CN103382344B - Fluorine-containing aqueous acrylate resin exterior coating and preparation method thereof - Google Patents
Fluorine-containing aqueous acrylate resin exterior coating and preparation method thereof Download PDFInfo
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- CN103382344B CN103382344B CN201310340532.5A CN201310340532A CN103382344B CN 103382344 B CN103382344 B CN 103382344B CN 201310340532 A CN201310340532 A CN 201310340532A CN 103382344 B CN103382344 B CN 103382344B
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- containing aqueous
- acrylate resin
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000011737 fluorine Substances 0.000 title claims abstract description 71
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 71
- 238000000576 coating method Methods 0.000 title claims abstract description 70
- 239000011248 coating agent Substances 0.000 title claims abstract description 68
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000839 emulsion Substances 0.000 claims abstract description 57
- -1 acrylic ester Chemical class 0.000 claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 239000000203 mixture Substances 0.000 claims description 45
- 239000008367 deionised water Substances 0.000 claims description 38
- 229910021641 deionized water Inorganic materials 0.000 claims description 38
- 239000003999 initiator Substances 0.000 claims description 33
- 239000003995 emulsifying agent Substances 0.000 claims description 28
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000013530 defoamer Substances 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 claims description 13
- 238000013019 agitation Methods 0.000 claims description 13
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 230000008719 thickening Effects 0.000 claims description 13
- 238000004581 coalescence Methods 0.000 claims description 11
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 11
- 239000004408 titanium dioxide Substances 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 239000000080 wetting agent Substances 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 claims description 7
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 7
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical compound [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 5
- 241001062009 Indigofera Species 0.000 claims description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 5
- 230000008030 elimination Effects 0.000 claims description 5
- 238000003379 elimination reaction Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 5
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-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
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 229920001495 poly(sodium acrylate) polymer Polymers 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
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 3
- 239000006174 pH buffer Substances 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 230000002209 hydrophobic effect Effects 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920000151 polyglycol Polymers 0.000 claims description 2
- 239000010695 polyglycol Substances 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- LPXFITACVAQQAL-UHFFFAOYSA-M sodium;prop-2-enoylazanide Chemical compound [Na+].[NH-]C(=O)C=C LPXFITACVAQQAL-UHFFFAOYSA-M 0.000 claims description 2
- 230000008961 swelling Effects 0.000 claims description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002562 thickening agent Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000012991 xanthate Substances 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 6
- 238000004140 cleaning Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 229920000178 Acrylic resin Polymers 0.000 abstract description 3
- 239000012752 auxiliary agent Substances 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 2
- 238000011109 contamination Methods 0.000 description 10
- 238000009835 boiling Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000004816 latex Substances 0.000 description 7
- 229920000126 latex Polymers 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000004945 emulsification Methods 0.000 description 6
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 101100412856 Mus musculus Rhod gene Proteins 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920006222 acrylic ester polymer Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- Paints Or Removers (AREA)
Abstract
The present invention relates to fluorine-containing aqueous acrylate resin exterior coating and preparation method thereof, comprise the synthesis of fluorine-containing aqueous acrylic ester emulsion and the preparation of coating.This coating is waterborne fluoro emulsion, overcome the shortcoming that acrylic resin easily stains, there is self-cleaning, the advantage such as glossiness is high, strong adhesion, surface hydrophobicity are good, excellent anti-corrosion performance, simultaneously, effectively overcome the shortcoming of bad, the easy shrinkage cavity of fluoro-containing coating wettability by preferred fluorinated auxiliary agent, show the excellent properties of fluoro-containing coating greatly.
Description
Technical field
The present invention relates to a kind of fluorine-containing aqueous acrylate resin exterior coating and preparation method thereof.
Background technology
Along with the enhancing of people's environmental consciousness, water-borne coatings obtains and develops rapidly.Compared with traditional solvent-borne coating water-borne coatings have that price is lower, use safety, saving resource and the energy, minimizing environmental pollution and the advantage such as nuisanceless.The exterior wall latex paint great majority used both at home and abroad at present take acrylic resin as main film forming substance, and it exists the shortcomings such as hot sticky cold crisp, abrasion resistance, erosion resistance, resistance to soiling, self-cleaning difference.Although patent No. CN 101338099A discloses a kind of exterior coating, it has early stage water resisting property and erosion resistance preferably, because it uses common ACRYLIC EMULSION, so the shortcoming that there is hot sticky cold crisp and easily stain.
