CN112321772A - Styrene-acrylic emulsion for quick-drying water-based metallic paint and preparation method thereof - Google Patents
Styrene-acrylic emulsion for quick-drying water-based metallic paint and preparation method thereof Download PDFInfo
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- CN112321772A CN112321772A CN202011329899.3A CN202011329899A CN112321772A CN 112321772 A CN112321772 A CN 112321772A CN 202011329899 A CN202011329899 A CN 202011329899A CN 112321772 A CN112321772 A CN 112321772A
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- 239000000839 emulsion Substances 0.000 title claims abstract description 80
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000003973 paint Substances 0.000 title claims abstract description 49
- 238000001035 drying Methods 0.000 title claims abstract description 37
- 229920001909 styrene-acrylic polymer Polymers 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 52
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 26
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 25
- 239000010452 phosphate Substances 0.000 claims abstract description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 24
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 18
- 239000007800 oxidant agent Substances 0.000 claims abstract description 18
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 17
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 16
- 238000004132 cross linking Methods 0.000 claims abstract description 15
- 230000001590 oxidative effect Effects 0.000 claims abstract description 13
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000004945 emulsification Methods 0.000 claims description 10
- -1 alkyl phosphate Chemical compound 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 5
- 229930003268 Vitamin C Natural products 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000004806 packaging method and process Methods 0.000 claims description 5
- 235000019154 vitamin C Nutrition 0.000 claims description 5
- 239000011718 vitamin C Substances 0.000 claims description 5
- QRIMLDXJAPZHJE-UHFFFAOYSA-N 2,3-dihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CO QRIMLDXJAPZHJE-UHFFFAOYSA-N 0.000 claims description 4
- WDFFWUVELIFAOP-UHFFFAOYSA-N 2,6-difluoro-4-nitroaniline Chemical compound NC1=C(F)C=C([N+]([O-])=O)C=C1F WDFFWUVELIFAOP-UHFFFAOYSA-N 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 4
- IEORSVTYLWZQJQ-UHFFFAOYSA-N 2-(2-nonylphenoxy)ethanol Chemical compound CCCCCCCCCC1=CC=CC=C1OCCO IEORSVTYLWZQJQ-UHFFFAOYSA-N 0.000 claims description 4
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 claims description 4
- 229920000847 nonoxynol Polymers 0.000 claims description 4
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- VKOMCYHZNCTOQL-UHFFFAOYSA-N 3-hydroxy-1,2,4,3lambda5,5-trioxaphosphasilolane 3-oxide Chemical compound OP1(=O)OO[SiH2]O1 VKOMCYHZNCTOQL-UHFFFAOYSA-N 0.000 claims description 3
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- HSJXWMZKBLUOLQ-UHFFFAOYSA-M potassium;2-dodecylbenzenesulfonate Chemical compound [K+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HSJXWMZKBLUOLQ-UHFFFAOYSA-M 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- WDHYRUBXLGOLKR-UHFFFAOYSA-N phosphoric acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OP(O)(O)=O WDHYRUBXLGOLKR-UHFFFAOYSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 8
- 150000003839 salts Chemical class 0.000 abstract description 4
- 230000001681 protective effect Effects 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 2
- 239000007921 spray Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 7
- 239000004816 latex Substances 0.000 description 7
- 229920000126 latex Polymers 0.000 description 7
- 238000010276 construction Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000012792 core layer Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 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 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a styrene-acrylic emulsion for quick-drying water-based metallic paint and a preparation method thereof, wherein the styrene-acrylic emulsion comprises the following raw materials in parts by weight: 15-20 parts of styrene, 10-20 parts of methyl methacrylate, 5-10 parts of butyl acrylate, 1-5 parts of acrylic acid, 1-5 parts of phosphate functional monomer, 1-5 parts of crosslinking monomer, 1-5 parts of emulsifier, 0.1-1 part of persulfate, 0.1-0.5 part of oxidant, 0.1-0.5 part of reducing agent and 45-55 parts of water. The styrene-acrylic emulsion can obviously improve the solid drying speed of a paint film, form a very compact protective film and ensure good water resistance, salt spray resistance and other anti-corrosion properties.
