CN105524499A - Preparation method and application of graphene microchip composite for anticorrosive coating - Google Patents
Preparation method and application of graphene microchip composite for anticorrosive coating Download PDFInfo
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- CN105524499A CN105524499A CN201610070783.XA CN201610070783A CN105524499A CN 105524499 A CN105524499 A CN 105524499A CN 201610070783 A CN201610070783 A CN 201610070783A CN 105524499 A CN105524499 A CN 105524499A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 185
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 124
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000000576 coating method Methods 0.000 title claims abstract description 13
- 239000002131 composite material Substances 0.000 title claims abstract description 12
- 239000011248 coating agent Substances 0.000 title abstract description 10
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 65
- 239000010439 graphite Substances 0.000 claims abstract description 65
- 238000009830 intercalation Methods 0.000 claims abstract description 32
- 230000002687 intercalation Effects 0.000 claims abstract description 32
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 claims abstract description 31
- 230000007547 defect Effects 0.000 claims abstract description 21
- 238000010008 shearing Methods 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000004567 concrete Substances 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 239000000539 dimer Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000011159 matrix material Substances 0.000 claims description 42
- 239000006185 dispersion Substances 0.000 claims description 41
- 230000001681 protective effect Effects 0.000 claims description 40
- 238000001125 extrusion Methods 0.000 claims description 39
- 238000009833 condensation Methods 0.000 claims description 12
- 230000005494 condensation Effects 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 239000010410 layer Substances 0.000 claims description 10
- -1 graphite alkene Chemical class 0.000 claims description 8
- 239000011229 interlayer Substances 0.000 claims description 7
- 239000003973 paint Substances 0.000 claims description 7
- GNHOJBNSNUXZQA-UHFFFAOYSA-J potassium aluminium sulfate dodecahydrate Chemical group O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GNHOJBNSNUXZQA-UHFFFAOYSA-J 0.000 claims description 7
- 239000003921 oil Substances 0.000 claims description 6
- 235000019198 oils Nutrition 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 5
- 229930195729 fatty acid Natural products 0.000 claims description 5
- 239000000194 fatty acid Substances 0.000 claims description 5
- 150000004665 fatty acids Chemical class 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 claims description 3
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 claims description 3
- 244000068988 Glycine max Species 0.000 claims description 3
- 235000010469 Glycine max Nutrition 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 239000010499 rapseed oil Substances 0.000 claims description 3
- 239000003171 wood protecting agent Substances 0.000 claims description 3
- 229920000742 Cotton Polymers 0.000 claims description 2
- 235000020238 sunflower seed Nutrition 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002023 wood Substances 0.000 abstract description 4
- 230000000903 blocking effect Effects 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract description 2
- 229940103272 aluminum potassium sulfate Drugs 0.000 abstract 1
- 239000012188 paraffin wax Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 16
- 238000005260 corrosion Methods 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000002421 anti-septic effect Effects 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 241000446313 Lamella Species 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
Abstract
The invention provides a preparation method and an application of a graphene microchip composite for an anticorrosive coating. According to the method, natural flake graphite is taken as a main raw material, a screw extruder is used as a continuous reactor and used for continuous grinding, dispersing, intercalation and shearing stripping, flaws are formed on the boundary of flake graphite through chlorinated paraffin and dimer acid, the flake graphite is effectively stripped to form graphene microchips through intercalation of an aluminum potassium sulfate solution, integrated stripping and composition of the graphene microchips are realized, follow-up cleaning and removal are not required, and the graphene microchip composite is directly used for the anticorrosive coating for concrete, wood and metal and has excellent dispersibility and blocking characteristic; the defects that the graphene microchips are difficult to disperse and are easily overlapped again and gathered when applied to the anticorrosive coating are overcome, continuous and closed production of the graphene microchip composite is realized, and the graphene microchip composite has remarkable market application value.
Description
Technical field
The present invention relates to grapheme material field, be specifically related to protective system special graphite alkene material, particularly relate to a kind of preparation method and application of protective system graphene microchip matrix material.
Background technology
Desirable Graphene has perfect physical structure, has excellent machinery, electronics, calorifics, chemical property.After the discoverer Univ Manchester UK science An Deliehaimu and the Constantine Nuo Woxiaoluofu acquisition Nobel prize of Graphene in 2010, the research of Graphene starts to be taken seriously.Graphene is prepared into the application that powder is more conducive to Graphene, as grapheme material powder can be used as the additive of protective system, improves coating wear resistance, erosion resistance etc.
