CN111363445A - High-fluorine-content water-based concrete protective coating - Google Patents
High-fluorine-content water-based concrete protective coating Download PDFInfo
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- CN111363445A CN111363445A CN202010297135.4A CN202010297135A CN111363445A CN 111363445 A CN111363445 A CN 111363445A CN 202010297135 A CN202010297135 A CN 202010297135A CN 111363445 A CN111363445 A CN 111363445A
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- Prior art keywords
- fluorine
- emulsion
- polymer emulsion
- content
- water
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000011253 protective coating Substances 0.000 title claims abstract description 47
- 239000000839 emulsion Substances 0.000 claims abstract description 242
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 198
- 239000011737 fluorine Substances 0.000 claims abstract description 198
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 195
- 229920000642 polymer Polymers 0.000 claims abstract description 123
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000000576 coating method Methods 0.000 claims abstract description 43
- 150000001343 alkyl silanes Chemical class 0.000 claims abstract description 41
- 239000011248 coating agent Substances 0.000 claims abstract description 40
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 13
- 239000003899 bactericide agent Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000000945 filler Substances 0.000 claims abstract description 9
- 238000013329 compounding Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 51
- 239000011259 mixed solution Substances 0.000 claims description 36
- 238000002360 preparation method Methods 0.000 claims description 29
- 239000003995 emulsifying agent Substances 0.000 claims description 27
- -1 fluoroalkyl silane Chemical compound 0.000 claims description 24
- 229910000077 silane Inorganic materials 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 14
- 239000002562 thickening agent Substances 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 9
- LQZZUXJYWNFBMV-UHFFFAOYSA-N ethyl butylhexanol Natural products CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- 229910052882 wollastonite Inorganic materials 0.000 claims description 7
- 239000010456 wollastonite Substances 0.000 claims description 7
- 239000002518 antifoaming agent Substances 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000008267 milk Substances 0.000 claims description 2
- 210000004080 milk Anatomy 0.000 claims description 2
- 235000013336 milk Nutrition 0.000 claims description 2
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 8
- 238000004140 cleaning Methods 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 4
- 229940089951 perfluorooctyl triethoxysilane Drugs 0.000 description 36
- AVYKQOAMZCAHRG-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical group CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F AVYKQOAMZCAHRG-UHFFFAOYSA-N 0.000 description 36
- 239000003973 paint Substances 0.000 description 32
- 238000002474 experimental method Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 15
- 239000002002 slurry Substances 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- VBHXIMACZBQHPX-UHFFFAOYSA-N 2,2,2-trifluoroethyl prop-2-enoate Chemical compound FC(F)(F)COC(=O)C=C VBHXIMACZBQHPX-UHFFFAOYSA-N 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- 239000011258 core-shell material Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 229960003493 octyltriethoxysilane Drugs 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical group CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 6
- 239000003707 silyl modified polymer Substances 0.000 description 6
- ODJMOVZKYZHQED-UHFFFAOYSA-N tris(trifluoromethoxy)-(1,1,2,2,3,3,4,4,5,5,5-undecafluoropentyl)silane Chemical compound FC(F)(F)O[Si](OC(F)(F)F)(OC(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ODJMOVZKYZHQED-UHFFFAOYSA-N 0.000 description 6
- DXODQEHVNYHGGW-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctyl-tris(trifluoromethoxy)silane Chemical compound FC(F)(F)O[Si](OC(F)(F)F)(OC(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F DXODQEHVNYHGGW-UHFFFAOYSA-N 0.000 description 5
- QTRSWYWKHYAKEO-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecyl-tris(1,1,2,2,2-pentafluoroethoxy)silane Chemical compound FC(F)(F)C(F)(F)O[Si](OC(F)(F)C(F)(F)F)(OC(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F QTRSWYWKHYAKEO-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000001804 emulsifying effect Effects 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- FZRMIZUBKZAWGO-UHFFFAOYSA-N tris(1,1,2,2,2-pentafluoroethoxy)-(1,1,2,2,3,3,4,4,5,5,5-undecafluoropentyl)silane Chemical compound FC(F)(F)C(F)(F)O[Si](OC(F)(F)C(F)(F)F)(OC(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F FZRMIZUBKZAWGO-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- ZJBHFQKJEBGFNL-UHFFFAOYSA-N methylsilanetriol Chemical compound C[Si](O)(O)O ZJBHFQKJEBGFNL-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229940089952 silanetriol Drugs 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000011538 cleaning material Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012407 engineering method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- 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
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
- C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
- C04B41/4922—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane
- C04B41/4933—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane containing halogens, i.e. organohalogen silanes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
- C04B41/61—Coating or impregnation
- C04B41/62—Coating or impregnation with organic materials
- C04B41/64—Compounds having one or more carbon-to-metal of carbon-to-silicon linkages
-
- 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
- C09D127/00—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 a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—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 a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/16—Homopolymers or copolymers of vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
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- 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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to the technical field of concrete protective coatings, in particular to a high-fluorine-content water-based concrete protective coating. The high-fluorine-content water-based concrete protective coating is prepared from the following raw materials in parts by weight: 30-80 parts of high-fluorine-content polymer emulsion, 0-50 parts of filler, 10-30 parts of water, 2-10 parts of film-forming assistant, 0-0.5 part of pH regulator, 0-0.3 part of bactericide and 0.2-4 parts of necessary assistant; wherein the high fluorine content polymer emulsion is prepared by compounding 10-80% of fluorine-containing alkyl silane emulsion and 20-90% of fluorocarbon emulsion. The coating has high fluorine content, excellent weather resistance, corrosion resistance and self-cleaning capability, and is suitable for coating the surface of porous substrates (such as concrete, tiles and other substrates).
Description
Technical Field
The invention relates to the technical field of concrete protective coatings, in particular to a high-fluorine-content water-based concrete protective coating.
