CN115433338A - Preparation method of water-soluble ultraviolet-curing matte hyperbranched polyurethane acrylic resin - Google Patents
Preparation method of water-soluble ultraviolet-curing matte hyperbranched polyurethane acrylic resin Download PDFInfo
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- CN115433338A CN115433338A CN202211216517.5A CN202211216517A CN115433338A CN 115433338 A CN115433338 A CN 115433338A CN 202211216517 A CN202211216517 A CN 202211216517A CN 115433338 A CN115433338 A CN 115433338A
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- water
- hydroxyl
- diisocyanate
- hyperbranched
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 53
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 53
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 23
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229920006150 hyperbranched polyester Polymers 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000003085 diluting agent Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 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 11
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 11
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 10
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 10
- 229920000570 polyether Polymers 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 150000002009 diols Chemical class 0.000 claims abstract description 9
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 22
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 12
- -1 hydroxyalkyl acrylate Chemical compound 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 8
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 7
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 6
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 5
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 5
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 5
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 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 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 4
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- 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 3
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 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 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 claims description 2
- NEUXNYBBKZBRAM-UHFFFAOYSA-N [Na]CC(N)CCO Chemical compound [Na]CC(N)CCO NEUXNYBBKZBRAM-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 238000006757 chemical reactions by type Methods 0.000 claims 1
- NVJMGQMXNBBZIU-UHFFFAOYSA-N dibutyltin;1-dodecylsulfanyldodecane Chemical compound CCCC[Sn]CCCC.CCCCCCCCCCCCSCCCCCCCCCCCC NVJMGQMXNBBZIU-UHFFFAOYSA-N 0.000 claims 1
- 239000001294 propane Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 14
- 239000003960 organic solvent Substances 0.000 abstract description 5
- 238000007865 diluting Methods 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 27
- 239000011248 coating agent Substances 0.000 description 10
- 238000004132 cross linking Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 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 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000011527 polyurethane coating Substances 0.000 description 5
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- WMIZCUWBOVPNNQ-UHFFFAOYSA-N [Na].C(C)S(=O)(=O)O.C(CN)N Chemical compound [Na].C(C)S(=O)(=O)O.C(CN)N WMIZCUWBOVPNNQ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- CFQLQLSIZOWFNV-UHFFFAOYSA-M sodium;2-[bis(2-hydroxyethyl)amino]ethanesulfonate Chemical compound [Na+].OCCN(CCO)CCS([O-])(=O)=O CFQLQLSIZOWFNV-UHFFFAOYSA-M 0.000 description 2
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- QDDZXPJEJCHUGE-UHFFFAOYSA-N 2,3-dihydroxypropane-1-sulfonic acid;sodium Chemical compound [Na].OCC(O)CS(O)(=O)=O QDDZXPJEJCHUGE-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- GMCXXHRAQIUECM-UHFFFAOYSA-N C(CCCCCCCCCCC)[S].C(CCCCCCCCCCC)[S].C(CCC)[Sn]CCCC Chemical compound C(CCCCCCCCCCC)[S].C(CCCCCCCCCCC)[S].C(CCC)[Sn]CCCC GMCXXHRAQIUECM-UHFFFAOYSA-N 0.000 description 1
- NTZRDKVFLPLTPU-UHFFFAOYSA-N CC[Na] Chemical compound CC[Na] NTZRDKVFLPLTPU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- FFGHLLOLFQHABK-UHFFFAOYSA-L dibutyltin(2+);dodecane-1-thiolate Chemical compound CCCCCCCCCCCCS[Sn](CCCC)(CCCC)SCCCCCCCCCCCC FFGHLLOLFQHABK-UHFFFAOYSA-L 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229920000587 hyperbranched polymer Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000010399 physical interaction Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- UZMKOEWHQQPOBJ-UHFFFAOYSA-M sodium;2,3-dihydroxypropane-1-sulfonate Chemical compound [Na+].OCC(O)CS([O-])(=O)=O UZMKOEWHQQPOBJ-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
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- 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
- C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- 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
- C08G18/4202—Two or more polyesters of different physical or chemical nature
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- C08G18/4833—Polyethers containing oxyethylene units
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- 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
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- 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
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the technical field of water-soluble polyurethane, and particularly discloses a preparation method of water-soluble ultraviolet-curing matte hyperbranched polyurethane acrylic resin. The preparation process comprises the following steps: (1) Diisocyanate, polyether diol, dimethylolpropionic acid and a bifunctional reactive emulsifier are subjected to chemical reaction to synthesize isocyanate-terminated oligomer; (2) Then sequentially reacting with (methyl) acrylic acid hydroxyl alkyl ester and terminal hydroxyl hyperbranched polyester with different molecular weights to obtain ultraviolet curing hyperbranched polyurethane; (3) Adding an active diluent, and neutralizing, emulsifying and diluting with deionized water to obtain the water-soluble ultraviolet-curing matte hyperbranched polyurethane acrylic resin with the solid content of 40-60%. The invention has the advantages of simple process, easy industrialization, no organic solvent in the product, water dilutability, excellent stability, excellent performance and the like, and is expected to be widely applied in the fields of water-soluble matte coatings and the like.