In view of the demand in market, people have developed the fluorocarbon coating with overlength weathering resistance, resistance to soiling and acid resistance, alkali resistance, for fluorocarbon coating, it is invested greatly, starting material are expensive, cost is high and production technique is relatively complicated, and this is very unfavorable to the marketing of fluorocarbon coating.Patent No. CN 101845261A has invented a kind of exterior wall self-cleaning water-based fluorocarbon paint and has had self-cleaning and contaminated resistance, and exterior wall surface can be made to keep permanent as new state.
Due to be use fluorine carbon emulsion so cost is higher.Polyacrylic acid fluorine band alkane esters is obtained by introducing fluoro-containing group in acrylic ester polymer; because the electronegativity of fluorine is large; C-F key is very stable; fluorine-containing side chain can to main chain and interior molecules shielding protection; acrylate is made not only to maintain its primary characteristic; also effectively can improve its stability, weathering resistance, pollution resistance and oil-proofness water tolerance, reduce production cost.Patent No. CN 101348595A has invented a kind of fluorine-silicon modified self-crosslinking acrylic ester emulsion and preparation method thereof and has used this complex operation of hud polymerization technique, its fluorinated monomer is aggregated on shell, due to fluorine monomer and other acrylic monomer copolymerizables poor, this can cause fluorine-containing latex low conversion rate, fluorine-containing latex in film process because the low surface energy of fluorine element can from the enrichment of trend interface, be aggregated on micelle shell without the need to deliberately designing, and it is not described in detail when being mixed with exterior coating.
Summary of the invention
Technical problem to be solved by this invention is the deficiency that exists for above-mentioned prior art and provides a kind of fluorine-containing aqueous acrylate resin exterior coating and preparation method thereof, prepared fluorine-containing exterior coating has good resistance to acids and bases, washability and contamination resistance, overcomes fluorine-containing latex and easily occurs the problem such as pin hole, bubble with the poor coating surface of conven-tional adjuvants compatibleness.
The technical scheme that the problem that the present invention is the above-mentioned proposition of solution adopts is:
The preparation method of fluorine-containing aqueous acrylate resin exterior coating, it comprises the following steps:
(1) synthesis of fluorine-containing aqueous acrylate resin emulsion:
A () is got the raw materials ready: take mix monomer, reactive emulsifier, deionized water and initiator, and reactive emulsifier is the 1%-5% of mix monomer total mass, and initiator is the 0.2%-0.6% of mix monomer total mass; Deionized water consumption is the 150%-300% of mix monomer total mass, and deionized water is divided into A, B, C tri-part; Reactive emulsifier is divided into a, b two portions, and a accounts for reactive emulsifier total mass 50%-90%, and surplus is b; Initiator is divided into I, II two portions, and I accounts for initiator total mass 15%-30%, and surplus is II, and initiator II is dissolved in deionized water C;
B deionized water A and reactive emulsifier a in mixing and stirring, is then added mix monomer by () under agitation, obtain monomer pre-emulsion, monomer pre-emulsion is divided into α, β two portions, α accounts for the 6%-14% of monomer pre-emulsion total mass, and surplus is β, for subsequent use;
In reaction vessel, add deionized water B, reactive emulsifier b, and add pH buffer reagent NaHCO