Background
The fluorine element has high electronegativity and smaller atomic radius, and the introduction of the fluorine element can improve the weather resistance and the chemical corrosion resistance of the coating. The main component of the existing water-based fluorocarbon coating is fluorine-containing acrylate emulsion, the fluorine content is generally not more than 10% due to the limitation of a technical route, and compared with oil-based fluorocarbon coatings, polymer materials with high fluorine content such as anti-fouling, aging-resistant and anti-corrosion performances such as PTFE, FVDF, PCTFE and FEP have larger differences, and the main reason of the performance difference is the fluorine content difference.
The method is influenced by factors such as cost and construction process, the solid content of the coating is generally 45-70%, filling and functional substances such as fillers and auxiliaries are removed, the content of film forming substances generally accounts for 15-40% of the coating system, and the fluorine content of the coating system is further limited, so that a novel fluorine-containing compound is added into the coating system and skillfully participates in the process of curing and film forming of the coating, and the method is an effective method for improving the fluorine content of the coating system.
The alkyl silane can be hydrolyzed to form the silanetriol under certain conditions, and the silanetriol is crosslinked to form a film and can be used as a film forming substance of the coating. The fluorine-containing alkyl silane refers to a compound in which hydrogen element in alkyl part of alkyl silane is substituted by fluorine element, and the hydrolysis crosslinking film-forming property of fluorine-containing alkyl silane is unchanged after fluorine substitution, so that the fluorine-containing alkyl silane can be used as a compound with high fluorine content for preparing coating. The mechanism of hydrolytic crosslinking of fluoroalkyl silanes is as follows:
macromolecular chains formed after crosslinking of the fluorine-containing alkyl silane and fluorine-containing acrylic acid macromolecules are mutually wound, and a stable coating system is formed through the interaction of hydrogen bonds, van der Waals force and the like.
Disclosure of Invention
The invention aims to provide a high-fluorine-content polymer emulsion, and the invention aims to provide a high-fluorine-content water-based concrete protective coating.
In order to realize the purpose of the invention, the technical scheme adopted by the invention is as follows:
the invention firstly provides a high fluorine content polymer emulsion which is prepared by compounding 10-80% of fluorine-containing alkyl silane emulsion and 20-90% of fluorocarbon emulsion by mass percentage.
According to the high fluorine content polymer emulsion, the fluorine-containing polymer emulsion is preferably prepared by compounding 30-70% of fluorine-containing alkyl silane emulsion and 30-70% of fluorocarbon emulsion by mass percentage. More preferably, the high fluorine content polymer emulsion is compounded by 50 percent of fluorine-containing alkyl silane emulsion and 50 percent of fluorocarbon emulsion by mass percentage.
According to the above-mentioned high fluorine content polymer emulsion, preferably, the fluorine-containing alkyl silane emulsion is a product obtained by emulsifying fluorine-containing alkyl silane, and the structural formula of the fluorine-containing alkyl silane is CnF2n+1(CH2)2Si(OR)3Wherein n is 3 to 16 and R represents-CH3or-CH2CH3(ii) a More preferably, n is 3 or 6 or 8.
Preferably, the fluorine-containing alkyl silane is perfluorooctyl triethoxysilane [ C ] according to the above-mentioned high fluorine content polymer emulsion6F13(CH2)2Si(OCH2CH3)3]Perfluoropentyltriethoxysilane [ C ]3F7(CH2)2Si(OCH2CH3)3]Perfluorodecyl triethoxysilane [ C ]8F17(CH2)2Si(OCH2CH3)3]Perfluorooctyltrimethoxysilane [ C ]6F13(CH2)2Si(OCH3)3]Perfluoropentyltrimethoxysilane [ C ]3F7(CH2)2Si(OCH3)3]Any one of them. More preferably, the fluoroalkyl silane is perfluorooctyl triethoxysilane [ C ]6F13(CH2)2Si(OCH2CH3)3]。
According to the high fluorine content polymer emulsion, preferably, the preparation method of the fluorine-containing alkyl silane emulsion comprises the following steps:
(1) adding an emulsifier A into the fluorine-containing alkyl silane, and stirring until the emulsifier A is uniformly dispersed to obtain a mixed solution A for later use;
(2) adding an emulsifier B into water, and stirring until the emulsifier B is uniformly dispersed to obtain a mixed solution B;
(3) and adding the mixed solution A into the mixed solution B while stirring, and continuously stirring until the mixed solution A and the mixed solution B are completely emulsified after the addition is finished to obtain the fluorine-containing alkyl silane emulsion.
According to the above high fluorine content polymer emulsion, preferably, the emulsifier A is milk T-80 or S-80; the emulsifier B is any one of S-40, OP-20 and OP-15.
According to the high fluorine content polymer emulsion, the stirring speed in the step (3) is preferably 800-1500 rpm.
According to the high fluorine content polymer emulsion, preferably, the fluorocarbon emulsion is one or more of a fluorine-containing acrylate emulsion, a PVDF type fluorocarbon emulsion and a FEVE type fluorocarbon emulsion.
According to the above-mentioned high fluorine content polymer emulsion, preferably, the fluorine-containing alkyl silane content in the fluorine-containing alkyl silane emulsion is 10% to 90% by mass. More preferably, the fluorine-containing alkyl silane emulsion contains 30-80% of fluorine-containing alkyl silane by mass percent.
The invention also provides a preparation method of the high fluorine content polymer emulsion, which comprises the following steps: adding the fluorocarbon emulsion into the fluorine-containing alkyl silane emulsion, and stirring until the fluorocarbon emulsion is uniformly dispersed to obtain the high-fluorine-content polymer emulsion.
According to the preparation method of the high-fluorine-content polymer emulsion, preferably, the stirring speed is 600-1000 rpm, and the stirring time is 5-20 min.
The invention also provides an application of the high-fluorine-content polymer emulsion in a water-based paint. Further, the high fluorine content polymer emulsion can be used as a film forming material of a coating for preparing a water-based coating.
