CN117363125A - Water-based paint and preparation process thereof - Google Patents
Water-based paint and preparation process thereof Download PDFInfo
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- CN117363125A CN117363125A CN202311563589.1A CN202311563589A CN117363125A CN 117363125 A CN117363125 A CN 117363125A CN 202311563589 A CN202311563589 A CN 202311563589A CN 117363125 A CN117363125 A CN 117363125A
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- water
- stirring
- based paint
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000003973 paint Substances 0.000 title claims abstract description 73
- 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 63
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000011347 resin Substances 0.000 claims abstract description 40
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 239000000839 emulsion Substances 0.000 claims abstract description 32
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 31
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 28
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 14
- 229920000767 polyaniline Polymers 0.000 claims abstract description 9
- 230000020477 pH reduction Effects 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 115
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 66
- 238000006243 chemical reaction Methods 0.000 claims description 65
- 239000000203 mixture Substances 0.000 claims description 35
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 32
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 30
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- 238000005086 pumping Methods 0.000 claims description 20
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 16
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 15
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 15
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 15
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 15
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 15
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- -1 polydimethylsiloxane Polymers 0.000 claims description 15
- 238000005303 weighing Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 12
- 239000000080 wetting agent Substances 0.000 claims description 12
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 10
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 10
- 239000005457 ice water Substances 0.000 claims description 10
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 238000007873 sieving Methods 0.000 claims description 10
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 10
- 229910052712 strontium Inorganic materials 0.000 claims description 10
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 10
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 10
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 10
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 10
- 229910021485 fumed silica Inorganic materials 0.000 claims description 8
- 238000001238 wet grinding Methods 0.000 claims description 7
- 239000002518 antifoaming agent Substances 0.000 claims description 6
- 239000013530 defoamer Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 239000003242 anti bacterial agent Substances 0.000 claims description 5
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical group [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 claims description 5
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 5
- WXENFNJZXUNZIN-UHFFFAOYSA-M decyl-dimethyl-tetradecylazanium bromide Chemical compound [Br-].C(CCCCCCCCC)[N+](C)(C)CCCCCCCCCCCCCC WXENFNJZXUNZIN-UHFFFAOYSA-M 0.000 claims description 5
- 229960004670 didecyldimethylammonium chloride Drugs 0.000 claims description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 5
- 150000002191 fatty alcohols Chemical class 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000011010 flushing procedure Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- NJBTXHDSKWAAPK-UHFFFAOYSA-M hexadecyl-dimethyl-octylazanium bromide Chemical compound [Br-].C(CCCCCCCCCCCCCCC)[N+](C)(C)CCCCCCCC NJBTXHDSKWAAPK-UHFFFAOYSA-M 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 5
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 claims description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 5
- ZBYSZWDYDUIDAZ-UHFFFAOYSA-M sodium octadec-2-enoate Chemical compound [Na+].CCCCCCCCCCCCCCCC=CC([O-])=O ZBYSZWDYDUIDAZ-UHFFFAOYSA-M 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 8
- 238000004132 cross linking Methods 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- 238000012360 testing method Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000010276 construction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000013473 artificial intelligence Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
-
- 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
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
-
- 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
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- 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
- C09D7/61—Additives non-macromolecular inorganic
-
- 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
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- 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
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Plant Pathology (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to the technical field of water-based paint, in particular to a water-based paint and a preparation process thereof, wherein polyaniline is grafted on the surface of graphene oxide after phosphoric acid acidification through dodecylbenzene sulfonic acid, so that the dispersibility and compatibility of graphene oxide in the water-based paint can be improved, and the water-based paint is assisted to have better anti-corrosion performance; antibacterial molecules in the mildew-proof component are dispersed in silicon dioxide adsorbed on the modified graphene oxide, and can be adsorbed on a pore structure, so that the mildew-proof property of the water-based paint can be enhanced; secondly, the invention introduces the acetoacetoxyethyl methacrylate as a self-crosslinking monomer into the self-made resin emulsion, can enhance the resin crosslinking density, can be connected with a grid structure formed by hydrogen bonds in the modified graphene oxide in the self-crosslinking process of the acetoacetoxyethyl methacrylate, and improves the water resistance and the stability of the water-based paint to a certain extent.
Description
Technical Field
The invention relates to the technical field of water-based paint, in particular to water-based paint and a preparation process thereof.
Background
With the continuous improvement of the national environmental protection requirements, solvent-free paint, water-based paint and powder paint quickly rise, and the water-based paint has the advantages of excellent performance, convenient construction, double functions of decoration and protection and the like, has become a main stream product for construction, decoration, containers, automobiles, ships, electric appliances, engineering machinery and other industrial and civil industries, and is also gradually pushed to the environmental protection process of the paint in the special fields of national defense weaponry, aerospace and the like. Through continuous technical improvement, the water-based anticorrosive paint is greatly improved in the aspects of a resin system, an antirust pigment and the like. At present, the water-based anticorrosive paint is developing towards green environment friendliness, long service life, artificial intelligence, performance integration and the like so as to adapt to the novel requirements of different fields.
At present, the resin of the traditional water-based paint has the problems of difficulty in considering the molecular weight, high molecular weight and excellent performance (hardness, salt fog and the like), but is not well constructed, low in gloss and low in molecular weight. If common self-crosslinking monomers (diacetone alcohol acrylamide and adipic dihydrazide) are introduced, the resin with small molecular weight is prepared first, so that the coating is self-crosslinked in the self-drying process to form the resin with large molecular weight, the defects can be avoided theoretically by taking the advantages into consideration, but the conditions of low resin crosslinking density and easy yellowing of the resin are easy to occur in practical application. In the improvement process of many water-based paints on the market, the corrosion resistance or the antibacterial property of the water-based paint is improved by adding the modifying auxiliary agent, so that the prepared water-based paint is not stable enough in performance and is difficult to reach an ideal optimal state in the actual use process, and therefore, if the water-based paint is modified and improved in a grafting modification mode, the stability of the water-based paint can be improved to a great extent.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects existing in the prior art, the invention provides the water-based paint and the preparation process thereof, and aims to ensure that the prepared water-based paint has relatively stable corrosion resistance and antibacterial property.