Description
Technical Field
The invention relates to a styrene-acrylic emulsion for quick-drying water-based metal paint and a preparation method thereof, belonging to the technical field of metal corrosion prevention.
Background
In recent years, with the rapid development of aqueous industrial paints, increasingly stringent anticorrosion requirements and market competition, the requirements on the construction efficiency of aqueous metallic paints are higher and higher, especially the requirements on the drying speed, the gloss, the hardness and the anticorrosion and antirust properties of aqueous metallic surface paint films are higher and higher, and the aqueous metallic paints not only have certain anticorrosion properties, gloss and hardness, but also meet the requirements on rapid actual drying speed.
The prior patent discloses a method for producing resin emulsion for water-based metallic paint and the produced resin emulsion (CN102432730A), wherein the resin emulsion is prepared from the following raw materials in parts by weight: 0-260 parts of styrene, 40-310 parts of methyl methacrylate, 3.0-5.0 parts of acrylamide, 16.5-23.5 parts of acrylic acid, 182-202 parts of butyl acrylate, 18-38 parts of functional unsaturated monomer, 1.1-2.1 parts of emulsifier, 5.4-7.4 parts of polymerizable surfactant containing phosphorus and double bonds, 8-12 parts of organic silicon monomer and 45-55 parts of Zn with the mass concentration of 12-16%2+And (3) solution.
In addition, the patent discloses a method for preparing acrylate emulsion containing phosphate group for anticorrosion coating (CN101250365), and the formula is as follows: acrylate ester monomer: accounting for 80 to 99 percent of the total amount of the polymerized monomers; acrylate monomer containing phosphate group: accounting for 1 to 20 percent of the total amount of the polymerized monomers; emulsifier: accounting for 3 to 10 percent of the total amount of the polymerization monomers; water-soluble initiator: accounting for 0.2 to 1 percent of the total amount of the polymerization monomers; deionized water: accounting for 70 to 50 percent of the total amount of the product.
Further, a patent discloses an acrylic ester emulsion for aqueous metallic paint and a method for preparing the same (CN105254800A), wherein the emulsion comprises the following components in parts by weight, and does not contain a vinyl monomer or a vinyl aromatic compound of carboxyl or hydroxyl: 33-45 parts of a hydroxyl-containing vinyl monomer: 1-7 parts of a vinyl monomer containing a carboxyl group: 0.5-1 part of functional monomer: 1-3 parts of an organic silicon monomer: 1-3 parts of initiator: 0.15-0.4 part of composite emulsifier: 1-4 parts of a neutralizer: 0.1-0.5 parts of pH buffering agent: 0.05-0.1 part of deionized water: 45-50 parts by weight, and polymerizing the core/shell emulsion.
The water-based metallic paint prepared by the water-based styrene-acrylic emulsion in the prior art and the current commercially available common metallic paint only has the basic anticorrosion requirement of the metallic paint, does not have the performances of quick surface drying and actual drying, cannot solve the problems of stacking steel members, rain and the like in a short time after construction is finished, prolongs the construction progress, and seriously reduces the working efficiency. The higher the actual drying speed is, the faster the paint film performance can be embodied, the better the corrosion resistance is, and the working efficiency can be effectively improved, so that the overall material labor cost is reduced. Particularly, at high temperature in summer, a paint film is easy to soften, the hardness building time is long, and the construction period is seriously influenced.
Therefore, it is an urgent task to develop a special water-based acrylic emulsion which has the performance of quick and actual drying, and also has good glossiness and hardness, and good water resistance, salt spray resistance and other anti-corrosion performances.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a styrene-acrylic emulsion for quick-drying water-based metallic paint and a preparation method thereof.
In order to achieve the purpose, the quick-drying styrene-acrylic emulsion for the water-based metallic paint comprises the following raw materials in parts by weight: 15-20 parts of styrene, 10-20 parts of methyl methacrylate, 5-10 parts of butyl acrylate, 1-5 parts of acrylic acid, 1-5 parts of phosphate functional monomer, 1-5 parts of crosslinking monomer, 1-5 parts of emulsifier, 0.1-1 part of persulfate, 0.1-0.5 part of oxidant, 0.1-0.5 part of reducing agent and 45-55 parts of water.