The invention also provides a high-fluorine-content water-based concrete protective coating which is prepared from the following raw materials in parts by weight: 30-80 parts of high-fluorine-content polymer emulsion, 0-50 parts of filler, 10-30 parts of water, 2-10 parts of film-forming assistant, 0-0.5 part of pH regulator, 0-0.3 part of bactericide and 0.2-4 parts of necessary assistant, wherein the high-fluorine-content polymer emulsion is the high-fluorine-content polymer emulsion.
According to the high fluorine content water-based concrete protective coating, the film forming auxiliary agent is preferably dodecyl alcohol ester.
According to the above-mentioned high fluorine content water-based concrete protective coating, preferably, the filler is one or more of titanium dioxide, barium sulfate and wollastonite.
According to the above-mentioned high fluorine content aqueous concrete protective coating, preferably, the necessary auxiliary agent is one or more of a dispersant, a defoamer and a thickener.
According to the high fluorine content water-based concrete protective coating, the coating is preferably prepared from the following raw materials in parts by weight: 50 parts of high-fluorine-content polymer emulsion, 35 parts of filler, 11.7 parts of water, 2 parts of film-forming auxiliary agent, 0.2 part of pH regulator, 0.1 part of bactericide, 0.6 part of dispersant, 0.2 part of defoamer and 0.2 part of thickener, wherein the high-fluorine-content polymer emulsion is the high-fluorine-content polymer emulsion.
According to the high fluorine content water-based concrete protective coating, preferably, the pH regulator is DMAE (N, N-dimethylethanolamine); the bactericide is MC.
The invention also provides a preparation method of the high-fluorine-content water-based concrete protective coating, which comprises the following steps:
a. adding a dispersing agent into water, stirring until the dispersing agent is uniformly dispersed, adding a defoaming agent, eliminating bubbles, adding a pH regulator, and adjusting the pH of the system to 8-10 to obtain slurry;
b. adding a filler into the slurry prepared in the step a, and stirring until the filler is uniformly dispersed;
c. b, grinding the slurry treated in the step b until the fineness is less than 10 mu m, and discharging;
d. and c, adding the high-fluorine-content polymer emulsion into the slurry treated in the step c, stirring until the dispersion is uniform, then adding the film-forming aid, stirring and dispersing uniformly, then adding the thickening agent and the bactericide, and stirring and dispersing uniformly to obtain the high-fluorine-content water-based concrete protective coating.
According to the preparation method of the high-fluorine-content water-based concrete protective coating, preferably, the stirring speed in the step b is 1200-1500 rpm, and the stirring time is 10-20 min.
According to the preparation method of the high-fluorine-content water-based concrete protective coating, preferably, the stirring speed in the step d is 800-1000 rpm, and the stirring time is 5-10 min.
Compared with the prior art, the invention has the following positive beneficial effects:
(1) the invention takes the fluorine-containing alkyl silane as a raw material, adopts two emulsifiers to emulsify the fluorine-containing alkyl silane in three steps, emulsifies the fluorine-containing alkyl silane into water-based emulsion, and has good compatibility with water-based paint.
(2) The alkyl silane can be hydrolyzed to form the silicon triol under certain conditions, the silicon triol is crosslinked to form a film, can be used as a film forming substance of paint, the fluorine-containing alkyl silane is a compound of which the hydrogen element of the alkyl part of the alkyl silane is replaced by fluorine element, the hydrolysis crosslinking film forming property of the fluorine-containing alkyl silane after fluorine replacement is not changed, can be used as a compound with high fluorine content for preparing coating, therefore, the invention uses the fluorine-containing alkyl silane emulsion to modify fluorocarbon emulsion to prepare polymer emulsion with high fluorine content, the polymer emulsion can be used as a film forming substance for preparing water-based paint, improves the fluorine content of the water-based paint by more than 15 percent, so that the fluorine content of the coating system can reach 17.5 percent to the maximum, and the weather resistance, the chemical corrosion resistance and the self-cleaning capability (namely the stain resistance) of the coating are greatly improved.
(3) The fluorine-containing alkyl silane is hydrolyzed into the silanetriol with the side chain containing the fluorine-containing alkyl in the film forming process of the paint and is continuously crosslinked into a main chain-Si-O-macromolecular chain, so that the water-based paint is prepared by taking the high-fluorine-content polymer emulsion as a film forming substance, the primer fluorine element is added into the water-based paint, and the primer is added into the film forming substance with the main chain of-Si-O-bond, thereby further improving the air permeability and the strength of the paint coating.
(4) The high-fluorine-content water-based concrete protective coating prepared by the invention has excellent weather resistance, corrosion resistance and self-cleaning capability, is suitable for coating the surface of a porous substrate (such as concrete, brick and tile and other substrates), is particularly suitable for coating the concrete in heavy-duty anti-corrosion areas such as coastal wharfs, seaside power plants and the like, can prolong the service life of the concrete in the heavy-duty anti-corrosion areas, reduces the maintenance and reconstruction cost, and has great economic benefit.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the scope of the present invention is not limited thereto.
(one) preparing high fluorine content polymer emulsion
Example 1:
the high fluorine content polymer emulsion consists of perfluoro amyl trimethoxy silane in 50 wt%3F7(CH2)2Si(OCH3)3]The emulsion is compounded with 50 percent of fluorocarbon emulsion. Wherein perfluoropentyltrimethoxysilane is contained in the perfluoropentyltrimethoxysilane emulsionThe mass percentage of the alkane is 30 percent; the fluorocarbon emulsion is a core-shell copolymer of trifluoroethyl acrylate and acrylate (the fluorine content is about 10%, the solid content is about 50%, the product specification is ZT-9612, Jiangsu Zhitai).
The preparation method of the high fluorine content polymer emulsion comprises the following steps:
(1) weighing 30g of perfluoropentyltrimethoxysilane, adding 0.5g of emulsifier A, and stirring at 300rpm for 15min to obtain a mixed solution A for later use; wherein the emulsifier A is T-80;
(2) weighing 69g of water, adding 0.5g of emulsifier B, and stirring until the mixture is uniformly dispersed to obtain a mixed solution B; wherein the emulsifier B is S-40;
(3) adding the mixed solution A into the mixed solution B while stirring, wherein the stirring speed is 800rpm, and the addition is finished within 5 min; emulsifying for 20min under the condition that the stirring speed is 1200rpm after the addition is finished until the mixed solution A and the mixed solution B are completely emulsified to obtain perfluoropentyl trimethoxy silane emulsion, and defoaming stably;
(4) and (3) adding 100g of fluorocarbon emulsion into the perfluoropentyl trimethoxy silane emulsion, and dispersing for 10min at 800rpm to obtain the high fluorine content polymer emulsion.