Description
Technical Field
The invention relates to the technical field of water-soluble polyurethane, in particular to a preparation method of water-soluble ultraviolet-curing matte hyperbranched polyurethane acrylic resin.
Background
Water-soluble polyurethanes are novel polyurethane systems which are water-dispersible, also known as water-dispersible polyurethanes, water-based polyurethanes or water-based polyurethanes. The water-soluble polyurethane takes water as a solvent, and has the advantages of environmental protection, no pollution, safe and reliable construction, excellent mechanical property, good compatibility, easy modification, excellent compatibility with other water-soluble resins and the like. The water-soluble polyurethane coating is an environment-friendly coating prepared by taking water-soluble polyurethane resin as a base material and assisting other auxiliary agents, is widely applied to the fields of surface coating, coating and the like, and the cross-linking density is not high, so that the mechanical properties of pencil hardness, adhesive force and the like of the obtained coating are not high, and the cross-linking density can be improved by the cross-linking modified water-soluble polyurethane coating, so that the water-soluble polyurethane coating has good storage stability, high mechanical property, high water resistance, excellent solvent resistance and aging resistance, and can be applied to the field of advanced coating materials. The curing form (thermal curing and light curing) of the water-soluble polyurethane is determined by means of crosslinking modification (acrylic acid, epoxy and the like), the curing efficiency and the application field of the product are influenced finally, and compared with thermal crosslinking curing, ultraviolet curing has the excellent characteristics of high curing speed, short curing time, high efficiency, no pollution, uniform film performance and the like, and becomes an important development direction of water-soluble polyurethane coating.
The hyperbranched polymer has an ellipsoidal topological structure, shows the advantages of excellent rheological property, low viscosity, high activity and the like, and has become a hotspot of research in the field of high molecular materials in recent years. The traditional linear polyurethane is designed into the polyurethane with the hyperbranched topological structure, so that the polyurethane not only has the excellent performance of the traditional polyurethane, but also has the excellent properties of a highly branched topological structure, such as a large number of active groups at the tail end, so that the polyurethane is easier to modify, has high crosslinking density and excellent mechanical property, and has extremely wide application prospect. Most of the existing water-soluble polyurethane and water-soluble hyperbranched polyurethane are prepared by directly using difunctional isocyanate and trihydroxy compounds as main raw materials, the activities of three hydroxyl groups of the trihydroxy compounds are similar, the hyperbranched polyurethane is easy to gel in the synthesis process and difficult to synthesize with stable performance, and the difficulty and industrialization of subsequent water-soluble modification and ultraviolet curing modification are increased; in addition, emulsifying is mainly added with an emulsifier, the emulsifier is only in physical interaction during curing, and the mechanical property, hydrolysis resistance and solvent resistance of the product are not high. If a matte coating is prepared, another component is usually required to be added, such as a matte filler, and the prepared water-soluble polyurethane resin has difficulty in simultaneously showing the characteristics of the matte coating.
In order to solve the problems, the development of a synthetic technology of the ultraviolet curing matte water-soluble polyurethane which has the advantages of simple process, no pollution, low cost, stable product and excellent mechanical property and can be applied industrially and massively is a fundamental way for solving the problems in the field at present.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a preparation method of water-soluble ultraviolet curing matte hyperbranched polyurethane acrylic resin.
