CN115029059A - Ultraviolet-curing water-based anti-graffiti coating and preparation method thereof - Google Patents
Ultraviolet-curing water-based anti-graffiti coating and preparation method thereof Download PDFInfo
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- CN115029059A CN115029059A CN202210786187.7A CN202210786187A CN115029059A CN 115029059 A CN115029059 A CN 115029059A CN 202210786187 A CN202210786187 A CN 202210786187A CN 115029059 A CN115029059 A CN 115029059A
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- coating
- water
- ultraviolet
- diisocyanate
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000000576 coating method Methods 0.000 title claims abstract description 74
- 239000011248 coating agent Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- -1 polysiloxane Polymers 0.000 claims abstract description 56
- 239000000178 monomer Substances 0.000 claims abstract description 45
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 39
- 239000004970 Chain extender Substances 0.000 claims abstract description 31
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 19
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 14
- 239000012153 distilled water Substances 0.000 claims abstract description 11
- 238000004945 emulsification Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 72
- 239000000463 material Substances 0.000 claims description 43
- 238000006116 polymerization reaction Methods 0.000 claims description 43
- 238000001723 curing Methods 0.000 claims description 30
- 238000000016 photochemical curing Methods 0.000 claims description 28
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 17
- 239000003112 inhibitor Substances 0.000 claims description 17
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 15
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 11
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 10
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 10
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 10
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 229920005749 polyurethane resin Polymers 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 9
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 8
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 8
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 8
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 7
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 4
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 claims description 4
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 4
- 229940044119 2-tert-butylhydroquinone Drugs 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 claims description 3
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 229960002887 deanol Drugs 0.000 claims description 3
- 239000012972 dimethylethanolamine Substances 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- 239000000839 emulsion Substances 0.000 abstract description 30
- 238000010521 absorption reaction Methods 0.000 abstract description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 7
- 239000002313 adhesive film Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 4
- 229920002554 vinyl polymer Polymers 0.000 abstract description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical group OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 230000000903 blocking effect Effects 0.000 abstract 1
- 125000002843 carboxylic acid group Chemical group 0.000 abstract 1
- 229920002545 silicone oil Polymers 0.000 description 22
- DDKIXUQHRSUCMN-UHFFFAOYSA-N n-butylbutan-1-amine;propan-2-one Chemical compound CC(C)=O.CCCCNCCCC DDKIXUQHRSUCMN-UHFFFAOYSA-N 0.000 description 20
- 238000004448 titration Methods 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 18
- 239000003973 paint Substances 0.000 description 10
- 230000003373 anti-fouling effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229920013822 aminosilicone Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- AYEFIAVHMUFQPZ-UHFFFAOYSA-N propane-1,2-diol;prop-2-enoic acid Chemical compound CC(O)CO.OC(=O)C=C AYEFIAVHMUFQPZ-UHFFFAOYSA-N 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- UZMKOEWHQQPOBJ-UHFFFAOYSA-M sodium;2,3-dihydroxypropane-1-sulfonate Chemical compound [Na+].OCC(O)CS([O-])(=O)=O UZMKOEWHQQPOBJ-UHFFFAOYSA-M 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- CMQCNTNASCDNGR-UHFFFAOYSA-N toluene;hydrate Chemical compound O.CC1=CC=CC=C1 CMQCNTNASCDNGR-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 1
- 235000019281 tert-butylhydroquinone Nutrition 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6541—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
- C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to an ultraviolet light curing water-based anti-graffiti coating and a preparation method thereof, wherein straight-chain polysiloxane with-OH at the two ends is utilized to react with diisocyanate for bridging, hydrophilic groups such as carboxylic acid, sulfonic acid and the like are introduced through a hydrophilic chain extender, then a (methyl) acrylic monomer containing hydroxyl or an oligomer thereof is used for blocking, a (methyl) acryloyloxy group capable of being cured by ultraviolet light is introduced, and finally, alkali is used for neutralization and distilled water is added for emulsification to obtain the required coating, so that the ultraviolet light curing property and the hydrophilicity of the coating are realized, the low surface activity of organosilicon is kept, and the anti-graffiti performance is realized. The raw materials adopted by the invention are low in price and simple to operate, the prepared coating has excellent emulsion stability, and the ultraviolet-cured adhesive film has high hardness, excellent hydrophobicity and low water absorption rate and can be mixed with other vinyl monomers or vinyl comonomers for use.
Description
Technical Field
The invention relates to the technical field of coatings, and particularly relates to an ultraviolet-curing water-based anti-doodling coating and a preparation method thereof.
Background
In recent years, with the emission limit of VOC and the stricter and more standard laws and regulations related to environmental protection, most of the conventional oil-based coatings are gradually replaced by water-based coatings, and compared with other coatings, the water-based coatings have excellent performance and high production efficiency, and are an important direction for the development of the current coatings. In water-based paints, resins mainly comprising water-based acrylates, water-based polyurethanes, and water-based epoxy resins are often used in water-based paints, and these water-based resins have been developed unprecedentedly. At present, the market share of the water-based paint is greatly increased, and the paint is one of the leading directions of future paints.