3, the PH keeping reaction system is 6-8, stirs and is warming up to 83-87 DEG C, then add monomer pre-emulsion α and initiator I; After until emulsion change indigo plant and without obvious monomers flow back, start at the uniform velocity to drip monomer pre-emulsion β and initiator II, initiator II is dissolved in deionized water C, and control time for adding is 3-4 hour; Dropwise rear insulation one hour; Be warming up to 90-93 DEG C and carry out rear elimination, react 30 minutes; Finally be cooled to room temperature, be 7.5-8.5 with ammonia neutralization to pH value, then filter, discharging obtains fluorine-containing aqueous acrylate resin emulsion;
(2) preparation of coating
Weighing by mass percentage, the mass ratio of described each component is deionized water: propylene glycol: dispersion agent: wetting agent: flow agent: defoamer: 2-amino-2-methyl-1-propanol (AMP-95): titanium dioxide: barium sulfate: fluorine-containing aqueous acrylate resin emulsion: film coalescence aid: thickening material=10% ~ 17%:1% ~ 3%:0.1% ~ 1%:0.1% ~ 1%:0.1% ~ 1%:0.1% ~ 4%:0.18% ~ 0.5%:14% ~ 30%:3% ~ 20%:45% ~ 61%:1% ~ 6%:0.4% ~ 4%, wherein defoamer adds at twice, adds 1/2nd of total amount at every turn;
Under agitation in order by deionized water, propylene glycol, wetting agent, dispersion agent, flow agent, (first time adds defoamer to defoamer, / 2nd of a total amount), 2-amino-2-methyl-1-propanol (AMP-95), titanium dioxide, 2000r/min ~ 3000r/min high speed dispersion is carried out 20 ~ 30 minutes after barium sulfate fully mixes, be dispersed to fineness and be less than 40 μm, then fluorine-containing emulsion is under agitation added, film coalescence aid, the defoamer (second time adds defoamer) of surplus, thickening material mixes rear filtration discharging, fluorine-containing aqueous acrylate resin exterior coating can be obtained.
By such scheme, the account for 10%-15% of ionized water total mass, B of described deionized water A accounts for the 35%-60% of ionized water total mass, and surplus is C.
By such scheme, the preferred mass of each component described in step 2 is than being deionized water: propylene glycol: dispersion agent: wetting agent: flow agent: defoamer: 2-amino-2-methyl-1-propanol (AMP-95): titanium dioxide: barium sulfate: fluorine-containing aqueous acrylate resin emulsion: film coalescence aid: thickening material=13% ~ 17%:1% ~ 1.5%:0.1% ~ 0.3%:0.1% ~ 0.3%:0.1% ~ 0.2%:0.1% ~ 0.2%:0.18% ~ 0.4%:19% ~ 30%:3% ~ 11%:45% ~ 52%:1% ~ 1.5%:0.5% ~ 1%.
By such scheme, described mix monomer is made up of acrylicacidandesters class monomer, fluorinated acrylate monomer, crosslinkers monomers, each components based on weight percentage is: methacrylic acid and esters monomer 45%-85% thereof, fluorinated Acrylic Acid Monomer 14%-47%, cross-linking monomer 0.5%-8%.
By such scheme, described acrylicacidandesters class monomer is the mixture of any one or any two or more in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, isobornyl acrylate, butyl acrylate, lauryl methacrylate(LMA), Tert-butyl Methacrylate, methacrylic acid, vinylformic acid, during any two above mixing be any than.
By such scheme, described fluorinated acrylate monomer is one or both the mixture in trifluoroethyl methacrylate, Hexafluorobutyl mathacrylate.
By such scheme, described cross-linking monomer is the mixing of any one or any two or more in glycidyl methacrylate, acrylamide, γ-methacryloxypropyl trimethoxy silane, during any two above mixing be any than.
By such scheme, described reactive emulsifier is any one or two or more mixtures in acrylamido sodium isopropyl xanthate (AMPS), sodium vinyl sulfonate (SVS), acrylic polyether phosphoric acid ester (APE-2003), is any proportioning during any two or more mixing.
By such scheme, described initiator is any one in Potassium Persulphate, ammonium persulphate, Sodium Persulfate.
By such scheme, described dispersion agent is one or both mixtures in any proportion in ammonium polyacrylate (BYK-154), sodium polyacrylate (Dispers 715W).
By such scheme, described wetting agent is one or more the mixture in water-soluble ethoxy base class non-ionic type fluorocarbon surfactant (FSN-100 E.I.Du Pont Company), polyoxyethylene groups ethers non-ionic type fluorocarbon surfactant (FS0-100 E.I.Du Pont Company), water-soluble phosphate anionoid type fluorocarbon surfactant (FSP E.I.Du Pont Company).