Preferably, the phosphate functional monomer is at least one of multifunctional acidic acrylate phosphate, alkyl acrylate phosphate, ethylene glycol methacrylate phosphate, 2-hydroxyethyl methacrylate phosphate, alkyl phosphate special monomer, and phosphate functional monomer such as siloxane phosphate.
Preferably, the emulsifier is at least one of allyloxy fatty alcohol ethoxylate sulfate, dodecylbenzene sulfonate, alkylphenol ethoxylate sulfate, and nonylphenol ethoxylate.
Preferably, the dodecylbenzene sulfonate is sodium dodecylbenzene sulfonate or potassium dodecylbenzene sulfonate.
Preferably, the crosslinking monomer is at least one of allyl methacrylate, hydroxyethyl acrylate, glycerol methacrylate, trimethylolpropane trimethacrylate, and diethylene glycol dimethacrylate.
Preferably, the persulfate is at least one of potassium persulfate, ammonium persulfate and sodium persulfate.
Preferably, the oxidizing agent is hydrogen peroxide; the reducing agent adopts vitamin C.
In addition, the invention also provides a preparation method of the styrene-acrylic emulsion for the quick-drying water-based metallic paint, which comprises the following steps:
1) preparation of a first-stage pre-emulsion: adding water with the formula amount of 20-30% and an emulsifier with the formula amount of 20-30% into a pre-emulsification cylinder, opening a stirrer, sequentially adding styrene, methyl methacrylate, butyl acrylate and acrylic acid monomers with the formula amount of 40-60%, and stirring and dispersing for 20-40 minutes;
2) preparation of a two-stage pre-emulsion: adding water with the formula amount of 20-30% and an emulsifier with the formula amount of 20-30% into a pre-emulsification cylinder, opening a stirrer, sequentially adding the rest of styrene, methyl methacrylate, butyl acrylate, acrylic acid, a crosslinking monomer and a phosphate functional monomer, and stirring and dispersing for 20-40 minutes;
3) adding the rest water and the rest emulsifier into the reactor, uniformly stirring, and heating to 70-90 ℃;
4) continuously and uniformly dripping persulfate solution, continuously and uniformly dripping the first-stage pre-emulsion prepared in the step 1) after 3-5 minutes, dripping for 1.5-2.5 hours, preserving heat for 1.5-2.5 hours, then continuously and uniformly dripping the second-stage pre-emulsion prepared in the step 2), dripping for 2-4 hours, heating to 80-85 ℃ after finishing dripping, and preserving heat for 0.5-1.5 hours;
5) cooling to 70-75 deg.C;
6) dripping aqueous solution of reducing agent with formula amount of 40-60% and oxidant with formula amount of 40-60% into the emulsion at the same time, dripping for 15-25 minutes, and keeping the temperature for 30-50 minutes;
7) continuously cooling to 60-65 ℃;
8) dropwise adding the rest aqueous solution of the reducing agent and the oxidant into the emulsion for 15-25 minutes at the same time, and preserving the temperature for 30-50 minutes;
9) and (5) closing the heater, cooling the emulsion to room temperature, filtering and packaging.
The mechanism of the invention is as follows:
according to the conventional latex particle film-forming theory, the higher the glass transition temperature is, the faster the drying speed is, and conversely, the slower the drying speed is. According to the influence factor of the drying speed of the coating, the less the amount of the film forming assistant is, the faster the drying speed is. The invention adopts the molecular design technology to control the molecular arrangement of the core-shell structure of the acrylic latex particles, soft monomers are mainly distributed in the core layer, and hard monomers are mainly distributed in the shell layer, thereby not only reducing the lowest film-forming temperature of the emulsion and reducing the addition of film-forming auxiliary agents in the coating, but also having higher glass-transition temperature of the shell layer and obviously improving the actual drying speed of the paint film; meanwhile, the crosslinking monomer is designed to be embedded on the surface layer of the latex particle, and by means of the high glass transition temperature of the shell layer, the crosslinking monomer can quickly form a very compact protective film, so that good water resistance, salt mist resistance and other anti-corrosion properties are ensured; meanwhile, a special phosphate functional monomer is grafted to the surface layer of the acrylic latex particle through polymerization reaction design, and the prepared metal coating has good complexing effect with metal ions by virtue of the high glass transition temperature of the shell layer, and meanwhile, the building time of the adhesive force with the base material is shortened, and the early water resistance is improved. The prepared metal coating not only reduces the addition of a film forming assistant, but also forms a compact, flat and smooth paint film by directly spraying or brushing on the surface of metal in one step, improves the hardness establishing time, saves the cost, improves the working efficiency, and is the styrene-acrylic emulsion for the water-based metal paint which quickly achieves the actual drying and simultaneously gives consideration to the anti-corrosion performance requirement.
