CN109293871B - Self-leveling water-based fluorine-containing polyurethane acrylic resin, preparation method thereof and water-based photocureable coating - Google Patents
Self-leveling water-based fluorine-containing polyurethane acrylic resin, preparation method thereof and water-based photocureable coating Download PDFInfo
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- CN109293871B CN109293871B CN201810974453.2A CN201810974453A CN109293871B CN 109293871 B CN109293871 B CN 109293871B CN 201810974453 A CN201810974453 A CN 201810974453A CN 109293871 B CN109293871 B CN 109293871B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000004814 polyurethane Substances 0.000 title claims abstract description 44
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 44
- 238000000576 coating method Methods 0.000 title claims abstract description 42
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 41
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 41
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 39
- 239000011737 fluorine Substances 0.000 title claims abstract description 39
- 239000011248 coating agent Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000011347 resin Substances 0.000 claims abstract description 41
- 229920005989 resin Polymers 0.000 claims abstract description 41
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000010702 perfluoropolyether Substances 0.000 claims abstract description 18
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 18
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 18
- 150000002009 diols Chemical class 0.000 claims abstract description 17
- 150000001412 amines Chemical class 0.000 claims abstract description 15
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims abstract description 13
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 239000003112 inhibitor Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000013638 trimer Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 239000002562 thickening agent Substances 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 230000003472 neutralizing effect Effects 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
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 5
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 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
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 229960002887 deanol Drugs 0.000 claims description 3
- 239000012972 dimethylethanolamine Substances 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- OELQSSWXRGADDE-UHFFFAOYSA-N 2-methylprop-2-eneperoxoic acid Chemical compound CC(=C)C(=O)OO OELQSSWXRGADDE-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 13
- 238000007599 discharging Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 239000003973 paint Substances 0.000 description 5
- 238000001723 curing Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009775 high-speed stirring Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000004131 Bayer process Methods 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- -1 acrylic ester Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Images
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- 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
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
- C08G18/5015—Polyethers having heteroatoms other than oxygen having halogens having fluorine atoms
-
- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/67—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
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
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- Chemical & Material Sciences (AREA)
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- Polyurethanes Or Polyureas (AREA)
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Abstract
The invention relates to a self-leveling water-based fluorine-containing polyurethane acrylic resin, a preparation method thereof and a water-based light-cured coating, belonging to the field of coatings. The self-leveling water-based fluorine-containing polyurethane acrylic resin is prepared from the following raw materials in percentage by mass: 10-20% of tripolymer polyisocyanate, 10-25% of monohydroxy acrylate substance, 2-10% of perfluoropolyether diol, 1-2% of trimethylolpropane, 2-6% of dimethylolpropionic acid, 1-3% of neutralized amine, 40-60% of water, 4-7% of acetone, 0.01-0.1% of catalyst and 0.1-1% of polymerization inhibitor. The leveling water-based fluorine-containing polyurethane acrylic resin has excellent water dispersibility, good stability, milky blue appearance, high resin solid content and moderate viscosity, and the prepared photocureable coating has good stability, strong impact resistance and good application prospect.
Description
Technical Field
The invention relates to a self-leveling water-based fluorine-containing polyurethane acrylic resin, a preparation method thereof and a water-based light-cured coating, belonging to the field of coatings.
Background
With the development of science and technology and the advancement of society, people have come to be aware of the importance of environmental protection. For solvent-based coatings, the volatilization of a large amount of organic matters not only causes ecological damage, but also brings serious influence on human health, so that the development of environment-friendly coatings such as water-based coatings, ultraviolet curing coatings and the like is more and more adapted to market demands.
Conventional photocurable coatings may, in some applications, add a certain amount of inert solvent to reduce the viscosity of the system. The main resin has higher viscosity, and strong volume shrinkage can be caused by dilution with an active monomer, so that the adhesive force of a paint film and the mechanical property of the paint film are influenced, and the viscosity of the system can be reduced and the leveling of the paint film can be promoted after the solvent is added, so that the obtained paint film is smoother. However, the solvent-based ultraviolet curing coating is not environment-friendly in production and use, and the volatilization of the solvent can bring health hazards to operators.
