CN116463022A - High weather-resistant water-based modified polyacrylic acid bridge concrete protective coating - Google Patents
High weather-resistant water-based modified polyacrylic acid bridge concrete protective coating Download PDFInfo
- Publication number
- CN116463022A CN116463022A CN202310420957.0A CN202310420957A CN116463022A CN 116463022 A CN116463022 A CN 116463022A CN 202310420957 A CN202310420957 A CN 202310420957A CN 116463022 A CN116463022 A CN 116463022A
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- CN
- China
- Prior art keywords
- component
- coating
- bridge concrete
- protective coating
- emulsion
- Prior art date
- 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.)
- Granted
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- 239000004567 concrete Substances 0.000 title claims abstract description 57
- 239000011253 protective coating Substances 0.000 title claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229920002125 Sokalan® Polymers 0.000 title claims abstract description 15
- 239000004584 polyacrylic acid Substances 0.000 title claims abstract description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 96
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 81
- 238000000576 coating method Methods 0.000 claims abstract description 75
- 239000011248 coating agent Substances 0.000 claims abstract description 73
- 239000000839 emulsion Substances 0.000 claims abstract description 55
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims abstract description 47
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 34
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000007864 aqueous solution Substances 0.000 claims abstract description 32
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 31
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 claims abstract description 28
- YPJUNDFVDDCYIH-UHFFFAOYSA-N perfluorobutyric acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000002829 reductive effect Effects 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 238000004821 distillation Methods 0.000 claims abstract description 15
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims abstract description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 14
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 7
- 229920000768 polyamine Polymers 0.000 claims abstract description 7
- -1 polyoxyethylene octyl phenol Polymers 0.000 claims description 58
- 239000007788 liquid Substances 0.000 claims description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 239000011737 fluorine Substances 0.000 claims description 23
- 229910052731 fluorine Inorganic materials 0.000 claims description 23
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 21
- 238000010008 shearing Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 13
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 8
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 8
- 238000004945 emulsification Methods 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 8
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 239000011733 molybdenum Substances 0.000 claims 1
- 238000004064 recycling Methods 0.000 claims 1
- FPSFKBGHBCHTOE-UHFFFAOYSA-N sodium 3-hydroxy-4-[(3-methyl-5-oxo-1-phenyl-4H-pyrazol-4-yl)diazenyl]naphthalene-1-sulfonic acid Chemical compound [Na+].O=C1C(N=NC=2C3=CC=CC=C3C(=CC=2O)S(O)(=O)=O)C(C)=NN1C1=CC=CC=C1 FPSFKBGHBCHTOE-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 12
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 6
- 239000008199 coating composition Substances 0.000 abstract description 2
- 125000003700 epoxy group Chemical group 0.000 description 54
- 238000000034 method Methods 0.000 description 36
- 230000000694 effects Effects 0.000 description 27
- 125000004185 ester group Chemical group 0.000 description 27
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 25
- 238000005886 esterification reaction Methods 0.000 description 25
- 239000003973 paint Substances 0.000 description 24
- 230000008569 process Effects 0.000 description 24
- 238000012360 testing method Methods 0.000 description 20
- 239000000203 mixture Substances 0.000 description 17
- 239000007795 chemical reaction product Substances 0.000 description 15
- 229920000058 polyacrylate Polymers 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- 238000010276 construction Methods 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000011150 reinforced concrete Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UWDMKTDPDJCJOP-UHFFFAOYSA-N 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-ium-4-carboxylate Chemical compound CC1(C)CC(O)(C(O)=O)CC(C)(C)N1 UWDMKTDPDJCJOP-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- PLXOUIVCSUBZIX-UHFFFAOYSA-N 2,2,3,3,4,4,4-heptafluorobutyl prop-2-enoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)COC(=O)C=C PLXOUIVCSUBZIX-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 239000005337 ground glass Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000002075 main ingredient Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
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- HPFWZNWHCWZFBD-UHFFFAOYSA-N 1,1,2,2,3,3,4-heptafluorobutan-1-ol Chemical compound OC(F)(F)C(F)(F)C(F)(F)CF HPFWZNWHCWZFBD-UHFFFAOYSA-N 0.000 description 1
- LCPUCXXYIYXLJY-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(F)CC(F)(F)F LCPUCXXYIYXLJY-UHFFFAOYSA-N 0.000 description 1
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 description 1
- COOBHJUVOWQEBE-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octamethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane;silicon Chemical compound [Si].C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 COOBHJUVOWQEBE-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- URFLCXSTNZSALZ-UHFFFAOYSA-N [F].C(C(=C)C)(=O)O Chemical compound [F].C(C(=C)C)(=O)O URFLCXSTNZSALZ-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
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- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- VNTLIPZTSJSULJ-UHFFFAOYSA-N chromium molybdenum Chemical compound [Cr].[Mo] VNTLIPZTSJSULJ-UHFFFAOYSA-N 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
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- 239000003085 diluting agent Substances 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000006341 heptafluoro n-propyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
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- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-Butanol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
Abstract
The invention belongs to the technical field of coating compositions, and particularly relates to a high weather-resistant water-based modified polyacrylic acid bridge concrete protective coating; the coating comprises an A component of aqueous emulsion containing modified acrylic resin and a B component of aliphatic polyamine aqueous solution serving as a curing agent, wherein the A component and the B component are uniformly mixed according to the weight ratio of 100:2-4 of organic matters before use; the preparation method of the aqueous emulsion of the modified acrylic resin comprises the following steps: (1) Triglycidyl isocyanurate and heptafluoro-n-butyric acid are reacted under the conditions of methyl methacrylate, 4-hydroxy-TEMPO and 65-70 ℃, then acrylic acid and triethylamine are added for reaction at 80-85 ℃, and then material liquid-1 is obtained after reduced pressure distillation; (2) Mixing the feed liquid-1 with an emulsifier, acrylic acid, butyl methacrylate, isooctyl acrylate and styrene to prepare a pre-emulsion; and (3) the pre-emulsion is obtained through emulsion polymerization. The coating has the advantages of low cost, high curing speed and long service life, and is suitable for protecting bridge concrete in non-coastal areas.
Description
Technical Field
The invention belongs to the technical field of coating compositions, and particularly relates to a high weather-resistant water-based modified polyacrylic acid bridge concrete protective coating.
Background
With the rapid development of traffic industry, millions of reinforced concrete bridges are built in China, including high-speed railways, expressway bridges, various high-grade overpasses and overpasses, and the design life is 100 years or 50 years. In the long-term use process, the bridge reinforced concrete needs to be subjected to frequent vibration, stress, temperature, humidity and illumination condition test, and frequent water, salt, acid and other corrosion; because concrete has a certain porosity, the problems of strength reduction, cracks and the like of the inner layer and the surface layer of the concrete can occur.