The ultraviolet curing technology is a novel technology which utilizes a photoinitiator to generate free radicals under the irradiation of ultraviolet light so as to cause the prepolymer containing carbon double bonds and the multifunctional low molecular monomer to be crosslinked and cured. Compared with the traditional thermosetting technology, the ultraviolet curing resin does not need to be heated, the monomers can be crosslinked and cured within several seconds to tens of seconds at normal temperature, the production time and the energy consumption are greatly reduced, and meanwhile, the system is free of organic solvents, so that the ultraviolet curing resin is more environment-friendly and safer. Compared with the traditional thermosetting coating, the ultraviolet curing coating can be rapidly cured to form a film under the irradiation of ultraviolet light, so that the comprehensive performance is improved, and the ultraviolet curing coating has unique advantages in the aspects of economy, environmental protection and the like.
The anti-graffiti paint belongs to an isolation protection paint, can prevent various oil stains from adhering to the surface due to low surface adhesive force, and can seal all pores and cracks on the surface after the anti-graffiti paint is used for coating equipment, so that the color of the paint cannot permeate into the paint at all. At present, the anti-graffiti material mainly comprises three types of fluorine-containing materials, fluorine-containing silicon and organic silicon, and the fluorine-containing materials are expensive, so that the organic silicon materials account for the largest market share. Therefore, the development of the preparation method of the low-cost ultraviolet-curing water-based anti-graffiti material has wide market prospect and important significance.
Disclosure of Invention
The invention provides an ultraviolet curing water-based anti-doodling coating and a preparation method thereof, aiming at the defects that the compatibility of the current anti-doodling coating and a water-based UV coating is difficult, and the price of a fluorine-silicon material is high.
The above object of the present invention is achieved by the following technical means:
the invention provides an ultraviolet-curing water-based anti-doodling coating, which is prepared by polymerizing straight-chain polysiloxane with-OH at two ends, diisocyanate, a hydrophilic chain extender, a polymerization inhibitor and a light-curing monomer material; wherein the ratio of the sum of the amounts of-OH in the-OH-terminated linear polysiloxane, the-OH in the hydrophilic chain extender, and the-OH in the photocurable monomer material to the amount of-NCO in the diisocyanate is 1: 1 to 1.2; the using amount of the hydrophilic chain extender is 6-15 wt% of the linear polysiloxane with the-OH at the two ends; the dosage of the light-cured monomer material is 1.5-6.5 wt% of the linear polysiloxane with both ends containing-OH; the amount of the polymerization inhibitor is 0.1-1.2 wt% of the photo-curing monomer material.
In a preferred embodiment, the molecular structural formula of the linear polysiloxane containing-OH at both ends is:
wherein a is a natural number of 2-5, n is a natural number of 20-60, and R' is-OH.
According to the ultraviolet-curing water-based anti-graffiti coating, polyol or dihydric alcohol is completely replaced by straight-chain polysiloxane containing-OH at both ends, so that all main chain segments of polyurethane resin are silica chains with methyl double side groups, the anti-fouling performance of the coating can be improved, and the coating has anti-graffiti performance; in addition, the ultraviolet light curability of the coating is realized through the introduction of the photo-curing monomer material. In addition, the degree of polymerization n of the selected linear polysiloxane with-OH at both ends is set to be 20-60, so that the viscosity of the linear polysiloxane is moderate, the smooth proceeding of polymerization reaction and the moderate polymerization rate are ensured, the smooth introduction of a hydrophilic chain extender is ensured, and the anti-fouling effect is ensured. In the present invention, the ratio of the sum of the amount of-OH in the-OH-terminated linear polysiloxane, the amount of-OH in the hydrophilic chain extender, and the amount of-OH in the photocurable monomer material to the amount of-NCO in the diisocyanate is set to 1: 1-1.2, and the reaction of a very small amount of water possibly contained in the raw materials with-NCO is prevented, so that the loss of the-NCO is caused, and the obtained intermediate products are all blocked by the-NCO, thereby facilitating the introduction of a subsequent photocuring monomer material. The stability of the emulsion of the coating is ensured by setting the using amount of the hydrophilic chain extender, and the viscosity is moderate. This application can guarantee coating emulsion's photocuring speed through setting up of photocuring monomer material and polymerization inhibitor quantity, and the polymerization process can not lead to gel. In a second aspect, the invention provides a preparation method of the ultraviolet-curable water-based anti-graffiti coating, which comprises the following steps:
(1) dissolving linear polysiloxane and diisocyanate containing-OH at both ends in an organic solvent, adding a catalyst, reacting at 70-80 ℃, and obtaining a prepolymer containing terminal-NCO when the-NCO content in the system does not change any more;
(2) adding a hydrophilic chain extender, carrying out chain extension reaction at the temperature of 75-90 ℃, and reacting until the-NCO content in the system is not changed any more, so as to obtain the organic silicon modified polyurethane resin containing carboxyl;
(3) adding a polymerization inhibitor and a photocuring monomer material, reacting at 55-65 ℃, and obtaining the organosilicon modified polyurethane resin containing the acryloxy group when the-NCO content in the system is not changed any more;
(4) and (3) cooling to 30-45 ℃, adding a neutralizing agent for neutralization, adding distilled water for emulsification, and removing the organic solvent through reduced pressure distillation to obtain the ultraviolet-cured water-based anti-graffiti coating.