Technical proposal
In order to achieve the above purpose, the invention is realized by the following technical scheme:
the raw materials of the water-based paint comprise the following components: self-made resin emulsion, modified graphene oxide and mildew-proof components;
the self-made resin emulsion is prepared by polymerization reaction of methyl methacrylate, styrene, butyl acrylate, acrylic acid, isobornyl methacrylate, hydroxyethyl methacrylate, acetoacetoxyethyl methacrylate and azobisisobutyronitrile;
the modified graphene oxide is prepared by introducing polyaniline into the surface of graphene oxide subjected to phosphoric acid acidification through dodecylbenzene sulfonic acid;
the mildew-proof component is prepared by mixing different quaternary ammonium salt antibacterial agents.
Further, the preparation method of the self-made resin emulsion comprises the following steps:
step1, weighing 80-90 parts by weight of methyl ethyl ketone, pouring the mixture into a reaction kettle, heating the mixture to 60 ℃ under stirring at a stirring speed of 50-100r/min, adding 10-25 parts by weight of methyl methacrylate, 10-20 parts by weight of styrene, 10-20 parts by weight of butyl acrylate, 3-10 parts by weight of acrylic acid, 3-10 parts by weight of isobornyl methacrylate, 5-10 parts by weight of hydroxyethyl methacrylate and 1-5 parts by weight of azobisisobutyronitrile under the protection of nitrogen, stirring the mixture to be transparent at a stirring speed of 50-100r/min, and pumping the mixture to a high-level tank;
step2, after the temperature of the reaction kettle is raised to 75-80 ℃, uniformly dropwise adding the components in the high-level tank in the step1, after the components are dropwise added within 2 hours, adding 10-25 parts by weight of methyl methacrylate, 10-20 parts by weight of styrene, 10-20 parts by weight of butyl acrylate, 3-10 parts by weight of acrylic acid, 3-10 parts by weight of isobornyl methacrylate, 15-20 parts by weight of acetoacetoxyethyl methacrylate and 1-5 parts by weight of azobisisobutyronitrile into the reaction kettle, continuously stirring at a stirring speed of 50-100r/min until the components are transparent, and pumping the components into the high-level tank again;
step3, dripping the components in the overhead tank in the step2 into a reaction kettle at a constant speed, controlling the dripping time to be 2 hours, adding 8-10 parts by weight of methyl ethyl ketone into the overhead tank for flushing, pouring the flushed methyl ethyl ketone into the reaction kettle again, heating the reaction kettle to 75-80 ℃, preserving heat for 4 hours, and respectively adding 0.5 and 0.1 parts by weight of azodiisobutyronitrile in the 1.5 hours and the 2.5 hours of heat preservation;
and 4, after the heat preservation in the step3 is finished, heating the reaction kettle to 100 ℃ to remove methyl ethyl ketone, pumping 3-10 parts by weight of N, N-dimethylethanolamine into a high-level tank, uniformly dripping the N, N-dimethylethanolamine into the reaction kettle at 60-70 ℃, pumping 80-100 parts by weight of deionized water into the high-level tank for dripping after dripping within 0.5h, and dripping within 0.5h to obtain the self-made resin emulsion.
Further, in the step 4, in the process of dropwise adding N, N-dimethylethanolamine, the pH value of the components in the reaction kettle is controlled to be 6.5-7.5.
Further, the preparation method of the modified graphene oxide comprises the following steps:
s1, according to 1: mixing dodecylbenzene sulfonic acid and deionized water according to the feed liquid ratio of 19g/mL, and performing ultrasonic dispersion for 30-35min at the frequency of 23-25kHz, wherein the obtained mixture is named as dodecylbenzene sulfonic acid solution; according to 1: dissolving ammonium persulfate in a phosphoric acid solution according to a feed liquid ratio of 50g/mL, and performing ultrasonic dispersion for 18-20min at a frequency of 22-23kHz, wherein the obtained solution is named ammonium persulfate/phosphoric acid solution;
s2, according to 1: pouring graphene oxide and concentrated phosphoric acid solution into a flask according to the feed liquid ratio of 80g/mL, mixing, placing the mixture into an oil bath at 50 ℃ and stirring at the stirring speed of 300-400r/min for 10-12h, transferring the mixture into an ice water bath, continuing stirring at the original stirring speed for 25-30min, and recording the mixture as a component to be reacted;
s3, pouring the dodecylbenzene sulfonic acid solution in the S1 into a component to be reacted, stirring at a stirring speed of 500-600r/min for 25-30min, adding aniline with the same weight as that of graphene oxide, stirring at an original stirring speed for 28-30min, dropwise adding the ammonium persulfate/phosphoric acid solution in the S1, stirring in an ice water bath at an original stirring speed for 10-12h for reaction after the dropwise adding is completed, and marking the obtained mixture as a reaction mixed component;
s4, adding fumed silica with the same weight as the graphene oxide into the reaction mixed components, continuously reacting for 8-10 hours, filtering to remove filtrate after the reaction is finished, washing filter residues with deionized water to be neutral, drying in a vacuum drying oven at 70 ℃ for 7-8 hours, grinding and sieving with a 200-mesh sieve to obtain the modified graphene oxide.
Further, the mass fraction of the phosphoric acid solution in S1 is 25-30%, and the mass fraction of the concentrated phosphoric acid solution in S2 is 80-85%.