In the bridge construction process, the surface of the steel bar can be subjected to sealing treatment, and concrete can be prepared by adopting proper ingredients, such as a certain amount of waterproof and carbonization-resistant additives, but the effect is limited. Therefore, after many bridges are built, the concrete surface is also required to be coated with a protective material so as to improve the weather resistance of the reinforced concrete; the protection of the bridge concrete at sea and on the sea is realized by adopting multi-coating heavy-duty coating materials with different materials due to high environmental humidity and high salinity throughout the year, and the multi-coating heavy-duty coating materials with high cost and long service life such as coating materials of resin with high silicon and/or fluorine content and complex coating construction process can be adopted, and thick film coating with the thickness of 0.5-1mm can be adopted. However, the protection of bridge concrete in non-coastal areas is realized, the water-based paint such as acrylic resin with lower cost is competitive, and the construction of the paint is also correspondingly simple.
CN107603359a provides a concrete protective coating for railway structures, and a preparation method and a use method thereof, wherein the protective coating comprises a closed primer layer, a polyurethane intermediate paint layer and a fluorocarbon finish paint layer, has excellent adhesion, is used for protecting railway concrete bridges, and achieves excellent concrete protective effect under the condition that the concrete bridge is coated with a relatively thin coating thickness (the thickness of the closed primer layer is a complete covering base surface, the thickness of the polyurethane intermediate paint layer is 30-60 μm, and the thickness of the fluorocarbon finish paint layer is 30-60 μm). However, the curing time of the seal coat, the polyurethane intermediate coat and the fluorocarbon finish coat is 12-36h, preferably 24h, the coating construction process is long and complex, and the curing process is influenced by dust and rain and dew.
CN102993946A provides a water-based fluorine-silicon resin modified acrylic concrete protective coating, which comprises 10-20 parts of fluorine emulsion, 20-40 parts of silicon resin emulsion, 10-20 parts of soap-free pure acrylic emulsion, 5-10 parts of sericite, 5-15 parts of talcum powder, 5-10 parts of heavy calcium carbonate, 0.5-1.0 part of dispersing agent, 0.05-0.2 part of pH regulator, 0.3-0.5 part of defoaming agent, 1.0-2.5 parts of propylene glycol, 0.5-2 parts of mildew-proof antibacterial agent, 0.5-1.0 part of thickening agent, 1.0-2.5 parts of film forming auxiliary agent, 1.0-5.0 parts of hydrophober, 0.3-0.5 part of flatting agent, 0.1-0.3 part of in-tank bactericide and 30-45 parts of deionized water. After the paint is constructed, the paint has certain weather resistance, alkali resistance, washing resistance, air permeability and mildew resistance, and has long-term protection effect on concrete. The coating has higher fluorine emulsion and silicone emulsion content, so that the cost is higher; the fluorine-containing resin, the silicon-containing resin and the acrylic resin are introduced by three emulsions, and the organic combination of the three resins is not realized in the preparation process, so that the practical application effect is more general.
CN103214628A discloses a modified acrylic resin for weather-resistant coating and a preparation method thereof, which takes acrylic esters (methyl methacrylate, mixture of butyl acrylate and acrylic acid), organic silicon (octamethyl cyclotetrasiloxane) and organic fluorine (hexafluorobutyl methacrylate or dodecafluoroheptyl methacrylate) as main raw materials, and the silicone resin emulsion is synthesized by the step of aqueous emulsion polymerization, then part of acrylic esters is added for polymerization, and the rest of acrylic esters and organic fluorine are added for copolymerization, so that the silicone fluorine modified acrylic resin emulsion for reinforced concrete and building exterior wall protective coating is prepared, and the application effect of the silicone fluorine modified acrylic resin emulsion in weather-resistant coating is better than that of silicone resin, fluorine resin and acrylic resin when being singly or mixed. But according to the proportion analysis of raw materials, the production cost is higher; according to the analysis of the preparation process, the chemical bonding of the silicon-containing group and the acrylic acid polymeric main chain is less, the fluorine-containing group (the fluorine-containing ester group of the methacrylic acid fluorine-containing ester) is used as a branched chain in the obtained acrylic acid polymeric main chain, and the distribution is not well-defined and the distribution uniformity is not stable, so that the application effect of the modified acrylic resin in weather-resistant paint is affected.
CN102585637a provides a water-based epoxy grafted acrylate concrete anticorrosive paint and a preparation method thereof, wherein the anticorrosive paint comprises a component A and a component B (61-135): (1-3) by weight ratio; the component A consists of water-based epoxy grafted acrylate emulsion, filler, auxiliary agent and water, wherein the water-based epoxy grafted acrylate emulsion accounts for 30-60% of the total weight of the raw materials, the filler (titanium pigment, silica fume powder and barium sulfate) accounts for 20-30% of the total weight of the raw materials, the auxiliary agent (wetting dispersant, thickener, defoamer, pH regulator and leveling agent) accounts for 1.8-3.3% of the total weight of the raw materials, and the water accounts for 10-50% of the total weight of the raw materials; the component B is an aqueous amine curing agent, accounting for 1 to 3 percent of the total weight of the raw materials, and is prepared into a 50 percent aqueous solution; when in use, the component A and the component B are uniformly mixed to obtain the water-based epoxy grafted acrylate concrete anticorrosive paint. The coating of the coating has certain mechanical, corrosion-resistant, hydrophobic and water-resistant properties, but the specific conditions of the components, the marks or the preparation method of the epoxy grafted acrylate are not disclosed.
The curing time of the coating film of the coating in the prior art is more than 6 hours; fluorine-containing resin or modified by organic fluorine, the fluorine content in the cured coating is higher than 4 weight percent, and the cost is high; or the universality is poor due to complex ingredients.
Therefore, it is necessary to develop a high weather resistance water-based acrylic bridge concrete protective coating which has low cost, good universality, uses a modified acrylic resin with a determined and stable structure/composition as a main ingredient, is suitable for bridge concrete protection in non-coastal areas, and has the advantages of simple coating construction process, high curing speed, good coating protection effect and long service life.
Disclosure of Invention
In order to solve the technical problems, the invention provides the high weather-resistant water-based modified polyacrylic acid bridge concrete protective coating, which takes modified acrylic resin with low cost and relatively determined structure/composition as a main ingredient, has good universality, simple coating construction process and high curing speed, and is little influenced by dust and rain and dew; the coating has good protection effect and long service life, and has certain competitiveness and application prospect in the protection application of bridge concrete in non-coastal areas.