The invention has the beneficial effects that:
1) compared with the prior art, the emulsion disclosed by the invention has the most remarkable characteristics that the actual drying time of a paint film is prolonged, the molecular arrangement of a core-shell structure of acrylic latex particles is controlled by utilizing a molecular design technology, soft monomers are mainly distributed in a core layer, hard monomers are mainly distributed in a shell layer, the minimum film forming temperature of the emulsion is reduced, the addition of a film forming auxiliary agent in the paint is reduced, meanwhile, the shell layer has higher glass transition temperature, the actual drying speed of the paint film is remarkably increased, the minimum film forming temperature of the emulsion is reduced, the actual drying speed of the paint film is remarkably increased, the paint film hardness and adhesive force establishment time of the prepared metal paint is greatly shortened, and the anti-adhesion effect of the paint film is improved. Particularly, at high temperature in summer, a paint film is easy to soften, the hardness establishment time is long, and the work efficiency of engineering is influenced.
2) According to the invention, the crosslinking monomer is embedded on the surface layer of the latex particle, and by virtue of the high glass transition temperature of the shell layer, the crosslinking monomer can quickly form a very compact protective film, so that good water resistance, salt mist resistance and other anti-corrosion properties are ensured.
3) The emulsion disclosed by the invention has the advantages of high glossiness, good hardness, excellent corrosion resistance and the like. The phosphate functional monomer is grafted to the surface layer of the acrylic latex particle through polymerization reaction design, and the metal coating prepared by the phosphate functional monomer has good complexing effect with metal ions by virtue of the high glass transition temperature of the shell layer, and meanwhile, the building time of the adhesive force with a base material is shortened, and the early water resistance is improved.
4) The emulsion disclosed by the invention is developed on the premise of being based on the water-based acrylic acid, and the characteristics of environmental protection, convenience in use, wide application and the like of the water-based acrylic acid are kept.
5) The emulsion is prepared into a coating and then directly sprayed or brushed on the surface of metal in one step to form a compact, flat and smooth paint film, so that the cost is saved, and the working efficiency is improved.
Detailed Description
The invention is described below by means of specific embodiments. Unless otherwise specified, the technical means used in the present invention are well known to those skilled in the art. In addition, the embodiments should be considered illustrative, and not restrictive, of the scope of the invention, which is defined solely by the claims. It will be apparent to those skilled in the art that various changes or modifications in the components and amounts of the materials used in these embodiments can be made without departing from the spirit and scope of the invention.
Example 1
The quick-drying styrene-acrylic emulsion for the water-based metallic paint comprises the following raw materials in parts by weight: 15 parts of styrene, 10 parts of methyl methacrylate, 8 parts of butyl acrylate, 1 part of acrylic acid, 2 parts of phosphate functional monomers (1 part of alkyl acrylate phosphate and 1 part of 2-hydroxyethyl methacrylate phosphate), 2 parts of a crosslinking monomer (allyl methacrylate), 2 parts of an emulsifier (1 part of sodium dodecyl benzene sulfonate and 1 part of allyloxy fatty alcohol polyoxyethylene ether ammonium sulfate), 0.3 part of persulfate (ammonium persulfate), 0.1 part of an oxidant (hydrogen peroxide), 0.1 part of a reducing agent (vitamin C) and 50 parts of water.