Example 2:
the high fluorine content polymer emulsion consists of perfluoro octyl trimethoxy silane in 50 wt%6F13(CH2)2Si(OCH3)3]The emulsion is compounded with 50 percent of fluorocarbon emulsion; wherein the mass percentage of the perfluorooctyl trimethoxy silane in the perfluorooctyl trimethoxy silane emulsion is 30 percent; the fluorocarbon emulsion was the same as in example 1.
The preparation process of the high fluorine content polymer emulsion is substantially the same as that of example 1 except that: the fluorine-containing alkyl silane is perfluorooctyl trimethoxy silane; the emulsifier A is T-80, and the using amount is 0.2 g; the emulsifier B is OP-20, and the dosage is 0.8 g.
Example 3:
the high fluorine content polymer emulsion is prepared with perfluoro amyl triethoxy silane in 50 wt%[C3F7(CH2)2Si(OCH2CH3)3]The emulsion is compounded with 50 percent of fluorocarbon emulsion; wherein the mass percentage of the perfluoropentyltriethoxysilane in the perfluoropentyltriethoxysilane emulsion is 30%; the fluorocarbon emulsion was the same as in example 1.
The preparation process of the high fluorine content polymer emulsion is substantially the same as that of example 1 except that: the fluorine-containing alkyl silane is perfluoropentyl triethoxysilane; the emulsifier A is S-80, and the using amount is 0.2 g; the emulsifier B is OP-15, and the dosage is 0.8 g.
Example 4:
the high fluorine content polymer emulsion consists of perfluoro octyl triethoxy silane in 50 wt%6F13(CH2)2Si(OCH2CH3)3]The emulsion is compounded with 50 percent of fluorocarbon emulsion; wherein the mass percentage of the perfluorooctyl triethoxysilane in the perfluorooctyl triethoxysilane emulsion is 30%; the fluorocarbon emulsion is a core-shell copolymer of trifluoroethyl acrylate and acrylate (the fluorine content is about 10%, the solid content is about 50%, the product specification is ZT-9612, Jiangsu Zhitai).
The preparation process of the high fluorine content polymer emulsion is substantially the same as that of example 1 except that: the fluorine-containing alkyl silane is perfluorooctyl triethoxysilane.
Example 5:
the high fluorine content polymer emulsion consists of perfluoro decyl triethoxy silane in 50 wt%8F17(CH2)2Si(OCH2CH3)3]The emulsion is compounded with 50 percent of fluorocarbon emulsion; wherein the mass percentage of the perfluorodecyl triethoxysilane in the perfluorodecyl triethoxysilane emulsion is 30%; the fluorocarbon emulsion is a core-shell copolymer of trifluoroethyl acrylate and acrylate (the fluorine content is about 10%, the solid content is about 50%, the product specification is ZT-9612, Jiangsu Zhitai).
Method for preparing the high fluorine content polymer emulsion the method for preparing the high fluorine content polymer emulsion is substantially the same as in example 1 except that: the fluorine-containing alkyl silane is perfluorodecyl triethoxysilane.
Example 6:
the high fluorine content polymer emulsion consists of perfluoro octyl triethoxy silane in 50 wt%6F13(CH2)2Si(OCH2CH3)3]The emulsion is compounded with 50 percent of fluorocarbon emulsion; wherein the mass percentage of the perfluorooctyl triethoxysilane in the perfluorooctyl triethoxysilane emulsion is 50%; the fluorocarbon emulsion is a core-shell copolymer of trifluoroethyl acrylate and acrylate (the fluorine content is about 10%, the solid content is about 50%, the product specification is ZT-9612, Jiangsu Zhitai).
The preparation method of the high fluorine content polymer emulsion comprises the following steps:
(1) weighing 50g of perfluorooctyl triethoxysilane, adding 0.5g of emulsifier T-80, and stirring at 300rpm for 15min to obtain a mixed solution A for later use;
(2) weighing 49g of water, adding 0.5g of emulsifier S-40, and stirring until the mixture is uniformly dispersed to obtain a mixed solution B;
(3) adding the mixed solution A into the mixed solution B while stirring, wherein the stirring speed is 800rpm, and the addition is finished within 5 min; emulsifying for 20min under the condition that the stirring speed is 1200rpm after the addition is finished until the mixed solution A and the mixed solution B are completely emulsified to obtain perfluorooctyl triethoxysilane emulsion, and defoaming is stable;
(4) and (3) adding 100g of fluorocarbon emulsion into the perfluorooctyl triethoxysilane emulsion, and dispersing for 10min at 800rpm to obtain the high fluorine content polymer emulsion.
Example 7:
the high fluorine content polymer emulsion consists of perfluoro octyl triethoxy silane in 50 wt%6F13(CH2)2Si(OCH2CH3)3]The emulsion is compounded with 50 percent of fluorocarbon emulsion; wherein, perfluorooctyl triethoxy silane is perfluorooctyl triethoxy silane emulsionThe mass percentage of the alkane is 80 percent; the fluorocarbon emulsion is a core-shell copolymer of trifluoroethyl acrylate and acrylate (the fluorine content is about 10%, the solid content is about 50%, the product specification is ZT-9612, Jiangsu Zhitai).