The invention relates to a high weather resistance water-based acrylic bridge concrete protective coating, which comprises 40-45wt% of an A component of water emulsion containing modified acrylic resin based on the content of organic matters, and 20-40wt% of an aqueous solution B component containing aliphatic polyamine as a curing agent, wherein the A component and the B component are uniformly mixed before use; the mixing proportion of the component A and the component B is 100:2-4 based on the weight of the contained organic matters or the non-aqueous matters;
The aqueous emulsion of the modified acrylic resin is prepared by the following steps:
(1) Adding required amount of triglycidyl isocyanurate (TGIC), methyl Methacrylate (MMA) and 4-hydroxy-TEMPO (4-hydroxy-2, 6-tetramethylpiperidine-N-oxide) into a first reactor with condensing reflux under nitrogen condition, stirring, heating and controlling the temperature to 60-70 ℃ to prepare a solution, adding required amount of heptafluoro-N-butyric acid, and stirring and reacting for 4-6h at 65-70 ℃; adding the required amount of Acrylic Acid (AA) and triethylamine into the feed liquid, stirring at 80-85 ℃ for reaction for 2-4h, and distilling at 60-70 ℃ under reduced pressure for 0.5-1h to recover triethylamine and part of methyl methacrylate to obtain feed liquid-1;
in the step (1), the feeding mole ratio of triglycidyl isocyanurate, heptafluoro-n-butyric acid and acrylic acid is 1:0.95-1.0:0.95-1.0, the feeding amount of methyl methacrylate is 300-400% of the weight of triglycidyl isocyanurate, the feeding amount of 4-hydroxy-TEMPO is 0.02-0.05% of the total weight of the feed liquid, and the feeding amount of triethylamine is 0.06-0.12% of the total weight of the feed liquid; controlling the recovery rate of triethylamine to be more than or equal to 95 percent and controlling the recovery rate of methyl methacrylate to be 40-50 percent during reduced pressure distillation;
(2) Adding 100 parts of emulsifier aqueous solution into a pre-emulsification shearing tank according to the weight proportion, and adding 3-5 parts of acrylic acid, 100-150 parts of butyl methacrylate, 150-200 parts of isooctyl acrylate, 20-40 parts of styrene, 130-60 parts of the feed liquid obtained in the step (1), and shearing for 20-30min to obtain a pre-emulsification liquid;
(3) Adding 100 parts of initiator aqueous solution, 30-50 parts of emulsifier aqueous solution, 1.5-2 parts of acrylic acid and 30-50 parts of pre-emulsion in the step (2) into a second reactor with condensing reflux according to the weight part ratio, stirring, heating and controlling the temperature to be 60-70 ℃ for reacting for 20-30min; continuously maintaining the temperature of 60-70 ℃, adding 250-300 parts of the pre-emulsion and 160-200 parts of the initiator aqueous solution in the step (2) at a constant speed and in parallel flow, and adding the liquid for 2-3h; heating the feed liquid to 75-80 ℃ for continuous reaction for 0.5-1h, cooling to below 50 ℃, and adding ammonia water to adjust the pH value to 6.5-7.5 to obtain an aqueous emulsion of the modified acrylic resin;
in the steps (2) and (3), the emulsifier aqueous solution contains 2-4wt% of Sodium Dodecyl Benzene Sulfonate (SDBS) and 1-2wt% of polyoxyethylene octyl phenol ether-10 (OP-10); the aqueous initiator solution contains 0.3-0.6wt% ammonium persulfate.
In the preparation process step (1) of the aqueous emulsion of the modified acrylic resin, methyl methacrylate plays a role of a solvent, and mainly undergoes stepwise addition esterification reaction of two of three epoxy groups of TGIC molecules, wherein the first step is the addition esterification reaction of the first epoxy group of the TGIC molecules and carboxyl of heptafluoro-n-butyric acid under the catalysis of 4-hydroxy-TEMPO, so that a triazine ring is connected with one heptafluoro-n-butyl group through hydroxypropyl; the second step is that one of the second epoxy group of TGIC molecule, namely the two epoxy groups of the first step reaction product molecule, is subjected to addition esterification reaction with carboxyl of acrylic acid under the catalysis of triethylamine and 4-hydroxy-TEMPO, so that the triazine ring is connected with an allyl ester group through hydroxypropyl; the selectivity of the first and second addition esterification reactions is higher than 85%, and the TGIC reaction is complete. The molecular structure of the reaction product in the second step is that three nitrogen of the triazine ring is respectively connected with an epoxy group, an allyl ester group is connected through hydroxypropyl, and a heptafluoro-n-butyl ester group is connected through hydroxypropyl, the reaction product is subjected to alkenyl copolymerization reaction with other allyl ester groups in the emulsion polymerization process in the step (3), so that the triazine ring, the epoxy group and the heptafluoro-n-butyl ester group connected through hydroxypropyl are grafted to the outer side of a polyacrylate molecular main chain generated by emulsion polymerization more uniformly, namely, the epoxy group and the heptafluoro-n-butyl ester group are indirectly and uniformly connected and distributed on the outer side of the polyacrylate molecular main chain through the triazine ring; in the emulsion polymerization process of the step (3), the triazine ring, the connected epoxy group and the heptafluoro-n-butyl ester group connected through the hydroxypropyl are basically not involved in the reaction, namely the structure and the number are basically not changed and reduced, wherein the number of the epoxy groups can be determined by measuring the epoxy value. The reaction conditions in the step (1), including concentration and structural change of reactants and products, can be comprehensively and judged through the test results of high performance liquid chromatography, infrared and other methods. The reaction condition in the step (3) can be known by comprehensively and judging the test result of the high performance liquid chromatography of the nanofiltration liquid of the feed liquid and the infrared test result of the polymer gel which is obtained by adding ethanol to the feed liquid to wash out the non-polymer components and simultaneously separating out the non-polymer components.
The concentration of the product in the step (1) is detected to be very low in the polymerization reaction process in the step (3), which shows that the allyl ester group has higher polymerization activity, is easy to be copolymerized with other acrylic ester and the like, and has relatively uniform distribution in the main chain of the copolymer, so that the distribution of the triazine ring structure, the connected epoxy group and the heptafluoro-n-butyl ester group connected through the hydroxypropyl is relatively uniform at the outer side of the main chain of the copolymer.
The 4-hydroxy-TEMPO added in the step (1) plays a role in catalyzing the addition esterification reaction, plays a role in inhibiting polymerization of alkenyl in the reaction of the step (1) and the storage of the feed liquid-1 and the preparation and storage of the pre-emulsion of the step (2), and conventional phenolic polymerization inhibitors such as 2, 6-di-tert-butylphenol cannot play the two roles simultaneously. The effect of 4-hydroxy-TEMPO in steps (1) and (2) may further comprise protection of the remaining epoxy groups in the first and second reaction product molecules, i.e. the second and third epoxy groups in the TGIC molecule, especially under the temperature conditions described in step (1), such that most of the triazine rings remain with one epoxy group, i.e. the epoxy group is substantially not reacted with other reactive groups but remains. However, during the emulsion polymerization in step (3), a small amount of 4-hydroxy-TEMPO introduced in the pre-emulsion is oxidized by a relatively large amount of ammonium persulfate, thereby losing the polymerization inhibition.
And (3) recovering triethylamine through reduced pressure distillation after the reaction of the step (1), so that the residual epoxy groups in the molecules of the reaction product of the second step, namely the third epoxy groups in TGIC molecules, are basically not reacted with other active groups and remain in the processes of preparing and storing the component A in the emulsion polymerization process of the step (3), and the components A and B are ring-opened and reacted under the action of introducing a large amount of amine curing agent after the components A and B are uniformly mixed before the coating is used, and the components B and triazine rings play a role of connecting the main chains of polyacrylate molecules.
In the step (1), a large amount of methyl methacrylate is adopted, firstly, the methyl methacrylate is used as a solvent of TGIC, and secondly, the methyl methacrylate is used as a diluent of reactants and products, and is an important factor that the selectivity of the addition esterification reaction in the first step and the second step is higher than 85 percent. Methyl methacrylate remaining after distillation under reduced pressure enters the pre-emulsion and participates in the polymerization reaction in step (3).