Specifically, the diisocyanate in the step (1) is any one of isophorone diisocyanate, toluene diisocyanate, 4-diphenylmethane diisocyanate, and hexamethylene diisocyanate.
Specifically, the organic solvent in the step (1) is any one or more of acetone, toluene, n-heptane, cyclohexane, ethyl acetate and methyl isobutyl ketone.
Specifically, the catalyst in the step (1) is dibutyltin dilaurate, and the using amount of the catalyst accounts for 0.1-1.2 wt% of the total solid content in the ultraviolet-curing water-based anti-graffiti coating.
Specifically, the hydrophilic chain extender in the step (2) is any one of dimethylolbutyric acid, dimethylolpropionic acid, sodium 1, 2-dihydroxy-3-propanesulfonate and sodium 1, 4-butanediol-2-sulfonate.
Specifically, the polymerization inhibitor in the step (3) is any one or more of p-hydroxyanisole, hydroquinone, p-benzoquinone, 2-tert-butylhydroquinone and 2, 5-di-tert-butylhydroquinone.
Specifically, the photo-curable monomer material in the step (3) is any one of 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate. Therefore, the photo-curing monomer is a hydroxyl-containing (methyl) acrylic monomer which contains a plurality of functional groups, and can improve the hardness of the material and reduce the water absorption rate of the material.
Specifically, the neutralizing agent in the step (4) is any one or more of triethylamine, diethanolamine, dimethylethanolamine, ammonia water and methylamine; the neutralization degree is 80-120%.
And (3) measuring the mass fraction of-NCO by a di-n-butylamine-acetone titration method during the reaction in the step (1), the step (2) and the step (3), and carrying out the next reaction when the reaction is carried out until the content of-NCO in the system is not changed any more.
According to the method, polyol or dihydric alcohol is completely replaced by linear polysiloxane containing-OH at both ends, so that the main chain section of the polyurethane resin is a silicone chain with methyl double side groups, the anti-fouling performance of the coating can be improved, and the coating has the anti-graffiti performance; in addition, the ultraviolet light curability of the coating is realized through the introduction of the photo-curing monomer material. In addition, the degree of polymerization n of the selected linear polysiloxane with-OH at both ends is set to be 20-60, so that the viscosity of the linear polysiloxane is moderate, the smooth proceeding of polymerization reaction and the moderate polymerization rate are ensured, the smooth introduction of a hydrophilic chain extender is ensured, and the anti-fouling effect is ensured. In the present invention, the ratio of the sum of the amount of-OH in the-OH-terminated linear polysiloxane, the amount of-OH in the hydrophilic chain extender, and the amount of-OH in the photocurable monomer material to the amount of-NCO in the diisocyanate is set to 1: 1-1.2, and the reaction of a very small amount of water possibly contained in the raw materials with-NCO is prevented, so that the loss of the-NCO is caused, and the obtained intermediate products are all blocked by the-NCO, thereby facilitating the introduction of a subsequent photocuring monomer material. The stability of the emulsion of the coating is ensured by setting the using amount of the hydrophilic chain extender, and the viscosity is moderate. The photocuring speed of coating emulsion can be guaranteed through setting up of photocuring monomer material and polymerization inhibitor quantity, and the polymerization process can not lead to the gel.
The ultraviolet curing water-based anti-graffiti coating and the preparation method thereof have the advantages that linear polysiloxane with-OH at the two ends reacts with diisocyanate to be bridged, hydrophilic groups such as carboxylic acid, sulfonic acid and the like are introduced through a hydrophilic chain extender, then a (methyl) acrylic monomer containing hydroxyl or an oligomer thereof is blocked, a (methyl) acryloyloxy group capable of being cured by ultraviolet is introduced, and finally, alkali is used for neutralization and distilled water is added for emulsification to obtain the required coating, so that the ultraviolet curing property and the hydrophilicity of the coating are realized, meanwhile, the low surface activity of organosilicon is reserved, and the anti-graffiti performance is realized. The raw materials adopted by the method are low in price and simple to operate, the prepared coating is excellent in emulsion stability, and the ultraviolet-cured adhesive film is high in hardness, excellent in hydrophobicity and water resistance, can be mixed with other vinyl monomers or vinyl comonomers for use, and plays a role in protection and pollution resistance.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to make the above objects, features and advantages of the present invention more comprehensible. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The ultraviolet-curing water-based anti-doodling coating is prepared by polymerizing straight-chain polysiloxane with-OH at two ends, diisocyanate, a hydrophilic chain extender, a polymerization inhibitor and a light-curing monomer material; wherein the ratio of the sum of the amounts of-OH in the-OH-terminated linear polysiloxane, the-OH in the hydrophilic chain extender, and the-OH in the photocurable monomer material to the amount of-NCO in the diisocyanate is 1: 1 to 1.2; the using amount of the hydrophilic chain extender is 6-15 wt% of the linear polysiloxane with both ends containing-OH; the dosage of the photo-curing monomer material is 1.5-6.5 wt% of the linear polysiloxane with-OH at both ends; the dosage of the polymerization inhibitor is 0.1-1.2 wt% of the photo-curing monomer material.