Compared with the traditional light-cured coating, the water-based light-cured coating has the following advantages: the water is easy to obtain, cheap and environment-friendly, and low VOC and zero VOC are realized; the coating is free of pungent smell in the processes of spraying, pre-drying and curing, and does not harm the body of a constructor and an end user; the coating equipment and the container are cleaned by the aqueous cleaning solution, so that the coating equipment and the container are convenient and environment-friendly. On the other hand, aqueous photopaints also have the following disadvantages: the evaporation heat of water is higher (40.6kJ/mol), and the energy consumption is higher when the water is removed by drying; the surface tension of water is high (72.8mN/m), the wettability of the base material is poor, and the leveling is not good; the glossiness of the cured film is low, and the water resistance is poor; poor storage stability and sensitivity to pH.
The waterborne polyurethane acrylate is a most studied class of waterborne light-cured resin at present, and a cured film of the waterborne polyurethane acrylate has excellent mechanical wear resistance and flexibility, higher expansion strength and impact resistance, and excellent high temperature resistance and chemical resistance.
Compared with the traditional light-cured coating, the water-based light-cured coating has the following advantages: the water is easy to obtain, cheap and environment-friendly, and low VOC and zero VOC are realized; the coating is free of pungent smell in the processes of spraying, pre-drying and curing, and does not harm the body of a constructor and an end user; the coating equipment and the container are cleaned by the aqueous cleaning solution, so that the coating equipment and the container are convenient and environment-friendly. On the other hand, aqueous photopaints also have the following disadvantages: the evaporation heat of water is higher (40.6kJ/mol), and the energy consumption is higher when the water is removed by drying; the surface tension of water is high (72.8mN/m), the wettability of the base material is poor, and the leveling is not good; the glossiness of the cured film is low, and the water resistance is poor; poor storage stability and sensitivity to pH. The properties of aqueous photocurable coatings need to be improved still further.
Disclosure of Invention
The first purpose of the invention is to provide a self-leveling water-based fluorine-containing polyurethane acrylic resin which has high solid content and can be used for preparing coatings with strong impact resistance.
The second purpose of the invention is to provide a preparation method of the self-leveling water-based fluorine-containing polyurethane acrylic resin.
The third purpose of the invention is to provide a water-based light-cured coating.
The self-leveling water-based fluorine-containing polyurethane acrylic resin is prepared from the following raw materials in percentage by mass: 10-20% of tripolymer polyisocyanate, 10-25% of monohydroxy acrylate substance, 2-10% of perfluoropolyether diol, 1-2% of trimethylolpropane, 2-6% of dimethylolpropionic acid, 1-3% of neutralized amine, 40-60% of water, 4-7% of acetone, 0.01-0.1% of catalyst and 0.1-1% of polymerization inhibitor.
The solid content of the trimeric polyisocyanate is 100%.
The trimer polyisocyanate is any one or more of hexamethylene diisocyanate trimer (HDI trimer) and pentamethylene diisocyanate trimer (PDI trimer).
The hexamethylene diisocyanate trimer (HDI trimer) and pentamethylene diisocyanate trimer (PDI trimer) are commercially available.
Preferably, the hexamethylene diisocyanate trimer (HDI trimer) is Bayer
N3300、
N3600, Basff
HI-100, Asahi chemical Synthesis
TKA-100、
TPA-100, Tri-well chemistry
D-170N, Rodiya
HDT-100, Wanhua chemistry
HT-100.
Preferably, the pentamethylene diisocyanate trimer (PDI trimer) is of triple well chemistry
D-370N、
D-376N, Bayer
Any one of N7300.
The trimeric polyisocyanates described above can also be prepared according to methods known from the prior art.
