keeping most of original physical characteristics, and the paint can discharge static electricity accumulation in a short time, thereby achieving the purpose of antistatic. However, these fillers cause deterioration of weather resistance and corrosion resistance of the coating, and affect stability of antistatic properties after long-term use, eventually rendering the antistatic coating ineffective. Thus, research has received considerable attention in preparing conductive fillers that have less impact on other properties of the coating.
The existing antistatic coating has the problem of poor weather resistance, and the surface coating can be chalked and shed due to frequent exposure to air, so that the antistatic performance of the coating can be reduced, the charge accumulation on the surface of equipment is caused, and the normal operation of the equipment is endangered due to the consequences of dirt accumulation, static electricity and the like. Meanwhile, most of conductive fillers in the market have poor dispersibility, which can seriously affect physical and chemical properties such as adhesive force of the coating. Therefore, in order to solve the problem of insufficient stability of the existing antistatic coating, development of an antistatic coating with good weather resistance, corrosion resistance and dispersibility is a problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a conductive filler, and a preparation method and application thereof. The conductive filler prepared by the invention can effectively overcome the problems of poor weather resistance, corrosion resistance and conductivity of the existing filler after being added into the coating, and realizes good weather resistance, corrosion resistance and conductivity.
In order to achieve the above purpose, the present invention adopts the following technical scheme: a method for preparing a conductive filler, comprising the steps of:
s1, preparing graphene oxide: weighing potassium permanganate, adding the potassium permanganate into mixed acid, uniformly mixing, adding graphite powder, stirring, carrying out heat preservation reaction, washing reactants to be neutral after the reaction is completed, adding water and hydrogen peroxide, uniformly stirring, standing, washing precipitates, and drying to obtain graphene oxide;
s2, preparing reduced graphene oxide: weighing graphene oxide prepared in the step S1, adding the graphene oxide into water, performing ultrasonic treatment, adjusting the pH, then adding a reducing agent, stirring for reaction, and washing reactants to be neutral to prepare reduced graphene oxide;
s3, preparation of functionalized silica: mixing a coupling agent and absolute ethyl alcohol under stirring, regulating the pH value, slowly adding deionized water, stirring uniformly, adding silicon dioxide into the mixture, stirring, washing and drying to obtain functionalized silicon dioxide;
s4, preparing modified graphene: dispersing the functionalized silica prepared in the step S3 in absolute ethyl alcohol to prepare a suspension, adding a reduced graphene oxide solution, stirring, centrifuging the mixed solution, washing to be neutral, and drying to obtain modified graphene;
and S5, weighing the modified graphene prepared in the step S4, adding deionized water, performing ultrasonic treatment to form a uniform sol system, adding an auxiliary agent, mixing, and grinding to prepare the conductive filler.
Preferably, the preparation method of the conductive filler at least comprises one of the following (1) to (8):
(1) In the step S1, the mass ratio of the potassium permanganate to the mixed acid is 1: (10-15);
(2) In the step S1, the mixed acid is a mixed solution of concentrated sulfuric acid and phosphoric acid, wherein the volume ratio of the concentrated sulfuric acid to the phosphoric acid is 9:1, a step of;
(3) In the step S1, the mass ratio of the graphite powder to the potassium permanganate is 1:1, a step of;
(4) The stirring condition in the step S1 is stirring for 30-60 min in ice water bath;
(5) The heat preservation reaction condition in the step S1 is that the heat preservation reaction is carried out for 12 to 15 hours at the temperature of 50 to 60 ℃;
(6) In the step S1, the reactant is washed, and the solvent for washing is deionized water;
(7) The volume ratio of the added water to the hydrogen peroxide in the step S1 is 59:1, a step of;
(8) And the temperature of the drying in the step S1 is 60-80 ℃ and the time is 10-15 h.
Preferably, the preparation method of the conductive filler at least comprises one of the following (1) to (6):
(1) The ratio of graphene oxide to water in step S2 is 1mg:1ml;
(2) The ultrasonic time in the step S2 is 2-5 h;
(3) In the step S2, the pH is adjusted to 9-10 by using a sodium carbonate aqueous solution with the concentration of 5%;
(4) In the step S2, the reducing agent is sodium borohydride, and the mass ratio of the reducing agent to the graphene oxide is (75-90): 1, a step of;
(5) The stirring reaction condition in the step S2 is that stirring reaction is carried out for 1-3 h at 85-95 ℃;
(6) The solvent used to wash the reactants to neutrality in step S2 is deionized water.