The preparation method of the high fluorine content polymer emulsion comprises the following steps:
(1) weighing 80g of perfluorooctyl triethoxysilane, adding 0.2g of emulsifier S-80, and stirring at 300rpm for 15min to obtain a mixed solution A for later use;
(2) weighing 19g of water, adding 0.8g of emulsifier OP-15, and stirring until the mixture is uniformly dispersed to obtain a mixed solution B;
(3) adding the mixed solution A into the mixed solution B while stirring, wherein the stirring speed is 800rpm, and the addition is finished within 5 min; emulsifying for 20min under the condition that the stirring speed is 1200rpm after the addition is finished until the mixed solution A and the mixed solution B are completely emulsified to obtain perfluorooctyl triethoxysilane emulsion, and defoaming is stable;
(4) and (3) adding 100g of fluorocarbon emulsion into the perfluorooctyl triethoxysilane emulsion, and dispersing for 10min at 800rpm to obtain the high fluorine content polymer emulsion.
Example 8:
the high fluorine content polymer emulsion consists of perfluoro octyl triethoxy silane C in 66.7 wt%6F13(CH2)2Si(OCH2CH3)3]The emulsion is compounded with 33.3 percent of fluorocarbon emulsion; wherein the mass percentage of the perfluorooctyl triethoxysilane in the perfluorooctyl triethoxysilane emulsion is 50%; the fluorocarbon emulsion is a core-shell copolymer of trifluoroethyl acrylate and acrylate (the fluorine content is about 10%, the solid content is about 50%, the product specification is ZT-9612, Jiangsu Zhitai).
The preparation method of the high fluorine content polymer emulsion comprises the following steps:
(1) weighing 50g of perfluorooctyl triethoxysilane, adding 0.5g of emulsifier T-80, and stirring at 300rpm for 15min to obtain a mixed solution A for later use;
(2) weighing 49g of water, adding 0.5g of emulsifier S-40, and stirring until the mixture is uniformly dispersed to obtain a mixed solution B;
(3) adding the mixed solution A into the mixed solution B while stirring, wherein the stirring speed is 800rpm, and the addition is finished within 5 min; emulsifying for 20min under the condition that the stirring speed is 1200rpm after the addition is finished until the mixed solution A and the mixed solution B are completely emulsified to obtain perfluorooctyl triethoxysilane emulsion, and defoaming is stable;
(4) and adding 50g of fluorocarbon emulsion into the perfluorooctyl triethoxysilane emulsion, and dispersing for 10min at 800rpm to obtain the high fluorine content polymer emulsion.
Example 9:
the high fluorine content polymer emulsion consists of perfluoro octyl triethoxy silane [ C ] in 10 wt%6F13(CH2)2Si(OCH2CH3)3]The emulsion is compounded with 90 percent of fluorocarbon emulsion; wherein the mass percentage of the perfluorooctyl triethoxysilane in the perfluorooctyl triethoxysilane emulsion is 90%; the fluorocarbon emulsion is PVDF fluorocarbon emulsion.
The preparation process of the high fluorine content polymer emulsion is substantially the same as that of example 1 except that: the usage amounts of the perfluorooctyl triethoxysilane, the water and the PVDF fluorocarbon emulsion in the preparation method are different.
Example 10:
the high fluorine content polymer emulsion consists of perfluoro octyl triethoxy silane C in 90 wt%6F13(CH2)2Si(OCH2CH3)3]The emulsion is compounded with 10 percent of fluorocarbon emulsion; wherein the mass percentage of the perfluorooctyl triethoxysilane in the perfluorooctyl triethoxysilane emulsion is 10%; the fluorocarbon emulsion is FEVE type fluorocarbon emulsion.
The preparation process of the high fluorine content polymer emulsion is substantially the same as that of example 1 except that: the dosages of the perfluorooctyl triethoxysilane, the water and the FEVE type fluorocarbon emulsion in the preparation method are different.
Example 11:
the high fluorine content polymer emulsion accounts for 30 percent by massPerfluorooctyltriethoxysilane [ C ]6F13(CH2)2Si(OCH2CH3)3]The emulsion is compounded with 70 percent of fluorocarbon emulsion; wherein the mass percentage of the perfluorooctyl triethoxysilane in the perfluorooctyl triethoxysilane emulsion is 40%; the fluorocarbon emulsion is a core-shell copolymer of trifluoroethyl acrylate and acrylate (the fluorine content is about 10%, the solid content is about 50%, the product specification is ZT-9612, Jiangsu Zhitai).
The preparation process of the high fluorine content polymer emulsion is substantially the same as that of example 1 except that: the dosage of the perfluorooctyl triethoxysilane, the water and the fluorocarbon emulsion in the preparation method is different.
(II) preparation of Water-based paint
Example 12:
a high fluorine content water-based concrete protective coating is prepared from the following raw materials: 50g of high-fluorine-content polymer emulsion, 10g of titanium dioxide, 15g of barium sulfate, 10g of wollastonite, 11.7g of water, 2g of dodecanol ester (film-forming aid), 50400.6g of dispersing agent, BYK-0280.2 g of defoaming agent, 0.2g of pH regulator, 0.1g of bactericide MC and RM-20200.2 g of thickening agent; wherein the high fluorine content polymer emulsion is the high fluorine content polymer emulsion prepared in example 1.
The preparation method of the high-fluorine-content water-based concrete protective coating comprises the following steps:
a. adding deionized water into a high-speed dispersion machine, adding a dispersing agent 5040, stirring at 500rpm until the deionized water is uniformly dispersed, adding a defoaming agent BYK-028, eliminating bubbles, adding a pH regulator DMAE, and adjusting the pH to 8-10 to obtain slurry;
b. b, sequentially adding titanium dioxide, barium sulfate and wollastonite into the slurry prepared in the step a, and stirring at 1400rpm until the titanium dioxide, the barium sulfate and the wollastonite are uniformly dispersed;
c. transferring the slurry treated in the step b to a grinder, grinding the slurry until the fineness of the slurry is less than 10 mu m, and discharging the slurry;
d. and c, adding the high-fluorine-content polymer emulsion into the slurry treated in the step c, stirring at 800rpm for 5min, then adding the dodecyl alcohol ester, continuing stirring for 5min, then adding the thickening agent and the bactericide, and stirring at 800rpm for 10min to obtain the high-fluorine-content water-based concrete protective coating, which is recorded as sample 1.