The preparation method of the styrene-acrylic emulsion for the quick-drying water-based metallic paint comprises the following steps:
1) preparation of a first-stage pre-emulsion: adding 10 parts of water and 0.4 part of emulsifier into a pre-emulsification cylinder, opening a stirrer, sequentially adding 5 parts of styrene, 1 part of methyl methacrylate, 6.4 parts of butyl acrylate and 0.4 part of acrylic acid, and stirring and dispersing for 20 minutes;
2) preparation of a two-stage pre-emulsion: adding 10 parts of water and 0.4 part of emulsifier into a pre-emulsification cylinder, opening a stirrer, sequentially adding the remaining 10 parts of styrene, 9 parts of methyl methacrylate, 1.6 parts of butyl acrylate, 0.6 part of acrylic acid, 1 part of alkyl acrylate phosphate, 1 part of 2-hydroxyethyl methacrylate phosphate and 2 parts of allyl methacrylate, and stirring and dispersing for 20 minutes;
3) adding the rest 30 parts of water and the rest 1.2 parts of emulsifier into the reactor, uniformly stirring, and heating to 70 ℃;
4) continuously and uniformly dripping persulfate solution, continuously and uniformly dripping the first-stage pre-emulsion prepared in the step 1) after 3 minutes, dripping for 1.5 hours, preserving heat for 1.5 hours, then continuously and uniformly dripping the second-stage pre-emulsion prepared in the step 2), dripping for 2 hours, raising the temperature to 80 ℃ after finishing dripping, and preserving heat for 0.5 hour;
5) cooling to 70 ℃;
6) simultaneously dripping 0.04 part of reducing agent and 0.04 part of oxidizing agent into the emulsion for 15 minutes, and preserving heat for 30 minutes;
7) continuously cooling to 60 ℃;
8) dropwise adding the rest of the aqueous solution prepared from 0.06 part of reducing agent and the aqueous solution prepared from 0.06 part of oxidizing agent into the emulsion at the same time, dropwise adding for 15 minutes, and keeping the temperature for 30 minutes;
9) and (5) closing the heater, cooling the emulsion to room temperature, filtering and packaging.
Example 2
The quick-drying styrene-acrylic emulsion for the water-based metallic paint comprises the following raw materials in parts by weight: 20 parts of styrene, 16 parts of methyl methacrylate, 5 parts of butyl acrylate, 5 parts of acrylic acid, 5 parts of phosphate functional monomer (alkyl acrylate phosphate), 1 part of crosslinking monomer (glycerol methacrylate), 3 parts of emulsifier (potassium dodecylbenzene sulfonate, 2 parts of nonylphenol ethoxylate), 0.6 part of persulfate (sodium persulfate), 0.3 part of oxidant (hydrogen peroxide), 0.3 part of reducer (vitamin C) and 48 parts of water.
The preparation method of the styrene-acrylic emulsion for the quick-drying water-based metallic paint comprises the following steps:
1) preparation of a first-stage pre-emulsion: adding 10 parts of water and 0.6 part of emulsifier into a pre-emulsification cylinder, opening a stirrer, sequentially adding 2 parts of styrene, 2 parts of methyl methacrylate, 4 parts of butyl acrylate and 1 part of acrylic acid, and stirring and dispersing for 30 minutes;
2) preparation of a two-stage pre-emulsion: adding 20 parts of water and 1.4 parts of emulsifier into a pre-emulsification cylinder, opening a stirrer, sequentially adding 18 parts of styrene, 14 parts of methyl methacrylate, 1 part of butyl acrylate, 4 parts of acrylic acid, 5 parts of alkyl acrylate phosphate and 1 part of glycerol methacrylate, and stirring and dispersing for 30 minutes;
3) adding the rest water and the rest emulsifier into the reactor, uniformly stirring, and heating to 80 ℃;
4) continuously and uniformly dripping a solution prepared by persulfate, continuously and uniformly dripping the first-stage pre-emulsion prepared in the step 1) after 4 minutes, dripping for 2 hours, preserving heat for 2 hours, then continuously and uniformly dripping the second-stage pre-emulsion prepared in the step 2), dripping for 3 hours, raising the temperature to 85 ℃ after finishing dripping, and preserving heat for 1 hour;
5) cooling to 75 ℃;
6) simultaneously dripping 0.15 part of reducing agent and 0.15 part of aqueous solution of oxidizing agent into the emulsion for 20 minutes, and preserving heat for 40 minutes;
7) continuously cooling to 60 ℃;
8) dropwise adding the rest aqueous solution of the reducing agent and the oxidant into the emulsion for 25 minutes at the same time, and keeping the temperature for 40 minutes;
9) and (5) closing the heater, cooling the emulsion to room temperature, filtering and packaging.