Preferably, the preparation method of the conductive filler at least comprises one of the following (1) to (9):
(1) The mass ratio of the coupling agent to the absolute ethyl alcohol in the step S3 is 1: (70-75);
(2) The coupling agent in step S3 comprises 3-aminopropyl triethoxysilane;
(3) The stirring and mixing time in the step S3 is 40-60 min;
(4) In the step S3, the pH is adjusted to 9-10 by using ammonia water;
(5) In the step S3, the weight ratio of the deionized water to the coupling agent is 8:1, a step of;
(6) The weight ratio of the silicon dioxide to the coupling agent in the step S3 is (2-3): 1, a step of;
(7) The stirring time in the step S3 is 1-2 h;
(8) The washing condition in the step S3 is that distilled water and absolute ethyl alcohol are used as solvents to be washed for 4 to 6 times respectively;
(9) The drying condition in the step S3 is that the drying is carried out for 24-36 hours at 50-60 ℃.
Preferably, the preparation method of the conductive filler at least comprises one of the following (1) to (6):
(1) The ratio of the functionalized silica to the absolute ethyl alcohol in the step S4 is (0.5-1) g:500ml;
(2) The solvent of the reduced graphene oxide solution in the step S4 is water, and the concentration of the reduced graphene oxide solution is 1mg/ml;
(3) The volume ratio of the reduced graphene oxide solution to the absolute ethanol in the step S4 is 1: (4-6);
(4) The stirring time in the step S4 is 1-3 h;
(5) The solvent washed to be neutral in the step S4 is deionized water;
(6) The drying time in the step S4 is 24-48 hours.
Preferably, the preparation method of the conductive filler at least comprises one of the following (1) to (5):
(1) In the step S5, the mass ratio of the modified graphene to deionized water is 1:100;
(2) The ultrasonic time in the step S5 is 20-40 min;
(3) In the step S5, the mass ratio of the modified graphene to the auxiliary agent is (2-3): 1, a step of;
(4) In the step S5, the auxiliary agent is a mixture of sodium linoleate and dioctyl phthalate; the mass ratio of the sodium linoleate to the dioctyl phthalate is 1:1;
(5) The grinding speed in the step S5 is 500-600 r/min, and the grinding time is 10-15 h.
After the functionalized silica is introduced into the coating, the resistivity of the coating is obviously reduced. With the help of the silane coupling agent, a unique core-shell structure is formed, the permeation of electrolyte is effectively prevented, and better conductivity is obtained. Sodium linoleate and dioctyl phthalate are adopted, and the dispersibility of graphene is improved through covalent interaction. And then, combining the mixture with an acrylic resin matrix through a hydrogen bond between carboxyl and ester groups to obtain the modified graphene with good dispersibility, weather resistance and corrosion resistance.
The conductive filler is prepared by the preparation method of the conductive filler.
An antistatic coating comprises the following components in parts by weight:
5 to 10 parts of conductive filler, 100 to 500 parts of acrylic resin, 0.5 to 1 part of defoamer, 0.1 to 0.5 part of dispersant, 0.1 to 0.5 part of flatting agent and 10 to 15 parts of curing agent.
Preferably, the antistatic coating comprises at least one of the following (1) to (4):
(1) The defoamer comprises a foam breaking polymer and a hydrophobic solid mixture;
(2) The dispersant comprises a high molecular weight block copolymer comprising pigment affinic groups;
(3) The leveling agent comprises fluorine modified polyacrylate copolymer;
(4) The curing agent comprises a trimer.
The preparation method of the antistatic coating comprises the following steps:
mixing the conductive filler with acrylic resin, respectively adding a defoaming agent, a dispersing agent and a leveling agent into the mixture, performing ultrasonic dispersion for 30-60 min, adding a curing agent, uniformly mixing, and curing for 30-60 min to obtain the antistatic coating.
The conductive filler is applied to the antistatic field of non-insulating part surfaces (such as direct current flexible direct current converter station hardware fittings, metal outer walls and the like).
Compared with the prior art, the invention has the following beneficial effects:
when the conductive filler prepared by the interaction modification of the components is used as the antistatic agent to be added into the coating, the coating has excellent conductive performance, weather resistance and corrosion resistance
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, 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.
In the examples and comparative examples, the experimental methods used were conventional methods, and the materials, reagents and the like used were commercially available, unless otherwise specified.