By such scheme, described flow agent is one or both mixtures in any proportion in fluorine-carbon modified flow agent (Efka 3570), fluorine-carbon modified polyacrylic ester (Efka 3772 BASF AG).
By such scheme, described defoamer is the special siliceous and multiple mixture of the oil base (A10 Kening Co., Ltd) in ore deposit, hydrophobic solid and broken bubble polysiloxane one or both mixtures in any proportion in polyglycol (Bi Ke company of BYK028 Germany).
By such scheme, described titanium dioxide is Rutile type Titanium Dioxide.
By such scheme, described film coalescence aid is one or both mixtures in any proportion in butyl, alcohol ester 12.
By such scheme, described thickening material is one or both mixtures in any proportion in acrylic acid series alkali swelling consonance type thickening material (Rhom and Hass of the TT-615 U.S.), non-ionic polyurethane associative thickener (RM-2020).
The fluorine-containing aqueous acrylate resin exterior coating prepared with raw material according to the method described above, all belongs to protection scope of the present invention.
The technique that the present invention uses pre-emulsification whole process to drip, first the 6%-14% of monomer pre-emulsion is reacted at reactor, superpolymer after this part pre-emulsion monomer polymerization reactions is equivalent to seed in the reaction in later stage, after a part of fluorine monomer is aggregated on macromolecular chain, the effect being similar to emulsifying agent is served in the middle of follow-up polymerization, because fluorochemical monomer has very strong hydrophobicity, fluorine-containing polymkeric substance can reduce the surface tension of emulsion, this is conducive to the carrying out be polymerized, thus improves the transformation efficiency of emulsion.For fluorine-containing latex and general aqueous promoter with the use of time easily produce the defects such as shrinkage cavity, froth breaking is incomplete, levelling property is bad, the present invention, by preferably using fluorinated auxiliary agent thus successfully solving the problems referred to above, makes fluorine-containing latex can play its performance better in use.
Compared with prior art, the invention has the beneficial effects as follows:
First, the exterior coating that the present invention produces is waterborne fluoro emulsion, which overcomes the shortcoming that acrylic resin easily stains, and has self-cleaning, the advantage such as glossiness is high, strong adhesion, surface hydrophobicity are good, excellent anti-corrosion performance, the simple easy handling of its production technique, advantage of lower cost;
The second, instant invention overcomes the easy hot sticky cold crisp of conventional propylene acid esters emulsion, the problem of fluorine-containing latex and the easy shrinkage cavity of ordinary adjuvants compatibility film coated surface;
3rd, particularly the use of fluorinated auxiliary agent overcomes that fluoro-containing coating froth breaking is incomplete, wettability is bad in the present invention, the problem of levelling property difference.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
embodiment 1:
The preparation method of fluorine-containing aqueous acrylate resin exterior coating, it comprises the following steps:
(1) synthesis of fluorine-containing aqueous acrylate resin emulsion:
A () is got the raw materials ready: take mix monomer, reactive emulsifier, deionized water and initiator, described mix monomer is made up of 20g methyl methacrylate, 10g β-dimethyl-aminoethylmethacrylate, 15g butyl acrylate, 12g trifluoroethyl methacrylate, 3g glycidyl methacrylate, reactive emulsifier is 1.8g, deionized water 97g, initiator potassium persulfate total mass 0.24 gram;
B () be mixing and stirring in pre-emulsification tank by the deionized water of 12g and 1.2g reactive emulsifier AMPS, then described mix monomer (i.e. above-mentioned load weighted 20g methyl methacrylate, 10g β-dimethyl-aminoethylmethacrylate, 15g butyl acrylate, 12g trifluoroethyl methacrylate, 3g glycidyl methacrylate) is under agitation added, obtain monomer pre-emulsion 73.2g, for subsequent use;
In four-hole boiling flask, add 55g deionized water, 0.6g reactive emulsifier AMPS and 0.10g sodium bicarbonate (pH buffer reagent), stir and be warming up to 83 DEG C, the 10g getting monomer pre-emulsion joins in four-hole boiling flask, adds 0.065g initiator; After until emulsion change indigo plant and without obvious monomers flow back, start at the uniform velocity to drip residual monomer pre-emulsion 63.2g and residue 30.175g initiator solution (solid content 0.58%, the effective constituent of initiator is 0.175g, and deionized water is 30g), controlling time for adding is 3 hours; Dropwise rear insulation one hour; Be warming up to 93 DEG C and carry out rear elimination, react 30 minutes; Finally be cooled to room temperature, be 8.5 with ammonia neutralization to pH value, then filter, discharging obtains fluorine-containing aqueous acrylate resin emulsion.