Example 3
The quick-drying styrene-acrylic emulsion for the water-based metallic paint comprises the following raw materials in parts by weight: 18 parts of styrene, 13 parts of methyl methacrylate, 10 parts of butyl acrylate, 3 parts of acrylic acid, 2 parts of phosphate functional monomer (siloxane phosphate), 3 parts of crosslinking monomer (1 part of hydroxyethyl acrylate and 2 parts of trimethylolpropane trimethacrylate), 2 parts of emulsifier (1 part of sodium dodecyl benzene sulfonate and 1 part of nonylphenol ethoxylate), 0.5 part of persulfate (sodium persulfate), 0.3 part of oxidant (hydrogen peroxide), 0.3 part of reducing agent (vitamin C) and 50 parts of water.
The preparation method of the styrene-acrylic emulsion for the quick-drying water-based metallic paint comprises the following steps:
1) preparation of a first-stage pre-emulsion: adding 15 parts of water and 0.5 part of emulsifier into a pre-emulsification cylinder, opening a stirrer, sequentially adding 5 parts of styrene, 1 part of methyl methacrylate, 8 parts of butyl acrylate and 1.5 parts of acrylic acid, and stirring and dispersing for 30 minutes;
2) preparation of a two-stage pre-emulsion: adding 20 parts of water and 0.5 part of emulsifier into a pre-emulsification cylinder, opening a stirrer, sequentially adding the rest of styrene, methyl methacrylate, butyl acrylate, acrylic acid, phosphate functional monomer and crosslinking monomer, and stirring and dispersing for 30 minutes;
3) adding the rest water and the rest emulsifier into the reactor, uniformly stirring, and heating to 80 ℃;
4) continuously and uniformly dripping persulfate solution, continuously and uniformly dripping the first-stage pre-emulsion prepared in the step 1) after 5 minutes, dripping for 2 hours, preserving heat for 2 hours, then continuously and uniformly dripping the second-stage pre-emulsion prepared in the step 2), dripping for 3 hours, heating to 83 ℃ after finishing dripping, and preserving heat for 1 hour;
5) cooling to 70 ℃;
6) simultaneously dripping 0.15 part of reducing agent and 0.15 part of aqueous solution of oxidizing agent into the emulsion for 20 minutes, and preserving heat for 40 minutes;
7) continuously cooling to 60 ℃;
8) dropwise adding the rest aqueous solution of the reducing agent and the oxidant into the emulsion for 20 minutes at the same time, and preserving the temperature for 40 minutes;
9) and (5) closing the heater, cooling the emulsion to room temperature, filtering and packaging.
The styrene-acrylic emulsion has the solid content of 25-55 percent, the pH value of 6-9 and the particle size of 50-150 nanometers.
The styrene-acrylic emulsion is emulsion resin for water-based metal paint, when in use, a certain amount of pigment and filler such as titanium dioxide, mica powder, barium sulfate, zinc phosphate and the like are added to prepare water-based primer-topcoat metal paint, and the water-based primer-topcoat metal paint is directly sprayed or brushed on the metal surface together to form a compact, flat and smooth paint film which can be dried within 12 hours at room temperature and has the performances of metal primer and topcoat.
According to the detection of the standard HG/T4758-2014 of the water-based acrylic resin coating, compared with the prior art, the emulsion prepared by the embodiment of the invention has the advantages of short hardness, short adhesion force establishment time, high glossiness, good hardness, good corrosion resistance, excellent anti-blocking performance and the like, and the specific performance detection indexes are shown in the following table 1.