Graphite, because natively have the layered struture that can peel off, therefore can be carried out stripping and obtain Graphene by Strong shear graphite being carried out to machinery.Such as usually use the strong mechanical shearing of the method such as ball milling, mortar to prepare Graphene.As Chinese invention patent application numbers 201510073825.0 discloses class mechanically peel device and production method thereof that a kind of tonne is produced Graphene, it is by rotor like a mill, during rotor turns, the outside surface of rotor and the internal grinding of material bin, thus make graphite be stripped thinning acquisition Graphene.Owing to being difficult to be separated in time by the Graphene peeled off in the process of lapping of brute force, very easily cause reunion.Therefore, the Graphene obtained in mechanical grinding process, owing to reaching Nano grade, is therefore very easily reunited and overlap, thus is made the Rotating fields degradation of Graphene.Thus affect the commercial application of grapheme material powder.
In order to realize peeling off Graphene fast, also grapheme material powder can be prepared by oxidation-reduction method, but when preparing grapheme material powder by this kind of method, object is crystalline flake graphite deep oxidation, the interlamellar spacing that various oxy radical supports large graphite is connected equably at graphite flake layer, then ultrasonic equipment easily peels away graphite flake layer, finally adds that chemical substance reduction produces Graphene.But the Graphene that such method is worked it out, strong oxidising process can cause a large amount of defects of graphene-structured, and these defects cause the significantly decline of Graphene performance.Even if the Graphene be oxidized in addition is through reduction, the defect of the laminated structure of graphite can not be repaired.
Even if adopt aforesaid method mechanically peel and redox to obtain Graphene, owing to still having strong Van der Waals force between graphene sheet layer, time dry or in post-treatment process, be easy to secondary overlap between lamella, thus balance out effect of physics stripping process.Therefore, Graphene is difficult to after being difficult to volume production and reaching nano-scale disperse the defects such as storage to make the application of Graphene be subject to once being hindered.
Given this, graphene microchip is the optimal selection solving Graphene application.Graphene microchip is a kind grapheme material, and its lamella mean thickness within 15nm, and does not meet the Graphene definition being less than 10 layers of strict demand.But remain excellent conduction, heat conduction, antiseptic property.The present invention is intended to the mass production and the dispersing property that solve graphene microchip, to reach the application in protective system.
Summary of the invention
In protective system, the defect being difficult to disperse is applied for current Graphene, and the easy overlapping defect of assembling again of the layer of Graphene, the present invention proposes a kind of preparation method and application of protective system graphene microchip matrix material, the method take natural flake graphite as main raw material, screw extrusion press continuously grinding, dispersion, intercalation, shearing is utilized to peel off and obtain graphene microchip matrix material, for protective system, there is good dispersiveness and barrier properties.
For solving the problem, the present invention by the following technical solutions:
A kind of preparation method of protective system graphene microchip matrix material, it is characterized in that: employing natural flake graphite is main raw material, utilize screw extrusion press as flow reactor, peeled off by continuously grinding, dispersion, intercalation, shearing, graphene microchip is remained on stable dispersion state by further condensation, miniaturization obtains Powdered protective system special graphite alkene microchip composite material, and concrete preparation method is as follows:
(1) dimeracid of the clorafin of the natural flake graphite of 40-50 weight part, 20-30 weight part, 10-15 weight part, the potassium aluminium sulfate of 5-15 weight part are obtained pre-composition by high-speed mixer dispersing and mixing 30-50min; Described potassium aluminium sulfate is Potassium aluminum sulfate dodecahydrate;
(2) pre-composition that step (1) obtains is pumped into screw extrusion press, screw extrusion press is set gradually ground section, dispersion section, intercalation section by feed end to discharge end, shears and peel off section, controls ground section temperature 80-100 DEG C; Dispersion section temperature 90-100 DEG C; Intercalation section temperature 100-120 DEG C; Shear and peel off section temperature 80-100 DEG C; Screw extrusion press is continuous rotation under the high rotational speeds of 800-1200rpm, dimeracid, clorafin melt make crystalline flake graphite produce boundary defect, potassium aluminium sulfate melt inserts the interlayer of crystalline flake graphite, at screw extrusion press end because Strong shear is peeled off, crystalline flake graphite phased separation is made to become graphene microchip;
(3) graphene microchip that step (2) obtains through screw extrusion press is cooled fast, because graphene microchip is remained on stable dispersion state by clorafin, potassium aluminium sulfate rapid condensation, form graphene microchip matrix material, thus prevent ply and the gathering of graphene microchip;
(4) the stable graphene microchip matrix material that step (3) obtains is crushed to the powder that particle diameter is less than 10 μm, namely can be used as protective system special graphite alkene microchip composite material.