The high-weatherability aqueous acrylic bridge concrete protective coating comprises aliphatic polyamine contained in the component B of a curing agent, wherein the aliphatic polyamine can be one or more of hexamethylenediamine, diethylenetriamine and triethylenetetramine; further preferred is an aqueous solution containing 25 to 35wt% of the aliphatic polyamine.
The high-weather-resistance water-based acrylic bridge concrete protective coating is prepared by uniformly mixing the component A and the component B according to the proportion in a stirring or shearing mode before use; the amine curing agent introduced by the component B has larger quantity and higher activity, can play a role along with air drying and water loss of a coating film at normal temperature, ensures that certain crosslinking (including chemical reaction bonding and physical connection) and three-dimensional network generation are generated between active groups of outer side branches of a polyacrylate molecular main chain, especially between epoxy groups grafted by triazine rings and other active groups and between hydroxyl groups of two hydroxypropyl groups connected by the triazine rings and other active groups, so that the protective coating layer is better cured, a hydrophobic coating layer with a stable micropore structure is formed, the volatilization of moisture in the coating film is accelerated, and the curing process is obviously shortened; meanwhile, the triazine ring structure grafted on the outer side of the main chain of the polyacrylate molecule and provided with epoxy groups and hydroxypropyl groups possibly has certain photoactivity, so that the hydroxyl groups of the epoxy groups and the hydroxypropyl groups are easier to participate in the crosslinking reaction, which is also one reason that the curing process of the concrete bridge protective coating is shorter, and the coating after curing under the sunlight condition is detected by infrared and almost does not contain the epoxy groups and the hydroxyl groups. The coating after curing is very stable under long-term light conditions, and can also show that the triazine ring-linked epoxy groups and hydroxypropyl groups almost completely participate in the crosslinking reaction during the curing process.
The high-weatherability water-based acrylic bridge concrete protective coating disclosed by the invention is characterized in that the hydrophobicity of the coating obtained by curing is mainly generated by the heptafluoro-n-propyl of the heptafluoro-n-butyl group; the heptafluoro-n-butyl ester groups are uniformly distributed in the coating after curing, and the surface of the micropores is slightly enriched, so that the coating has good intrinsic hydrophobicity and weather resistance. The heptafluoro-n-butyl group is connected with one nitrogen of the triazine ring through hydroxypropyl, and is indirectly and uniformly connected and distributed on the outer side of the main chain of the polyacrylate molecule through the other nitrogen of the triazine ring and the hydroxypropyl. This is different from the way that perfluoro ester groups are directly grafted on the outer side of the main chain of polyacrylate molecules through acrylic acid perfluoro ester (esterification reaction products of acrylic acid and perfluoro alcohol, such as esterification reaction products of acrylic acid and heptafluoro-n-butyl alcohol) raw materials, the perfluoro ester groups are quite strong in oleophobic and hydrophobic capabilities, and the perfluoro ester groups are directly grafted on the outer side of the main chain of the polyacrylate molecules, so that the acrylic acid perfluoro ester is not easy to be copolymerized with other acrylic acid esters and the like, and the grafting distribution of the perfluoro ester groups on the outer side of the main chain of the copolymer is uneven, so that the use effect of acrylic acid perfluoro ester such as heptafluoro-n-butyl acrylate is general.
The high-weatherability aqueous acrylic bridge concrete protective coating has better intrinsic weatherability, the triazine ring introduced by TGIC and the third epoxy group which plays a crosslinking role when the coating is cured are uniformly distributed in the coating after the coating is cured, the crosslinking effect of the third epoxy group on the polyacrylate molecular main chain is stronger, the structure of the triazine ring is very stable, and the three-dimensional network and the micropore structure generated by curing can withstand long-term cold and hot weather conditions, dry and wet weather conditions, sun weather conditions and the like; the better intrinsic hydrophobicity brought by the heptafluoro-n-butyl ester group further improves the weather resistance of the coating.
The high-weatherability aqueous acrylic bridge concrete protective coating disclosed by the invention is colorless and transparent, and the color of concrete is not changed. Inorganic pigment with the particle size of 0.3-2 mu m can be added into the component A to obtain the required coating color; the pigment is added in an amount of 1-5wt% of the component A, and comprises iron oxide red, molybdenum chromium red, chromium oxide green, iron blue, cobalt yellow, white titanium dioxide and calcium carbonate.
The high-weatherability aqueous acrylic bridge concrete protective coating disclosed by the invention has the advantages that foam is not generated in the uniformly mixing process of the component A and the component B, the surface and the inside of a sprayed coating hardly contain bubbles, and the thickness is uniform; the component A and the component B have no mildewed and bacteria growing problem in the production and storage processes; these two points should be related to the chemical composition characteristics of the aqueous emulsion of the modified acrylic resin contained in the A-component. Therefore, the paint does not need to be added with components such as defoamer, flatting agent, mildew-proof antibacterial agent and the like.
The high-weather-resistance water-based acrylic bridge concrete protective coating has the beneficial effects that:
1. the paint is water paint, and has extremely low Volatile Organic Compound (VOC) content; after the component A and the component B are uniformly mixed according to the proportion, the viscosity is moderate, the thixotropic property is certain, and the film is easy to form; the adhesive force on the surface of the dry concrete is strong, the dry concrete is easy to spread and wet, is not easy to flow, and has certain permeability;
2. the coating construction process is simple, can be used as a base coat or a single coat, and has low requirements on construction environment, temperature and humidity; the thickness of 50-100 mu m can play a good role in the protection application of bridge concrete in non-coastal areas, the curing time is 1.5-4 hours, and the bridge concrete is not easily influenced by dust and rain and dew;
3. the cured coating has stable and uniform quality and high strength, achieves better hydrophobic, dirt-resistant and weather-resistant effects with lower fluorine content (the fluorine content in the cured coating is 1-2wt%) and has a certain competitiveness and application prospect, wherein the service life of the coating can reach more than 10 years.
Detailed Description
The technical scheme of the present invention is specifically described and illustrated below with reference to examples.
