CN114591487A - Double-component UV-cured waterborne polyurethane emulsion and preparation method and application thereof - Google Patents
Double-component UV-cured waterborne polyurethane emulsion and preparation method and application thereof Download PDFInfo
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- CN114591487A CN114591487A CN202210417166.8A CN202210417166A CN114591487A CN 114591487 A CN114591487 A CN 114591487A CN 202210417166 A CN202210417166 A CN 202210417166A CN 114591487 A CN114591487 A CN 114591487A
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- polyurethane emulsion
- chain
- polyurethane
- aqueous polyurethane
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 64
- 239000004814 polyurethane Substances 0.000 title claims abstract description 64
- 239000000839 emulsion Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000004945 emulsification Methods 0.000 title claims description 7
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 45
- 150000002009 diols Chemical group 0.000 claims abstract description 17
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000003848 UV Light-Curing Methods 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 238000006386 neutralization reaction Methods 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- -1 small molecule diol Chemical class 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 230000001804 emulsifying 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
- 239000002904 solvent Substances 0.000 claims description 5
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 4
- 239000004970 Chain extender Substances 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- 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 4
- 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 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- 229940035437 1,3-propanediol Drugs 0.000 claims description 2
- VOXZDWNPVJITMN-ZBRFXRBCSA-N 17β-estradiol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 VOXZDWNPVJITMN-ZBRFXRBCSA-N 0.000 claims description 2
- RXZHXOJAHDKBKK-UHFFFAOYSA-N 2-(2-aminoethylamino)propane-1-sulfonic acid Chemical compound OS(=O)(=O)CC(C)NCCN RXZHXOJAHDKBKK-UHFFFAOYSA-N 0.000 claims description 2
- BVIXTPMSXQAQBG-UHFFFAOYSA-N 2-(2-hydroxyethylamino)ethanesulfonic acid Chemical compound OCCNCCS(O)(=O)=O BVIXTPMSXQAQBG-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- DUFKCOQISQKSAV-UHFFFAOYSA-N Polypropylene glycol (m w 1,200-3,000) Chemical compound CC(O)COC(C)CO DUFKCOQISQKSAV-UHFFFAOYSA-N 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 229940113120 dipropylene glycol Drugs 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 2
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- 229960004063 propylene glycol Drugs 0.000 claims description 2
- 235000013772 propylene glycol Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 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 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims 1
- 229910002092 carbon dioxide Inorganic materials 0.000 claims 1
- 239000001569 carbon dioxide Substances 0.000 claims 1
- 125000005587 carbonate group Chemical group 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 19
- 238000001723 curing Methods 0.000 abstract description 15
- 239000011527 polyurethane coating Substances 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 4
- 238000005286 illumination Methods 0.000 abstract 1
- 239000003973 paint Substances 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 5
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000013530 defoamer Substances 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- BVJSUAQZOZWCKN-UHFFFAOYSA-N p-hydroxybenzyl alcohol Chemical compound OCC1=CC=C(O)C=C1 BVJSUAQZOZWCKN-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 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 description 1
- 239000002023 wood Substances 0.000 description 1
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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
- C08G18/67—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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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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
- C08G18/67—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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
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- 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)
- Macromonomer-Based Addition Polymer (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The application belongs to the technical field of ultraviolet curing water-based paint, and particularly relates to a two-component UV curing water-based polyurethane emulsion and a preparation method and application thereof, wherein the two-component UV curing water-based polyurethane emulsion comprises at least two hydroxyl acrylate terminated polyurethane prepolymers and a long-chain polyurethane prepolymer with a small molecular diol chain extended chain, the hydroxyl acrylate of the at least two hydroxyl acrylate terminated polyurethane prepolymers is subjected to a cross-linking reaction under ultraviolet illumination, a cross-linking network and linear polyurethane form a semi-interpenetrating network structure, the semi-interpenetrating network structure enables a two-component UV curing water-based polyurethane coating film to have excellent hardness, tensile strength and elongation at break simultaneously, and the technical problem that the existing single film-forming component ultraviolet curing water-based polyurethane emulsion cannot have toughness and strength after forming a film is solved.