2) preparation of coating
Get 100g above-mentioned fluorine-containing aqueous acrylate resin emulsion for subsequent use;
Get 25g deionized water, 2g propylene glycol, 0.4g BYK-154(dispersion agent), 2-amino-2-methyl-1-propanol AMP-95 0.8g, 0.4g water-soluble ethoxy base class non-ionic type fluorocarbon surfactant FSN-100(wetting agent), 0.4g fluorine-carbon modified flow agent Efka3570(BASF AG), 0.2g defoamer A10 under agitation stirs, be adjusted to 2000r/min high speed dispersion, add 40g titanium dioxide, 20g barium sulfate, be dispersed to fineness and be less than 40 μm, then 100g fluorine-containing emulsion is under agitation added, 3g alcohol ester 12 (film coalescence aid), 0.2g A10(defoamer), 1.2gRM-2020(thickening material), mix rear filtration discharging, fluorine-containing aqueous acrylate resin exterior coating can be obtained.
performance Detection:
(1) contamination resistance contrast: the contamination resistance determining fluorine-containing exterior coating and common exterior coating according to GB/T9755-2001;
(2) coating performance: the coating performance determining fluorine-containing exterior coating and common exterior coating according to GB/T17748-1999.
Fluorine-containing aqueous acrylate resin exterior coating performance test results prepared by embodiment 1 is as shown in table 1:
As can be seen from Table 1, compared with common exterior coating, fluorine-containing aqueous acrylate resin exterior coating prepared by the present invention, contamination resistance improves 3 times, washability number of times improves 5000 times, water tolerance, the row of resistance to boiling water, acid resistance all achieve better effect, and hardness, ageing resistance and outward appearance are also all fine simultaneously.
embodiment 2:
The preparation method of fluorine-containing aqueous acrylate resin exterior coating, it comprises the following steps:
(1) synthesis of fluorine-containing aqueous acrylate resin emulsion:
A () is got the raw materials ready: take mix monomer, reactive emulsifier, deionized water and initiator, described mix monomer is made up of 13g methyl methacrylate, 6g isobornyl acrylate, 10g butyl acrylate, 10g lauryl methacrylate(LMA), 18g trifluoroethyl methacrylate, 2g glycidyl methacrylate, 1g γ-methacryloxypropyl trimethoxy silane, reactive emulsifier is 2.2g, deionized water 118g, initiator Sodium Persulfate total mass 0.25g;
B () is by the deionized water of 13g, 0.8g reactive emulsifier AMPS and 0.6g reactive emulsifier SVS mixing and stirring in pre-emulsification tank, then described mix monomer (i.e. above-mentioned load weighted 20g methyl methacrylate, 10g β-dimethyl-aminoethylmethacrylate, 15g butyl acrylate, 12g trifluoroethyl methacrylate, 3g glycidyl methacrylate) is under agitation added, obtain monomer pre-emulsion 74.4g, for subsequent use;
In four-hole boiling flask, add 45g deionized water, 0.6g reactive emulsifier AMPS, 0.2g reactive emulsifier SVS and 0.10g sodium bicarbonate, stir and be warming up to 83 DEG C, the 8g getting monomer pre-emulsion joins in four-hole boiling flask, adds 0.07g initiator; After until emulsion change indigo plant and without obvious monomers flow back, start at the uniform velocity drip residual monomer pre-emulsion 66.4g and remain 60.18g initiator solution (solid content 0.3%, the effective constituent of initiator is 0.18g), control time for adding is 4 hours; Dropwise rear insulation one hour; Be warming up to 92 DEG C and carry out rear elimination, react 30 minutes; Finally be cooled to room temperature, be 7.5 with ammonia neutralization to pH value, then filter, discharging obtains fluorine-containing aqueous acrylate resin emulsion.