Example 1
An aqueous emulsion of a modified acrylic resin is first prepared by:
(1) Adding required amount of triglycidyl isocyanurate (TGIC), methyl Methacrylate (MMA) and 4-hydroxy-TEMPO (4-hydroxy-2, 6-tetramethylpiperidine-N-oxide) into a first reactor with condensing reflux under nitrogen condition, stirring, heating and controlling the temperature to 60 ℃ to prepare a solution, adding required amount of heptafluoro-N-butyric acid, and stirring and reacting for 4 hours at 68-70 ℃; adding the required amount of Acrylic Acid (AA) and triethylamine into the feed liquid, stirring at 84-85 ℃ for reaction for 2 hours, and distilling at 70 ℃ under reduced pressure for 0.5 hour to recover triethylamine and part of methyl methacrylate to obtain feed liquid-1;
in the reaction of the step (1), the feeding amount of triglycidyl isocyanurate, heptafluoro-n-butyric acid and acrylic acid is 59.4g, 42.8g and 14.4g (the molar ratio is 1:1.0:1.0), the feeding amount of methyl methacrylate is 178.2g (300% of the weight of triglycidyl isocyanurate), the feeding amount of 4-hydroxy-TEMPO is 0.15g (0.05% of the total weight of the feed liquid), and the feeding amount of triethylamine is 0.18g (0.06% of the total weight of the feed liquid); the distillation recovery rate of triethylamine after reduced pressure distillation is 97 percent, and the distillation recovery rate of methyl methacrylate solvent is 48 percent; the weight of the obtained feed liquid-1 is 212g;
(2) Adding 100g of emulsifier aqueous solution into a pre-emulsification shearing tank, and adding 5g of acrylic acid, 150g of butyl methacrylate, 150g of isooctyl acrylate, 20g of styrene and 130g of the feed liquid obtained in the step (1), and shearing for 20min to obtain 455g of pre-emulsification liquid;
(3) Adding 100g of initiator aqueous solution, 40g of emulsifier aqueous solution, 2g of acrylic acid and 40g of pre-emulsion in the step (2) into a second reactor with condensing reflux, stirring, heating and controlling the temperature to be 65 ℃ for reaction for 30min; continuously maintaining the temperature condition of 65 ℃, and adding 300g of the pre-emulsion and 160g of the initiator aqueous solution in the step (2) at a constant speed and in parallel flow for 3h; heating the feed liquid to 78 ℃ for continuous reaction for 1 hour, cooling to below 50 ℃, and adding a proper amount of ammonia water to adjust the pH value to 7.5 to obtain 641g of aqueous emulsion of modified acrylic resin;
in the steps (2) and (3), the emulsifier aqueous solution contains 4 weight percent of Sodium Dodecyl Benzene Sulfonate (SDBS) and 1 weight percent of polyoxyethylene octyl phenol ether-10 (OP-10); the aqueous initiator solution contained 0.6wt% ammonium persulfate.
In the steps (1) - (3), the purity of triglycidyl isocyanurate, methyl methacrylate, heptafluoro-n-butyric acid, acrylic acid, butyl methacrylate, isooctyl acrylate and styrene is above 99.5%; 4-hydroxy-TEMPO, triethylamine, triethylenetetramine, sodium dodecyl benzene sulfonate, polyoxyethylene octyl phenol ether-10 and ammonium persulfate are all chemically pure.
In the steps (1) and (3), the nitrogen condition is that the reactor is fully replaced by 99.9% nitrogen before feeding; the temperature of the circulating cooling water for the condensation reflux and the reduced pressure distillation was 5 ℃, and it was considered that the organic material and the intermediate product were not lost.
The water emulsion of the modified acrylic resin obtained in the step (3) is used for calculating the content of organic matters to be 42.7 weight percent; the viscosity was measured at 580 mPas, and the number average molecular weight of the polymer was 42000.
146g of the aqueous emulsion containing the modified acrylic resin is used as a component A, 5g of an aqueous solution containing 25wt% of triethylenetetramine is used as a component B of a curing agent, and the aqueous acrylic bridge concrete protective coating with high weather resistance is used as the aqueous acrylic bridge concrete protective coating, wherein the proportion of the component A and the component B is 100:2 in terms of the weight proportion of water-free substances; and (3) testing the paint, and shearing and uniformly mixing the component A and the component B before use. The fluorine content of the cured coating was estimated to be 1.0wt%.
Example 2
146g of the aqueous emulsion containing the modified acrylic resin prepared in the example 1 is used as a component A, 10g of the aqueous solution containing 25wt% of triethylenetetramine is used as a component B of a curing agent, and the aqueous acrylic bridge concrete protective coating with high weather resistance is prepared in the example, wherein the proportion of the component A to the component B in terms of the weight proportion of water-free substances is 100:4; and (3) shearing and mixing the component A and the component B uniformly before testing and using.
Example 3
An aqueous emulsion of a modified acrylic resin was prepared substantially as described in steps (2) - (3) of example 1, except that step (2) was performed using different pre-emulsion ratios:
(2) In a pre-emulsification shearing tank, adding 100g of an emulsifier aqueous solution, adding 3g of acrylic acid, 100g of butyl methacrylate, 150g of isooctyl acrylate, 40g of styrene and 160g of the feed liquid obtained in the step (1) of the example 1, and shearing for 30min to obtain 453g of pre-emulsion.
The water emulsion of the modified acrylic resin obtained in the step (3) is used for calculating the content of organic matters to be 42.5 weight percent; the viscosity was measured for 740 mPas and the number average molecular weight of the polymer was 70000.
Then 147g of aqueous emulsion of modified acrylic resin is prepared in the step (3), 5g of aqueous solution containing 25wt% of triethylenetetramine is still adopted as a curing agent for the component A of the aqueous acrylic bridge concrete protective coating with high weather resistance, wherein the mixing ratio of the component A to the component B is 100:2 based on the weight of the non-aqueous matters; and (3) testing the paint, and shearing and uniformly mixing the component A and the component B before use. The fluorine content of the cured coating was estimated to be 2.0wt%.
Example 4
147g of the aqueous emulsion containing the modified acrylic resin prepared in the example 3 is used as a component A, 5.4g of an aqueous solution containing 15wt% of hexamethylenediamine and 20wt% of diethylenetriamine is used as a component B of a curing agent, and the aqueous acrylic bridge concrete protective coating with high weather resistance is used as the example, wherein the proportion of the component A and the component B is 100:3 in terms of the weight proportion of water-free substances; and (3) testing the paint, and shearing and uniformly mixing the component A and the component B before use. The fluorine content of the cured coating was estimated to be 2.0wt%.
Example 5
An aqueous emulsion of the modified acrylic resin was prepared essentially as in steps (1) - (3) of example 1, with slight differences in process conditions:
(1) Adding required amount of triglycidyl isocyanurate (TGIC), methyl Methacrylate (MMA) and 4-hydroxy-TEMPO (4-hydroxy-2, 6-tetramethylpiperidine-N-oxide) into a first reactor with condensing reflux under nitrogen condition, stirring, heating and controlling the temperature to 60 ℃ to prepare a solution, adding required amount of heptafluoro-N-butyric acid, and stirring and reacting for 4 hours at 68-70 ℃; adding the required amount of Acrylic Acid (AA) and triethylamine into the feed liquid, stirring at 84-85 ℃ for reaction for 2 hours, and distilling at 65 ℃ under reduced pressure for 0.75 hour to recover triethylamine and part of methyl methacrylate to obtain feed liquid-1;
in the reaction of the step (1), the feeding amount of triglycidyl isocyanurate, heptafluoro-n-butyric acid and acrylic acid is 59.4g, 40.7g and 13.7g (the molar ratio is 1:0.95:0.95), the feeding amount of methyl methacrylate is 237.6g (400% of the weight of triglycidyl isocyanurate), the feeding amount of 4-hydroxy-TEMPO is 0.124g (0.035% of the total weight of the feed liquid), and the feeding amount of triethylamine is 0.316g (0.09% of the total weight of the feed liquid); the distillation recovery rate of triethylamine after reduced pressure distillation is 98 percent, and the distillation recovery rate of methyl methacrylate solvent is 46 percent; the weight of the obtained feed liquid-1 is 242g;
(2) In a pre-emulsification shearing tank, adding 100g of an emulsifier aqueous solution, and adding 4g of acrylic acid, 120g of butyl methacrylate, 180g of isooctyl acrylate, 30g of styrene and 148g of the feed liquid obtained in the step (1) of the example 1, and shearing for 30min to obtain 482g of pre-emulsion.