TABLE 1 index for testing emulsion performance of each example
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (8)
1. The quick-drying styrene-acrylic emulsion for the water-based metallic paint is characterized by comprising the following raw materials in parts by weight: 15-20 parts of styrene, 10-20 parts of methyl methacrylate, 5-10 parts of butyl acrylate, 1-5 parts of acrylic acid, 1-5 parts of phosphate functional monomer, 1-5 parts of crosslinking monomer, 1-5 parts of emulsifier, 0.1-1 part of persulfate, 0.1-0.5 part of oxidant, 0.1-0.5 part of reducing agent and 45-55 parts of water.
2. The styrene-acrylic emulsion for quick-drying water-based metallic paint according to claim 1, wherein the phosphate functional monomer is at least one of multifunctional acidic acrylate phosphate, alkyl acrylate phosphate, glycol methacrylate phosphate, 2-hydroxyethyl methacrylate phosphate, alkyl phosphate special monomer, siloxane phosphate and other phosphate functional monomers.
3. The styrene-acrylic emulsion for a quick-drying water-based metallic paint according to claim 1, wherein the emulsifier is at least one of allyloxy fatty alcohol ethoxylate sulfate, dodecylbenzene sulfonate, alkylphenol ethoxylate sulfate, and nonylphenol ethoxylate.
4. The styrene-acrylic emulsion for a quick-drying water-based metallic paint according to claim 3, wherein the dodecylbenzene sulfonate is sodium dodecylbenzene sulfonate or potassium dodecylbenzene sulfonate.
5. The styrene-acrylic emulsion for quick-drying water-based metallic paint according to claim 1, wherein the crosslinking monomer is at least one of allyl methacrylate, hydroxyethyl acrylate, glycerol methacrylate, trimethylolpropane trimethacrylate and diethylene glycol dimethacrylate.
6. The styrene-acrylic emulsion for a quick-drying water-based metallic paint according to claim 1, wherein the persulfate is at least one of potassium persulfate, ammonium persulfate and sodium persulfate.
7. The styrene-acrylic emulsion for quick-drying water-based metallic paint according to claim 1, wherein the oxidant is hydrogen peroxide; the reducing agent adopts vitamin C.
8. A method for preparing a styrene-acrylic emulsion for a quick-drying water-based metallic paint according to any one of claims 1 to 7, comprising the steps of:
1) preparation of a first-stage pre-emulsion: adding water with the formula amount of 20-30% and an emulsifier with the formula amount of 20-30% into a pre-emulsification cylinder, opening a stirrer, sequentially adding styrene, methyl methacrylate, butyl acrylate and acrylic acid monomers with the formula amount of 40-60%, and stirring and dispersing for 20-40 minutes;
2) preparation of a two-stage pre-emulsion: adding water with the formula amount of 20-30% and an emulsifier with the formula amount of 20-30% into a pre-emulsification cylinder, opening a stirrer, sequentially adding the rest of styrene, methyl methacrylate, butyl acrylate, acrylic acid, a crosslinking monomer and a phosphate functional monomer, and stirring and dispersing for 20-40 minutes;
3) adding the rest water and the rest emulsifier into the reactor, uniformly stirring, and heating to 70-90 ℃;
4) continuously and uniformly dripping persulfate solution, continuously and uniformly dripping the first-stage pre-emulsion prepared in the step 1) after 3-5 minutes, dripping for 1.5-2.5 hours, preserving heat for 1.5-2.5 hours, then continuously and uniformly dripping the second-stage pre-emulsion prepared in the step 2), dripping for 2-4 hours, heating to 80-85 ℃ after finishing dripping, and preserving heat for 0.5-1.5 hours;
5) cooling to 70-75 deg.C;
6) dripping aqueous solution of reducing agent with formula amount of 40-60% and oxidant with formula amount of 40-60% into the emulsion at the same time, dripping for 15-25 minutes, and keeping the temperature for 30-50 minutes;
7) continuously cooling to 60-65 ℃;
8) dropwise adding the rest aqueous solution of the reducing agent and the oxidant into the emulsion for 15-25 minutes at the same time, and preserving the temperature for 30-50 minutes;
9) and (5) closing the heater, cooling the emulsion to room temperature, filtering and packaging.
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