Preferably, the molecular structural general formula of the linear polysiloxane containing-OH at both ends is as follows:
wherein a is a natural number of 2-5, n is a natural number of 20-60, and R' is-OH.
According to the ultraviolet-curing water-based anti-graffiti coating, polyol or dihydric alcohol is completely replaced by straight-chain polysiloxane containing-OH at both ends, so that all main chain segments of polyurethane resin are silica chains with methyl double side groups, the anti-fouling performance of the coating can be improved, and the coating has anti-graffiti performance; in addition, the ultraviolet light curability of the coating is realized through the introduction of the light-cured monomer material.
In the present invention, the ratio of the sum of the amounts of-OH in the-OH-terminated linear polysiloxane, of-OH in the photocurable monomer material, of-OH in the hydrophilic chain extender, and of-NCO in the diisocyanate is set to 1: 1-1.2, and the reaction of a small amount of water possibly contained in the raw materials with-NCO is prevented, so that the-NCO is lost, and the obtained intermediate products are ensured to be blocked by the-NCO, and the subsequent introduction of a photocuring monomer material is facilitated.
The polymerization degree n determines the viscosity and the hydroxyl content of the silicone oil, the higher the n is, the higher the viscosity is, the difficulty in polymerization can be caused by the overhigh viscosity, and the introduction of a hydrophilic chain extender is more unfavorable; the smaller n is, the higher the hydroxyl content is, which results in too fast a polymerization rate; in addition, the higher the hydroxyl content, the more diisocyanate and the less silane chains, resulting in a marked reduction in the antifouling effect. According to the application, the selected straight-chain polysiloxane with-OH at both ends has the polymerization degree n of preferably 20-60, so that the viscosity of the straight-chain polysiloxane is moderate, the smooth polymerization reaction and the moderate polymerization rate are ensured, the smooth introduction of a hydrophilic chain extender is ensured, and the anti-fouling effect is ensured.
When the dosage of the hydrophilic chain extender is too low, the emulsion is unstable, and when the dosage is too high, the viscosity of the emulsion is too high, so that the subsequent coating emulsion is not coated favorably. The stability of the emulsion of the coating is ensured by setting the using amount of the hydrophilic chain extender, and the viscosity is moderate.
Too low dosage of the photo-curing monomer material can result in too low photo-curing speed of the coating and even incomplete curing, and too high dosage is easy to gel in the polymerization process; too high an amount of polymerization inhibitor can affect the photocuring of the coating. The photocuring speed of coating emulsion can be guaranteed through setting up of photocuring monomer material and polymerization inhibitor quantity, and the polymerization process can not lead to the gel.
The invention discloses a preparation method of the ultraviolet-curing water-based anti-doodling coating, which comprises the following steps:
(1) dissolving linear polysiloxane and diisocyanate containing-OH at both ends in an organic solvent, adding a catalyst, reacting at the temperature of 70-80 ℃, and obtaining a prepolymer containing terminal-NCO when the-NCO content in the system does not change any more;
(2) adding a hydrophilic chain extender, carrying out chain extension reaction at the temperature of 75-90 ℃, and reacting until the-NCO content in the system is not changed any more, so as to obtain the organic silicon modified polyurethane resin containing carboxyl;
(3) adding a polymerization inhibitor and a photocuring monomer material, reacting at 55-65 ℃, and obtaining the organosilicon modified polyurethane resin containing the acryloxy group when the-NCO content in the system is not changed any more;
(4) and (3) cooling to 30-45 ℃, adding a neutralizing agent for neutralization, adding distilled water for emulsification, and removing the organic solvent through reduced pressure distillation to obtain the ultraviolet-cured water-based anti-graffiti coating.
Specifically, the diisocyanate in the step (1) is any one of isophorone diisocyanate (IPDI), Toluene Diisocyanate (TDI), 4-diphenylmethane diisocyanate (MDI), and Hexamethylene Diisocyanate (HDI).
Specifically, the organic solvent in the step (1) is any one or more of acetone, toluene, n-heptane, cyclohexane, ethyl acetate and methyl isobutyl ketone.
Specifically, the catalyst in the step (1) is dibutyltin dilaurate (DBTDL), and the using amount of the catalyst accounts for 0.1-1.2 wt% of the total solid content in the ultraviolet-curing water-based anti-graffiti coating.
Specifically, the hydrophilic chain extender in the step (2) is any one of dimethylolbutyric acid (DMBA), dimethylolpropionic acid (DMPA), sodium 1, 2-dihydroxy-3-propanesulfonate (DHPA), and sodium 1, 4-butanediol-2-sulfonate.