The invention solves the technical problems by the following technical scheme:
a preparation method of water-soluble ultraviolet-curing matte hyperbranched polyurethane acrylic resin comprises the following specific steps:
(1) Adding diisocyanate, polyether diol, dimethylolpropionic acid, a bifunctional reactive emulsifier and a catalyst into a reaction bottle, and stirring and reacting for 1-3 hours at the temperature of 40-80 ℃ to obtain an oligomer with isocyanate groups at two ends;
(2) Adding hydroxyalkyl (meth) acrylate containing 0.1wt% of polymerization inhibitor p-hydroxyanisole into a reaction bottle, and stirring and reacting for 1-3 hours at 50-90 ℃ to obtain an oligomer with one end being isocyanate group and one end being acrylate group;
(3) Adding hydroxyl-terminated hyperbranched polyesters with different molecular weights into a reaction bottle, stirring and reacting for 2-4 hours at 50-90 ℃ until isocyanate groups react completely to obtain the ultraviolet curing hyperbranched polyurethane, wherein the synthetic principle reaction formula is as follows:
reaction formula of ultraviolet curing hyperbranched polyurethane containing emulsifier
(4) Cooling to 30-50 ℃, adding an active diluent, adding an amine neutralizer to neutralize until the pH value is 6.8-7.5, adding deionized water, and emulsifying for 0.5-2 hours under the condition that the stirring speed is 500-1000rpm to obtain the water-soluble ultraviolet-cured matte hyperbranched polyurethane acrylic resin with the solid content of 40-60%;
the hydroxyalkyl (meth) acrylate is a hydroxyalkyl acrylate and/or a hydroxyalkyl methacrylate.
Furthermore, the catalyst is one or more of dibutyltin dilaurate, dibutyltin bis (dodecyl sulfur), dibutyltin diacetate and stannous octoate, and the using amount of the catalyst is 0.05-0.5% of the total mass of the diisocyanate, and is preferably 0.05-0.2%.
Furthermore, the mole ratio of the diisocyanate, the polyether diol, the dimethylolpropionic acid, the bifunctional reactive emulsifier, the (methyl) acrylic acid hydroxyalkyl ester and the hydroxyl-terminated hyperbranched polyester is (1.0-2.0): (0.1-0.5): (0.5-1.2): (0.1-0.5): (0.01-0.6): (0.01-0.6), the molar ratio of the high molecular weight hydroxyl-terminated hyperbranched polyester to the low molecular weight hydroxyl-terminated hyperbranched polyester in the hydroxyl-terminated hyperbranched polyesters with different molecular weights is as follows: 1.0: (0.2-4.0).
Further, the diisocyanate is one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 1,6-Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (HMDI), lysine Diisocyanate (LDI), and Xylylene Diisocyanate (XDI).
Furthermore, the polyether diol is one or more of polytetrahydrofuran, polypropylene glycol and polyethylene glycol which are commercially available, and the number average molecular weight of the polyether diol is 400-20000g/mol.
Further, the bifunctional reactive emulsifier is one or more of 1,2-dihydroxy-3-sodium propane sulfonate, ethylene diamine ethyl sodium sulfonate, N-bis (2-hydroxyethyl) -2-aminoethyl sodium sulfonate and N, N-bis (2-hydroxypropyl) -2-aminoethyl sodium sulfonate.
Further, the hydroxyalkyl (meth) acrylate is one or more of hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), hydroxyethyl methacrylate (HEMA), hydroxypropyl methacrylate (HPMA), 4-hydroxybutyl acrylate (HBA), and 2-hydroxybutyl methacrylate (HBMA).
Furthermore, the hydroxyl-terminated hyperbranched polyester is one or more of HyPer H101, hyPer H102, hyPer H103, hyPer H104, hyPer H201, hyPer H202, hyPer H203, hyPer H204, hyPer H301, hyPer H302, hyPer H303, hyPer H304, hyPer H401, hyPer H402 and HyPer H403 of Wuhan hyperbranched resin science and technology Limited, the number-average molecular weight of the hydroxyl-terminated hyperbranched polyester is 500-11500 g/mol, and the hydroxyl value is 160-670 mgKOH/g; wherein, the high molecular weight hydroxyl-terminated hyperbranched polyester is HyPer H104, hyPer H204, hyPer H303, hyPer H304, hyPer H402 and HyPer H403, and the others are low molecular weight hydroxyl-terminated hyperbranched polyester. Their properties are shown in table 1.