The acrylic resin, defoamer, dispersant, leveling agent, and curing agent used in the examples and comparative examples of the present invention are shown in table 1 with the brands and manufacturer information.
TABLE 1
Example 1
S1, weighing 10g of potassium permanganate, adding the potassium permanganate into a three-neck flask filled with 100mL of concentrated sulfuric acid and phosphoric acid (the volume ratio of the concentrated sulfuric acid to the phosphoric acid is 9:1), uniformly mixing, adding 10g of graphite powder into the three-neck flask, stirring in an ice-water bath for 30min, then carrying out thermal insulation reaction for 12h at 50 ℃, washing reactants for multiple times by deionized water to neutrality, adding 295mL of deionized water after washing is finished, adding 5mL of hydrogen peroxide into the three-neck flask, uniformly stirring, standing, washing a precipitate by deionized water, and drying for 12h at 60 ℃ to obtain graphene oxide;
s2, weighing 500mg of graphene oxide, adding the graphene oxide into 500mL of deionized water, carrying out ultrasonic treatment for 2 hours, adding 5% sodium carbonate aqueous solution into the colloid solution, adjusting the pH to 9, then adding 40g of sodium borohydride into the colloid solution, placing the mixture into a water bath at 90 ℃ for stirring reaction for 1 hour, and then washing the graphene with deionized water to be neutral to obtain reduced graphene oxide.
S3, weighing 2g of coupling agent KH-550 (3-aminopropyl triethoxysilane) and 144g of absolute ethyl alcohol, placing the coupling agent KH-550 (3-aminopropyl triethoxysilane) and 144g of absolute ethyl alcohol in a three-necked flask, stirring and mixing for 45min, regulating the pH to 10 by using ammonia water, slowly adding 16g of deionized water into the coupling agent KH-550 (3-aminopropyl triethoxysilane), stirring uniformly, adding 5g of silicon dioxide into the mixture, stirring for 1.5h, finally washing for 6 times by using distilled water and absolute ethyl alcohol respectively, and drying in a 55 ℃ oven for 24h to obtain functionalized silicon dioxide;
s4, dispersing 0.7g of functionalized silica in 500mL of absolute ethyl alcohol to prepare a suspension, adding 109.2mL of reduced graphene oxide solution (1 mg/mL) into the suspension, stirring for 1h, centrifuging and washing the mixed solution to be neutral, and drying for 24h to obtain modified graphene;
s5, weighing 500mg of modified graphene, adding 50mL of deionized water into the modified graphene, performing ultrasonic treatment for 20min to form a uniform sol system, adding 250mg of an auxiliary agent (the mass ratio of sodium linoleate to dioctyl phthalate is 1:1), mixing, adding the mixture into a planetary ball mill, and grinding for 12h at the speed of 600r/min to obtain the conductive filler.
A preparation method of an antistatic coating comprises the following steps:
mixing 5 parts of the prepared conductive filler with 100 parts of acrylic resin, respectively adding 0.5 part of defoaming agent, 0.3 part of dispersing agent, 0.3 part of leveling agent, and ultrasonic dispersing for 30min, adding 10 parts of curing agent, uniformly mixing, curing for 30min, coating on the surface of a substrate, and drying for 24h to obtain the antistatic coating.