Specifically, the polymerization inhibitor in the step (3) is any one or more of p-hydroxyanisole (MEHQ), Hydroquinone (HQ), p-benzoquinone (PBQ), 2-tert-butylhydroquinone (TBHQ) and 2, 5-di-tert-butylhydroquinone (DBHQ).
Specifically, the photo-curing monomer material in the step (3) is any one of 2-hydroxypropyl acrylate (HPA), 2-hydroxyethyl acrylate (HEA), 2-hydroxypropyl methacrylate (HPMA), 2-hydroxyethyl methacrylate (HEMA), pentaerythritol triacrylate (PETA), and dipentaerythritol pentaacrylate. Therefore, the photo-curing monomer is a hydroxyl-containing (methyl) acrylic monomer which contains a plurality of functional groups, and can improve the hardness of the material and reduce the water absorption rate of the material.
Specifically, the neutralizing agent in the step (4) is any one or more of triethylamine, diethanolamine, dimethylethanolamine, ammonia water and methylamine; the neutralization degree is 80-120%.
And (3) measuring the mass fraction of-NCO by a di-n-butylamine-acetone titration method during the reaction in the step (1), the step (2) and the step (3), and carrying out the next reaction when the reaction is carried out until the content of-NCO in the system is not changed any more.
According to the method, polyol or dihydric alcohol is completely replaced by linear polysiloxane containing-OH at both ends, so that the main chain section of the polyurethane resin is a silicone chain with methyl double side groups, the anti-fouling performance of the coating can be improved, and the coating has the anti-graffiti performance; in addition, the ultraviolet light curability of the coating is realized through the introduction of the light-cured monomer material. In addition, the degree of polymerization n of the selected straight-chain polysiloxane with-OH at both ends is set to be 20-60, so that the viscosity of the straight-chain polysiloxane is moderate, the smooth proceeding of polymerization reaction and the moderate polymerization rate are ensured, the smooth introduction of a hydrophilic chain extender is ensured, and the anti-fouling effect is ensured. In the present invention, the ratio of the sum of the amounts of-OH in the-OH-terminated linear polysiloxane, the-OH in the photocurable monomer material, and the-OH in the hydrophilic chain extender to the amount of-NCO in the diisocyanate is set to 1: 1-1.2, and the reaction of a very small amount of water possibly contained in the raw materials with-NCO is prevented, so that the loss of the-NCO is caused, and the obtained intermediate products are all blocked by the-NCO, thereby facilitating the introduction of a subsequent photocuring monomer material.
The stability of the emulsion of the coating is ensured by setting the using amount of the hydrophilic chain extender, and the viscosity is moderate. This application can guarantee coating emulsion's photocuring speed through setting up of photocuring monomer material and polymerization inhibitor quantity, and the polymerization process can not lead to gel.
Example 1:
60g of double-end hydroxypropyl silicone oil with the polymerization degree of 30 (-OH content is 1.7 wt%) is added into a reaction bottle, and the double-end hydroxypropyl silicone oil is dehydrated for 1.5 hours at the temperature of 90 ℃ and the vacuum degree of-0.1 MPa, so that the water content in the silicone oil is reduced to the minimum, and the reaction probability of the subsequently added isophorone diisocyanate and water is reduced as much as possible. Then cooling the dehydrated double-end hydroxypropyl silicone oil to below 45 ℃, adding 11.74g of isophorone diisocyanate, 50g of acetone and 1.2g of dibutyltin dilaurate, uniformly stirring, heating to 75 ℃ for reaction, measuring the-NCO content by a di-n-butylamine-acetone titration method in the reaction process, after 3 hours of reaction, adding 4.8g of dimethylolpropionic acid, heating to 85 ℃ for reaction, measuring the-NCO content by the di-n-butylamine-acetone titration method in the reaction process, after 2 hours of reaction, measuring the-NCO content, cooling to below 45 ℃, adding 0.02g of p-hydroxy anisole and 2.8g of pentaerythritol triacrylate, heating to 65 ℃ for reaction, measuring the-NCO content by the di-n-butylamine-acetone titration method in the reaction process, reacting for 2 hours, and (3) after the-NCO is completely consumed, cooling to below 45 ℃, adding 3.7g of triethylamine for neutralization, then adding 120g of distilled water for emulsification, and finally removing acetone through reduced pressure distillation to obtain 192.28g of the ultraviolet-curing water-based anti-graffiti coating with the solid content of 41.0%.
The reaction principle of the reaction involved in the production process of the present invention is described below by way of example 1:
the reaction formula in the step (1) is as follows:
the reaction formula of the reaction in the step (2) is as follows:
the reaction formula in the step (3) is as follows:
wherein, the structural formula of R in the reaction formulas (2) and (3) is as follows:
n is a natural number between 20 and 60; m is a natural number greater than n.