Still further, the mildew-resistant component is dodecyl dimethyl benzyl ammonium chloride, didecyl dimethyl ammonium chloride, cetyl trimethyl ammonium chloride, tetradecyl dimethyl decyl ammonium bromide, and hexadecyl dimethyl octyl ammonium bromide according to 2:1:3:1:1 weight ratio.
The preparation process of the water-based paint comprises the following raw materials: defoaming agent, wetting agent, leveling agent, dispersing agent, zinc phosphate, aluminum tripolyphosphate, strontium chrome yellow and deionized water;
the preparation process of the water-based paint comprises the following steps:
step1, weighing 5-6 parts by weight of modified graphene oxide, dispersing in 80-90 parts by weight of deionized water, stirring for 5-8min, adding 2-3 parts by weight of mildew-proof component, continuing stirring for 5-6min, and performing ultrasonic dispersion for 1-2h at a frequency of 25-27kHz, wherein the obtained mixture is taken as a filler component;
step2, adding 0.1-0.2 part by weight of defoamer, 0.2-0.3 part by weight of wetting agent, 0.1-0.2 part by weight of flatting agent, 1-2 parts by weight of dispersing agent, 2-3 parts by weight of zinc phosphate, 2-3 parts by weight of aluminum tripolyphosphate and 1-2 parts by weight of strontium chrome yellow into a filler component in Step1, stirring for 2-3min, pouring into a ball mill for wet grinding until the fineness reaches 20 mu m, and sieving with a 200-mesh sieve to obtain a pre-mixed component;
step3, weighing 100-120 parts by weight of self-made resin emulsion, pouring the pre-mixed components in Step2 into the self-made resin emulsion, and stirring the pre-mixed components for 8-10min at a stirring speed of 1000-1200r/min to obtain the water-based paint.
Still further, the defoamer, dispersant, wetting agent and leveling agent are polydimethylsiloxane, sodium octadecenoate, polyoxyethylene fatty alcohol ether and polymethylphenylsiloxane, respectively.
Further, the stirring speed in Step1 is 500-600r/min, and the stirring speed in Step2 is 600-700r/min.
Further, the rotating speed of wet grinding in Step2 is 2500-3000r/min.
Advantageous effects
The invention provides a water-based paint and a preparation process thereof, and compared with the prior art, the water-based paint has the following beneficial effects:
1. according to the invention, polyaniline is grafted on the surface of graphene oxide after phosphoric acid acidification through dodecylbenzene sulfonic acid, so that the dispersibility and compatibility of graphene oxide in the water-based paint can be improved, and water molecules can be prevented from forming an ion conducting path of electrolyte through the higher specific surface area and physical barrier of the graphene oxide, so that the water-based paint is assisted to have better anti-corrosion performance, and the adhesive force, passivation effect and corrosion inhibition effect of the water-based paint coating can be enhanced through the introduction of polyaniline, and electrons are prevented from corroding in the form of metal particles; through the addition of the fumed silica, the fumed silica can be adsorbed on the surface of the graphene oxide coated with polyaniline, and a grid structure can be formed through hydrogen bonds formed by silicon hydroxyl groups, so that the graphene oxide is prevented from precipitating in the water-based paint, and the dispersibility of the graphene oxide in the water-based paint is further improved.
2. According to the invention, the modified graphene oxide and the mildew-proof component are mixed in an ultrasonic dispersion manner, so that antibacterial molecules in the mildew-proof component can be dispersed in silica adsorbed on the modified graphene oxide, and as the surface of the silica contains more porous structures, the antibacterial molecules in the mildew-proof component can be adsorbed on the porous structures, so that the modified graphene oxide has stable antibacterial performance, and the mildew-proof performance of the water-based paint can be enhanced when the modified graphene oxide is added into the water-based paint; secondly, the invention introduces the acetoacetoxyethyl methacrylate as a self-crosslinking monomer into the self-made resin emulsion, can enhance the resin crosslinking density, can be connected with a grid structure formed by hydrogen bonds in the modified graphene oxide in the self-crosslinking process of the acetoacetoxyethyl methacrylate, and improves the water resistance and the stability of the water-based paint to a certain extent.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. 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.
The invention is further described below with reference to examples.
Example 1
The raw materials of the water-based paint in the embodiment comprise the following components: self-made resin emulsion, modified graphene oxide and mildew-proof components;
the self-made resin emulsion is prepared by polymerizing methyl methacrylate, styrene, butyl acrylate, acrylic acid, isobornyl methacrylate, hydroxyethyl methacrylate, acetoacetoxyethyl methacrylate and azobisisobutyronitrile;
the modified graphene oxide is prepared by introducing polyaniline into the surface of the graphene oxide after phosphoric acid acidification through dodecylbenzene sulfonic acid;
the mildew-proof component is prepared by mixing different quaternary ammonium salt antibacterial agents.