Example 13:
example 13 is substantially the same as example 12 except that: the high fluorine polymer emulsion was the high fluorine polymer emulsion prepared in example 2.
The high fluorine content aqueous concrete protective coating prepared in example 13 is designated as sample 2.
Example 14:
example 14 is substantially the same as example 12 except that: the high fluorine polymer emulsion was the high fluorine polymer emulsion prepared in example 3.
The high fluorine content aqueous concrete protective coating prepared in example 14 is designated as sample 3.
Example 15:
example 15 is substantially the same as example 12 except that: the high fluorine polymer emulsion was the high fluorine polymer emulsion prepared in example 4.
The high fluorine content aqueous concrete protective coating prepared in example 15 is designated as sample 4.
Example 16:
example 16 is substantially the same as example 12 except that: the high fluorine polymer emulsion was the high fluorine polymer emulsion prepared in example 5.
The high fluorine content aqueous concrete protective coating prepared in example 16 is designated as sample 5.
Example 17:
a high fluorine content water-based concrete protective coating is prepared from the following raw materials: 80g of high-fluorine-content polymer emulsion, 15.1g of water, 4g of dodecyl alcohol ester (film-forming aid), 0.5g of pH regulator DMAE, 0.1g of bactericide MC and 0.3g of thickener U5050; wherein the high fluorine content polymer emulsion is the high fluorine content polymer emulsion prepared in example 4.
The preparation method of the high-fluorine-content water-based concrete protective coating comprises the following steps:
a. adding the high-fluorine-content polymer emulsion and water into a high-speed dispersion machine at the same time, and stirring at 600rpm until the polymer emulsion and the water are uniformly dispersed to obtain slurry;
b. adding dodecyl alcohol ester, a pH regulator DMAE and a bactericide MC into the slurry prepared in the step a in sequence, and stirring at 600rpm until the mixture is uniformly dispersed;
c. and c, adding a thickening agent U505 into the slurry treated in the step b, stirring and dispersing at 1000rpm for 15min to obtain the high-fluorine-content water-based concrete protective coating. This coating was a water-borne varnish and was designated sample 6.
Example 18:
example 18 is substantially the same as example 12 except that: the high fluorine polymer emulsion was the high fluorine polymer emulsion prepared in example 6.
The high fluorine content waterborne concrete protective coating prepared in example 18 was designated as sample 7.
Example 19:
example 19 is substantially the same as example 17 except that: the high fluorine polymer emulsion was the high fluorine polymer emulsion prepared in example 6.
The high fluorine content aqueous concrete protective coating prepared in example 19 was designated as sample 8.
Example 20:
the contents of example 20 are substantially the same as those of example 12, except that: the high fluorine polymer emulsion was the high fluorine polymer emulsion prepared in example 7.
The high fluorine content aqueous concrete protective coating prepared in example 20 is designated as sample 9.
Example 21:
example 21 is substantially the same as example 17 except that: the high fluorine polymer emulsion was the high fluorine polymer emulsion prepared in example 7.
The high fluorine content aqueous concrete protective coating prepared in example 21 was designated as sample 10.
Example 22:
the contents of example 22 are substantially the same as those of example 12, except that: the high fluorine polymer emulsion was the high fluorine polymer emulsion prepared in example 8.
The high fluorine content aqueous concrete protective coating prepared in example 22 is designated as sample 11.
Example 23:
example 23 is substantially the same as example 17 except that: the high fluorine polymer emulsion was the high fluorine polymer emulsion prepared in example 8.
The high fluorine content waterborne concrete protective coating prepared in example 23 is designated as sample 12.
Example 24:
a high fluorine content water-based concrete protective coating is prepared from the following raw materials: 30g of high-fluorine-content polymer emulsion, 20g of titanium dioxide, 20g of barium sulfate, 10g of wollastonite, 14.7g of water, 2g of dodecyl alcohol ester (film-forming aid), 50402g of dispersing agent, 0.1g of defoaming agent BYK-0281 g of pH regulator, 0.1g of bactericide MC and 0.78 g of thickening agent RM-20200.1 g; wherein the high fluorine content polymer emulsion is the high fluorine content polymer emulsion prepared in example 7.
The preparation method of the high fluorine content water-based concrete protective coating is the same as that of the example 12.
Example 25:
a high fluorine content water-based concrete protective coating is prepared from the following raw materials: 40g of high fluorine content polymer emulsion, 8g of titanium dioxide, 15g of barium sulfate, 5g of wollastonite, 27g of water, 3g of dodecyl alcohol ester (film forming additive), 50400.5 g of dispersing agent, BYK-0280.2 g of defoaming agent, 0.5g of pH regulator, 0.3g of bactericide MC and RM-20200.5 g of thickening agent; wherein the high fluorine content polymer emulsion is the high fluorine content polymer emulsion prepared in example 7.
The preparation method of the high fluorine content water-based concrete protective coating is the same as that of the example 12.
Example 26:
a high fluorine content water-based concrete protective coating is prepared from the following raw materials: 65g of high-fluorine polymer emulsion, 27.3g of water, 6g of dodecyl alcohol ester (film-forming aid), 0.5g of pH regulator DMAE, 0.2g of bactericide MC, and thickener U5051 g; wherein the high fluorine content polymer emulsion is the high fluorine content polymer emulsion prepared in example 7.
The preparation method of the high fluorine content water-based concrete protective coating is the same as that of the example 17.
And (III) detecting the fluorine content and the performance index of the water-based concrete protective coating prepared by the invention:
1. detecting fluorine content and performance indexes of samples 1 to 5:
the coating samples (sample 1 to sample 5) prepared in examples 12 to 16 were subjected to fluorine content measurement and performance index measurement, and the measurement results are shown in table 1. Wherein, the performance index detection comprises stability (the state of the coating after being placed for 7 days at room temperature), hardness, acid resistance, weather resistance and scrawling resistance (namely the cleanable grade); the hardness test refers to the standard GB/T6739 Pencil determination method for coating hardness; the acid resistance test refers to standard HG/T3792-; weather resistance test and evaluation reference standard GB/T1865-1997 Artificial weathering and Artificial radiation Exposure (filtered xenon arc radiation) for paints and varnishes; anti-graffiti reference standard JG/T304 & 2011 anti-graffiti paint for building (cleanable grade assessment is shown in Table 2).