Example 2:
60g of double-ended hydroxypropyl silicone oil with the polymerization degree of 30 (-OH content is 1.7 wt%) is added into a reaction bottle, and the double-ended hydroxypropyl silicone oil is dehydrated for 1.5 hours at the temperature of 90 ℃ and the vacuum degree of-0.1 MPa, so that the water content in the silicone oil is reduced to the minimum, and the reaction probability of subsequently added isophorone diisocyanate and water is reduced as much as possible. Then cooling the dehydrated double-end hydroxypropyl silicone oil to below 45 ℃, adding 12.84g of isophorone diisocyanate, 50g of n-heptane and 1.3g of dibutyltin dilaurate, uniformly stirring, heating to 75 ℃ for reaction, measuring the-NCO content by a di-n-butylamine-acetone titration method in the reaction process, after 3 hours of reaction, adding 6g of dimethylolpropionic acid until the-NCO content is not changed, heating to 85 ℃ for reaction, measuring the-NCO content by a di-n-butylamine-acetone titration method in the reaction process, measuring the-NCO content after 2 hours of reaction, cooling to below 45 ℃, adding 0.02g of p-hydroxyanisole and 1.36g of acrylic acid-2-hydroxypropyl ester, heating to 65 ℃ for reaction, measuring the-NCO content by a di-n-butylamine-acetone titration method in the reaction process, after reacting for 2 hours, after-NCO is consumed, cooling to below 45 ℃, adding 4.55g of triethylamine for neutralization, then adding 120g of distilled water for emulsification, and finally carrying out reduced pressure distillation to remove n-heptane, thereby obtaining 197.72g of ultraviolet-curing water-based anti-graffiti coating with the solid content of 41.2%.
Example 3:
60g of double-ended hydroxypropyl silicone oil with the polymerization degree of 30 (-OH content is 1.7 wt%) is added into a reaction bottle, and the double-ended hydroxypropyl silicone oil is dehydrated for 1.5 hours at the temperature of 90 ℃ and the vacuum degree of-0.1 MPa, so that the water content in the silicone oil is reduced to the minimum, and the reaction probability of subsequently added toluene diisocyanate and water is reduced as much as possible. Then cooling the dehydrated double-end hydroxypropyl silicone oil to below 45 ℃, adding 10.92g of toluene diisocyanate, 50g of ethyl acetate and 1.3g of dibutyltin dilaurate, uniformly stirring, heating to 70 ℃ for reaction, measuring the-NCO content by a di-n-butylamine-acetone titration method in the reaction process, reacting for 2.5 hours, adding 7.2g of dimethylolpropionic acid until the-NCO content is not changed, heating to 80 ℃ for reaction, measuring the-NCO content by the di-n-butylamine-acetone titration method in the reaction process, cooling to below 45 ℃ after reacting for 2 hours, adding 0.04g of p-hydroxy anisole and 3.4g of pentaerythritol triacrylate, heating to 65 ℃ for reaction, measuring the-NCO content by the di-n-butylamine-acetone titration method in the reaction process, reacting for 2 hours, and (3) after the-NCO is completely consumed, cooling to below 45 ℃, adding 5.68g of diethanolamine for neutralization, then adding 120g of distilled water for emulsification, and finally carrying out reduced pressure distillation to remove ethyl acetate to obtain 205.4g of the ultraviolet-curing water-based anti-graffiti coating with the solid content of 42.3%.
Example 4:
60g of double-ended hydroxypropyl silicone oil with the polymerization degree of 50 (-OH content is 0.8 wt%) is added into a reaction bottle, and the double-ended hydroxypropyl silicone oil is dehydrated for 1.5 hours at the temperature of 90 ℃ and the vacuum degree of-0.1 MPa, so that the water content in the silicone oil is reduced to the minimum, and the reaction probability of subsequently added isophorone diisocyanate and water is reduced as much as possible. Then cooling the dehydrated double-end hydroxypropyl silicone oil to below 45 ℃, adding 8.93g of isophorone diisocyanate, 50g of ethyl acetate and 1.2g of dibutyltin dilaurate, uniformly stirring, heating to 75 ℃ for reaction, measuring the-NCO content by a di-n-butylamine-acetone titration method in the reaction process, reacting for 3 hours, adding 6g of dimethylolpropionic acid when the-NCO content does not change, heating to 85 ℃ for reaction, measuring the-NCO content by a di-n-butylamine-acetone titration method in the reaction process, reacting for 2 hours, measuring the-NCO content which does not change, cooling to below 45 ℃, adding 0.02g of p-hydroxy-phenyl methyl ether and 2.18g of pentaerythritol triacrylate, heating to 65 ℃ for reaction, measuring the-NCO content by a di-n-butylamine-acetone titration method in the reaction process, after reacting for 2 hours, after-NCO is consumed, cooling to below 45 ℃, adding 4.55g of triethylamine for neutralization, then adding 120g of distilled water for emulsification, and finally carrying out reduced pressure distillation to remove ethyl acetate so as to obtain 193.16g of ultraviolet-curing water-based anti-graffiti coating with the solid content of 42.2%.