The preparation method of the self-made resin emulsion comprises the following steps:
step1, weighing 80 parts by weight of methyl ethyl ketone, pouring the 80 parts by weight of methyl ethyl ketone into a reaction kettle, heating to 60 ℃ under stirring at a stirring speed of 50r/min, adding 10 parts by weight of methyl methacrylate, 10 parts by weight of styrene, 10 parts by weight of butyl acrylate, 3 parts by weight of acrylic acid, 3 parts by weight of isobornyl methacrylate, 5 parts by weight of hydroxyethyl methacrylate and 1 part by weight of azobisisobutyronitrile under the protection of nitrogen, stirring to be transparent at the stirring speed of 50r/min, and pumping the mixture to a high-level tank;
step2, after the reaction kettle is heated to 75 ℃, dripping the components in the high-level tank in the step1 at a constant speed, after dripping is completed within 2 hours, adding 10 parts by weight of methyl methacrylate, 10 parts by weight of styrene, 10 parts by weight of butyl acrylate, 3 parts by weight of acrylic acid, 3 parts by weight of isobornyl methacrylate, 15 parts by weight of acetoacetoxyethyl methacrylate and 1 part by weight of azodiisobutyronitrile into the reaction kettle, continuously stirring at a stirring speed of 50r/min until the components are transparent, and pumping the components into the high-level tank again;
step3, dripping the components in the overhead tank in the step2 into a reaction kettle again at a constant speed, controlling the dripping time to be 2 hours, adding 8 parts by weight of methyl ethyl ketone into the overhead tank for flushing, pouring the flushed methyl ethyl ketone into the reaction kettle again, heating the reaction kettle to 75 ℃, preserving heat for 4 hours, and respectively adding 0.5 and 0.1 parts by weight of azodiisobutyronitrile in the 1.5h and the 2.5h of heat preservation;
and 4, after the heat preservation in the step3 is finished, heating the reaction kettle to 100 ℃ to remove methyl ethyl ketone, pumping 3 parts by weight of N, N-dimethylethanolamine into a high-level tank, uniformly dripping the N, N-dimethylethanolamine into the reaction kettle at the temperature of 60 ℃, controlling the dripping time to be within 0.5h, pumping 80 parts by weight of deionized water into the high-level tank to drip, controlling the dripping time to be within 0.5h, and obtaining the self-made resin emulsion, wherein the pH value of components in the reaction kettle is controlled to be 6.5 in the process of dripping the N, N-dimethylethanolamine.
The preparation method of the modified graphene oxide comprises the following steps:
s1, according to 1: mixing dodecylbenzene sulfonic acid and deionized water according to the feed liquid ratio of 19g/mL, and performing ultrasonic dispersion for 30min at the frequency of 23kHz to obtain a dodecylbenzene sulfonic acid solution; according to 1:50g/mL of ammonium persulfate is dissolved in a phosphoric acid solution with the mass fraction of 25%, and is subjected to ultrasonic dispersion for 18min at the frequency of 22kHz, so that the ammonium persulfate/phosphoric acid solution is obtained;
s2, according to 1: pouring graphene oxide and concentrated phosphoric acid solution with the mass fraction of 80% into a flask for mixing according to the feed liquid ratio of 80g/mL, placing the mixture into an oil bath at 50 ℃ for stirring at the stirring speed of 300r/min for 10h, transferring the mixture into an ice water bath, and continuing stirring at the original stirring speed for 25min, wherein the obtained mixture is recorded as a component to be reacted;
s3, pouring the dodecylbenzene sulfonic acid solution in the S1 into a component to be reacted, stirring at a stirring speed of 500r/min for 25min, adding aniline with the same weight as that of graphene oxide, stirring at an original stirring speed for 28min, dropwise adding the ammonium persulfate/phosphoric acid solution in the S1, stirring in an ice water bath at an original stirring speed for 10h after the dropwise adding is completed, and reacting to obtain a reaction mixed component;
and S4, adding fumed silica with the same weight as the graphene oxide into the reaction mixed components for continuous reaction for 8 hours, filtering to remove filtrate after the reaction is finished, washing filter residues with deionized water to be neutral, drying in a vacuum drying oven at 70 ℃ for 7 hours, and grinding and sieving with a 200-mesh sieve to obtain the modified graphene oxide.
The mildew-proof components are dodecyl dimethyl benzyl ammonium chloride, didecyl dimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, tetradecyl dimethyl decyl ammonium bromide and hexadecyl dimethyl octyl ammonium bromide according to the following weight ratio of 2:1:3:1:1 weight ratio.
The preparation process of the water-based paint comprises the following raw materials: the defoaming agent, the wetting agent, the leveling agent, the dispersing agent, the zinc phosphate, the aluminum tripolyphosphate, the strontium chrome yellow and the deionized water are respectively polydimethylsiloxane, sodium octadecenoate, polyoxyethylene fatty alcohol ether and polymethylphenylsiloxane;
the preparation process of the water-based paint comprises the following steps:
step1, weighing 5 parts by weight of modified graphene oxide, dispersing in 80 parts by weight of deionized water, stirring at a stirring speed of 500r/min for 5min, adding 2 parts by weight of mildew-proof component, continuing stirring for 5min, and performing ultrasonic dispersion at a frequency of 25kHz for 1h to obtain a filler component;
step2, adding 0.1 part by weight of defoamer, 0.2 part by weight of wetting agent, 0.1 part by weight of flatting agent, 1 part by weight of dispersing agent, 2 parts by weight of zinc phosphate, 2 parts by weight of aluminum tripolyphosphate and 1 part by weight of strontium chrome yellow into the filler component in Step1, stirring at a stirring speed of 600r/min for 2min, pouring into a ball mill, performing wet milling at a rotating speed of 2500r/min until the fineness reaches 20 mu m, and sieving with a 200-mesh sieve to obtain a pre-mixed component;
step3, weighing 100 parts by weight of self-made resin emulsion, pouring the pre-mixed components in Step2 into the self-made resin emulsion, and stirring the mixture for 8min at a stirring speed of 1000r/min to obtain the water-based paint.
Example 2
The raw materials of the water-based paint in the embodiment comprise the following components: self-made resin emulsion, modified graphene oxide and mildew-proof components;
the self-made resin emulsion is prepared by polymerizing methyl methacrylate, styrene, butyl acrylate, acrylic acid, isobornyl methacrylate, hydroxyethyl methacrylate, acetoacetoxyethyl methacrylate and azobisisobutyronitrile;
the modified graphene oxide is prepared by introducing polyaniline into the surface of the graphene oxide after phosphoric acid acidification through dodecylbenzene sulfonic acid;
the mildew-proof component is prepared by mixing different quaternary ammonium salt antibacterial agents.