The monohydroxy acrylate substance is any one or more of hydroxyethyl methacrylate, hydroxypropyl methacrylate, caprolactone grafted hydroxy acrylate, caprolactone grafted hydroxy methacrylate and pentaerythritol triacrylate.
The caprolactone grafted hydroxyl acrylate is any one of FA2D, FA3 and FA1 DDM.
The caprolactone grafted methyl methacrylate is FM1D or FM 2D.
The perfluoropolyether diol is HO (CH)2CH2O)mCH2CF2O(CF2CF2O)nCF2CH2(OCH2CH2)mOH， 1≤m≤2，n≥1。
Molecular weight M of the perfluoropolyether dioln1000-.
The neutralizing amine is any one of triethylamine, dimethylethanolamine and triethanolamine.
The polymerization inhibitor is any one of p-hydroxyanisole and hydroquinone.
The catalyst is any one of dibutyltin dilaurate and stannous octoate.
The self-leveling water-based fluorine-containing polyurethane acrylic resin selects isocyanate as trimer polyisocyanate, and has a plurality of advantages compared with diisocyanate (the following structural formula is only shown as a schematic diagram):
compared with diisocyanate, the trimer polyisocyanate has more isocyanate groups and a branched chain structure, and after the monohydroxy acrylate monomer is grafted, the density of carbon-carbon double bonds in the resin can be greatly improved, so that the cured coating has higher crosslinking property and high hardness. In addition, the trimer polyisocyanate used in the invention has the characteristics of low toxicity, excellent gloss retention, good yellowing resistance and good solubility, and most of diisocyanate has higher toxicity.
The invention synthesizes leveling water-based fluorine-containing polyurethane acrylic resin, and the selected organic fluorine polymer is perfluoropolyether diol. The fluorine-containing polymer has excellent performances of three high (namely high weather resistance, high heat resistance and high stability) and two high (hydrophobic and oleophobic), not only can obviously improve the heat resistance of the resin, but also can reduce the surface energy, effectively improve the self-leveling property of the resin, and further improve the flatness and the glossiness of a coating film. Two hydroxyl groups in the perfluoropolyether diol are positioned at the tail end of a molecular structure, can be introduced into a main chain segment of the polyurethane acrylate, and have higher stability compared with an organic fluorine chain segment of a side branched chain. In addition, the main chain containing fluorine does not have a coating effect on the main resin, and the compatibility of the resin with other resins is not affected while the surface tension is reduced, so that the interlayer adhesion of the cured coating film is also very excellent.
The preparation method of the self-leveling water-based fluorine-containing polyurethane acrylic resin comprises the following steps:
1) mixing trimeric polyisocyanate and a polymerization inhibitor, heating to 40-50 ℃, adding monohydroxy acrylate and acetone, and keeping the temperature at 60-70 ℃ for 4-5 hours to obtain a mixture a;
2) adding perfluoropolyether diol, trimethylolpropane, dimethylolpropionic acid, a catalyst and acetone into the mixture a, heating to 70-75 ℃ for reaction for 2-3 h, heating to 80-85 ℃ for reaction for 2-3 h, then adding the rest monohydroxy acrylate and acetone, and reacting at 80-85 ℃ for 2-3 h to obtain resin b;
3) and uniformly mixing the resin b with water and neutralized amine, stirring for 1-1.5 h under the conditions that the vacuum degree is 0.090-0.100 MPa and the temperature is 45-50 ℃, and cooling to obtain the resin.
The trimer polyisocyanate and the polymerization inhibitor in the step 1) are mixed and stirred at the speed of 150-200 r/min.
Dropwise adding the monohydroxy acrylate substance and the acetone in the step 1) within 30-40 min.
The resin b, water and neutralizing amine are uniformly mixed in the step 3) as follows: and firstly, uniformly mixing water and neutralizing amine, and then adding the resin b while stirring, wherein the stirring speed is 800-1000 r/min.
The addition of the resin b is finished within 20-30 min.
In the above preparation method, the amounts of acetone added in three times are 1/3 of the total amount of acetone.