TABLE 1 results of measuring fluorine content and performance index of coating samples prepared in examples 9 to 13
TABLE 2 cleanability grade of human engineering method
| Grade | Graffiti removal situation |
| Level 1 | Can be removed by dry lint-free cotton cloth |
| Stage 2 | Can be removed by 1% neutral water-based weak cleaning agent |
| Grade 3 | Can be removed with orange-based detergent |
| 4 stage | Can be removed by anhydrous alcohol |
| Grade 5 | The 4 cleaning materials can not be removed, or the coating after cleaning has obvious light loss, color change or other damages |
The aqueous coating formulations described in examples 12-16 were identical in all components and amounts except for the fluoroalkyl silane-containing component of the fluoroalkyl silane-containing emulsion. As is clear from Table 1, the water-based paints prepared in examples 12 to 16 are significantly different in fluorine content and properties, and among them, the water-based paint prepared in example 12 (sample 4) is high in fluorine content, excellent in acid resistance and weather resistance, and excellent in anti-graffiti property, i.e., class 3, and is the best in overall properties. Therefore, the water paint prepared by taking the perfluorooctyl triethoxysilane emulsion as the raw material has good comprehensive performance.
2. And (3) detecting fluorine content and performance indexes of samples 6 to 12:
the coating samples (sample 6 to sample 12) prepared in examples 17 to 23 were subjected to fluorine content measurement and performance index measurement, and the measurement results are shown in table 3.
Table 3 results of measuring fluorine content and performance index of coating samples prepared in examples 17 to 23
As can be seen from table 3, in the preparation of the colored paint coating (see example 15, example 18, and example 20), as the content of the fluoroalkyl silane, which is an active ingredient in the fluoroalkyl silane emulsion, increases, the fluorine content of the aqueous coating system gradually increases, and the weather resistance and the anti-graffiti property of the coating are gradually improved, with the anti-graffiti property level being at most 2; when the varnish coating (see example 17, example 19 and example 21) is prepared, along with the increase of the content of the fluorine-containing alkyl silane which is an active ingredient in the fluorine-containing alkyl silane emulsion, the fluorine content of a water-based coating system is gradually increased, the fluorine content reaches 17.5 percent at most, the weather resistance and the anti-graffiti property of the coating are also gradually improved, and the anti-graffiti property grade reaches 1 grade at most, which shows that the water-based coating prepared by the invention has strong stain resistance and better self-cleaning capability. Furthermore, it can be seen from the data in Table 3 that the graffiti resistance of the clear coat coating systems is superior to that of the pigmented coat coatings.
3. Comparison of the Properties of the aqueous concrete protective coating of the invention
To further verify the effect of the high fluorine content polymer emulsion of the present invention on the performance of the aqueous concrete protective coating, the aqueous concrete protective coating prepared in example 23 of the present invention was taken as an example for performance verification. Meanwhile, for comparison, the invention also provides the following comparison experiments, namely a comparison experiment 1, a comparison experiment 2 and a comparison experiment 3.
Comparative experiment 1:
the content of comparative experiment 1 is substantially the same as in example 23, except that: the high fluorine content polymer emulsion in the water paint formula is replaced by fluorocarbon emulsion, and the dosage of the fluorocarbon emulsion is the same as that of the high fluorine content polymer emulsion in the embodiment 23; wherein the fluorocarbon emulsion is a core-shell copolymer of trifluoroethyl acrylate and acrylate (the fluorine content is about 10%, the solid content is about 50%, the product specification is ZT-9612, Jiangsu Zhitai).
Comparative experiment 2:
the content of comparative experiment 2 is substantially the same as in example 23, except that: the high fluorine polymer emulsion in the water paint formulation was replaced with octyl triethoxysilane modified fluorocarbon emulsion, which was designated as polymer emulsion, and the amount of polymer emulsion used was the same as the high fluorine polymer emulsion in example 23.
The polymer emulsion is prepared by compounding 33.3 percent of octyl triethoxysilane, 33.3 percent of fluorocarbon emulsion and 33.4 percent of water in percentage by mass. Wherein the fluorocarbon emulsion is a core-shell copolymer of trifluoroethyl acrylate and acrylate (the fluorine content is about 10%, the solid content is about 50%, the product specification is ZT-9612, Jiangsu Zhitai).
The preparation method of the polymer emulsion comprises the following steps: 33.3g of fluorocarbon emulsion is weighed in a high-speed disperser, 33.3g of octyl triethoxysilane is added under the rotation speed of 600rpm for dispersing for 10min, and 33.4g of water is added for dispersing for 5 min. Thus obtaining the octyl triethoxy silane modified polymer emulsion.
Comparative experiment 3:
the content of comparative experiment 3 is substantially the same as in example 23, except that: the high fluorine content polymer emulsion in the water paint formula is replaced by hydrolyzed silane modified fluorocarbon emulsion, which is recorded as hydrolyzed silane modified polymer emulsion. The hydrolyzed silane-modified polymer emulsion was used in the same amount as the high fluorine content polymer emulsion of example 23.
The hydrolyzed silane modified polymer emulsion is prepared from 33.3 percent of hydrolyzed octyl triethoxysilane, 33.3 percent of fluorocarbon emulsion and 33.4 percent of deionized water in percentage by mass. Wherein the fluorocarbon emulsion is a core-shell copolymer of trifluoroethyl acrylate and acrylate (the fluorine content is about 10%, the solid content is about 50%, the product specification is ZT-9612, Jiangsu Zhitai).