The preparation method of the self-made resin emulsion comprises the following steps:
step1, weighing 90 parts by weight of methyl ethyl ketone, pouring the mixture into a reaction kettle, heating the mixture to 60 ℃ under stirring at a stirring speed of 100r/min, adding 25 parts by weight of methyl methacrylate, 20 parts by weight of styrene, 20 parts by weight of butyl acrylate, 10 parts by weight of acrylic acid, 10 parts by weight of isobornyl methacrylate, 10 parts by weight of hydroxyethyl methacrylate and 5 parts by weight of azobisisobutyronitrile under the protection of nitrogen, stirring the mixture to be transparent at the stirring speed of 100r/min, and pumping the mixture to a high-level tank;
step2, after the temperature of the reaction kettle is raised to 80 ℃, dripping the components in the high-level tank in the step1 at a constant speed, after dripping is completed within 2 hours, adding 25 parts by weight of methyl methacrylate, 20 parts by weight of styrene, 20 parts by weight of butyl acrylate, 10 parts by weight of acrylic acid, 10 parts by weight of isobornyl methacrylate, 20 parts by weight of acetoacetoxyethyl methacrylate and 5 parts by weight of azodiisobutyronitrile into the reaction kettle, continuously stirring at a stirring speed of 100r/min until the components are transparent, and pumping the components into the high-level tank again;
step3, dripping the components in the elevated tank in the step2 into a reaction kettle again at a constant speed, controlling the dripping time to be 2 hours, adding 10 parts by weight of methyl ethyl ketone into the elevated tank for flushing, pouring the flushed methyl ethyl ketone into the reaction kettle again, heating the reaction kettle to 80 ℃, preserving heat for 4 hours, and respectively adding 0.5 and 0.1 parts by weight of azodiisobutyronitrile in the 1.5h and the 2.5h of heat preservation;
and 4, after the heat preservation in the step3 is finished, heating the reaction kettle to 100 ℃ to remove methyl ethyl ketone, pumping 10 parts by weight of N, N-dimethylethanolamine into a high-level tank, uniformly dripping the N, N-dimethylethanolamine into the reaction kettle at 70 ℃, controlling the dripping time to be within 0.5h, pumping 100 parts by weight of deionized water into the high-level tank to drip, controlling the dripping time to be within 0.5h, and obtaining the self-made resin emulsion, wherein the pH value of components in the reaction kettle is controlled to be 7.5 in the process of dripping the N, N-dimethylethanolamine.
The preparation method of the modified graphene oxide comprises the following steps:
s1, according to 1: mixing dodecylbenzene sulfonic acid and deionized water according to a feed liquid ratio of 19g/mL, and performing ultrasonic dispersion for 35min at a frequency of 25kHz to obtain a dodecylbenzene sulfonic acid solution; according to 1:50g/mL of ammonium persulfate is dissolved in a phosphoric acid solution with the mass fraction of 30%, and is subjected to ultrasonic dispersion for 20min at the frequency of 23kHz, so that the ammonium persulfate/phosphoric acid solution is obtained;
s2, according to 1: pouring graphene oxide and concentrated phosphoric acid solution with the mass fraction of 85% into a flask for mixing at the feed liquid ratio of 80g/mL, stirring at the stirring speed of 400r/min for 12h under the oil bath condition of 50 ℃, transferring into ice water bath, continuing stirring at the original stirring speed for 30min, and recording the obtained mixture as a component to be reacted;
s3, pouring the dodecylbenzene sulfonic acid solution in the S1 into a component to be reacted, stirring at a stirring speed of 600r/min for 30min, adding aniline with the same weight as that of graphene oxide, stirring at an original stirring speed for 30min, dropwise adding the ammonium persulfate/phosphoric acid solution in the S1, stirring in an ice water bath at an original stirring speed for 12h after the dropwise adding is completed, and reacting to obtain a reaction mixed component;
and S4, adding fumed silica with the same weight as the graphene oxide into the reaction mixed components for continuous reaction for 10 hours, filtering to remove filtrate after the reaction is finished, washing filter residues with deionized water to be neutral, drying in a vacuum drying oven at 70 ℃ for 8 hours, and grinding and sieving with a 200-mesh sieve to obtain the modified graphene oxide.
The mildew-proof components are dodecyl dimethyl benzyl ammonium chloride, didecyl dimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, tetradecyl dimethyl decyl ammonium bromide and hexadecyl dimethyl octyl ammonium bromide according to the following weight ratio of 2:1:3:1:1 weight ratio.
The preparation process of the water-based paint comprises the following raw materials: the defoaming agent, the wetting agent, the leveling agent, the dispersing agent, the zinc phosphate, the aluminum tripolyphosphate, the strontium chrome yellow and the deionized water are respectively polydimethylsiloxane, sodium octadecenoate, polyoxyethylene fatty alcohol ether and polymethylphenylsiloxane;
the preparation process of the water-based paint comprises the following steps:
step1, weighing 6 parts by weight of modified graphene oxide, dispersing in 90 parts by weight of deionized water, stirring at a stirring speed of 600r/min for 8min, adding 3 parts by weight of mildew-proof component, continuing stirring for 6min, and performing ultrasonic dispersion at a frequency of 27kHz for 2h to obtain a filler component;
step2, adding 0.2 part by weight of defoamer, 0.3 part by weight of wetting agent, 0.2 part by weight of flatting agent, 2 parts by weight of dispersing agent, 3 parts by weight of zinc phosphate, 3 parts by weight of aluminum tripolyphosphate and 2 parts by weight of strontium chrome yellow into the filler component in Step1, stirring for 3min at a stirring speed of 700r/min, pouring into a ball mill, wet-milling at a rotating speed of 3000r/min until the fineness reaches 20 mu m, and sieving with a 200-mesh sieve to obtain a pre-mixed component;
step3, weighing 120 parts by weight of self-made resin emulsion, pouring the pre-mixed components in Step2 into the self-made resin emulsion, and stirring the mixture for 10 minutes at a stirring speed of 1200r/min to obtain the water-based paint.