Stirring for 1-1.5 h in the step 3) and removing more than 95% of acetone.
Cooling to 20-25 ℃ in the step 3), and filtering and discharging by using a filter bag with 80 meshes.
The preparation method of the leveling water-based fluorine-containing polyurethane acrylic resin is based on the reaction of isocyanate and hydroxyl to generate a urethane bond, and belongs to a step-by-step polymerization reaction. Firstly, taking tripolymer polyisocyanate as a main body, grafting monohydroxy acrylate monomer to introduce unsaturated carbon-carbon double bonds, using a polymerization inhibitor to prevent active double bonds from self polymerization, ensuring the long-term storage stability of resin, and controlling formula composition and reaction process to obtain partially-terminated multifunctional polyurethane prepolymer; then, introducing an organic fluorine chain segment on the main chain structure of the polyurethane prepolymer by utilizing perfluoropolyether diol, and introducing a hydrophilic group on the main chain of the polyurethane prepolymer by utilizing a water-based chain extender dimethylolpropionic acid; adding a proper amount of trimethylolpropane to improve the branching degree of the resin; the catalyst is used for improving the reaction activity and accelerating the reaction time; adding a monohydroxy acrylate monomer to carry out complete end capping; and finally adding neutralizing amine for neutralization to endow the resin with water dispersibility.
Taking pentaerythritol triacrylate and hydroxypropyl acrylate as the monohydroxy acrylate as an example, the reaction mechanism of the leveling aqueous fluorine-containing polyurethane acrylic resin is shown in fig. 1.
An aqueous photocureable coating is prepared by a preparation method comprising the following steps: and (3) uniformly mixing the self-leveling water-based fluorine-containing polyurethane acrylic resin with a photoinitiator and a thickening agent to obtain the self-leveling water-based fluorine-containing polyurethane acrylic resin.
The photoinitiator is a liquid photoinitiator. Preferably, the liquid photoinitiator is
1173、
500、
2959、
819DW、
TPO-L、
4265、
2100. The liquid photoinitiator was obtained from basf.
The thickening agent is a nonionic associative thickening agent. Preferably, the nonionic associative thickener is a dow thickener
RM-2050D, Kening
DSX-1550 and Haimines
FX1010 winning wound
3060. Raimanfusl
Any one or more of ATUR 20.
The addition amount of the photoinitiator is 3-5% of the solid content of the self-leveling water-based fluorine-containing polyurethane acrylic resin.
The addition amount of the thickening agent is 0.05-1% of the solid content of the self-leveling aqueous fluorinated polyurethane acrylic resin.
The aqueous photocurable coating may further contain a pigment as required.
The leveling water-based fluorine-containing polyurethane acrylic resin has high solid content, low toxicity and excellent gloss retention, the main chain contains fluorine, the main resin cannot form a coating effect, the surface tension is reduced, and the compatibility of the resin and other resins is not influenced, so that the interlayer adhesion of a cured coating film is also excellent.
The prepared leveling aqueous fluorine-containing polyurethane acrylic resin has excellent water dispersibility, good stability, milky white color blue light appearance, high solid content and moderate viscosity by strictly controlling the proportion of reaction materials, the reaction time, the reaction temperature and the charging sequence.
The water-based photocureable coating has the advantages of high photocuring speed, high storage stability, good leveling property, high hardness of a cured coating, high glossiness, strong impact resistance, good heat resistance and good water resistance, and can be widely applied to plastic and woodware finishing protection finish paint.
Drawings
FIG. 1 is a schematic diagram of the reaction mechanism of the leveling aqueous fluorinated polyurethane acrylic resin of the present invention, taking pentaerythritol triacrylate and hydroxypropyl acrylate as an example of monohydroxy acrylate; wherein A is a representation of a trimeric polyisocyanate; b is a schematic representation of pentaerythritol triacrylate; c is a schematic representation of dimethylolpropionic acid; d is a representation of hydroxypropyl acrylate; rf is a schematic of perfluoropolyether diols.