Example 2
S1, weighing 10g of potassium permanganate, adding the potassium permanganate into a three-neck flask filled with 120mL of concentrated sulfuric acid and phosphoric acid (the volume ratio of the concentrated sulfuric acid to the phosphoric acid is 9:1), uniformly mixing, adding 10g of graphite powder into the three-neck flask, stirring in an ice-water bath for 40min, then carrying out thermal insulation reaction for 13h at 55 ℃, repeatedly cleaning reactants by deionized water, washing to be neutral, adding 295mL of deionized water after cleaning is finished, adding 5mL of hydrogen peroxide into the three-neck flask, uniformly stirring, standing, cleaning a precipitate by deionized water, and drying for 15h at 70 ℃ to obtain graphene oxide;
s2, weighing 500mg of graphene oxide, adding the graphene oxide into 500mL of deionized water, carrying out ultrasonic treatment for 3 hours, adding 5% sodium carbonate aqueous solution into the colloid solution, adjusting the pH to 9, then adding 37.5g of sodium borohydride into the colloid solution, placing the mixture into a water bath kettle at 85 ℃ for stirring reaction for 3 hours, and then washing the graphene to be neutral by using the deionized water to obtain reduced graphene oxide;
s3, weighing 2g of coupling agent KH-550 (3-aminopropyl triethoxysilane) and 140g of absolute ethyl alcohol, placing the coupling agent KH-550 (3-aminopropyl triethoxysilane) and 140g of absolute ethyl alcohol in a three-necked flask, stirring and mixing for 40min, regulating the pH to 10 by using ammonia water, slowly adding 16g of deionized water into the coupling agent KH-550 (3-aminopropyl triethoxysilane), stirring uniformly, adding 4g of silicon dioxide into the mixture, stirring for 1h, finally washing for 4 times by using distilled water and absolute ethyl alcohol respectively, and drying in a 50 ℃ oven for 36h to obtain functionalized silicon dioxide;
s4, dispersing 0.5g of functionalized silica in 500mL of absolute ethyl alcohol to prepare a suspension, adding 109.5mL of reduced graphene oxide solution (1 mg/mL) into the suspension, stirring for 1h, centrifuging and washing the mixed solution to be neutral, and drying for 24h to obtain modified graphene;
s5, weighing 500mg of modified graphene, adding 50mL of deionized water into the modified graphene, performing ultrasonic treatment for 30min to form a uniform sol system, adding 167mg of auxiliary agent (the mass ratio of sodium linoleate to dioctyl phthalate is 1:1), mixing, adding into a planetary ball mill, and grinding for 12h at the speed of 500r/min to obtain the conductive filler.
The preparation method of the antistatic coating comprises the following steps:
the conductive filler prepared in example 2 was used instead of the conductive filler of example 1, and other preparation methods were referred to in example 1.
Example 3
S1, weighing 10g of potassium permanganate, adding the potassium permanganate into a three-neck flask filled with 150mL of concentrated sulfuric acid and phosphoric acid (the volume ratio of the concentrated sulfuric acid to the phosphoric acid is 9:1), uniformly mixing, adding 10g of graphite powder into the three-neck flask, stirring in an ice-water bath for 60min, then carrying out thermal insulation reaction for 15h at 60 ℃, repeatedly cleaning reactants by deionized water, washing to be neutral, adding 295mL of deionized water after cleaning is finished, adding 5mL of hydrogen peroxide into the three-neck flask, uniformly stirring, standing, cleaning a precipitate by deionized water, and drying for 10h at 80 ℃ to obtain graphene oxide;
s2, weighing 500mg of graphene oxide, adding the graphene oxide into 500mL of deionized water, carrying out ultrasonic treatment for 5 hours, adding 5% sodium carbonate aqueous solution into the colloid solution, adjusting the pH to 10, then adding 45g of sodium borohydride into the colloid solution, placing the mixture into a water bath at the temperature of 95 ℃ for stirring reaction for 2 hours, and then washing the graphene with deionized water to be neutral to obtain reduced graphene oxide.
S3, weighing 2g of coupling agent KH-550 (3-aminopropyl triethoxysilane) and 150g of absolute ethyl alcohol, placing the coupling agent KH-550 (3-aminopropyl triethoxysilane) and 150g of absolute ethyl alcohol in a three-necked flask, stirring and mixing for 60min, regulating the pH to 9 by using ammonia water, slowly adding 16g of deionized water into the coupling agent KH-550, stirring uniformly, adding 6g of silicon dioxide into the mixture, stirring for 2h, finally washing for 6 times by using distilled water and absolute ethyl alcohol respectively, and drying in an oven at 60 ℃ for 24h to obtain functionalized silicon dioxide;
s4, dispersing 1.0g of functionalized silica in 500mL of absolute ethyl alcohol to prepare a suspension, adding 109mL of reduced graphene oxide solution (1 mg/mL) into the suspension, stirring for 1h, centrifuging the mixed solution, washing to be neutral, and drying for 48h to obtain modified graphene;
s5, weighing 500mg of modified graphene, adding 50mL of deionized water into the modified graphene, performing ultrasonic treatment for 40min to form a uniform sol system, adding 250mg of an auxiliary agent (the mass ratio of sodium linoleate to dioctyl phthalate is 1:1), mixing, adding the mixture into a planetary ball mill, and grinding for 12h at the speed of 600r/min to obtain the conductive filler.
The preparation method of the antistatic coating comprises the following steps:
the conductive filler prepared in example 3 was used instead of the conductive filler of example 1, and other preparation methods were referred to in example 1.