2) preparation of coating
Get 100g above-mentioned fluorine-containing aqueous acrylate resin emulsion for subsequent use
Get 30g deionized water, 2.5g propylene glycol, 0.4g dispersion agent sodium polyacrylate Dispers 715W, AMP-95 0.6g, 0.4g FSO-100(E.I.Du Pont Company), 0.4gEfka3772(BASF AG), 0.2g A10 (defoamer) stirs under stirring at low speed, be adjusted to 2000r/min ~ 3000r/min high speed dispersion, enter 55g titanium dioxide, 10g process white, be dispersed to fineness and be less than 40 μm, then 100g fluorine-containing emulsion is under agitation added, 3g butyl (film coalescence aid), 0.2g BYK028(defoamer), 2gRM-2020(thickening material), mix rear filtration discharging and can obtain fluorine-containing aqueous acrylate resin exterior coating.
performance Detection:
(1) contamination resistance contrast: the contamination resistance determining fluorine-containing exterior coating and common exterior coating according to GB/T9755-2001;
(2) coating performance: the coating performance determining fluorine-containing exterior coating and common exterior coating according to GB/T17748-1999.
Fluorine-containing aqueous acrylate resin exterior coating performance test results prepared by embodiment 2 is as shown in table 2:
As can be seen from Table 2, compared with common exterior coating, fluorine-containing aqueous acrylate resin exterior coating prepared by the present invention, contamination resistance improves 4 times, washability number of times improves 8000 times, water tolerance, the row of resistance to boiling water, acid resistance all achieve better effect, and hardness, ageing resistance and outward appearance are also all fine simultaneously.
embodiment 3:
The preparation method of fluorine-containing aqueous acrylate resin exterior coating, it comprises the following steps:
(1) synthesis of fluorine-containing aqueous acrylate resin emulsion:
A () is got the raw materials ready: take mix monomer, reactive emulsifier, deionized water and initiator, described mix monomer is made up of 15g isobornyl acrylate, 18g butyl acrylate, 5g lauryl methacrylate(LMA), 13g trifluoroethyl methacrylate, 6g vinylformic acid hexafluoro butyl ester, 2g glycidyl methacrylate, 1g acrylamide, reactive emulsifier APE-2003 is 3g, deionized water 100g, initiator Sodium Persulfate total mass 0.36 gram;
B () be mixing and stirring in pre-emulsification tank by the deionized water of 10g and 2g response type emulsification APE-2003, then under agitation add mix monomer, stirs and obtains monomer pre-emulsion 72g, for subsequent use.
In four-hole boiling flask, add 45g deionized water, 1g reactive emulsifier APE-2003 and 0.10g sodium bicarbonate, stir and be warming up to 83 DEG C, the 10g getting monomer pre-emulsion joins in four-hole boiling flask, adds 0.06g initiator; After until emulsion change indigo plant and without obvious monomers flow back, start at the uniform velocity to drip residue 62g monomer pre-emulsion and 45.3g residue initiator solution (admittedly contain 0.66%, the effective constituent of initiator is 0.3g), controlling time for adding is 3.5 hours; Dropwise rear insulation one hour; Be warming up to 92 DEG C and carry out rear elimination, react 30 minutes; Finally be cooled to room temperature, be 8.5 with ammonia neutralization to pH value, then filter, discharging obtains fluorine-containing aqueous acrylate resin emulsion.