Described natural flake graphite is that radial dimension is greater than 50 microns, the carbon content crystalline flake graphite that is greater than 95%.
Described clorafin is No. 70 clorafins, and clorafin, making to become melt more than 90 DEG C, effectively disperses crystalline flake graphite, and due to clorafin structure heterogencity, is easily combined with crystalline flake graphite and produces boundary defect.
Described dimeracid is by C 18 unsaturated fatty acid, as ready denier oil acid, cotton oil acid, soybean oleic acid, sunflower seed oil fatty acids, low erucic acid rape oil fatty acid are polymerized, unsaponifiable matter content is at 3-5%, not only make crystalline flake graphite produce boundary defect, and be easy to disperse in protective system.
The preferred hydrogenated dimer acids of described dimeracid.
Described potassium aluminium sulfate is Potassium aluminum sulfate dodecahydrate, make to become melt more than 90 DEG C in temperature, graphite layers is inserted by the boundary defect of crystalline flake graphite, promote that graphite is peeled off into graphene microchip gradually under screw rod shearing condition, further, after condensation, potassium aluminium sulfate fixes graphene microchip, thus prevents overlap and the gathering of graphene microchip.
The ground section of described screw extrusion press, dispersion section, intercalation section, shearing are peeled off section and are assembled on screw rod with modular system with the form of screwing element, thus define a flow reactor, wherein: ground section is plane roll-type screwing element; Dispersion section is rotor-type screwing element; Intercalation section is profile of tooth screwing element; Shearing and peeling off section is gear block screwing element; Crystalline flake graphite and clorafin, dimeracid, potassium aluminium sulfate is made to form large sheet by pulverizing of plane roll-type screwing element, continue through rotor-type screwing element, rotor-type screwing element carries out internal mixing and plasticizing processing makes crystalline flake graphite form boundary defect, further across profile of tooth screwing element, material is produced disorderly, potassium aluminium sulfate melt inserts the interlayer of graphite, and the Strong shear stripping eventually passing gear block obtains graphene microchip.
Described screw extrusion press is meshed double screw machine, the machine of engagement screws in the same way that engages three screw machines in the same way, engage four screw machines or more multiscrew in the same way in the same way.
Described rapid condensation utilizes solidifying of clorafin, potassium aluminium sulfate that graphene microchip is remained on stable dispersion state in the environment lower than 0 DEG C, and preventing layer is overlapping and assemble.
Although Graphene has excellent anticorrosion barrier property, reunite because Graphene can produce self, destroy homogeneity, the compactness of its dispersion, reunite when it is applied to coating, film inside produces stress concentration, causes mechanical property, antiseptic property to decline.The screw extrusion press that utilizes of the invention is peeled off by continuously grinding, dispersion, intercalation, shearing, crystalline flake graphite is peeled off into graphene microchip, and directly utilize stripping subsidiary material clorafin, dimeracid, potassium aluminium sulfate to disperse, solidify, fix graphene microchip, form protective system graphene microchip matrix material, this protective system graphene microchip matrix material dispersion and fining to 10 μm can directly add for protective system.
The graphene microchip matrix material that preparation method of the present invention obtains itself has hydrophobic and lyophobic property, is adapted to wood preservation, anti-corrosion of metal, antiseptic concrete, is preferred for metal anti-corrosive paint.Its laminated structure has and blocks water, prevents corrosive ion etc. to the infiltration of metal base, delays the corrosion speed of metal base, and then plays rot-resistant effect to ground.It is a kind of protective system proprietary material, can to be added in protective system for buried pipeline outer wall, various chemical industry equipment metal, sewage disposal metal, space flight anti-corrosion of metal, liquid storage tank and base plate, be under water with the steel construction, Concrete Anti corrosion application etc. of dry wet alternating environment.After adding with 10% the graphene microchip matrix material that the inventive method obtains to protective system system, the over-all properties of film significantly improves, and its coating adhesion, wear resistance increase, and salt spray resistance can reach more than 3200h.Typical application performance is as shown in table 1.