TABLE 1 Properties of the hydroxyl-terminated hyperbranched polyesters
Further, the reactive diluent is one or more of (methyl) acrylic ester with three or more functionality degrees, and the using amount of the reactive diluent is 2-20% of the total mass of the final water-soluble ultraviolet-curing matte hyperbranched polyurethane acrylic resin.
Further, the reactive diluent is one or more of trimethylolpropane triacrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate.
Further, the amine neutralizer is one or more of triethanolamine, diethanolamine, methyldiethanolamine, N-dimethylethanolamine, triethylamine and ammonia water.
Compared with the products in the prior art, the water-soluble ultraviolet-curing matte hyperbranched polyurethane acrylic resin prepared by the invention has the following advantages:
(1) The oligomer of isocyanate is synthesized firstly, and then the hydroxyl-terminated hyperbranched polyester is used for modification, so that the whole process does not involve the reaction among polyfunctional groups, the gel phenomenon is effectively avoided, the reaction condition is easy to control, the product quality is stable, and the industrialization is easy to realize;
(2) The hydroxyl-terminated hyperbranched polyester has an ellipsoidal topological structure, the prepared hyperbranched polyurethane has low viscosity, small particle size and high solid content, and an organic solvent is not used in the reaction process, so that the pollution of the organic solvent in the traditional coating can be reduced, the complicated process of removing the organic solvent is also reduced, and the production cost is reduced;
(3) The hyperbranched topological structure can effectively improve the leveling performance of the coating, and the thin coating can be prepared under the condition of no organic solvent;
(4) In the system, the multifunctional reactive diluent can be crosslinked with (methyl) acrylate groups on the surface of the hyperbranched polyurethane in the ultraviolet curing process, so that the crosslinking density, hardness and adhesive force are further improved;
(5) The emulsifier adopted by the system directly participates in chemical reaction, is grafted on the main chain of the matrix resin, has no residue after curing, and can effectively improve the stability, hardness, solvent resistance and the like of the product;
(6) The invention simultaneously utilizes two hydroxyl-terminated hyperbranched polyesters with different molecular weights as raw materials, and two water-soluble polyurethane coatings with larger particle size difference are prepared by a simple one-pot method, so that the matte function of the coatings is realized, and the coatings prepared by the technology are higher in stability and simpler in method than the coatings prepared by the traditional technology of adding a matte agent and the like;
(7) The paint prepared by the invention integrates the advantages of hyperbranched topological structure, ultraviolet curing and matte, and is not reported in documents;
(8) The process is simple, the emulsifying rotating speed is low, the performance is excellent, and the industrial application is facilitated.
Drawings
Fig. 1 is a particle size distribution diagram of the water-soluble ultraviolet light-curable matte hyperbranched polyurethane acrylic resin prepared in example 5.
Detailed Description
The following examples further illustrate embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
All of the following examples:
the used hydroxyl-terminated hyperbranched polyesters are purchased from Wuhan hyperbranched resin science and technology Limited, and specific properties are shown in Table 1 in the summary of the invention.
The polyether polyol, diisocyanate and other raw materials are all commercial products.