(3) Adding 100g of initiator aqueous solution, 40g of emulsifier aqueous solution, 2g of acrylic acid and 40g of pre-emulsion in the step (2) into a second reactor with condensing reflux, stirring, heating and controlling the temperature to be 65 ℃ for reaction for 25min; continuously maintaining the temperature condition of 65 ℃, and adding 275g of the pre-emulsion and 180g of the initiator aqueous solution in the step (2) at a constant speed and in parallel flow for 3h; heating the feed liquid to 75 ℃ for continuous reaction for 0.75h, cooling to below 50 ℃, and adding a proper amount of ammonia water to adjust the pH value to 7.5 to obtain 637g of aqueous emulsion of the modified acrylic resin;
in the steps (2) and (3), the emulsifier aqueous solution contains 3 weight percent of Sodium Dodecyl Benzene Sulfonate (SDBS) and 1.5 weight percent of polyoxyethylene octyl phenol ether-10 (OP-10); the aqueous initiator solution contained 0.45wt% ammonium persulfate.
The water emulsion of the modified acrylic resin obtained in the step (3) is used for calculating the content of organic matters to 40.4 weight percent; the viscosity was measured for 650 mPas, and the number average molecular weight of the polymer was 58000.
154g of aqueous emulsion of modified acrylic resin is prepared in the step (3), 5g of aqueous solution containing 15wt% of hexamethylenediamine and 20wt% of triethylenetetramine is used as a curing agent, wherein the mixing ratio of the component A and the component B is 100:3 based on the weight of the non-aqueous matters; and (3) testing the paint, and shearing and uniformly mixing the component A and the component B before use. The fluorine content of the cured coating was estimated to be 1.5wt%.
Example 6
154g of aqueous emulsion of modified acrylic resin prepared in the step (3) of the example 5 is added with 5g of rutile type titanium dioxide with the particle size of 0.5 mu m and pre-coated with 0.2wt% of titanate coupling agent, and uniformly mixed, and 5g of aqueous solution containing 15wt% of hexamethylenediamine and 20wt% of triethylenetetramine is adopted as a component A of the high-weather-resistance aqueous acrylic bridge concrete protective coating of the example, wherein the mixing proportion of the component A and the component B is 100:2.6 based on the weight of the non-aqueous matters; and (3) testing the paint, and shearing and uniformly mixing the component A and the component B before use. The fluorine content of the cured coating was estimated to be 1.39wt%.
In the operations of examples 1 to 5, the reaction conditions in step (1), including the concentration of the reactant and the product, and the structural change, were comprehensively determined by the measurement results of the epoxy value, the measurement results of the high performance liquid chromatography/infrared and other methods. The reaction condition in the step (3) can be known by comprehensively and judging the epoxy value measurement result of the nanofiltration liquid of the feed liquid, the test result of the high performance liquid chromatography and the infrared test result of the polymer gel which is obtained by adding ethanol into the feed liquid to wash out the non-polymer components and simultaneously separating out the non-polymer components. Judging to be: step (1) mainly comprises the step of performing addition esterification reaction on two of three epoxy groups of TGIC molecules, wherein the first step is performed by performing addition esterification reaction on the first epoxy group of the TGIC molecules and carboxyl of heptafluoro-n-butyl acid under the catalysis of 4-hydroxy-TEMPO, so that a triazine ring is connected with one heptafluoro-n-butyl group through hydroxypropyl; the second step is that one of the second epoxy group of TGIC molecule, namely the two epoxy groups of the first step reaction product molecule, is subjected to addition esterification reaction with carboxyl of acrylic acid under the catalysis of triethylamine and 4-hydroxy-TEMPO, so that the triazine ring is connected with an allyl ester group through hydroxypropyl; the selectivity of the first and second addition esterification reactions was higher than 88% in example 1 and higher than 91% in example 5; TGIC, heptafluoro-n-butyric acid, acrylic acid were all reacted completely. The molecular structure of the reaction product in the second step is that three nitrogen of a triazine ring is respectively connected with an epoxy group, an allyl ester group is connected through hydroxypropyl, and a heptafluoro-n-butyl ester group is connected through hydroxypropyl, so that the reaction product is subjected to alkenyl copolymerization reaction with other allyl ester groups in the emulsion polymerization process of the step (3), the triazine ring, the epoxy group and the heptafluoro-n-butyl ester group connected through hydroxypropyl are grafted to the outer side of a polyacrylate molecular main chain generated by emulsion polymerization more uniformly, namely the epoxy group and the heptafluoro-n-butyl ester group are indirectly and uniformly connected and distributed on the outer side of the polyacrylate molecular main chain through the triazine ring; in the emulsion polymerization process of the step (3), the triazine ring, the connected epoxy group and the heptafluoro-n-butyl ester group connected through the hydroxypropyl group basically do not participate in the reaction, i.e. the structure and the quantity are basically not changed and reduced. This is different from the way in which the perfluoro ester groups are grafted directly on the outside of the polyacrylate molecular backbone by the perfluoro ester (esterification reaction product of acrylic acid with a perfluoro alcohol, such as that of acrylic acid with heptafluoro n-butanol) type of starting material. Those skilled in the art know: the perfluoroalkyl group contained in the perfluoro ester group has strong oleophobic and hydrophobic capabilities, and the perfluoro ester group containing the perfluoroalkyl group is directly grafted on the outer side of the main chain of the polyacrylate molecule, so that the perfluoro ester acrylate is not easy to be copolymerized with other acrylic esters and the like, and the grafting distribution of the perfluoro ester group on the outer side of the main chain of the copolymer is uneven, so that the use effect of the perfluoro ester acrylate such as heptafluoro-n-butyl acrylate is general.
In the step (1) of examples 1 and 5, the decomposition or participation of methyl methacrylate was not detected, and only the reaction solvent was used; after the reaction, the distillate obtained by distillation under reduced pressure was found to contain almost no component other than triethylamine or methyl methacrylate, and thus the distillate was recycled as a substitute for a part of the reaction raw materials.
The A component of each of the above examples 1 to 6 was separately prepared as a part and separately filled into a ground glass reagent bottle, and was sealed, light-shielded, left at room temperature for 3 months without visible change, and in the following test example 1, effect comparison was performed with the B component immediately after preparation, which was subjected to shearing mixing and coating.
Comparative example 1
Part of the procedure of step (1) of example 1 was repeated:
(1) 59.4g of triglycidyl isocyanurate and 178.2g of methyl methacrylate are added into a first reactor under the condition of nitrogen and with condensation reflux, stirred, heated and controlled at 60 ℃ to prepare a solution, 42.8g of heptafluoro-n-butyric acid is added, and the mixture is stirred and reacted for 4 hours at 68-70 ℃.
4-hydroxy-TEMPO was not added during the above procedure. The detection result is: only 38% of the heptafluoro-n-butyric acid participates in the reaction, and 27% of the TGIC participates in the reaction, wherein 16% of epoxy groups in TGIC molecules and one heptafluoro-n-butyric acid molecule undergo addition esterification reaction; two epoxy groups in 7% of TGIC molecules and two heptafluoro-n-butyric acid molecules are subjected to addition esterification reaction respectively, and three epoxy groups in 1% of TGIC molecules and three heptafluoro-n-butyric acid molecules are subjected to addition esterification reaction respectively.