Comparative example 1
The comparative example differs from example 1 only in that the graphene was not subjected to the modification treatment.
The preparation method of the antistatic coating comprises the following steps:
mixing 5 parts of graphene with 100 parts of acrylic resin, adding 0.5 part of defoaming agent, 0.3 part of dispersing agent and 0.3 part of leveling agent into the mixture, performing ultrasonic dispersion for 30min, adding 10 parts of curing agent, uniformly mixing, coating the mixture on the surface of a substrate, and drying for 24h to obtain the antistatic coating.
Comparative example 2
The difference of this comparative example compared to example 1 is only that step S3 and step S4 are absent in the preparation of the conductive filler.
The preparation method is described in example 1.
Comparative example 3
The difference of this comparative example compared to example 1 is only that step S5 is absent in the preparation of the conductive filler.
The preparation method is described in example 1.
Test example one, performance test
The conductive fillers and antistatic coatings prepared in examples 1 to 3 and comparative examples 1 to 3 were subjected to performance tests, and the test results are shown in table 2.
The testing method comprises the following steps:
testing corrosion resistance of the coating: soaking the coating in 5% sodium chloride solution for 1000h, 3000h and 5000h, and observing the surface condition of the coating;
conductive filler dispersion performance test: removing 20 parts of each group of conductive fillers, mixing with 100 parts of acrylic acid and 100 parts of solvent, stirring and mixing, standing and observing transparency;
conducting performance test: the surface resistance of the coating was measured according to standard ASTM F105-98, 1X 10 5 ～1×10 9 And omega is qualified.
TABLE 2
As can be seen from the data in Table 2, the conductive filler prepared by the invention has better dispersion performance and conductivity, and meanwhile, the conductive filler can be added as an antistatic agent to prepare a coating to realize excellent corrosion resistance and weather resistance, so that the problems of poor weather resistance, corrosion resistance and conductivity existing after the conventional filler is added into the coating are effectively solved.
In comparative example 1, graphene which is not subjected to modification treatment is directly selected as a conductive filler, the prepared antistatic coating has poor corrosion resistance and weather resistance, foaming, rust and other phenomena occur after the antistatic coating is soaked in 5% sodium chloride solution for 1000 hours, and the conductive filler has poor dispersion property and conductivity; the conductive filler in comparative example 2 lacks steps S3 and S4 in the preparation process, and the prepared conductive filler has inferior corrosion resistance and weather resistance in the coating layer compared with the examples; in the preparation process of the conductive filler in comparative example 3, step S5 is absent, the prepared conductive filler has poorer corrosion resistance and weather resistance than those of the embodiment, the dispersibility of the conductive filler is poorer, a slight agglomeration phenomenon occurs, and the conductive property cannot meet the standard requirement. Therefore, the graphene is modified through a specific process, the finally prepared conductive filler can achieve excellent dispersion performance, and meanwhile, the conductive filler can be added as an antistatic agent to prepare a coating with better corrosion resistance, weather resistance and conductivity.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (10)
1. A method for preparing a conductive filler, comprising the steps of:
s1, preparing graphene oxide: weighing potassium permanganate, adding the potassium permanganate into mixed acid, uniformly mixing, adding graphite powder, stirring, carrying out heat preservation reaction, washing reactants after the reaction is completed, adding water and hydrogen peroxide, uniformly stirring, standing, washing and drying precipitate, and thus obtaining graphene oxide;
s2, preparing reduced graphene oxide: weighing graphene oxide prepared in the step S1, adding the graphene oxide into water, performing ultrasonic treatment, adjusting pH, adding a reducing agent, stirring for reaction, and washing reactants to be neutral to prepare reduced graphene oxide;
s3, preparation of functionalized silica: mixing a coupling agent and absolute ethyl alcohol under stirring, adjusting the pH, adding deionized water, uniformly stirring, adding silicon dioxide, stirring, washing and drying to obtain functional silicon dioxide;
s4, preparing modified graphene: dispersing the functionalized silica prepared in the step S3 in absolute ethyl alcohol, adding a reduced graphene oxide solution, stirring, centrifuging, washing to be neutral, and drying to obtain modified graphene;
s5, weighing the modified graphene prepared in the step S4, adding deionized water, performing ultrasonic treatment, adding an auxiliary agent, mixing, and grinding to prepare a conductive filler;
the ratio of the functionalized silica to the absolute ethyl alcohol in the step S4 is (0.5-1) g:500ml;
the solvent of the reduced graphene oxide solution in the step S4 is water, and the concentration of the reduced graphene oxide solution is 1mg/ml;
the volume ratio of the reduced graphene oxide solution to the absolute ethanol in the step S4 is 1: (4-6);
in the step S5, the mass ratio of the modified graphene to the auxiliary agent is (2-3): 1, a step of;
the auxiliary agent in the step S5 is a mixture of sodium linoleate and dioctyl phthalate.