Detailed Description
Example 1
The self-leveling water-based fluorine-containing polyurethane acrylic resin is prepared from the following raw materials in percentage by mass: bayer process
N330015%, monohydroxy acrylate substance 11%, perfluoropolyether diol (molecular weight Mn is 1300) 7%, trimethylolpropane 2%, dimethylolpropionic acid 5%, triethylamine 2%, deionized water 52%, acetone 5%, dibutyltin dilaurate 0.02%, p-hydroxyanisole 0.98%; the monohydroxy acrylate is a mixture of pentaerythritol triacrylate, hydroxyethyl methacrylate and hydroxypropyl acrylate in a mass ratio of 2:5: 3.
The preparation method of the self-leveling water-based fluorine-containing polyurethane acrylic resin of the embodiment comprises the following steps:
1) adding into a reaction vessel
Stirring N3300 and p-hydroxyanisole at a stirring speed of 200r/min, heating to 50 ℃, slowly dropwise adding monohydroxy acrylate and one third of acetone by mass within 30min, and then preserving heat at 65 ℃ for 4h to obtain a mixture a;
2) sequentially adding perfluoropolyether diol, trimethylolpropane, dimethylolpropionic acid, dibutyltin dilaurate and one third of acetone by mass into a reaction vessel, heating to 70 ℃ for reaction for 2.5h, heating to 80 ℃ for reaction for 3h, then adding the rest monohydroxy acrylate substance and the rest one third of acetone by mass, and reacting for 2h at 80 ℃ to obtain resin b;
3) adding stirred deionized water and neutralized amine into a high-speed dispersing device container with a reduced pressure distillation device in advance, slowly pouring the resin b prepared in the step 2) into the high-speed dispersing device container under high-speed stirring, wherein the stirring speed is 800r/min, the resin b is added within 30min, then starting the reduced pressure distillation device and heating, stirring for 1h under the conditions that the vacuum degree is 0.090MPa and the temperature is 50 ℃, removing over 95 wt% of acetone, cooling to 25 ℃, filtering by a filter bag of 80 meshes, and discharging to obtain a product.
In the waterborne photocurable coating of the embodiment, the self-leveling waterborne fluorinated polyurethane acrylic resin is stirred at a high speed of 1000r/min, and added with the resin with a solid content of 3 wt%
2959 photoinitiator, resin solid content 0.5 wt%
RM-2050D thickener, stirring for 30-40min, and discharging.
Example 2
The self-leveling water-based fluorine-containing polyurethane acrylic resin is prepared from the following raw materials in percentage by mass: of three-well chemistry
20% of D-370N, 18% of monohydroxy acrylate, 5% of perfluoropolyether diol (the molecular weight Mn is 1700), 1% of trimethylolpropane, 4% of dimethylolpropionic acid, 2% of dimethylethanolamine, 44% of deionized water, 5% of acetone, 0.05% of dibutyltin dilaurate and 0.95% of hydroquinone; the monohydroxy acrylate is a mixture of pentaerythritol triacrylate, hydroxyethyl acrylate and FA2D mixed according to a mass ratio of 3:3: 4.
The preparation method of the self-leveling water-based fluorine-containing polyurethane acrylic resin of the embodiment comprises the following steps:
1) with addition of Mitsui chemistry to the reaction vessel
D-370N and hydroquinone are stirred at the stirring speed of 180r/min, the temperature is raised to 45 ℃, monohydroxy acrylic ester substances and one third of acetone are slowly dripped in the mixture for 40minAfter the dropwise addition is finished, preserving the heat for 5 hours at the temperature of 60 ℃ to obtain a mixture a;
2) sequentially adding perfluoropolyether diol, trimethylolpropane, dimethylolpropionic acid, dibutyltin dilaurate and one third of acetone by mass into a reaction vessel, heating to 70 ℃ for reaction for 3 hours, heating to 80 ℃ for reaction for 2.5 hours, then adding the rest monohydroxy acrylate substance and the rest one third of acetone by mass, and reacting for 3 hours at 85 ℃ to obtain resin b;
3) adding stirred deionized water and neutralizing amine into a high-speed dispersing device container with a reduced pressure distillation device in advance, slowly pouring the resin b prepared in the step 2) into the high-speed dispersing device container under high-speed stirring, wherein the stirring speed is 1000r/min, the resin b is added within 25min, starting the reduced pressure distillation device and heating, stirring for 1.5h under the conditions that the vacuum degree is 0.095MPa and the temperature is 45 ℃, removing more than 95 wt% of acetone, cooling to 23 ℃, filtering by a filter bag of 80 meshes, and discharging to obtain a product.
In the waterborne photocurable coating of the embodiment, the self-leveling waterborne fluorinated polyurethane acrylic resin is stirred at a high speed of 900r/min, and a photoinitiator (with a resin solid content of 5 wt%) (
500 and
TPO-L mixture), a thickener having a resin solids content of 0.8 wt%
FX1010, stirring for 50min, and discharging.
Example 3
The self-leveling water-based fluorine-containing polyurethane acrylic resin is prepared from the following raw materials in percentage by mass: 11% of tripolymer polyisocyanate, 20% of monohydroxy acrylate substance, 4% of perfluoropolyether diol (the molecular weight Mn is 1500), 2% of trimethylolpropane, 5% of dimethylolpropionic acid, 2% of triethanolamine, 49% of deionized water, 6% of acetone, 0.08% of stannous octoate, p-hydroxyanisole0.92 percent; the trimeric polyisocyanate is rosidiya
HDT-100 and Bayer
N7300 a mixture mixed in a mass ratio of 1: 1; the monohydroxy acrylate is a mixture of hydroxyethyl methacrylate, hydroxypropyl acrylate and FA1DDM mixed according to a mass ratio of 4:4: 2.
The preparation method of the self-leveling water-based fluorine-containing polyurethane acrylic resin of the embodiment comprises the following steps:
1) adding tripolymer polyisocyanate and p-hydroxyanisole into a reaction container, stirring at a stirring speed of 200r/min, heating to 40 ℃, slowly dropwise adding monohydroxy acrylate and acetone of one third of the mass fraction within 30min, and then preserving heat at 70 ℃ for 4h to obtain a mixture a;
2) sequentially adding perfluoropolyether diol, trimethylolpropane, dimethylolpropionic acid, stannous octoate and one third of acetone by mass into a reaction vessel, heating to 75 ℃ for reaction for 2.5h, heating to 85 ℃ for reaction for 2h, then adding the rest monohydroxy acrylate substance and the rest one third of acetone by mass, and reacting at 85 ℃ for 3h to obtain resin b;
3) adding stirred deionized water and neutralized amine into a high-speed dispersing device container with a reduced pressure distillation device in advance, slowly pouring the resin b prepared in the step 2) into the high-speed dispersing device container under high-speed stirring, wherein the stirring speed is 900r/min, the resin b is added within 30min, starting the reduced pressure distillation device and heating, stirring for 1.5h under the conditions that the vacuum degree is 0.096MPa and the temperature is 48 ℃, removing more than 95 wt% of acetone, cooling to 24 ℃, filtering by a filter bag of 80 meshes, and discharging to obtain a product.
In the waterborne photocurable coating of the embodiment, the self-leveling waterborne fluorinated polyurethane acrylic resin is stirred at a high speed of 800r/min, and a photoinitiator (with a resin solid content of 5 wt%) (
1173 and
819DW mixtures), a thickener with a resin solids content of 0.8% by weight
ATUR20, stirring for 50min, and discharging.
Examples of the experiments
The self-leveling aqueous fluorine-containing polyurethane acrylic resin and the aqueous photocurable coating in examples 1-3 were subjected to performance tests, and the results are shown in table 1:
TABLE 1 test data for leveling waterborne fluorinated polyurethane acrylic resins and waterborne photocurable coatings of examples 1-3
Various other modifications and changes may be made by those skilled in the art based on the above-described technical solutions and concepts, and all such modifications and changes should fall within the scope of the claims of the present invention.
Claims (8)
1. The self-leveling water-based fluorine-containing polyurethane acrylic resin is characterized by being prepared from the following raw materials in percentage by mass: 10-20% of tripolymer polyisocyanate, 10-25% of monohydroxy acrylate substance, 2-10% of perfluoropolyether diol, 1-2% of trimethylolpropane, 2-6% of dimethylolpropionic acid, 1-3% of neutralized amine, 40-60% of water, 4-7% of acetone, 0.01-0.1% of catalyst and 0.1-1% of polymerization inhibitor, wherein the perfluoropolyether diol is HO (CH)2CH2O)mCH2CF2O(CF2CF2O)nCF2CH2(OCH2CH2)mOH，1≤m≤2，n≥1；
The preparation method of the self-leveling water-based fluorine-containing polyurethane acrylic resin comprises the following steps:
1) mixing trimeric polyisocyanate and a polymerization inhibitor, heating to 40-50 ℃, adding monohydroxy acrylate and acetone, and keeping the temperature at 60-70 ℃ for 4-5 hours to obtain a mixture a;
2) adding perfluoropolyether diol, trimethylolpropane, dimethylolpropionic acid, a catalyst and acetone into the mixture a, heating to 70-75 ℃ for reaction for 2-3 h, heating to 80-85 ℃ for reaction for 2-3 h, then adding the rest monohydroxy acrylate and acetone, and reacting at 80-85 ℃ for 2-3 h to obtain resin b;
3) and uniformly mixing the resin b with water and neutralized amine, stirring for 1-1.5 h under the conditions that the vacuum degree is 0.090-0.100 MPa and the temperature is 45-50 ℃, and cooling to obtain the resin.
2. The self-leveling water-based fluorine-containing polyurethane acrylic resin according to claim 1, wherein the trimeric polyisocyanate is any one or more of hexamethylene diisocyanate trimer and pentamethylene diisocyanate trimer.
3. The self-leveling water-based fluorine-containing polyurethane acrylic resin according to claim 1, wherein the monohydroxy acrylate is any one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, caprolactone grafted hydroxy methacrylate and pentaerythritol triacrylate.
4. The self-leveling water-based fluorine-containing polyurethane acrylic resin according to claim 1, wherein the neutralizing amine is any one of triethylamine, dimethylethanolamine and triethanolamine.
5. The self-leveling water-based fluorine-containing polyurethane acrylic resin according to claim 1, wherein the polymerization inhibitor is any one of p-hydroxyanisole and hydroquinone.
6. The self-leveling water-based fluorine-containing polyurethane acrylic resin according to claim 1, wherein the catalyst is any one of dibutyltin dilaurate and stannous octoate.
7. The self-leveling water-based fluorine-containing polyurethane acrylic resin according to claim 1, wherein the blending of the resin b with water and a neutralizing amine in the step 3) is as follows: and firstly, uniformly mixing water and neutralizing amine, and then adding the resin b while stirring, wherein the stirring speed is 800-1000 r/min.
8. The aqueous photocureable coating is characterized by being prepared by a preparation method comprising the following steps: the self-leveling water-based fluorine-containing polyurethane acrylic resin of claim 1 is uniformly mixed with a photoinitiator and a thickening agent.
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| CN111057203B (en) * | 2019-12-31 | 2022-03-22 | 北京松井工程技术研究院有限公司 | Silicon-fluorine polyurethane acrylic resin and preparation method and application thereof |
| KR20220137751A (en) | 2020-02-18 | 2022-10-12 | 아크조노벨코팅스인터내셔널비.브이. | Water-Based UV Curable Coating Composition for Antifouling and Scratch Resistant Coatings |
| CN113980234A (en) * | 2021-11-30 | 2022-01-28 | 江苏三木化工股份有限公司 | Polyurethane acrylate with good pigment wetting performance and preparation method thereof |
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