Comparative example 2
Part of the procedure of step (1) of example 1 was repeated:
(1) 59.4g of triglycidyl isocyanurate, 178.2g of methyl methacrylate and 0.15g of 4-hydroxy-TEMPO are added into a first reactor with condensing reflux under the condition of nitrogen, the mixture is stirred, heated and controlled to be at 60 ℃ to prepare a solution, 42.8g of heptafluoro-n-butyric acid is added, the mixture is stirred and reacted for 4 hours at 68-70 ℃, the temperature is reduced to 25 ℃, a proper amount of chlorine is used for destroying 4-hydroxy-TEMPO, the mixture is placed for 1 hour to consume redundant chlorine, 14.4g of acrylic acid and 0.18g of triethylamine are added into the mixture, and the mixture is stirred and reacted for 2 hours at 84-85 ℃.
The detection result is: the acrylic acid is completely reacted; the second epoxy group of the TGIC molecule, namely one of the two epoxy groups of the first reaction product molecule, has an addition esterification reaction with acrylic acid, and the two epoxy groups of the TGIC molecule and the two acrylic acid molecules have an addition esterification reaction respectively with 14 percent.
The above comparative examples 1, 2, in comparison with the corresponding effects of step (1) of example 1, demonstrate that: the 4-hydroxy-TEMPO added in the step (1) has a catalytic effect in the two-step addition esterification reaction, and also has a certain protection effect on the residual epoxy groups in the molecule of the first-step reaction product, namely the second epoxy group and the third epoxy group in the TGIC molecule, so that most triazine rings retain one epoxy group, namely the third epoxy group is basically not reacted with other active groups and is retained.
Comparative example 3
Part of the procedure of step (1) of example 1 was repeated:
(1) 59.4g of triglycidyl isocyanurate, 178.2g of methyl methacrylate and 0.15g of 4-hydroxy-TEMPO are added into a first reactor with condensing reflux under the condition of nitrogen, the mixture is stirred, heated and controlled at 60 ℃ to prepare a solution, 42.8g of heptafluoro-n-butyric acid is added, the mixture is stirred and reacted for 4 hours at 68-70 ℃, 14.4g of acrylic acid is added, and the mixture is stirred and reacted for 2 hours at 84-85 ℃.
Triethylamine was not added during the above procedure. The detection result is: only 45% of the acrylic acid is reacted and essentially undergoes an addition esterification reaction with the second epoxy group of the TGIC molecule.
Comparative example 4
Part of the procedure of step (1) of example 1 was repeated:
(1) 59.4g of triglycidyl isocyanurate, 178.2g of methyl methacrylate and 0.15g of 4-hydroxy-TEMPO are added into a first reactor with condensation reflux under the condition of nitrogen, the mixture is stirred, heated and controlled at 60 ℃ until a solution is prepared, 42.8g of heptafluoro-n-butyric acid is added, the mixture is stirred and reacted for 4 hours at 68-70 ℃, 14.4g of acrylic acid and 0.54g of triethylamine (0.18 percent of the total weight of the feed liquid) are added, and the mixture is stirred and reacted for 2 hours at 84-85 ℃.
A relatively large amount of triethylamine was added in the above procedure. The detection result is: the second epoxy group of 82% TGIC molecule, namely one of the two epoxy groups of the first step reaction product molecule, is subjected to addition esterification reaction with acrylic acid, and the two epoxy groups of 7% TGIC molecule and two acrylic acid molecules are respectively subjected to addition esterification reaction.
Comparison of comparative examples 3, 4 with the corresponding effects of step (1) of example 1, shows that: in the invention, triethylamine added in the step (1) and 4-hydroxy-TEMPO play a role in catalysis in the second-step addition esterification reaction, but the problems of proportioning ratio exist between the triethylamine and the 4-hydroxy-TEMPO: the 4-hydroxy-TEMPO has a catalytic effect in the two-step addition esterification reaction, and also has a certain protection effect on the residual epoxy groups in the molecules of the first-step reaction product, namely the second epoxy group and the third epoxy group in the TGIC molecules, so that most triazine rings remain one epoxy group, namely the third epoxy group is basically not reacted with other active groups and is kept. Description of the reaction effect of comparative example 4: in the second-step addition esterification reaction, the protection effect of the 4-hydroxy-TEMPO on the residual epoxy groups in the molecules of the product of the first-step reaction, namely the second epoxy group and the third epoxy group in TGIC molecules, is slightly insufficient compared with the effect of the added triethylamine with a larger amount.
Comparative example 5
The procedure of steps (1) to (3) of example 1 was basically repeated to prepare an aqueous emulsion of the modified acrylic resin of this comparative example, but in step (1), the reaction was stirred at 84 to 85℃for 2 hours, distillation under reduced pressure at 70℃was not performed, i.e., triethylamine was not recovered, and the resulting feed solution was used in step (2) to prepare a pre-emulsion.
The result shows that: the pre-emulsion obtained in step (2) was unstable, increased in viscosity and significantly reduced in fluidity when left at room temperature for 2 days, presumably due to the fact that triethylamine resulted in a significant amount of polymerization, which was undesirable.
Test example 1
The coatings prepared in examples 1-6 were subjected to film coating and curing tests, respectively; the preparation method comprises the steps of immediately mixing the component A with the component B on the same day, shearing for 3-5min to be uniform and coating for 20min, preparing a part of component A which is respectively filled into ground glass reagent bottles, sealing, shading, standing at room temperature for 3 months, mixing the component A with the component B, shearing for 3-5min to be uniform and coating for 20 min.
Each coating, including the use immediately on the day after the preparation of the A component and the use after 3 months of standing, was first coated with 200x300mm of flat glass, 4 sheets each (single-sided coating); then using No. 525 Portland cement sheet (pre-dried at 80 ℃ for 1h, embedded with stainless steel wire mesh, slurry without sand, stone and other aggregates) with 200x300mm, wherein each coating is coated with 4 sheets (single-sided coating) and 2 sheets (outer surface full coating); high-pressure airless spraying is adopted, and the thickness of a coating film (wet film) is 80 mu m; each coating, 2 sheets in each panel/coating, was cured at room temperature and 60% relative humidity in still air and in the shade, and the other 2 sheets coated on one side were cured at room temperature and 60% relative humidity in still air and 1kw of mercury lamp illumination (panel coating plane facing the mercury lamp, distance 2.1 m).
The results included: when the film is cured under the shading condition, the film on the plate glass is cured for 2.5-3 hours, and the dry film thickness is 50-55 mu m; the film on the cement sheet is solidified in 2-2.5h, and the dry film thickness is 45-50 mu m; when the paint is cured under the illumination condition of a mercury lamp, the curing time is shortened by about 0.5h (the paint in the embodiment is shortened by about 0.3 h), and the dry film thickness is basically the same as that when shading; under the light shielding condition and the mercury lamp illumination condition, the curing processes of the surface layer and the inner layer are almost the same in the curing process of the coating film; the dry films obtained are bubble-free, pinhole-free, smooth and flat in surface, good in adhesion with the surface of the test board and pencil hardness between HB-H, wherein the dry films obtained from the coatings of examples 1-5 are colorless and transparent, and the dry film obtained from the coating of example 6 is white.