2. The method for producing the conductive filler according to claim 1, comprising at least one of the following (1) to (8):
(1) In the step S1, the mass ratio of the potassium permanganate to the mixed acid is 1: (10-15);
(2) The mixed acid in the step S1 is a mixed solution of concentrated sulfuric acid and phosphoric acid;
(3) In the step S1, the mass ratio of the graphite powder to the potassium permanganate is 1:1, a step of;
(4) The stirring condition in the step S1 is stirring for 30-60 min in ice water bath;
(5) The heat preservation reaction condition in the step S1 is that the heat preservation reaction is carried out for 12 to 15 hours at the temperature of 50 to 60 ℃;
(6) In the step S1, the reactant is washed, and the solvent for washing is deionized water;
(7) The volume ratio of the added water to the hydrogen peroxide in the step S1 is 59:1, a step of;
(8) And the temperature of the drying in the step S1 is 60-80 ℃ and the time is 10-15 h.
3. The method for producing the conductive filler according to claim 1, comprising at least one of the following (1) to (6):
(1) The ratio of graphene oxide to water in step S2 is 1mg:1ml;
(2) The ultrasonic time in the step S2 is 2-5 h;
(3) In the step S2, the pH is adjusted to 9-10 by using a sodium carbonate aqueous solution with the concentration of 5%;
(4) In the step S2, the reducing agent is sodium borohydride, and the mass ratio of the reducing agent to the graphene oxide is (75-90): 1, a step of;
(5) The stirring reaction condition in the step S2 is that stirring reaction is carried out for 1-3 h at 85-95 ℃;
(6) The solvent used to wash the reactants to neutrality in step S2 is deionized water.
4. The method for producing the conductive filler according to claim 1, comprising at least one of the following (1) to (9):
(1) The mass ratio of the coupling agent to the absolute ethyl alcohol in the step S3 is 1: (70-75);
(2) The coupling agent in step S3 comprises 3-aminopropyl triethoxysilane;
(3) The stirring and mixing time in the step S3 is 40-60 min;
(4) In the step S3, the pH is adjusted to 9-10 by using ammonia water;
(5) In the step S3, the weight ratio of the deionized water to the coupling agent is 8:1, a step of;
(6) The weight ratio of the silicon dioxide to the coupling agent in the step S3 is (2-3): 1, a step of;
(7) The stirring time in the step S3 is 1-2 h;
(8) The washing condition in the step S3 is that distilled water and absolute ethyl alcohol are used as solvents to be washed for 4 to 6 times respectively;
(9) The drying condition in the step S3 is that the drying is carried out for 24-36 hours at 50-60 ℃.
5. The method of producing a conductive filler according to claim 1, comprising at least one of the following (1) to (3):
(1) The stirring time in the step S4 is 1-3 h;
(2) The solvent washed to be neutral in the step S4 is deionized water;
(3) The drying time in the step S4 is 24-48 hours.
6. The method of producing a conductive filler according to claim 1, comprising at least one of the following (1) to (3):
(1) In the step S5, the mass ratio of the modified graphene to deionized water is 1:100;
(2) The ultrasonic time in the step S5 is 20-40 min;
(3) The grinding speed in the step S5 is 500-600 r/min, and the grinding time is 10-15 h.
7. A conductive filler prepared by the method for preparing a conductive filler according to any one of claims 1 to 6.
8. The antistatic coating is characterized by comprising the following components in parts by weight:
the conductive filler according to claim 7, wherein the conductive filler comprises 5 to 10 parts of an acrylic resin, 100 to 500 parts of an antifoaming agent, 0.5 to 1 part of a dispersant, 0.1 to 0.5 part of a leveling agent, and 10 to 15 parts of a curing agent.
9. A method of preparing the antistatic coating according to claim 8, comprising the steps of:
mixing the conductive filler according to claim 7 with acrylic resin, adding an antifoaming agent, a dispersing agent and a leveling agent respectively, performing ultrasonic dispersion for 30-60 min, adding a curing agent, uniformly mixing, and curing for 30-60 min to obtain the antistatic coating.