Example 3
The raw materials of the water-based paint in the embodiment comprise the following components: self-made resin emulsion, modified graphene oxide and mildew-proof components;
the self-made resin emulsion is prepared by polymerizing methyl methacrylate, styrene, butyl acrylate, acrylic acid, isobornyl methacrylate, hydroxyethyl methacrylate, acetoacetoxyethyl methacrylate and azobisisobutyronitrile;
the modified graphene oxide is prepared by introducing polyaniline into the surface of the graphene oxide after phosphoric acid acidification through dodecylbenzene sulfonic acid;
the mildew-proof component is prepared by mixing different quaternary ammonium salt antibacterial agents.
The preparation method of the self-made resin emulsion comprises the following steps:
step1, weighing 85 parts by weight of methyl ethyl ketone, pouring the methyl ethyl ketone into a reaction kettle, heating to 60 ℃ under stirring at a stirring speed of 80r/min, adding 18 parts by weight of methyl methacrylate, 15 parts by weight of styrene, 15 parts by weight of butyl acrylate, 8 parts by weight of acrylic acid, 8 parts by weight of isobornyl methacrylate, 8 parts by weight of hydroxyethyl methacrylate and 3 parts by weight of azobisisobutyronitrile under the protection of nitrogen, stirring to be transparent at the stirring speed of 80r/min, and pumping the mixture to a high-level tank;
step2, after the reaction kettle is heated to 78 ℃, dripping the components in the high-level tank in the step1 at a constant speed, after dripping is completed within 2 hours, adding 18 parts by weight of methyl methacrylate, 18 parts by weight of styrene, 18 parts by weight of butyl acrylate, 8 parts by weight of acrylic acid, 8 parts by weight of isobornyl methacrylate, 18 parts by weight of acetoacetoxyethyl methacrylate and 3 parts by weight of azodiisobutyronitrile into the reaction kettle, continuously stirring at a stirring speed of 80r/min until the components are transparent, and pumping the components into the high-level tank again;
step3, dripping the components in the overhead tank in the step2 into a reaction kettle again at a constant speed, controlling the dripping time to be 2 hours, adding 9 parts by weight of methyl ethyl ketone into the overhead tank for flushing, pouring the flushed methyl ethyl ketone into the reaction kettle again, raising the temperature of the reaction kettle to 78 ℃, preserving heat for 4 hours, and respectively adding 0.5 and 0.1 parts by weight of azodiisobutyronitrile in the 1.5h and the 2.5h of heat preservation;
and 4, after the heat preservation in the step3 is finished, heating the reaction kettle to 100 ℃ to remove methyl ethyl ketone, pumping 8 parts by weight of N, N-dimethylethanolamine into a high-level tank, uniformly dripping the N, N-dimethylethanolamine into the reaction kettle at 65 ℃, controlling the dripping time to be within 0.5h, pumping 90 parts by weight of deionized water into the high-level tank to drip, controlling the dripping time to be within 0.5h, and obtaining the self-made resin emulsion, wherein the pH value of components in the reaction kettle is controlled to be 7.0 in the process of dripping the N, N-dimethylethanolamine.
The preparation method of the modified graphene oxide comprises the following steps:
s1, according to 1: mixing dodecylbenzene sulfonic acid and deionized water according to the feed liquid ratio of 19g/mL, and performing ultrasonic dispersion for 33min at the frequency of 24kHz to obtain a dodecylbenzene sulfonic acid solution; according to 1:50g/mL of ammonium persulfate is dissolved in a phosphoric acid solution with the mass fraction of 28%, and is subjected to ultrasonic dispersion for 19min at the frequency of 23kHz, so that the ammonium persulfate/phosphoric acid solution is obtained;
s2, according to 1: pouring graphene oxide and 83% of concentrated phosphoric acid solution into a flask according to the feed liquid ratio of 80g/mL, mixing, stirring at the stirring speed of 400r/min under the oil bath condition of 50 ℃ for 11h, transferring into ice water bath, continuing stirring at the original stirring speed for 28min, and recording the obtained mixture as a component to be reacted;
s3, pouring the dodecylbenzene sulfonic acid solution in the S1 into a component to be reacted, stirring at a stirring speed of 500r/min for 28min, adding aniline with the same weight as that of graphene oxide, stirring at an original stirring speed for 29min, dropwise adding the ammonium persulfate/phosphoric acid solution in the S1, stirring in an ice water bath at an original stirring speed for 11h after the dropwise adding is completed, and reacting to obtain a reaction mixed component;
and S4, adding fumed silica with the same weight as the graphene oxide into the reaction mixed components for continuous reaction for 9 hours, filtering to remove filtrate after the reaction is finished, washing filter residues with deionized water to be neutral, drying in a vacuum drying oven at 70 ℃ for 8 hours, and grinding and sieving with a 200-mesh sieve to obtain the modified graphene oxide.
The mildew-proof components are dodecyl dimethyl benzyl ammonium chloride, didecyl dimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, tetradecyl dimethyl decyl ammonium bromide and hexadecyl dimethyl octyl ammonium bromide according to the following weight ratio of 2:1:3:1:1 weight ratio.