The coating life and the protection effect of 1 piece of each coating, each test board/coating and each test board obtained under the curing condition are tested under the reinforced test condition of simulating the outdoor natural climate of the non-coastal area, and as a result, the coating life under the outdoor natural climate condition is estimated to exceed 10 years, and the protection effect on the silicate cement sheet with the fully coated outer surface is still better when the simulation is carried out for 10 years.
The component A is used immediately after being prepared and used after being placed for 3 months, the test effect hardly differs, and the component A is stable and the use effect is not affected after being placed for 3 months.
Application example 1
A plurality of batches of paint are produced according to the method of the embodiment 5, and the paint is used for protecting the concrete of a plurality of bridges in non-coastal areas, so that a good effect is achieved. The component A and the component B are mixed and sheared for 10-15min to be uniform under the conditions of sunny, breeze and sufficient sunshine, the single mixing amount is about 50kg, then the mixture is applied in a single coating and high-pressure airless spraying mode within 20min, and the thickness of the coating after curing is 60-70 mu m. The application effect comprises: the natural curing time is 2-3 hours, and the curing process is not easily affected by dust and rain and dew; the quality of the cured coating is stable and uniform, the strength meets the requirement, and the good hydrophobic, pollution-resistant and weather-resistant effects are achieved with the lower fluorine content of 1.5 wt%; in 6 years after the application of the coating, the protection effect of a certain bridge is always good in 2-5 years after the application of the coating, the main performance of the concrete is maintained, and the service life of the coating is expected to be longer than 10 years.
Claims (10)
1. A high weather-resistant water-based modified polyacrylic acid bridge concrete protective coating comprises 40-45wt% of an A component based on the organic content of an aqueous emulsion containing modified acrylic resin and 20-40wt% of an aqueous solution B component containing aliphatic polyamine as a curing agent, wherein the A component and the B component are uniformly mixed before use; the mixing proportion of the component A and the component B is 100:2-4 based on the weight of the contained organic matters or the non-aqueous matters;
The aqueous emulsion of the modified acrylic resin is prepared by the following steps:
(1) Adding required amount of triglycidyl isocyanurate, methyl methacrylate and 4-hydroxy-TEMPO into a first reactor with condensing reflux under the condition of nitrogen, stirring, heating and controlling the temperature to be 60-70 ℃ to prepare a solution, adding required amount of heptafluoro-n-butyric acid, and stirring and reacting for 4-6 hours at 65-70 ℃; adding the required amount of acrylic acid and triethylamine into the feed liquid, stirring at 80-85 ℃ for reaction for 2-4h, and distilling at 60-70 ℃ under reduced pressure for 0.5-1h to recover triethylamine and part of methyl methacrylate to obtain feed liquid-1;
in the step (1), the feeding mole ratio of triglycidyl isocyanurate, heptafluoro-n-butyric acid and acrylic acid is 1:0.95-1.0:0.95-1.0, the feeding amount of methyl methacrylate is 300-400% of the weight of triglycidyl isocyanurate, the feeding amount of 4-hydroxy-TEMPO is 0.02-0.05% of the total weight of the feed liquid, and the feeding amount of triethylamine is 0.06-0.12% of the total weight of the feed liquid; controlling the recovery rate of triethylamine to be more than or equal to 95 percent and controlling the recovery rate of methyl methacrylate to be 40-50 percent during reduced pressure distillation;
(2) Adding 100 parts of emulsifier aqueous solution into a pre-emulsification shearing tank according to the weight proportion, and adding 3-5 parts of acrylic acid, 100-150 parts of butyl methacrylate, 150-200 parts of isooctyl acrylate, 20-40 parts of styrene, 130-60 parts of the feed liquid obtained in the step (1), and shearing for 20-30min to obtain a pre-emulsification liquid;
(3) Adding 100 parts of initiator aqueous solution, 30-50 parts of emulsifier aqueous solution, 1.5-2 parts of acrylic acid and 30-50 parts of pre-emulsion in the step (2) into a second reactor with condensing reflux according to the weight part ratio, stirring, heating and controlling the temperature to be 60-70 ℃ for reacting for 20-30min; continuously maintaining the temperature of 60-70 ℃, adding 250-300 parts of the pre-emulsion and 160-200 parts of the initiator aqueous solution in the step (2) at a constant speed and in parallel flow, and adding the liquid for 2-3h; heating the feed liquid to 75-80 ℃ for continuous reaction for 0.5-1h, cooling to below 50 ℃, and adding ammonia water to adjust the pH value to 6.5-7.5 to obtain an aqueous emulsion of the modified acrylic resin;
in the steps (2) and (3), the emulsifier aqueous solution contains 2-4wt% of sodium dodecyl benzene sulfonate and 1-2wt% of polyoxyethylene octyl phenol ether-10; the aqueous initiator solution contains 0.3-0.6wt% ammonium persulfate.
2. The high weather-resistant water-based modified polyacrylic acid bridge concrete protective coating according to claim 1, wherein in the reaction of the step (1), the feeding molar ratio of triglycidyl isocyanurate, heptafluoro-n-butyric acid and acrylic acid is 1:1:1, the feeding amount of methyl methacrylate is 400% of the weight of triglycidyl isocyanurate, the feeding amount of 4-hydroxy-TEMPO is 0.035% of the total weight of the feed liquid, and the feeding amount of triethylamine is 0.09% of the total weight of the feed liquid; and (3) controlling the proportion of the pre-emulsion in the step (2) to control the fluorine content in the cured coating to be 1.5wt%.
3. The high weather-resistant water-based modified polyacrylic acid bridge concrete protective coating according to claim 1, wherein the distillate obtained in the reduced pressure distillation in the step (1) replaces part of reaction raw materials for recycling.
4. The high weather-resistant water-based modified polyacrylic acid bridge concrete protective coating according to claim 1, wherein pigment with the particle size of 0.3-2 μm is further added into the component A, and the addition amount is 1-5wt% of the component A; the pigment comprises iron oxide red, molybdenum chrome red, chromium oxide green, iron blue, cobalt yellow, titanium dioxide or calcium carbonate.
5. The modified polyacrylic acid bridge concrete protective coating with high weather resistance according to claim 1, wherein the aliphatic polyamine contained in the B component is one or more of hexamethylenediamine, diethylenetriamine and triethylenetetramine.
6. The high weather-resistant water-based modified polyacrylic acid bridge concrete protective coating according to any one of claims 1 to 5, which is characterized by being used for protecting bridge concrete in non-coastal areas.
7. The modified polyacrylic acid bridge concrete protective coating with high weather resistance according to claim 6, wherein the modified polyacrylic acid bridge concrete protective coating is used as a single coating.
8. The modified polyacrylic acid bridge concrete protective coating with high weather resistance according to claim 6, wherein the application mode is high-pressure airless spraying.
9. The modified polyacrylic acid bridge concrete protective coating with high weather resistance according to claim 6, wherein the thickness of the coating after curing is 50-100 μm, and the curing time is 1.5-4h.
10. The modified acrylic bridge concrete protective coating with high weatherability according to claim 6, wherein the curing of the coating is performed under sunlight conditions.
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