2) preparation of coating
Get 100g above-mentioned fluorine-containing aqueous acrylate resin emulsion for subsequent use;
Get 36g deionized water, 3g propylene glycol, 0.6g sodium polyacrylate Dispers 715W(dispersion agent), AMP-95 0.4g, 0.2g wetting agent FSP(E.I.Du Pont Company), 0.2gEfka3772, 0.2g flow agent Efka3570(BASF AG), 0.1g A10 (defoamer) under agitation stirs, be adjusted to 2000r/min ~ 3000r/min high speed dispersion, enter 65g titanium dioxide, 8g process white, be dispersed to fineness and be less than 40 μm, then under stirring at low speed, 100g fluorine-containing emulsion is added, 3g alcohol ester 12 (film coalescence aid), 0.2g BYK028(defoamer), 2gRM-2020(thickening material), mix rear filtration discharging, fluorine-containing aqueous acrylate resin exterior coating can be obtained.
performance Detection:
(1) contamination resistance contrast: the contamination resistance determining fluorine-containing exterior coating and common exterior coating according to GB/T9755-2001;
(2) coating performance: the coating performance determining fluorine-containing exterior coating and common exterior coating according to GB/T17748-1999.
Fluorine-containing aqueous acrylate resin exterior coating performance test results prepared by embodiment 3 is as shown in table 3:
As can be seen from Table 3, compared with common exterior coating, fluorine-containing aqueous acrylate resin exterior coating prepared by the present invention, contamination resistance improves 4 times, washability number of times improves 10000 times, water tolerance, ageing resistance, the row of resistance to boiling water, acid resistance all achieve better effect, simultaneously hardness and outward appearance also all fine.
Claims (7)
1. the preparation method of fluorine-containing aqueous acrylate resin exterior coating, is characterized in that it comprises the following steps:
(1) synthesis of fluorine-containing aqueous acrylate resin emulsion:
A () is got the raw materials ready: take mix monomer, reactive emulsifier, deionized water and initiator, and reactive emulsifier is the 1%-5% of mix monomer total mass, and initiator is the 0.2%-0.6% of mix monomer total mass; Deionized water consumption is the 150%-300% of mix monomer total mass, and deionized water is divided into A, B, C tri-part; Reactive emulsifier is divided into a, b two portions, and a accounts for reactive emulsifier total mass 50%-90%, and surplus is b; Initiator is divided into I, II two portions, and I accounts for initiator total mass 15%-30%, and surplus is II, and initiator II is dissolved in deionized water C;
B (), by deionized water A and reactive emulsifier a mixing and stirring, then adds mix monomer under agitation, obtains monomer pre-emulsion, monomer pre-emulsion is divided into α, β two portions, α accounts for the 6%-14% of monomer pre-emulsion total mass, and surplus is β, for subsequent use;
In reaction vessel, add deionized water B, reactive emulsifier b, and add pH buffer reagent NaHCO
3, the pH keeping reaction system is 6-8, stirs and is warming up to 83-87 DEG C, then add monomer pre-emulsion α and initiator I; After until emulsion change indigo plant and without obvious monomers flow back, start at the uniform velocity to drip monomer pre-emulsion β and initiator II, initiator II is dissolved in deionized water C, and control time for adding is 3-4 hour; Dropwise rear insulation one hour, be warming up to 90-93 DEG C and carry out rear elimination, react 30 minutes; Finally be cooled to room temperature, be 7.5-8.5 with ammonia neutralization to pH value, then filter, discharging obtains fluorine-containing aqueous acrylate resin emulsion;
(2) preparation of coating
Weighing by mass percentage, the mass ratio of described each component is deionized water: propylene glycol: dispersion agent: wetting agent: flow agent: defoamer: 2-amino-2-methyl-1-propanol: titanium dioxide: barium sulfate: fluorine-containing aqueous acrylate resin emulsion: film coalescence aid: thickening material=10% ~ 17%:1% ~ 3%:0.1% ~ 1%:0.1% ~ 1%:0.1% ~ 1%:0.1% ~ 4%:0.18% ~ 0.5%:14% ~ 30%:3% ~ 20%:45% ~ 61%:1% ~ 6%:0.4% ~ 4%, wherein defoamer adds at twice, adds 1/2nd of defoamer total amount at every turn;