The preparation process of the water-based paint comprises the following raw materials: the defoaming agent, the wetting agent, the leveling agent, the dispersing agent, the zinc phosphate, the aluminum tripolyphosphate, the strontium chrome yellow and the deionized water are respectively polydimethylsiloxane, sodium octadecenoate, polyoxyethylene fatty alcohol ether and polymethylphenylsiloxane;
the preparation process of the water-based paint comprises the following steps:
step1, weighing 6 parts by weight of modified graphene oxide, dispersing in 85 parts by weight of deionized water, stirring for 7min at a stirring speed of 600r/min, adding 3 parts by weight of mildew-proof component, continuing stirring for 6min, and performing ultrasonic dispersion for 2h at a frequency of 26kHz, wherein the obtained mixture is recorded as a filler component;
step2, adding 0.1 part by weight of defoamer, 0.3 part by weight of wetting agent, 0.1 part by weight of flatting agent, 2 parts by weight of dispersing agent, 3 parts by weight of zinc phosphate, 2 parts by weight of aluminum tripolyphosphate and 2 parts by weight of strontium chrome yellow into the filler component in Step1, stirring for 3min at a stirring speed of 700r/min, pouring into a ball mill, wet-milling at a rotating speed of 2800r/min until the fineness reaches 20 mu m, and sieving with a 200-mesh sieve to obtain a pre-mixed component;
step3, weighing 110 parts by weight of self-made resin emulsion, pouring the pre-mixed components in Step2 into the self-made resin emulsion, and stirring the mixture for 9 minutes at a stirring speed of 1100r/min to obtain the water-based paint.
Comparative example 1:
the water-based paint and the preparation process thereof provided in this comparative example are substantially the same as those in example 1, and the main differences are that: this comparative example 1 replaces the modified graphene oxide in example 1 with unmodified graphene oxide.
Comparative example 2:
the water-based paint and the preparation process thereof provided in this comparative example are substantially the same as those in example 1, and the main differences are that: in this comparative example 1, fumed silica was not added to the process for producing modified graphene oxide.
Performance testing
The aqueous paints prepared in examples 1-3 and comparative examples 1-2 were labeled as example 1, example 2, example 3, comparative example 1 and comparative example 2, respectively, and then the properties of examples 1-3 and comparative examples 1-2 were examined, with the following specific detection methods and detection items:
1. the aqueous paints of examples 1 to 3 and comparative examples 1 to 2 were subjected to acid resistance test, alkali resistance test and salt spray resistance test with reference to the standards of GB/T9274-88 "determination of liquid medium resistance of paint and varnish" and GB/T1771-2007 "determination of neutral salt spray resistance of paint and varnish", and the test results are recorded in Table 1;
2. the water-based paint of examples 1-3 and comparative examples 1-2 were tested for antibacterial efficiency according to GB/T2591-2003, and the test results are recorded in Table 2;
3. the water-based paints of examples 1 to 3 and comparative examples 1 to 2 were tested for impact resistance according to the GB/T1732-93 Standard of paint film impact resistance assay, and the test results are recorded in Table 2;
4. the pencil hardness of the aqueous coating compositions of examples 1 to 3 and comparative examples 1 to 2 was measured in accordance with the standard of GB/T67391996 pencil test for coating hardness, and the measurement results are shown in Table 2.
TABLE 1
TABLE 2
As is apparent from the data in tables 1 and 2, the aqueous coating materials prepared in the present examples 1 to 3 have more excellent acid-alkali salt mist corrosion resistance than the comparative examples 1 to 2, and are superior to the comparative examples 1 to 2 in both of the antibacterial property impact resistance and pencil hardness, thus demonstrating that the aqueous coating materials prepared in the present invention have better market application prospects.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The water-based paint is characterized by comprising the following raw materials: self-made resin emulsion, modified graphene oxide and mildew-proof components;
the self-made resin emulsion is prepared by polymerization reaction of methyl methacrylate, styrene, butyl acrylate, acrylic acid, isobornyl methacrylate, hydroxyethyl methacrylate, acetoacetoxyethyl methacrylate and azobisisobutyronitrile;
the modified graphene oxide is prepared by introducing polyaniline into the surface of graphene oxide subjected to phosphoric acid acidification through dodecylbenzene sulfonic acid;
the mildew-proof component is prepared by mixing different quaternary ammonium salt antibacterial agents.
2. The water-based paint according to claim 1, wherein the preparation method of the self-made resin emulsion comprises the following steps:
step1, weighing 80-90 parts by weight of methyl ethyl ketone, pouring the mixture into a reaction kettle, heating the mixture to 60 ℃ under stirring at a stirring speed of 50-100r/min, adding 10-25 parts by weight of methyl methacrylate, 10-20 parts by weight of styrene, 10-20 parts by weight of butyl acrylate, 3-10 parts by weight of acrylic acid, 3-10 parts by weight of isobornyl methacrylate, 5-10 parts by weight of hydroxyethyl methacrylate and 1-5 parts by weight of azobisisobutyronitrile under the protection of nitrogen, stirring the mixture to be transparent at a stirring speed of 50-100r/min, and pumping the mixture to a high-level tank;
step2, after the temperature of the reaction kettle is raised to 75-80 ℃, uniformly dropwise adding the components in the high-level tank in the step1, after the components are dropwise added within 2 hours, adding 10-25 parts by weight of methyl methacrylate, 10-20 parts by weight of styrene, 10-20 parts by weight of butyl acrylate, 3-10 parts by weight of acrylic acid, 3-10 parts by weight of isobornyl methacrylate, 15-20 parts by weight of acetoacetoxyethyl methacrylate and 1-5 parts by weight of azobisisobutyronitrile into the reaction kettle, continuously stirring at a stirring speed of 50-100r/min until the components are transparent, and pumping the components into the high-level tank again;
step3, dripping the components in the overhead tank in the step2 into a reaction kettle at a constant speed, controlling the dripping time to be 2 hours, adding 8-10 parts by weight of methyl ethyl ketone into the overhead tank for flushing, pouring the flushed methyl ethyl ketone into the reaction kettle again, heating the reaction kettle to 75-80 ℃, preserving heat for 4 hours, and respectively adding 0.5 and 0.1 parts by weight of azodiisobutyronitrile in the 1.5 hours and the 2.5 hours of heat preservation;
and 4, after the heat preservation in the step3 is finished, heating the reaction kettle to 100 ℃ to remove methyl ethyl ketone, pumping 3-10 parts by weight of N, N-dimethylethanolamine into a high-level tank, uniformly dripping the N, N-dimethylethanolamine into the reaction kettle at 60-70 ℃, pumping 80-100 parts by weight of deionized water into the high-level tank for dripping after dripping within 0.5h, and dripping within 0.5h to obtain the self-made resin emulsion.