The specific preparation method of the hydrolyzed silane modified polymer emulsion comprises the following steps:
(1) 152g of octyl triethoxysilane and 50g of ethanol are weighed in a 500mL three-neck flask, heated to 75 ℃ under the stirring state, 24g of deionized water is dripped, the dripping is completed within 1h, the reaction is carried out for 0.5h under the heat preservation condition after the dripping, and the ethanol generated in the reaction and added in the early stage is pumped out in a vacuum manner, so that the hydrolyzed triethoxysilane can be obtained.
(2) 33.3g of fluorocarbon emulsion is taken to be placed in a high-speed dispersion machine, 33.3g of hydrolyzed octyl triethoxysilane prepared in the step (1) is added under the rotating speed of 600rpm and is dispersed for 10min, and 33.4g of deionized water is added and is dispersed for 5 min. Thus obtaining the hydrolyzed silane modified polymer emulsion.
The fluorine content and the performance of the aqueous coating materials prepared in example 23 of the present invention, comparative experiment 1, comparative experiment 2 and comparative experiment 3 were measured, and the measurement results are shown in table 4.
TABLE 4 results of fluorine content and performance measurements of waterborne coatings prepared in example 23, comparative experiment 1-comparative experiment 3
As shown in Table 4, in comparative experiment 1, when the water-based paint is prepared by using the conventional water-based fluorocarbon emulsion without modification, the water-based paint has poor hardness, acid resistance, weather resistance and anti-graffiti property, the anti-graffiti property of the paint is tested by using an oil-based marking pen, and yellow traces remain after the paint is wiped by using alcohol. In a comparison experiment 2, the polymer emulsion is prepared by modifying fluorocarbon emulsion without special treatment by using common silane, the stability of the water-based paint prepared by the polymer emulsion is poor, and when the silane content is excessively large, a paint system is very easy to layer; in addition, the acid resistance, weather resistance and graffiti resistance of the water-based paint are poor. Comparative experiment 3 adopts modified fluorocarbon emulsion after silane hydrolysis to prepare polymer emulsion, and the compatibility of the water-based paint prepared from the polymer emulsion is improved to some extent, but hydrolyzed silane is extremely unstable, and gel is easily generated when the addition amount is too large, so that the use of the paint is influenced. Compared with a comparative experiment 1, a comparative experiment 2 and a comparative experiment 3, the water-based paint prepared by the polymer emulsion modified by the fluoroalkyl silane has the advantages that the hardness, the acid resistance, the weather resistance and the anti-graffiti property are greatly improved, the anti-graffiti property can reach level 1, and the performance is optimal. Therefore, the high-fluorine-content polymer emulsion prepared by modifying fluorocarbon emulsion with the fluoroalkyl silane-containing emulsion can be used as a film forming substance for preparing water-based paint, improves the fluorine content of the water-based paint, and greatly improves the weather resistance, chemical corrosion resistance and self-cleaning capability (stain resistance) of the paint.
The above description is only a few preferred examples of the present invention and is not limited to the content of the embodiments of the present invention. Various changes can be made within the scope of the concept of the technical scheme of the invention, and the changes are all within the protection scope of the invention.
Claims (10)
1. The high fluorine content polymer emulsion is characterized by being prepared by compounding 10-80% of fluorine-containing alkyl silane emulsion and 20-90% of fluorocarbon emulsion by mass percentage.
2. The high fluorine content polymer emulsion according to claim 1, wherein the fluoroalkyl silane emulsion is an emulsified product of fluoroalkyl silane having a structural formula of CnF2n+1(CH2)2Si(OR)3Wherein n =3 to 16, and R represents-CH3or-CH2CH3。
3. The high fluorine content polymer emulsion according to claim 2, wherein the preparation method of the fluorine-containing alkylsilane emulsion comprises the following steps:
(1) adding an emulsifier A into the fluorine-containing alkyl silane, and stirring until the emulsifier A is uniformly dispersed to obtain a mixed solution A for later use;
(2) adding an emulsifier B into water, and stirring until the emulsifier B is uniformly dispersed to obtain a mixed solution B;
(3) and adding the mixed solution A into the mixed solution B while stirring, and continuously stirring until the mixed solution A and the mixed solution B are completely emulsified after the addition is finished to obtain the fluorine-containing alkyl silane emulsion.
4. The high fluorine content polymer emulsion according to claim 3, wherein the emulsifier A is milk T-80 or S-80; the emulsifier B is any one of S-40, OP-20 and OP-15.
5. The high fluorine content polymer emulsion according to claim 4, wherein the rotation speed of the stirring in the step (3) is 800 to 1500 rpm.
6. The high fluorine content polymer emulsion according to claim 1, wherein the fluorocarbon emulsion is one or more of a fluoroacrylate emulsion, a PVDF fluorocarbon emulsion, and a FEVE fluorocarbon emulsion.
7. The high fluorine content polymer emulsion according to claim 1, wherein the content of the fluoroalkyl silane in the fluoroalkyl silane containing emulsion is 10 to 90% by mass.
8. Use of the high fluorine content polymer emulsion according to any one of claims 1 to 4 in an aqueous coating.
9. The high-fluorine-content water-based concrete protective coating is characterized by being prepared from the following raw materials in parts by weight: 30-80 parts of high-fluorine-content polymer emulsion, 0-50 parts of filler, 10-30 parts of water, 2-10 parts of film forming auxiliary agent, 0-0.5 part of pH regulator, 0-0.3 part of bactericide and 0.2-4 parts of necessary auxiliary agent, wherein the high-fluorine-content polymer emulsion is the high-fluorine-content polymer emulsion disclosed by any one of claims 1-7.
10. The high fluorine content aqueous concrete protective coating of claim 9 wherein the coalescent is a dodecyl alcohol ester; the necessary auxiliary agent is one or more of a dispersing agent, a defoaming agent and a thickening agent; the filler is one or more of titanium dioxide, barium sulfate and wollastonite.
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| CN112852236A (en) * | 2021-01-13 | 2021-05-28 | 宣城市政建设集团有限公司 | Protective agent for fair-faced concrete decorative surface and preparation method thereof |
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