Under agitation by deionized water, propylene glycol, wetting agent, dispersion agent, flow agent, defoamer total amount 1/2nd, 2-amino-2-methyl-1-propanol, titanium dioxide, barium sulfate carries out 2000r/min ~ 3000r/min high speed dispersion 20 ~ 30 minutes after fully mixing, be dispersed to fineness and be less than 40 μm, then under agitation add fluorine-containing aqueous acrylate resin emulsion, film coalescence aid, the defoamer of surplus, thickening material mix rear filtration discharging, fluorine-containing aqueous acrylate resin exterior coating can be obtained;
Described mix monomer is made up of acrylicacidandesters class monomer, fluorinated acrylate monomer, cross-linking monomer, each components based on weight percentage is: acrylicacidandesters class monomer 45%-85%, fluorinated acrylate monomer 14%-47%, cross-linking monomer 0.5%-8%; Described acrylicacidandesters class monomer is the mixture of any one or any two or more in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, isobornyl acrylate, butyl acrylate, lauryl methacrylate(LMA), Tert-butyl Methacrylate, methacrylic acid, vinylformic acid, during any two above mixing be any than; Described fluorinated acrylate monomer is one or both the mixture in trifluoroethyl methacrylate, Hexafluorobutyl mathacrylate; Described cross-linking monomer is the mixing of any one or any two or more in glycidyl methacrylate, acrylamide, γ-methacryloxypropyl trimethoxy silane, during any two above mixing be any than;
Described wetting agent is one or more mixtures in any proportion in water-soluble ethoxy base class non-ionic type fluorocarbon surfactant, polyoxyethylene groups ethers non-ionic type fluorocarbon surfactant, water-soluble phosphate anionoid type fluorocarbon surfactant; Described flow agent is one or both mixtures in any proportion in fluorine-carbon modified flow agent, fluorine-carbon modified polyacrylic ester.
2. the preparation method of fluorine-containing aqueous acrylate resin exterior coating according to claim 1, it is characterized in that the account for 10%-15% of ionized water total mass, B of described deionized water A accounts for the 35%-60% of ionized water total mass, surplus is C.
3. the preparation method of fluorine-containing aqueous acrylate resin exterior coating according to claim 1, is characterized in that the mass ratio of each component described in step (2) is deionized water: propylene glycol: dispersion agent: wetting agent: flow agent: defoamer: 2-amino-2-methyl-1-propanol: titanium dioxide: barium sulfate: fluorine-containing aqueous acrylate resin emulsion: film coalescence aid: thickening material=13% ~ 17%:1% ~ 1.5%:0.1% ~ 0.3%:0.1% ~ 0.3%:0.1% ~ 0.2%:0.1% ~ 0.2%:0.18% ~ 0.4%:19% ~ 30%:3% ~ 11%:45% ~ 52%:1% ~ 1.5%:0.5% ~ 1%.
4. the preparation method of fluorine-containing aqueous acrylate resin exterior coating according to claim 1, it is characterized in that described reactive emulsifier is any one or two or more mixtures in acrylamido sodium isopropyl xanthate, sodium vinyl sulfonate, acrylic polyether phosphoric acid ester, is any proportioning during any two or more mixing.
5. the preparation method of fluorine-containing aqueous acrylate resin exterior coating according to claim 1, is characterized in that described initiator is any one in Potassium Persulphate, ammonium persulphate, Sodium Persulfate; Described dispersion agent is one or both mixtures in any proportion in ammonium polyacrylate, sodium polyacrylate.
6. the preparation method of fluorine-containing aqueous acrylate resin exterior coating according to claim 1, is characterized in that described defoamer is the siliceous and multiple mixture of the special oil base in ore deposit, hydrophobic solid and broken bubble polysiloxane one or both mixtures in any proportion in polyglycol; Described film coalescence aid is one or both mixtures in any proportion in butyl, alcohol ester 12; Described thickening material is one or both mixtures in any proportion in acrylic acid series alkali swelling consonance type thickening material, non-ionic polyurethane associative thickener.
7. the fluorine-containing aqueous acrylate resin exterior coating that obtains of the preparation method of claim 1-6 any one.
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