Example 5:
60g of double-ended hydroxypropyl silicone oil with the polymerization degree of 50 (-OH content is 0.8 wt%) is added into a reaction bottle, and the double-ended hydroxypropyl silicone oil is dehydrated for 1.5 hours at the temperature of 90 ℃ and the vacuum degree of-0.1 MPa, so that the water content in the silicone oil is reduced to the minimum, and the reaction probability of subsequently added isophorone diisocyanate and water is reduced as much as possible. Then cooling the dehydrated double-end hydroxypropyl silicone oil to below 45 ℃, adding 10.03g of isophorone diisocyanate, 50g of ethyl acetate and 1.2g of dibutyltin dilaurate, uniformly stirring, heating to 75 ℃ for reaction, measuring the-NCO content by a di-n-butylamine-acetone titration method in the reaction process, reacting for 3 hours, adding 7.2g of dimethylolpropionic acid when the-NCO content does not change, heating to 85 ℃ for reaction, measuring the-NCO content by a di-n-butylamine-acetone titration method in the reaction process, measuring the-NCO content after reacting for 2 hours, cooling to below 45 ℃, adding 0.02g of p-hydroxy-phenyl methyl ether and 1.07g of acrylic acid-2-hydroxypropyl ester, heating to 65 ℃ for reaction, measuring the-NCO content by a di-n-butylamine-acetone titration method in the reaction process, after reacting for 2 hours, after-NCO is completely consumed, cooling to below 45 ℃, adding 5.68g of diethanolamine for neutralization, then adding 120g of distilled water for emulsification, and finally carrying out reduced pressure distillation to remove ethyl acetate, thereby obtaining 199.78g of ultraviolet-curing water-based anti-graffiti coating with the solid content of 43.1%.
Comparative example:
60g of double-end amino silicone oil with the polymerization degree of 40 is added into a reaction bottle, and dehydration is carried out for 1.5 hours at the temperature of 90 ℃ and the vacuum degree of-0.1 MPa, so that the water content in the silicone oil is reduced to the minimum, and the reaction probability of the subsequently added toluene diisocyanate and water is reduced as much as possible. Then cooling the dehydrated double-end amino silicone oil to below 45 ℃, adding 10.63g of toluene diisocyanate, 50g of acetone and 1.3g of dibutyltin dilaurate, uniformly stirring, heating to 75 ℃ for reaction, measuring the-NCO content by a di-n-butylamine-acetone titration method in the reaction process, after reacting for 4 hours, adding 4.2g of dimethylolpropionic acid, heating to 85 ℃ for reaction, measuring the-NCO content by the di-n-butylamine-acetone titration method in the reaction process, after reacting for 2.5 hours, measuring the-NCO content without changing, cooling to below 45 ℃, adding 0.02g of hydroquinone and 1.29g of 2-hydroxyethyl acrylate, heating to 65 ℃ for reaction, measuring the-NCO content by the di-n-butylamine-acetone titration method in the reaction process, reacting for 2 hours, after the consumption of-NCO, cooling to below 45 ℃, adding 3.26g of diethanolamine for neutralization, then adding 120g of distilled water for emulsification, and finally removing acetone by reduced pressure distillation to obtain 190.88g of aqueous organosilicon polyurethane emulsion with the solid content of 40.1%.
And (3) performance testing:
the performances of the ultraviolet-curable aqueous graffiti-resistant coating emulsion prepared in examples 1 to 5 and the aqueous silicone polyurethane emulsion prepared in comparative example 1 were tested, including emulsion stability test and hardness, contact angle and water absorption of the cured coating.
1. Emulsion stability test
The storage stability of the above emulsions was determined according to GB/T6753.3-1986. Selecting artificial condition simulation test emulsion stability experiment, placing about 50g of emulsion in a conical flask, sealing and placing in a constant temperature drying oven, storing at 50 +/-1 ℃ for 30 days, and checking whether precipitation exists.
2. Taking 15g of the emulsion, adding 0.3g of photoinitiator 1173, uniformly mixing, coating on a sample plate, drying at 65 ℃ to remove water, and carrying out UV curing through a high-pressure tube mercury lamp to test the following properties.
(1) Hardness of
Preparing samples by GB/T531.1-2008, testing according to Shore D hardness, testing each sample in parallel for 5 times, and taking an average value.
(2) Contact angle
And measuring the static contact angle of the cured coating surface at room temperature by using a contact angle measuring instrument, recording contact angle data of 5 groups of deionized water on the coating surface, and taking an average value.
(3) Water absorption rate
Cutting the fully dried adhesive film into square samples of 2.0cm x 2.0cm, weighing the samples, then soaking the samples in deionized water for 48 hours, taking out the samples, drying the water on the surfaces of the samples by using filter paper, weighing the samples, and calculating the water absorption rate according to the mass difference before and after soaking and the mass ratio before soaking.