Description
Technical Field
The application belongs to the technical field of water-based coatings, and particularly relates to a two-component UV-cured water-based polyurethane emulsion, and a preparation method and application thereof.
Background
In recent years, environmental protection is more and more emphasized by countries in the world, strict laws and regulations are established by countries in the world to regulate the release of organic volatile matters in the coating, and compared with the conventional coating, the water-based coating does not use an organic solvent on a large scale, so that the release amount of the organic volatile matters is small, and the environmental protection requirement is met.
The existing UV-curable aqueous polyurethane emulsion only contains one film-forming component, such as an ultraviolet-curable aqueous polyurethane emulsion with a single film-forming component, and the preparation method of the ultraviolet-curable aqueous polyurethane emulsion generally comprises the following steps: polyether diol or polyester diol, diisocyanate and hydrophilic monomer react under the action of catalyst to produce prepolymer terminated with isocyanate group, and the prepolymer is further terminated with hydroxy acrylate, neutralized with neutralizer and emulsified with deionized water to obtain the ultraviolet cured water-thinned polyurethane emulsion. However, when the double bond content of the system is low, the crosslinking density of the cured coating film is low, the cured coating film is in a soft and sticky state, and the performances such as hardness, tensile resistance, scratch resistance and solvent resistance are not ideal; when the double bond content in the system is higher, the double bond crosslinking density of the cured coating film is high, the cured coating film is in a hard and brittle state, and the flexibility is poor although the hardness, the scratch resistance and the solvent resistance are better.
CN110615885A discloses a preparation method of an ultraviolet curing aqueous polyurethane emulsion, which comprises the following steps: firstly, reacting dihydric alcohol with diisocyanate and a hydrophilic monomer under the action of a catalyst to obtain an intermediate, carrying out chain extension on the intermediate by using micromolecular dihydric alcohol to obtain a prepolymer, and carrying out end capping, neutralization and emulsification on the prepolymer by using hydroxy acrylate containing a carbon-carbon double bond to obtain the ultraviolet curing waterborne polyurethane emulsion. The emulsion curing film has the tensile strength of 6-16MPa and the elongation at break of 48-80%, and although the curing film has certain flexibility, the tensile strength and the elongation at break are poor, so that the application range of the emulsion is limited.
CN106866912 discloses a preparation method of ultraviolet curing waterborne polyurethane: firstly, using dihydric alcohol, diisocyanate and hydrophilic monomer to synthesize polyurethane prepolymer, then using acrylic hydroxyl ester to make partial end capping, then making neutralization and emulsification, finally making the non-end capped portion undergo the process of emulsification and chain extension by using amine chain extender. The emulsion prepared by the improved method has better coating flexibility after forming a coating.
Although the preparation methods of the two patents are innovative in preparation method, the emulsion only contains one film forming component, and the ultraviolet curing aqueous polyurethane curing film with both toughness and strength cannot be prepared.
Disclosure of Invention
In view of the above, the application provides a two-component UV-curable aqueous polyurethane emulsion, and a preparation method and an application thereof, which are used for solving the technical problem that after an existing aqueous polyurethane emulsion with a single film-forming component is formed into a film, the existing aqueous polyurethane emulsion cannot have both toughness and strength.
The application provides a two-component UV curing aqueous polyurethane emulsion in a first aspect; the emulsion comprises: at least two hydroxyl acrylate terminated polyurethane prepolymers and a long chain polyurethane prepolymer chain extended with a small molecule diol.
Preferably, at least two hydroxyl acrylates of the at least two hydroxyl acrylate-terminated polyurethane prepolymers are pentaerythritol triacrylate and at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, 2-hydroxyethyl acrylate.
Preferably, the small molecular diol in the polyurethane prepolymer with the small molecular diol chain extended is at least one of 1, 4-butanediol, ethylene glycol, diethylene glycol, pentanediol, 1, 2-propanediol, 1, 3-propanediol, dipropylene glycol and 1, 6-hexanediol.
The second aspect of the application provides a preparation method of a two-component UV-cured aqueous polyurethane emulsion, which comprises the following steps:
step 1, reacting macromolecular diol, diisocyanate and hydrophilic monomer under the action of a catalyst to obtain a polyurethane prepolymer;
step 2, at least two hydroxyl acrylates end-cap the first part of the polyurethane prepolymer to obtain at least two hydroxyl acrylate end-capped polyurethane prepolymers;
step 3, chain extension is carried out on the second part of polyurethane prepolymer by using a micromolecular dihydric alcohol chain extender, so that a micromolecular dihydric alcohol chain-extended long-chain polyurethane prepolymer is obtained;
step 4, mixing the at least two hydroxyl acrylate-terminated polyurethane prepolymers obtained in the step 2 and the long-chain polyurethane prepolymer obtained in the step 3 to obtain a two-component aqueous polyurethane mixed solution;
step 5, sequentially carrying out neutralization reaction, emulsification reaction, post-chain extension reaction and solvent removal on the mixed solution of the two-component waterborne polyurethane obtained in the step 4 to obtain a two-component waterborne polyurethane emulsion;
and 6, mixing the two-component waterborne polyurethane emulsion obtained in the step 5 with a photoinitiator to obtain the two-component UV curing waterborne polyurethane emulsion.
Preferably, in the step 1, the reaction temperature is 80-100 ℃ and the reaction time is 3-5 h.
Preferably, in the step 2, the temperature of the end capping is 70-90 ℃ and the time is 3-5 h.
Preferably, in the step 3, the temperature of the chain extension is 60-80 ℃, and the time is 1-3 h.
Preferably, in the step 5, the temperature of the neutralization reaction is 40-50 ℃, and the time is 5-15 min; the emulsifying temperature is room temperature, and the time is 10-20 min; the temperature of the post-chain extension reaction is room temperature, the time is 20-40 min, the temperature for removing the acetone is 50-60 ℃, and the time is 3-5 h.
Preferably, in step 1, the macrodiol is at least one of polypropylene carbonate diol, polyether diol, polyester diol and polypropylene carbonate diol.
Preferably, in step 1, the diisocyanate is at least one of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and diphenylmethane diisocyanate.
Preferably, in step 1, the hydrophilic monomer is at least one of 2, 2-dimethylolpropionic acid, 2-dimethylolbutyric acid, N-dihydroxyethylmonomaleate, N- (2-aminoethyl) -2-aminopropanesulfonic acid and N- (2-hydroxyethyl) -2-aminoethanesulfonic acid.
Preferably, in step 1, the catalyst is at least one of stannous isooctanoate and dibutyltin dilaurate.
Preferably, in step 6, the photoinitiator is at least one of benzoin and derivatives thereof, dialkoxyacetophenone, α -hydroxyalkylphenone, α -aminoalkylphenone, and acylphosphine oxide.
Preferably, in step 5, the neutralizing agent used in the neutralization reaction is at least one of triethylamine and triethanolamine; the rear chain extender is at least one of ethylenediamine, propylenediamine, hexamethylenediamine, decamethylenediamine and p-phenylenediamine.
The third aspect of the application provides the application of the two-component UV-cured aqueous polyurethane emulsion as an ultraviolet-cured coating.
It should be noted that in the bi-component UV-curable aqueous polyurethane emulsion provided by the present application, the long-chain polyurethane prepolymer chain-extended by the small-molecular diol is of a linear structure, and therefore, after natural drying without ultraviolet irradiation, the coating film still has a certain mechanical strength due to the long-chain polyurethane with a very high molecular weight contained in the system, and meanwhile, when the bi-component UV-curable aqueous polyurethane emulsion is applied as an ultraviolet-curable coating film, a cross-linked network formed by the long-chain polyurethane prepolymer and the polyurethane prepolymer terminated by hydroxyl acrylate under ultraviolet irradiation can form a semi-interpenetrating structure.
The ultraviolet curing coating is particularly applied to ultraviolet curing inner and outer wall coatings, ultraviolet curing metal coatings or ultraviolet curing wood coatings.
To sum up, the application provides a two-component UV-curable aqueous polyurethane emulsion, a preparation method and an application thereof, wherein the two-component UV-curable aqueous polyurethane coating film comprises: the two-component UV curing aqueous polyurethane coating film has excellent hardness, tensile strength and elongation at break by virtue of the semi-interpenetrating network structure, and the technical problem that the existing UV curing aqueous polyurethane emulsion with a single film-forming component cannot have toughness and strength after being formed into a film is solved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without inventive exercise.
Fig. 1 is a schematic diagram of a semi-interpenetrating network structure formed by a two-component UV-curable aqueous polyurethane emulsion provided in embodiment 1 of the present application.
Fig. 2 is a schematic diagram of a two-component UV-curable aqueous polyurethane emulsion prepared according to example 1 of the present application.
Detailed Description
The application provides a two-component UV-curable aqueous polyurethane emulsion, and a preparation method and application thereof, which are used for solving the technical problem that the existing aqueous polyurethane coating with a single film-forming component cannot have toughness and strength after film forming.
The technical solutions in the embodiments of the present application will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The reagents or raw materials used in the following examples are commercially available or self-made.
Example 1
The embodiment 1 provides a preparation method of a two-component UV-curable aqueous polyurethane emulsion, which comprises the following steps:
1.1 preparation of at least two hydroxyl acrylate-terminated polyurethane prepolymers
Putting 37 parts by mass of polypropylene carbonate glycol (PPC), 4.08 parts by mass of 2, 2-dimethylolpropionic acid, 15 parts by mass of N, N-dimethylformamide and 30 parts by mass of isophorone diisocyanate into a three-neck flask provided with a mechanical stirrer and a thermometer, heating in a water bath, adding 0.1 part by mass of stannous isooctoate catalyst at the temperature of 30-40 ℃, heating to 90 ℃ and reacting for 4 hours to obtain a first part of polyurethane prepolymer;
and cooling to 40-50 ℃, sequentially adding 0.0358 parts by mass of p-hydroxymethyl phenol, 8.22 parts by mass of hydroxyethyl acrylate and 21.14 parts by mass of pentaerythritol triacrylate, heating to 80 ℃, reacting for 4 hours, cooling to 40-50 ℃, and adding 20 parts by mass of acetone to dilute the viscosity of the system to obtain at least two hydroxyl acrylate-terminated polyurethane prepolymers.
1.2 preparation of Long-chain polyurethane prepolymer with chain extended by micromolecular dihydric alcohol
Placing 69.47 parts by mass of polypropylene carbonate glycol PPC, 4.40 parts by mass of 2, 2-dimethylolpropionic acid, 15 parts by mass of N, N-dimethylformamide and 30 parts by mass of isophorone diisocyanate in a three-neck flask provided with a mechanical stirrer and a thermometer, heating in a water bath, adding 0.12 part by mass of stannous octoate catalyst at the temperature of 30-40 ℃, heating to 90 ℃ and reacting for 4 hours to obtain a second part of polyurethane prepolymer;
and cooling to 40-50 ℃, adding 2.61 parts by mass of 1, 4-butanediol, heating to 70 ℃, reacting for 2 hours, cooling to 40-50 ℃, adding 21 parts by mass of acetone to dilute the viscosity of the system, and obtaining the long-chain polyurethane prepolymer with the chain extended by the small molecular dihydric alcohol.
1.3 preparation of two-component UV-curable aqueous polyurethane emulsion
Placing 36 parts by mass of at least two hydroxyl acrylate-terminated polyurethane prepolymers and 24 parts by mass of a long-chain polyurethane prepolymer chain-extended by a small molecular diol into a three-neck flask, uniformly mixing, adding 1.37 parts by mass of triethylamine for neutralization reaction, continuing the reaction for 10-15 min, then emulsifying at a high speed for 10-15 min by using 5 ℃ and 82.3 parts by mass of deionized water at 2000r/min, adding 1 drop of defoamer midway for defoaming, pouring into the three-neck flask after complete defoaming, adding 0.44 part by mass of ethylenediamine diluted by the deionized water, reacting for 30min, heating to 55 ℃ to remove acetone, and finally adding 0.96 part by mass of a photoinitiator 2959 for uniform mixing to obtain the two-component ultraviolet curing aqueous polyurethane emulsion.
Example 2
This example 2 provides a method for preparing a two-component UV-curable aqueous polyurethane emulsion, which is different from example 1 in the following steps: step 1.3, preparing a bicomponent UV-curable aqueous polyurethane emulsion
Placing 27 parts by mass of at least two hydroxyl acrylate-terminated polyurethane prepolymers and 33 parts by mass of a long-chain polyurethane prepolymer chain-extended by a micromolecular diol into a three-neck flask, uniformly mixing, adding 1.38 parts by mass of triethylamine for neutralization reaction, continuing the reaction for 10-15 min, then emulsifying at a high speed for 10-15 min by using 5 ℃ and 82.5 parts by mass of deionized water at 2000r/min, adding 1 drop of defoamer midway for defoaming, pouring into the three-neck flask after complete defoaming, adding 0.54 part by mass of ethylenediamine diluted by the deionized water, reacting for 30min, heating to 55 ℃ to remove acetone, and finally adding 0.72 part by mass of a photoinitiator 2959 for uniform mixing to obtain the bi-component UV-cured waterborne polyurethane emulsion.
Example 3
This example 3 provides a method for preparing a two-component UV-curable aqueous polyurethane emulsion, which is different from example 1 in the following steps: step 1.3, preparing a bicomponent UV-curable aqueous polyurethane emulsion
Placing 18 parts by mass of at least two hydroxyl acrylate-terminated polyurethane prepolymers and 42 parts by mass of long-chain polyurethane prepolymer chain-extended by micromolecular dihydric alcohol into a three-neck flask, uniformly mixing, adding 1.39 parts by mass of triethylamine for neutralization reaction, continuing the reaction for 10-15 min, then emulsifying at a high speed for 10-15 min by using 5 ℃ and 80.9 parts by mass of deionized water at 2000r/min, adding 1 drop of defoamer midway for defoaming, pouring into the three-neck flask after complete defoaming, adding 0.63 part by mass of ethylenediamine diluted by the deionized water, reacting for 30min, heating to 55 ℃ to remove acetone, and finally adding 0.48 part by mass of photoinitiator 2959 for uniform mixing to obtain the bi-component UV-cured waterborne polyurethane emulsion.
Example 4
This example 4 provides a method for preparing a two-component UV-curable aqueous polyurethane emulsion, which is different from example 1 in the following steps: step 1.3, preparing a bicomponent UV-curable aqueous polyurethane emulsion
Placing 9 parts by mass of at least two hydroxyl acrylate-terminated polyurethane prepolymers and 51 parts by mass of long-chain polyurethane prepolymer chain-extended by micromolecular dihydric alcohol into a three-neck flask, uniformly mixing, adding 1.39 parts by mass of triethylamine for neutralization reaction, continuing the reaction for 10-15 min, then emulsifying at a high speed for 10-15 min by using 5 ℃ and 80.2 parts by mass of deionized water at 2000r/min, adding 1 drop of defoamer midway for defoaming, pouring into the three-neck flask after complete defoaming, adding 0.77 part by mass of ethylenediamine diluted by the deionized water, reacting for 30min, heating to 55 ℃ to remove acetone, and finally adding 0.24 part by mass of photoinitiator 2959 for uniform mixing to obtain the bi-component UV-cured waterborne polyurethane emulsion.
Example 5
This example 5 is a performance test of the two-component UV curable aqueous polyurethane emulsion in examples 1-4, wherein the adhesion test is performed according to the international GB/T5210-; the results are shown in table 1:
TABLE 1
As can be seen from table 1, the two-component aqueous polyurethane emulsion provided in examples 1 to 4 of the present application has excellent hardness, tensile strength and elongation at break after being cured by uv light to form a film, which indicates that the aqueous polyurethane coating film has toughness and strength due to the semi-interpenetrating network structure formed by the cross-linked network of at least two hydroxyl acrylate-terminated polyurethane prepolymers and the long-chain polyurethane prepolymer chain-extended by the small-molecule diol.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A two-component UV-curable aqueous polyurethane emulsion, characterized in that the emulsion comprises: at least two hydroxyl acrylate terminated polyurethane prepolymers and a long chain polyurethane prepolymer chain extended with a small molecule diol.
2. The two-component UV-curable aqueous polyurethane emulsion according to claim 1, wherein at least two hydroxyl acrylates of the at least two hydroxyl acrylate-terminated polyurethane prepolymers are pentaerythritol triacrylate and at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, 2-hydroxyethyl acrylate.
3. The two-component UV-curable aqueous polyurethane emulsion according to claim 1, wherein the small-molecular diol in the small-molecular diol chain-extended long-chain polyurethane prepolymer is at least one of 1, 4-butanediol, ethylene glycol, diethylene glycol, pentanediol, 1, 2-propanediol, 1, 3-propanediol, dipropylene glycol, and 1, 6-hexanediol.
4. The method for preparing the two-component UV-curable aqueous polyurethane emulsion according to any one of claims 1 to 3, comprising the steps of:
step 1, reacting macromolecular diol, diisocyanate and hydrophilic monomer under the action of a catalyst to obtain a polyurethane prepolymer;
step 2, at least two hydroxyl acrylates end-cap the first part of the polyurethane prepolymer to obtain at least two hydroxyl acrylate end-capped polyurethane prepolymers;
step 3, chain extension is carried out on the second part of polyurethane prepolymer by using a micromolecular dihydric alcohol chain extender, so that a micromolecular dihydric alcohol chain-extended long-chain polyurethane prepolymer is obtained;
step 4, mixing the at least two hydroxyl acrylate-terminated polyurethane prepolymers obtained in the step 2 and the long-chain polyurethane prepolymer obtained in the step 3 to obtain a two-component aqueous polyurethane mixed solution;
step 5, sequentially carrying out neutralization reaction, emulsification, post-chain extension reaction and solvent removal on the mixed liquid of the two-component waterborne polyurethane obtained in the step 4 to obtain a two-component waterborne polyurethane emulsion;
and 6, mixing the two-component waterborne polyurethane emulsion obtained in the step 5 with a photoinitiator to obtain the two-component UV curing waterborne polyurethane emulsion.
5. The preparation method of the two-component UV-curable aqueous polyurethane emulsion according to claim 4, wherein in the step 1, the reaction temperature is 80-100 ℃ and the reaction time is 3-5 h.
6. The method for preparing a two-component UV-curable aqueous polyurethane emulsion according to claim 4, wherein in step 1, the diisocyanate is at least one of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and diphenylmethane diisocyanate.
7. The method for preparing a two-component UV-curable aqueous polyurethane emulsion according to claim 4, wherein in step 1, the hydrophilic monomer is at least one of 2, 2-dimethylolpropionic acid, 2-dimethylolbutyric acid, N-dihydroxyethylmonomaleate, N- (2-aminoethyl) -2-aminopropanesulfonic acid, and N- (2-hydroxyethyl) -2-aminoethanesulfonic acid.
8. The method for preparing the two-component UV-curable aqueous polyurethane emulsion according to claim 4, wherein in step 1, the macrodiol is polypropylene carbonate diol;
the molecular weight of the polypropylene carbonate dihydric alcohol is 500-4000, and the mole fraction of carbonate groups in molecules is 0.25-0.45;
the synthesis method of the macromolecular dihydric alcohol comprises the following steps: carbon dioxide and propylene oxide are synthesized under the action of a catalyst.
9. The preparation method of the two-component UV-curable aqueous polyurethane emulsion according to claim 4, wherein in the step 5, the temperature of the neutralization reaction is 40-50 ℃ and the time is 5-15 min;
the emulsifying temperature is room temperature, and the time is 10-20 min;
the temperature of the post chain extension reaction is room temperature, and the time is 20-40 min;
the temperature for removing the solvent is 50-60 ℃, and the time is 3-5 h.
10. The use of the two-component UV-curable aqueous polyurethane emulsion according to claims 1 to 3 or the two-component UV-curable aqueous polyurethane emulsion prepared by the preparation method according to claims 4 to 9 as an ultraviolet-curable coating film.
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