Table 1:
The preparation method of a kind of protective system graphene microchip of the present invention matrix material, compared with prior art, its outstanding feature and excellent effect are:
1, peeled off by screw extrusion press continuously grinding, dispersion, intercalation, shearing, clorafin, dimeracid is utilized to produce defect to the border of crystalline flake graphite, and the intercalation of potassium aluminium sulfate solution, crystalline flake graphite is effectively peeled off into graphene microchip, achieve graphene microchip to peel off, be compound in one, stripping subsidiary material are effectively utilized, removes without the need to follow-up cleaning.
2, utilize clorafin, the condensation of potassium aluminium sulfate fix, overcome graphene microchip apply in protective system be difficult to disperse, easy overlapping defect of assembling again, for protective system, there is good dispersiveness and barrier properties.
3, preparation method of the present invention be easy to control, the closed production of serialization can be realized, drop into little, cost is low, non-environmental-pollution, output are high, has significant market using value.
Embodiment
Below by way of embodiment, the present invention is described in further detail, but this should be interpreted as scope of the present invention is only limitted to following example.When not departing from aforesaid method thought of the present invention, the various replacement made according to ordinary skill knowledge and customary means or change, all should be within the scope of the present invention.
embodiment 1
The preparation method of metal anti-corrosive paint graphene microchip matrix material:
(1) No. 70 clorafins of the natural flake graphite of 40 weight parts, 20 weight parts, the hydrogenated dimer acids of 15 weight parts, the Potassium aluminum sulfate dodecahydrate of 5 weight parts are obtained pre-composition by high-speed mixer dispersing and mixing 30min;
(2) pre-composition that step (1) obtains is pumped into meshed double screw machine in the same way, screw extrusion press is set gradually ground section, dispersion section, intercalation section by feed end to discharge end, shears and peel off section, the ground section of screw extrusion press, dispersion section, intercalation section, shearing are peeled off section and are assembled on screw rod with the form of screwing element with modular system, thus define a flow reactor, wherein: ground section is plane roll-type screwing element, dispersion section is rotor-type screwing element, intercalation section is profile of tooth screwing element, shearing and peeling off section is gear block screwing element, the Strong shear stripping eventually passing gear block obtains graphene microchip, controls ground section temperature 80-100 DEG C, dispersion section temperature 90-100 DEG C, intercalation section temperature 100-120 DEG C, shear and peel off section temperature 80-100 DEG C, screw extrusion press is continuous rotation under the high rotational speeds of 800-1200rpm, crystalline flake graphite and clorafin is made by pulverizing of plane roll-type screwing element, dimeracid, potassium aluminium sulfate forms large sheet, continue through rotor-type screwing element, rotor-type screwing element carries out internal mixing and plasticizing processing dimeracid, clorafin melt makes crystalline flake graphite produce boundary defect, further across profile of tooth screwing element, material is produced disorderly, potassium aluminium sulfate melt inserts the interlayer of graphite, at screw extrusion press end because Strong shear is peeled off, crystalline flake graphite phased separation is made to become graphene microchip,
(3) graphene microchip that step (2) obtains through screw extrusion press is cooled fast under lower than 0 DEG C of condition, because graphene microchip is remained on stable dispersion state by clorafin, potassium aluminium sulfate rapid condensation, form graphene microchip matrix material, thus prevent ply and the gathering of graphene microchip;
(4) the stable graphene microchip matrix material that step (3) obtains is crushed to the powder that particle diameter is less than 10 μm, namely can be used as protective system special graphite alkene microchip composite material.
Graphene microchip matrix material embodiment 1 obtained makes an addition in corrosion-resistant epoxy paint with the consumption of 10wt%, as the protective system of metallic surface, by test, when coat-thickness 25-30 micron, and more than salt fog resistance 3200h; Coating acid fastness (10%H2SO290 DEG C of 5h) is greater than 98; Time pickling stability (40%H2SO2 soaks 48h), coating is unchanged.Therefore, by graphene microchip matrix material, solve Graphene in protective system, apply the defect being difficult to disperse, and the easy overlapping defect of assembling again of the layer of Graphene, the layer performance of Graphene is obtained and fully plays.
embodiment 2
The preparation method of concrete anti-corrosive paint graphene microchip matrix material:
(1) radial dimension of 50 weight parts is greater than 50 microns, the carbon content crystalline flake graphite, No. 70 clorafins of 25 weight parts, the dimeracid be polymerized by soybean oleic acid of 10 weight parts, the Potassium aluminum sulfate dodecahydrate of 5 weight parts that are greater than 95% obtain pre-composition by high-speed mixer dispersing and mixing 30min;
(2) pre-composition that step (1) obtains is pumped into engage three screw machines in the same way, screw extrusion press is set gradually ground section, dispersion section, intercalation section by feed end to discharge end, shears and peel off section, the ground section of screw extrusion press, dispersion section, intercalation section, shearing are peeled off section and are assembled on screw rod with the form of screwing element with modular system, thus define a flow reactor, wherein: ground section is plane roll-type screwing element, dispersion section is rotor-type screwing element, intercalation section is profile of tooth screwing element, shearing and peeling off section is gear block screwing element, the Strong shear stripping eventually passing gear block obtains graphene microchip, controls ground section temperature 80-100 DEG C, dispersion section temperature 90-100 DEG C, intercalation section temperature 100-120 DEG C, shear and peel off section temperature 80-100 DEG C, screw extrusion press is continuous rotation under the high rotational speeds of 800-1200rpm, crystalline flake graphite and clorafin is made by pulverizing of plane roll-type screwing element, dimeracid, potassium aluminium sulfate forms large sheet, continue through rotor-type screwing element, rotor-type screwing element carries out internal mixing and plasticizing processing dimeracid, clorafin melt makes crystalline flake graphite produce boundary defect, further across profile of tooth screwing element, material is produced disorderly, potassium aluminium sulfate melt inserts the interlayer of graphite, at screw extrusion press end because Strong shear is peeled off, crystalline flake graphite phased separation is made to become graphene microchip,
(3) graphene microchip that step (2) obtains through screw extrusion press is cooled fast under lower than 0 DEG C of condition, because graphene microchip is remained on stable dispersion state by clorafin, potassium aluminium sulfate rapid condensation, form graphene microchip matrix material, thus prevent ply and the gathering of graphene microchip;
(4) the stable graphene microchip matrix material that step (3) obtains is crushed to the powder that particle diameter is less than 10 μm, namely can be used as protective system special graphite alkene microchip composite material.
embodiment 3
The preparation method of wood preservative coatings graphene microchip matrix material:
(1) Potassium aluminum sulfate dodecahydrate of No. 70 clorafins of the natural flake graphite of 45 weight parts, 30 weight parts, dimeracid that the low erucic acid rape oil fatty acid of 15 weight parts is polymerized, 5 weight parts is obtained pre-composition by high-speed mixer dispersing and mixing 45min;
(2) pre-composition that step (1) obtains is pumped into engage four screw machines in the same way, screw extrusion press is set gradually ground section, dispersion section, intercalation section by feed end to discharge end, shears and peel off section, the ground section of screw extrusion press, dispersion section, intercalation section, shearing are peeled off section and are assembled on screw rod with the form of screwing element with modular system, thus define a flow reactor, wherein: ground section is plane roll-type screwing element, dispersion section is rotor-type screwing element, intercalation section is profile of tooth screwing element, shearing and peeling off section is gear block screwing element, the Strong shear stripping eventually passing gear block obtains graphene microchip, controls ground section temperature 80-100 DEG C, dispersion section temperature 90-100 DEG C, intercalation section temperature 100-120 DEG C, shear and peel off section temperature 80-100 DEG C, screw extrusion press is continuous rotation under the high rotational speeds of 800-1200rpm, crystalline flake graphite and clorafin is made by pulverizing of plane roll-type screwing element, dimeracid, potassium aluminium sulfate forms large sheet, continue through rotor-type screwing element, rotor-type screwing element carries out internal mixing and plasticizing processing dimeracid, clorafin melt makes crystalline flake graphite produce boundary defect, further across profile of tooth screwing element, material is produced disorderly, potassium aluminium sulfate melt inserts the interlayer of graphite, at screw extrusion press end because Strong shear is peeled off, crystalline flake graphite phased separation is made to become graphene microchip,
(3) graphene microchip that step (2) obtains through screw extrusion press is cooled fast under lower than 0 DEG C of condition, because graphene microchip is remained on stable dispersion state by clorafin, potassium aluminium sulfate rapid condensation, form graphene microchip matrix material, thus prevent ply and the gathering of graphene microchip;
(4) the stable graphene microchip matrix material that step (3) obtains is crushed to the powder that particle diameter is less than 10 μm, namely can be used as protective system special graphite alkene microchip composite material.
Graphene microchip matrix material embodiment 3 obtained makes an addition in wood preservative coatings with the consumption of 10wt%, and its laminated structure has the infiltration blocking water, prevent the wood substrates such as caustic acid basic ion, and then plays the effect of wood preservation.
embodiment 4
The preparation method of concrete anti-corrosive paint graphene microchip matrix material:
(1) No. 70 clorafins of the natural flake graphite of 50 weight parts, 20 weight parts, the hydrogenated dimer acids of 10 weight parts, the Potassium aluminum sulfate dodecahydrate of 15 weight parts are obtained pre-composition by high-speed mixer dispersing and mixing 40min;
(2) pre-composition that step (1) obtains is pumped into meshed double screw machine in the same way, screw extrusion press is set gradually ground section, dispersion section, intercalation section by feed end to discharge end, shears and peel off section, the ground section of screw extrusion press, dispersion section, intercalation section, shearing are peeled off section and are assembled on screw rod with the form of screwing element with modular system, thus define a flow reactor, wherein: ground section is plane roll-type screwing element, dispersion section is rotor-type screwing element, intercalation section is profile of tooth screwing element, shearing and peeling off section is gear block screwing element, the Strong shear stripping eventually passing gear block obtains graphene microchip, controls ground section temperature 80-100 DEG C, dispersion section temperature 90-100 DEG C, intercalation section temperature 100-120 DEG C, shear and peel off section temperature 80-100 DEG C, screw extrusion press is continuous rotation under the high rotational speeds of 800-1200rpm, crystalline flake graphite and clorafin is made by pulverizing of plane roll-type screwing element, dimeracid, potassium aluminium sulfate forms large sheet, continue through rotor-type screwing element, rotor-type screwing element carries out internal mixing and plasticizing processing dimeracid, clorafin melt makes crystalline flake graphite produce boundary defect, further across profile of tooth screwing element, material is produced disorderly, potassium aluminium sulfate melt inserts the interlayer of graphite, at screw extrusion press end because Strong shear is peeled off, crystalline flake graphite phased separation is made to become graphene microchip,
(3) graphene microchip that step (2) obtains through screw extrusion press is cooled fast under lower than 0 DEG C of condition, because graphene microchip is remained on stable dispersion state by clorafin, potassium aluminium sulfate rapid condensation, form graphene microchip matrix material, thus prevent ply and the gathering of graphene microchip;
(4) the stable graphene microchip matrix material that step (3) obtains is crushed to the powder that particle diameter is less than 10 μm, namely can be used as protective system special graphite alkene microchip composite material.
Graphene microchip matrix material embodiment 4 obtained makes an addition in fluorocarbon coating with the consumption of 10wt%, as the protective system that concrete in marine environment builds, by test, when coat-thickness 50 microns, and more than salt fog resistance 4000h.