And (3) testing results:
the test results are shown in the following table:
TABLE 1 test results
| Group of | Emulsion stability | Shore D hardness/HD | Contact Angle/° | Water absorption/%) |
| Example 1 | White emulsion, stable | 75 | 91.4 | 0.428 |
| Example 2 | Opalescent and semi-permeable, stable | 68 | 87.6 | 0.817 |
| Example 3 | White emulsion, stable | 78 | 88.9 | 0.447 |
| Example 4 | White emulsion, stable | 82 | 93.2 | 0.385 |
| Example 5 | Milky bluish and stable | 81 | 90.3 | 0.424 |
| Comparative example | White emulsion, separation of layers | 64 | 78.9 | 1.116 |
As can be seen from Table 1, the emulsions of the UV-curable waterborne anti-graffiti coatings prepared in examples 1-5 of the present invention did not delaminate and precipitate after standing for a certain period of time, and were stable. After the ultraviolet curing water-based doodling-resistant coating prepared in the embodiments 1 to 5 is cured, the Shore D hardness of a glue film is 68 to 82, the contact angle of deionized water on the surface of the glue film is 87.6 to 93.2 degrees, and the water absorption is 0.385 to 0.817 percent, which shows that the glue film has excellent hardness, hydrophobicity and low water absorption. In the comparative example, after double-end amino silicone oil is used for replacing polyhydric alcohol or dihydric alcohol, the prepared emulsion is layered after standing for a certain time, and the stability cannot meet the requirement; in addition, compared with the prior art, the double-end amino silicone oil is adopted to replace polyhydric alcohol or dihydric alcohol, the hardness and the contact angle of the adhesive film of the prepared emulsion after curing are obviously lower than those of the adhesive films in the examples 1-5, and the water absorption is obviously higher than those of the adhesive films in the examples 1-5.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (10)
1. The ultraviolet-cured water-based anti-doodling coating is characterized by being prepared by polymerizing straight-chain polysiloxane with-OH at two ends, diisocyanate, a hydrophilic chain extender, a polymerization inhibitor and a light-cured monomer material; wherein the ratio of the sum of the amounts of-OH in the-OH-terminated linear polysiloxane, the-OH in the hydrophilic chain extender, and the-OH in the photocurable monomer material to the amount of-NCO in the diisocyanate is 1: 1 to 1.2; the using amount of the hydrophilic chain extender is 6-15 wt% of the linear polysiloxane with both ends containing-OH; the dosage of the light-cured monomer material is 1.5-6.5 wt% of the linear polysiloxane with both ends containing-OH; the dosage of the polymerization inhibitor is 0.1-1.2 wt% of the photo-curing monomer material.
2. The ultraviolet-curable water-based anti-graffiti coating of claim 1, wherein: the molecular structure general formula of the straight-chain polysiloxane containing-OH at both ends is as follows:
wherein a is a natural number of 2-5, n is a natural number of 20-60, and R' is-OH.
3. The preparation method of the ultraviolet-curing water-based anti-graffiti coating as claimed in claim 1 or 2, wherein the preparation method comprises the following steps:
(1) dissolving linear polysiloxane and diisocyanate containing-OH at both ends in an organic solvent, adding a catalyst, reacting at the temperature of 70-80 ℃, and obtaining a prepolymer containing terminal-NCO when the-NCO content in the system does not change any more;
(2) adding a hydrophilic chain extender, carrying out chain extension reaction at the temperature of 75-90 ℃, and reacting until the-NCO content in the system is not changed any more, so as to obtain the organic silicon modified polyurethane resin containing carboxyl;
(3) adding a polymerization inhibitor and a photocuring monomer material, reacting at 55-65 ℃, and obtaining the organosilicon modified polyurethane resin containing the acryloxy group when the-NCO content in the system is not changed any more;
(4) and (3) cooling to 30-45 ℃, adding a neutralizing agent for neutralization, adding distilled water for emulsification, and removing the organic solvent through reduced pressure distillation to obtain the ultraviolet-cured water-based anti-graffiti coating.
4. The production method according to claim 3, characterized in that: the diisocyanate in the step (1) is any one of isophorone diisocyanate, toluene diisocyanate, 4-diphenylmethane diisocyanate and hexamethylene diisocyanate.
5. The production method according to claim 3, characterized in that: the organic solvent in the step (1) is any one or more of acetone, toluene, n-heptane, cyclohexane, ethyl acetate and methyl isobutyl ketone.
6. The production method according to claim 3, characterized in that: the catalyst in the step (1) is dibutyltin dilaurate, and the using amount of the catalyst accounts for 0.1-1.2 wt% of the total solid content in the ultraviolet-curing water-based anti-graffiti coating.
7. The production method according to claim 3, characterized in that: the hydrophilic chain extender in the step (2) is any one of dimethylolbutyric acid, dimethylolpropionic acid, 1, 2-dihydroxy-3-sodium propane sulfonate and 1, 4-butanediol-2-sodium sulfonate.
8. The production method according to claim 3, characterized in that: the polymerization inhibitor in the step (3) is any one or more of p-hydroxyanisole, hydroquinone, p-benzoquinone, 2-tert-butylhydroquinone and 2, 5-di-tert-butylhydroquinone.
9. The production method according to claim 3, characterized in that: the photo-curing monomer material in the step (3) is any one of 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, pentaerythritol triacrylate and dipentaerythritol pentaacrylate.
10. The production method according to claim 3, characterized in that: the neutralizing agent in the step (4) is any one or more of triethylamine, diethanolamine, dimethylethanolamine, ammonia water and methylamine; the neutralization degree is 80-120%.
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