3. The water-based paint according to claim 2, wherein the pH of the components in the reaction vessel is controlled to be 6.5-7.5 during the process of dropwise adding N, N-dimethylethanolamine in the step 4.
4. The water-based paint according to claim 1, wherein the preparation method of the modified graphene oxide is as follows:
s1, according to 1: mixing dodecylbenzene sulfonic acid and deionized water according to the feed liquid ratio of 19g/mL, and performing ultrasonic dispersion for 30-35min at the frequency of 23-25kHz, wherein the obtained mixture is named as dodecylbenzene sulfonic acid solution; according to 1: dissolving ammonium persulfate in a phosphoric acid solution according to a feed liquid ratio of 50g/mL, and performing ultrasonic dispersion for 18-20min at a frequency of 22-23kHz, wherein the obtained solution is named ammonium persulfate/phosphoric acid solution;
s2, according to 1: pouring graphene oxide and concentrated phosphoric acid solution into a flask according to the feed liquid ratio of 80g/mL, mixing, placing the mixture into an oil bath at 50 ℃ and stirring at the stirring speed of 300-400r/min for 10-12h, transferring the mixture into an ice water bath, continuing stirring at the original stirring speed for 25-30min, and recording the mixture as a component to be reacted;
s3, pouring the dodecylbenzene sulfonic acid solution in the S1 into a component to be reacted, stirring at a stirring speed of 500-600r/min for 25-30min, adding aniline with the same weight as that of graphene oxide, stirring at an original stirring speed for 28-30min, dropwise adding the ammonium persulfate/phosphoric acid solution in the S1, stirring in an ice water bath at an original stirring speed for 10-12h for reaction after the dropwise adding is completed, and marking the obtained mixture as a reaction mixed component;
s4, adding fumed silica with the same weight as the graphene oxide into the reaction mixed components, continuously reacting for 8-10 hours, filtering to remove filtrate after the reaction is finished, washing filter residues with deionized water to be neutral, drying in a vacuum drying oven at 70 ℃ for 7-8 hours, grinding and sieving with a 200-mesh sieve to obtain the modified graphene oxide.
5. The water-based paint according to claim 4, wherein the mass fraction of the phosphoric acid solution in S1 is 25-30%, and the mass fraction of the concentrated phosphoric acid solution in S2 is 80-85%.
6. A water paint according to claim 1, wherein the mildew-resistant component is dodecyldimethylbenzyl ammonium chloride, didecyldimethyl ammonium chloride, cetyltrimethylammonium chloride, tetradecyldimethyldecyl ammonium bromide and hexadecyldimethyloctyl ammonium bromide according to 2:1:3:1:1 weight ratio.
7. The process for preparing a water-based paint according to any one of claims 1 to 6, wherein the raw materials of the water-based paint further comprise the following components: defoaming agent, wetting agent, leveling agent, dispersing agent, zinc phosphate, aluminum tripolyphosphate, strontium chrome yellow and deionized water;
the preparation process of the water-based paint comprises the following steps:
step1, weighing 5-6 parts by weight of modified graphene oxide, dispersing in 80-90 parts by weight of deionized water, stirring for 5-8min, adding 2-3 parts by weight of mildew-proof component, continuing stirring for 5-6min, and performing ultrasonic dispersion for 1-2h at a frequency of 25-27kHz, wherein the obtained mixture is taken as a filler component;
step2, adding 0.1-0.2 part by weight of defoamer, 0.2-0.3 part by weight of wetting agent, 0.1-0.2 part by weight of flatting agent, 1-2 parts by weight of dispersing agent, 2-3 parts by weight of zinc phosphate, 2-3 parts by weight of aluminum tripolyphosphate and 1-2 parts by weight of strontium chrome yellow into a filler component in Step1, stirring for 2-3min, pouring into a ball mill for wet grinding until the fineness reaches 20 mu m, and sieving with a 200-mesh sieve to obtain a pre-mixed component;
step3, weighing 100-120 parts by weight of self-made resin emulsion, pouring the pre-mixed components in Step2 into the self-made resin emulsion, and stirring the pre-mixed components for 8-10min at a stirring speed of 1000-1200r/min to obtain the water-based paint.
8. The process for preparing a water-based paint according to claim 7, wherein the antifoaming agent, the dispersing agent, the wetting agent and the leveling agent are polydimethylsiloxane, sodium octadecenoate, polyoxyethylene fatty alcohol ether and polymethylphenylsiloxane, respectively.
9. The process for preparing a water-based paint according to claim 7, wherein the stirring speed in Step1 is 500-600r/min, and the stirring speed in Step2 is 600-700r/min.
10. The process for preparing a water-based paint according to claim 7, wherein the wet-milling speed in Step2 is 2500-3000r/min.
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| CN116426205A (en) * | 2023-06-12 | 2023-07-14 | 几何智慧城市科技(广州)有限公司 | Preparation method of high-hardness water-based paint |
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