Claims (9)
1. the preparation method of a protective system graphene microchip matrix material, it is characterized in that: employing natural flake graphite is main raw material, utilize screw extrusion press as flow reactor, peeled off by continuously grinding, dispersion, intercalation, shearing, utilize clorafin further, graphene microchip remains on stable dispersion state by potassium aluminium sulfate rapid condensation, then miniaturization obtains Powdered protective system graphene microchip matrix material, and concrete preparation method is as follows:
(1) dimeracid of the clorafin of the natural flake graphite of 40-50 weight part, 20-30 weight part, 10-15 weight part, the potassium aluminium sulfate of 5-15 weight part are obtained pre-composition by high-speed mixer dispersing and mixing 30-50min; Described potassium aluminium sulfate is Potassium aluminum sulfate dodecahydrate;
(2) pre-composition that step (1) obtains is pumped into screw extrusion press, screw extrusion press is set gradually ground section, dispersion section, intercalation section by feed end to discharge end, shears and peel off section, controls ground section temperature 80-100 DEG C; Dispersion section temperature 90-100 DEG C; Intercalation section temperature 100-120 DEG C; Shear and peel off section temperature 80-100 DEG C; Screw extrusion press is continuous rotation under the high rotational speeds of 800-1200rpm, dimeracid, clorafin melt make crystalline flake graphite produce boundary defect, potassium aluminium sulfate melt inserts the interlayer of crystalline flake graphite, at screw extrusion press end because Strong shear is peeled off, crystalline flake graphite phased separation is made to become graphene microchip;
(3) graphene microchip that step (2) obtains through screw extrusion press is cooled fast, because graphene microchip is remained on stable dispersion state by clorafin, potassium aluminium sulfate rapid condensation, form graphene microchip matrix material, thus prevent ply and the gathering of graphene microchip;
(4) the stable graphene microchip matrix material that step (3) obtains is crushed to the powder that particle diameter is less than 10 μm, namely can be used as protective system special graphite alkene microchip composite material.
2. the preparation method of a kind of protective system graphene microchip matrix material according to claim 1, is characterized in that: described natural flake graphite is that radial dimension is greater than 50 microns, the carbon content crystalline flake graphite that is greater than 95%.
3. the preparation method of a kind of protective system graphene microchip matrix material according to claim 1, is characterized in that: described clorafin is No. 70 clorafins.
4. the preparation method of a kind of protective system graphene microchip matrix material according to claim 1, it is characterized in that: described dimeracid is polymerized by ready denier oil acid, cotton oil acid, soybean oleic acid, sunflower seed oil fatty acids, low erucic acid rape oil fatty acid, and unsaponifiable matter content is at 3-5%.
5. the preparation method of a kind of protective system graphene microchip matrix material according to claim 1, is characterized in that: described dimeracid is hydrogenated dimer acids.
6. the preparation method of a kind of protective system graphene microchip matrix material according to claim 1, it is characterized in that: the ground section of described screw extrusion press, dispersion section, intercalation section, shearing are peeled off section and be assembled on screw rod with the form of screwing element with modular system, thus define a flow reactor, wherein: ground section is plane roll-type screwing element; Dispersion section is rotor-type screwing element; Intercalation section is profile of tooth screwing element; Shearing and peeling off section is gear block screwing element.
7. the preparation method of a kind of protective system graphene microchip matrix material according to claim 1, is characterized in that: described screw extrusion press is meshed double screw machine, the machine of engagement screws in the same way that engages three screw machines in the same way, engage four screw machines or more multiscrew in the same way in the same way.
8. the preparation method of a kind of protective system graphene microchip matrix material according to claim 1, it is characterized in that: described rapid condensation utilizes solidifying of clorafin, potassium aluminium sulfate that graphene microchip is remained on stable dispersion state in the environment lower than 0 DEG C, preventing layer is overlapping and assemble.
9. the preparation method of a kind of protective system graphene microchip matrix material according to claim 1, it is characterized in that: described graphene microchip matrix material is used for metal anti-corrosive paint, wood preservative coatings or concrete anti-corrosive paint, the addition of graphene microchip matrix material in protective system is 10wt%, more than salt fog resistance 3200h.
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| CN109608891A (en) * | 2018-11-26 | 2019-04-12 | 国宏中晶集团有限公司 | A kind of plateau modulus composite material and preparation method containing graphene |
| CN109694529A (en) * | 2017-10-23 | 2019-04-30 | 中国科学院理化技术研究所 | A kind of preparation method of graphene PVC anti-static composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106118324A (en) * | 2016-06-27 | 2016-11-16 | 上海多希石墨烯材料科技有限公司 | A kind of conductive coating materials peeling off Graphene containing physics and preparation method thereof |
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| CN109608891B (en) * | 2018-11-26 | 2021-03-23 | 国宏中晶集团有限公司 | Graphene-containing high-elastic modulus composite material and preparation method thereof |
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