10. Use of the conductive filler according to claim 7 in the field of antistatic properties of non-insulating surfaces.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211594774.2A CN115975424B (en) | 2022-12-13 | 2022-12-13 | Conductive filler and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211594774.2A CN115975424B (en) | 2022-12-13 | 2022-12-13 | Conductive filler and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115975424A CN115975424A (en) | 2023-04-18 |
| CN115975424B true CN115975424B (en) | 2024-01-19 |
Family
ID=85969164
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211594774.2A Active CN115975424B (en) | 2022-12-13 | 2022-12-13 | Conductive filler and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115975424B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105542228A (en) * | 2016-01-31 | 2016-05-04 | 华南理工大学 | Preparation method of functionalized nano-silica based on graphene |
| CN107400396A (en) * | 2017-07-26 | 2017-11-28 | 青岛科技大学 | A kind of graphene nano particulate composite and preparation method thereof |
| CN107501853A (en) * | 2017-08-02 | 2017-12-22 | 济南大学 | A kind of functionalization redox graphene phenol-formaldehyde resin modified and preparation method thereof |
-
2022
- 2022-12-13 CN CN202211594774.2A patent/CN115975424B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105542228A (en) * | 2016-01-31 | 2016-05-04 | 华南理工大学 | Preparation method of functionalized nano-silica based on graphene |
| CN107400396A (en) * | 2017-07-26 | 2017-11-28 | 青岛科技大学 | A kind of graphene nano particulate composite and preparation method thereof |
| CN107501853A (en) * | 2017-08-02 | 2017-12-22 | 济南大学 | A kind of functionalization redox graphene phenol-formaldehyde resin modified and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Reduced graphene oxide/silica nanocomposite-reinforced anticorrosive fluorocarbon coating;Beijie Zhong等;《Journal of Applied Polymer Science》(第138期);第e49689(1-10)页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115975424A (en) | 2023-04-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108183192B (en) | Ceramic slurry and lithium ion battery diaphragm | |
| CN114023494B (en) | Graphene solar HJT battery front silver paste and preparation method thereof | |
| CN114045071B (en) | Building aluminum veneer curtain wall finish paint and preparation method thereof | |
| CN109575782A (en) | Graphene oxide modified polyurethane electrophoresis resin, polyurethane electrophoretic paint and preparation method thereof | |
| CN108400297A (en) | A kind of silicon substrate lithium ion battery negative material and preparation method thereof | |
| CN111484658A (en) | High-performance conductive rubber material and preparation method thereof | |
| CN112521834A (en) | Water-based graphene static-conducting anticorrosive paint and preparation method thereof | |
| CN115975424B (en) | Conductive filler and preparation method and application thereof | |
| CN114479639A (en) | Preparation method and application of radiation heat-dissipation coating | |
| CN114273188B (en) | Fluorine-carbon aluminum veneer and preparation method thereof | |
| CN115746701A (en) | RTV anti-pollution flashover coating and preparation method and application thereof | |
| CN110746794A (en) | Preparation method of super-hydrophobic white carbon black | |
| CN110343347B (en) | Polyvinylidene fluoride SiO2Modified graphene composite material and preparation method thereof | |
| CN110429331B (en) | Graphene composite coating material filled solid electrolyte and preparation method thereof | |
| CN115584095B (en) | Method for preparing high-conductivity fluororubber sealing material by ionic liquid assisted dispersion | |
| CN115260763B (en) | Polyimide black film with high insulating strength and preparation method thereof | |
| CN114512261B (en) | Low-temperature curing conductive silver paste and preparation method thereof | |
| CN114574062B (en) | Preparation method of emulsion for water-based paint | |
| CN115241424A (en) | Positive electrode water-based carbon-coated aluminum foil coating and preparation method thereof | |
| CN114974655A (en) | Organic vehicle, conductive paste and solar cell | |
| CN113637204A (en) | Solar cell back film | |
| CN113429693A (en) | Preparation method and application of quaternized carbon nanotube modified polystyrene insulation board | |
| CN112778855A (en) | Anti-fouling antistatic elastic exterior wall coating and preparation method thereof | |
| CN117238570B (en) | High-temperature-resistant high-voltage cable for new energy automobile | |
| CN114891404A (en) | Anti-static Teflon film and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |