CN114591487B - 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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- CN114591487B CN114591487B CN202210417166.8A CN202210417166A CN114591487B CN 114591487 B CN114591487 B CN 114591487B CN 202210417166 A CN202210417166 A CN 202210417166A CN 114591487 B CN114591487 B CN 114591487B
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- component
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- polyurethane emulsion
- aqueous polyurethane
- 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 13
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 51
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 150000002009 diols Chemical class 0.000 claims description 13
- 238000006386 neutralization reaction Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 11
- 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
- -1 polypropylene carbonate Polymers 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
- 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
- 125000002887 hydroxy group Chemical group [H]O* 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
- 239000011259 mixed solution Substances 0.000 claims description 4
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical group C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 3
- 230000035484 reaction time Effects 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
- 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
- 239000002253 acid Substances 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
- 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
- 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 1
- 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
- 238000001308 synthesis method Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 19
- 239000003973 paint Substances 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 4
- 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
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 7
- 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011527 polyurethane coating Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 3
- 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 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
- 230000003472 neutralizing effect 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
- 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 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-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
- 230000006978 adaptation Effects 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003153 chemical reaction reagent 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
- 230000001804 emulsifying effect Effects 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical group 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification 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
- 229920000642 polymer Polymers 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
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- 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
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)
- Macromonomer-Based Addition Polymer (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The application belongs to the technical field of ultraviolet light curing water-based paint, and particularly relates to a two-component ultraviolet light curing water-based polyurethane emulsion, a preparation method and application thereof, wherein the two-component ultraviolet light curing water-based polyurethane emulsion comprises at least two hydroxyl acrylate end-capped polyurethane prepolymers and a small molecular dihydric alcohol chain-extended long-chain polyurethane prepolymer, the at least two hydroxyl acrylate end-capped polyurethane prepolymers undergo a crosslinking reaction under ultraviolet light irradiation, a crosslinking network and linear polyurethane form a semi-interpenetrating network structure, and the semi-interpenetrating network structure enables the two-component ultraviolet light curing water-based polyurethane emulsion to have excellent hardness, tensile strength and elongation at break at the same time, so that the technical problem that the existing ultraviolet light curing water-based polyurethane emulsion with a single film forming component cannot have toughness and strength after being formed is solved.
Description
Technical Field
The application belongs to the technical field of water-based paint, and particularly relates to a double-component UV-cured water-based polyurethane emulsion, and a preparation method and application thereof.
Background
In recent years, environmental protection is increasingly paid attention to by countries in the world, strict laws and regulations are formulated in the countries in the world at present to regulate the release of organic volatile matters in the paint, and compared with conventional paint, the water-based paint does not use organic solvents 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 waterborne polyurethane emulsion only contains one film-forming component, such as a single film-forming component of the ultraviolet-curable waterborne polyurethane emulsion, and the preparation method of the ultraviolet-curable waterborne polyurethane emulsion is generally as follows: polyether glycol or polyester glycol, diisocyanate and hydrophilic monomer react under the action of a catalyst to generate an isocyanate group-terminated prepolymer, and then ultraviolet light-cured waterborne polyurethane emulsion is obtained after hydroxyl acrylate end-capping, neutralization by a neutralizing agent and deionized water emulsification. However, when the system double bond content of the ultraviolet light curing aqueous polyurethane emulsion 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 hardness, the stretching resistance, the scratch resistance and the solvent resistance are not ideal in performance; when the double bond content in the system is higher, the double bond crosslinking density of the cured coating film is high, and the cured coating film is in a hard and brittle state, and has better hardness, scratch resistance and solvent resistance, but poorer flexibility.
CN110615885a discloses a preparation method of an ultraviolet light curing aqueous polyurethane emulsion: firstly, dihydric alcohol reacts with diisocyanate and a hydrophilic monomer under the action of a catalyst to obtain an intermediate, a prepolymer is obtained through chain extension of micromolecular dihydric alcohol, and then ultraviolet light curing aqueous polyurethane emulsion is obtained through end capping, neutralization and emulsification of hydroxyl acrylate containing a carbon-carbon double bond. The tensile strength of the emulsion cured film is 6-16MPa, the elongation at break is 48% -80%, and the cured film has certain flexibility, but 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 light curing aqueous polyurethane: firstly, synthesizing polyurethane prepolymer by using dihydric alcohol, diisocyanate and hydrophilic monomer, then using hydroxy acrylate to make partial end-capping, then making neutralization and emulsification, etc., finally using amine chain extender to make chain extension after emulsification. The emulsion prepared by the improved method has better coating flexibility after forming the coating.
Although the preparation methods of the two patents are innovative, the emulsion only contains one film forming component, and the ultraviolet light 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, a preparation method and application thereof, which are used for solving the technical problem that the existing aqueous polyurethane emulsion with a single film-forming component cannot have toughness and strength after film formation.
The first aspect of the application provides a two-component UV-curable aqueous polyurethane emulsion; the emulsion comprises: at least two hydroxyl acrylate terminated polyurethane prepolymers and a small molecule glycol chain extended long chain polyurethane prepolymer.
Preferably, the at least two hydroxyl acrylates in 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 small molecular diol chain-extended 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.
The second aspect of the application provides a preparation method of a two-component UV-curable aqueous polyurethane emulsion, which comprises the following steps:
step 1, reacting macromolecular dihydric alcohol, diisocyanate and hydrophilic monomer under the action of a catalyst to obtain polyurethane prepolymer;
step 2, at least two hydroxyl acrylate end-capping a first part of the polyurethane prepolymer to obtain at least two hydroxyl acrylate end-capped polyurethane prepolymers;
step 3, the chain extender of the small molecular dihydric alcohol chain extends the second part of the polyurethane prepolymer to obtain a long-chain polyurethane prepolymer of the chain extension of the small molecular dihydric alcohol;
step 4, mixing the at least two hydroxyl acrylate end-capped polyurethane prepolymers in the step 2 and the long-chain polyurethane prepolymer 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 two-component aqueous polyurethane mixed solution in the step 4 to obtain a two-component aqueous polyurethane emulsion;
and 6, mixing the two-component aqueous polyurethane emulsion obtained in the step 5 with a photoinitiator to obtain the two-component UV-cured aqueous 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 end capping temperature is 70-90 ℃ and the time is 3-5 h.
Preferably, in the step 3, the chain extension temperature 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 temperature of the emulsification is room temperature, and the time is 10-20 min; the temperature of the post-chain extension reaction is room temperature for 20-40 min, the temperature of the acetone removal reaction is 50-60 ℃ and the time is 3-5 h.
Preferably, in step 1, the macromolecular diol is at least one of polypropylene carbonate diol, polyether diol, polyester diol and polypropylene carbonate diol.
Preferably, in the 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-dihydroxyethyl monomaleic acid, 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 iso-octoate and dibutyl tin dilaurate.
Preferably, in step 6, the photoinitiator is at least one of benzoin and its derivatives, dialkoxyacetophenone, alpha-hydroxyalkyl benzophenone, alpha-aminoalkylbenzophenone, 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, decylenediamine and p-phenylenediamine.
The third aspect of the application provides the application of the two-component UV-curable waterborne polyurethane emulsion as an ultraviolet-curable coating film.
In the bi-component UV-curable aqueous polyurethane emulsion provided by the application, the long-chain polyurethane prepolymer with the chain extended by the micromolecular dihydric alcohol is of a linear structure, so that after the bi-component UV-curable aqueous polyurethane emulsion is not subjected to ultraviolet irradiation and natural drying, a coating film still has a certain mechanical strength due to the fact that the system contains the long-chain polyurethane with high molecular weight, 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 blocked by hydroxyl acrylate under the ultraviolet irradiation can form a semi-interpenetrating structure.
The application of the ultraviolet light curing coating film is particularly the application of the ultraviolet light curing coating film of an inner and outer wall, an ultraviolet light curing metal coating film or an ultraviolet light curing wood coating film and the like.
In summary, the application provides a two-component UV-curable aqueous polyurethane emulsion, a preparation method and application thereof, wherein the two-component UV-curable aqueous polyurethane coating comprises the following components: at least two hydroxyl acrylate end-capped polyurethane prepolymers and a small molecular diol chain-extended long-chain polyurethane prepolymer, and at least two hydroxyl acrylate end-capped polyurethane prepolymers and the small molecular diol chain-extended long-chain polyurethane prepolymers react to form a polymer network under ultraviolet irradiation, and form a semi-interpenetrating network structure with unreacted long-chain polyurethane prepolymers, so that the two-component UV-cured aqueous polyurethane coating film has excellent hardness, tensile strength and elongation at break at the same time, and the technical problem that the existing UV-cured aqueous polyurethane emulsion with a single film-forming component cannot have toughness and strength after film formation is solved.
Drawings
In order to more clearly illustrate the embodiments of the application or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the application, and that other drawings can be obtained from these drawings without inventive faculty for a person skilled in the art.
Fig. 1 is a schematic diagram of a semi-interpenetrating network structure formed by the two-component UV-curable aqueous polyurethane emulsion provided in embodiment 1 of the present application.
Fig. 2 is a schematic diagram of the preparation of a two-component UV-curable aqueous polyurethane emulsion according to example 1 of the present application.
Detailed Description
The application provides a double-component UV-cured aqueous polyurethane emulsion, 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 being formed into a film.
The following description of the technical solutions in the embodiments of the present application will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Among them, the reagents and raw materials used in the following examples are all commercially available or homemade.
Example 1
The embodiment 1 provides a preparation method of a two-component UV-curable waterborne polyurethane emulsion, which comprises the following steps:
1.1 preparation of at least two hydroxyl acrylate terminated polyurethane prepolymers
Placing 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 with a mechanical stirrer and a thermometer, heating in a water bath, adding 0.1 part by mass of stannous octoate catalyst within the range of 30-40 ℃, and heating to 90 ℃ for reaction for 4 hours to obtain a first part of polyurethane prepolymer;
cooling to 40-50 ℃, sequentially adding 0.0358 mass parts of p-methylol phenol, 8.22 mass parts of hydroxyethyl acrylate and 21.14 mass parts of pentaerythritol triacrylate, heating to 80 ℃ for reaction for 4 hours, cooling to 40-50 ℃, adding 20 mass parts of acetone to dilute the system viscosity, and obtaining at least two hydroxyl acrylate end-capped polyurethane prepolymers.
1.2 preparation of a Long-chain polyurethane prepolymer chain-extended with a Small-molecule diol
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 are placed in a three-neck flask with a mechanical stirrer and a thermometer, heated in a water bath, 0.12 part by mass of stannous octoate catalyst is added within the range of 30-40 ℃, and heated to 90 ℃ for reaction for 4 hours to obtain a second part of polyurethane prepolymer;
cooling to 40-50 ℃, adding 2.61 parts by mass of 1, 4-butanediol, heating to 70 ℃ for reaction 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 of the micromolecular dihydric alcohol chain extension.
1.3 preparing a two-component UV-curable waterborne polyurethane emulsion
Placing 36 parts by mass of at least two hydroxyl acrylate end-capped polyurethane prepolymers and 24 parts by mass of small molecular dihydric alcohol chain-extended long-chain polyurethane prepolymers into a three-neck flask, uniformly mixing, adding 1.37 parts by mass of triethylamine for neutralization reaction, continuously stirring at 2000r/min with the temperature of 5 ℃ and 82.3 parts by mass of deionized water for emulsification for 10-15 min, adding 1 drop of defoamer halfway for defoaming, pouring the mixture into the three-neck flask after defoaming is completed, adding 0.44 parts by mass of ethylenediamine diluted by deionized water for reaction for 30min, heating to 55 ℃ for removing acetone, finally adding 0.96 parts by mass of photoinitiator 2959 for uniformly mixing, and obtaining the double-component ultraviolet light-cured aqueous polyurethane emulsion.
Example 2
The present example 2 provides a method for preparing a two-component UV-curable aqueous polyurethane emulsion, the preparation steps differ from those of example 1 in that: step 1.3, preparing a bi-component UV-cured aqueous polyurethane emulsion
Placing 27 parts by mass of at least two hydroxyl acrylate-terminated polyurethane prepolymers and 33 parts by mass of small molecular dihydric alcohol chain-extended long-chain polyurethane prepolymers into a three-neck flask, uniformly mixing, adding 1.38 parts by mass of triethylamine for neutralization reaction, continuously stirring at a high speed for 10-15 min at a temperature of 5 ℃ with 82.5 parts by mass of deionized water at 2000r/min, emulsifying for 10-15 min, adding 1 drop of defoamer halfway for defoaming, pouring the mixture into the three-neck flask after defoaming is completed, adding 0.54 part by mass of ethylenediamine diluted by deionized water for reaction for 30min, heating to 55 ℃ for removing acetone, finally adding 0.72 part by mass of photoinitiator 2959, and uniformly mixing to obtain the double-component UV-curable aqueous polyurethane emulsion.
Example 3
The present example 3 provides a method for preparing a two-component UV-curable aqueous polyurethane emulsion, the preparation steps differ from those of example 1 in that: step 1.3, preparing a bi-component UV-cured aqueous polyurethane emulsion
Placing 18 parts by mass of at least two hydroxyl acrylate end-capped polyurethane prepolymers and 42 parts by mass of small molecular dihydric alcohol chain-extended long-chain polyurethane prepolymers into a three-neck flask, uniformly mixing, adding 1.39 parts by mass of triethylamine for neutralization reaction, continuously stirring at 2000r/min with 80.9 parts by mass of deionized water at 5 ℃ for emulsification for 10-15 min, adding 1 drop of defoamer halfway for defoaming, pouring the mixture into the three-neck flask after defoaming is completed, adding 0.63 part by mass of ethylenediamine diluted by deionized water for reaction for 30min, heating to 55 ℃ for removing acetone, finally adding 0.48 part by mass of photoinitiator 2959 for uniformly mixing, and thus obtaining the double-component UV-curable aqueous polyurethane emulsion.
Example 4
The present example 4 provides a method for preparing a two-component UV-curable aqueous polyurethane emulsion, the preparation steps differ from those of example 1 in that: step 1.3, preparing a bi-component UV-cured aqueous polyurethane emulsion
9 parts by mass of at least two hydroxyl acrylate-terminated polyurethane prepolymers and 51 parts by mass of small molecular dihydric alcohol chain-extended long-chain polyurethane prepolymers are placed in a three-neck flask, after being uniformly mixed, 1.39 parts by mass of triethylamine is added for neutralization reaction, the reaction lasts for 10-15 min, then deionized water with the temperature of 5 ℃ and the mass of 80.2 parts by mass is stirred at a high speed for emulsification for 10-15 min, 1 drop of defoamer is added in the middle for defoaming, after defoaming is completed, the mixture is poured into the three-neck flask, 0.77 parts by mass of ethylenediamine diluted by deionized water is added for reaction for 30min, acetone is removed after the temperature is raised to 55 ℃, and finally 0.24 parts by mass of photoinitiator 2959 is added for uniform mixing, so that the two-component UV-curable aqueous polyurethane emulsion is obtained.
Example 5
This example 5 is a performance test of the two-component UV-curable aqueous polyurethane emulsion of examples 1-4, wherein the adhesion test is performed according to national standard GB/T5210-2006, the pencil hardness test is performed according to national standard GB/T5210-2006, the gloss test is performed according to national standard GB/T9754-2007, and the tensile strength and elongation at break test is performed according to national standard GB/T16777-2008; 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 1-4 of the present application has excellent hardness, tensile strength and elongation at break after ultraviolet curing to form a film, which indicates that the semi-interpenetrating network structure composed of the crosslinked network of at least two hydroxyl acrylate-terminated polyurethane prepolymers and the long-chain polyurethane prepolymer of the chain extension of the small molecular diol can make the aqueous polyurethane coating film have both toughness and strength.
The foregoing is merely a preferred embodiment of the present application and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present application, which are intended to be comprehended within the scope of the present application.
Claims (8)
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 small molecule diol chain extended long chain polyurethane prepolymer;
the preparation method of the two-component UV-curable waterborne polyurethane emulsion comprises the following steps:
step 1, reacting macromolecular dihydric alcohol, diisocyanate and a hydrophilic monomer under the action of a catalyst to respectively obtain a first part of polyurethane prepolymer and a second part of polyurethane prepolymer;
step 2, at least two hydroxyl acrylate end-capping the first part of polyurethane prepolymer to obtain at least two hydroxyl acrylate end-capped polyurethane prepolymers;
step 3, the second part of polyurethane prepolymer is subjected to chain extension by a small molecular dihydric alcohol chain extender to obtain a small molecular dihydric alcohol chain-extended long-chain polyurethane prepolymer;
step 4, mixing the at least two hydroxyl acrylate end-capped polyurethane prepolymers in the step 2 and the long-chain polyurethane prepolymer 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 two-component aqueous polyurethane mixed solution in the step 4 to obtain a two-component aqueous polyurethane emulsion;
step 6, mixing the two-component aqueous polyurethane emulsion obtained in the step 5 with a photoinitiator to obtain a two-component UV-cured aqueous polyurethane emulsion;
the at least two hydroxyl acrylate in the polyurethane prepolymer terminated by at least two hydroxyl acrylate is pentaerythritol triacrylate and at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and 2-hydroxyethyl acrylate.
2. The two-component UV-curable aqueous polyurethane emulsion according to claim 1, wherein the small-molecular diol 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 in the small-molecular diol chain-extended long-chain polyurethane prepolymer.
3. The two-component UV-curable waterborne polyurethane emulsion according to claim 1, wherein in the step 1, the reaction temperature is 80-100 ℃ and the reaction time is 3-5 h.
4. The two-component UV-curable aqueous polyurethane emulsion according to claim 1, wherein in step 1, the diisocyanate is at least one of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and diphenylmethane diisocyanate.
5. The two-component UV-curable aqueous polyurethane emulsion according to claim 1, wherein in step 1, the hydrophilic monomer is at least one of 2, 2-dimethylolpropionic acid, 2-dimethylolbutyric acid, N-dihydroxyethyl monomaleic acid, N- (2-aminoethyl) -2-aminopropanesulfonic acid, and N- (2-hydroxyethyl) -2-aminoethanesulfonic acid.
6. The two-component UV-curable aqueous polyurethane emulsion of claim 1, wherein in step 1, the macrodiol is a polypropylene carbonate diol;
the molecular weight of the polypropylene carbonate dihydric alcohol is 500-4000, and the mole fraction of carbonate groups in the molecule 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.
7. The two-component UV-curable aqueous polyurethane emulsion according to claim 1, wherein in the step 5, the neutralization reaction temperature is 40-50 ℃ and the neutralization reaction time is 5-15 min;
the temperature of the emulsification 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 of the solvent is 50-60 ℃ and the time is 3-5 h.
8. Use of the two-component UV-curable aqueous polyurethane emulsion according to any one of claims 1 to 7 as an UV-curable coating film.
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