Example 1
Toluene diisocyanate (0.1mol, 17.4 g), polyethylene glycol (0.03mol, 12.0g) having a molecular weight of 400g/mol, dimethylolpropionic acid (0.05mol, 6.7g), 1,2-dihydroxy-3-propanesulfonic acid sodium salt (0.01mol, 1.78g) and 0.02g dibutyltin dilaurate were added to a reaction flask, and stirred and reacted at 40 ℃ for 3 hours; subsequently, hydroxyethyl acrylate containing p-hydroxyanisole as a polymerization inhibitor in an amount of about 0.1wt% (0.01mol, 1.16g) was added to the reaction flask and the mixture was stirred at 50 ℃ for 3 hours; then adding 0.008mol (41.6 g) of hydroxyl-terminated hyperbranched polyester HyPer H104 and 0.002mol (1.0 g) of hydroxyl-terminated hyperbranched polyester HyPer H101 into a reaction bottle, and stirring and reacting for about 4 hours at 50 ℃ until isocyanate groups are completely reacted to obtain the ultraviolet curing hyperbranched polyurethane; cooling to 30 ℃, adding 5.0g of active diluent trimethylolpropane triacrylate, adding triethanolamine to neutralize until the pH value is 6.8, adding 90.0g of deionized water to dilute, and finally emulsifying for 2 hours under the condition that the stirring speed is 500rpm to obtain 180g of water-soluble ultraviolet-cured matte hyperbranched polyurethane acrylic resin with the solid content of about 50 percent.
Example 2
Diphenylmethane diisocyanate (0.2mol, 50.0g), polytetrahydrofuran (0.05mol, 50.0g) having a molecular weight of 1000g/mol, dimethylolpropionic acid (0.12mol, 16.08g), ethylenediamine ethanesulfonic acid sodium (0.02mol, 3.80g) and 0.025g of di (dodecylthio) dibutyltin were added to a reaction flask, and stirred and reacted at 60 ℃ for 2 hours; then, hydroxypropyl acrylate (0.01mol, 1.30g) containing about 0.1wt% of p-hydroxyanisole as a polymerization inhibitor was added into the reaction flask, and the mixture was stirred and reacted for 2 hours at 70 ℃; then adding 0.002mol (10.8 g) of hydroxyl-terminated hyperbranched polyester HyPer H204 and 0.008mol (8.8 g) of hydroxyl-terminated hyperbranched polyester HyPer H102 into a reaction bottle, and stirring and reacting for about 3 hours at 70 ℃ until isocyanate groups are completely reacted to obtain the ultraviolet curing hyperbranched polyurethane; and cooling to 40 ℃, adding 48.0g of reactive diluent pentaerythritol triacrylate, adding methyldiethanolamine to neutralize until the pH value is 7.0, adding 300.0g of deionized water for dilution, and emulsifying at the stirring speed of 700rpm for 1 hour to obtain 500g of water-soluble ultraviolet-cured matte hyperbranched polyurethane acrylic resin with the solid content of about 40%.
Example 3
Isophorone diisocyanate (0.18mol, 40.0g), polyethylene glycol having a molecular weight of 6000g/mol (0.01mol, 60.0g), dimethylolpropionic acid (0.06mol, 8.04g), sodium N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonate (0.05mol, 11.75g), and 0.025g dibutyltin diacetate were added to a reaction flask, and reacted with stirring at 80 ℃ for 1 hour; then, hydroxyethyl methacrylate (0.06mol, 7.80g) containing about 0.1% by weight of p-hydroxyanisole as a polymerization inhibitor was added to the reaction flask, and the reaction was stirred at 90 ℃ for 1 hour; then adding 0.05mol (275.0 g) of hydroxyl-terminated hyperbranched polyester HyPer H303 and 0.01mol (24.0 g) of hydroxyl-terminated hyperbranched polyester HyPer H103 into a reaction bottle, and stirring and reacting for about 2 hours at 90 ℃ until isocyanate groups are completely reacted to obtain the ultraviolet curing hyperbranched polyurethane; and cooling to 50 ℃, adding 100.0g of reactive diluent pentaerythritol triacrylate, adding N, N-dimethylethanolamine to neutralize until the pH value is 7.5, adding 350.0g of deionized water to dilute, and emulsifying at the stirring speed of 1000rpm for 0.5 hour to obtain 900g of water-soluble ultraviolet-cured matte hyperbranched polyurethane acrylic resin with the solid content of about 60 percent.
Example 4
1,6-hexamethylene diisocyanate (0.15mol, 25.2g), polypropylene glycol having a molecular weight of 20000g/mol (0.01mol, 200.0g), dimethylolpropionic acid (0.1mol, 13.4g), sodium N, N-bis (2-hydroxypropyl) -2-aminoethanesulfonate (0.02mol, 5.26g) and 0.025g of stannous octoate were added to a reaction flask, and reacted with stirring at 60 ℃ for 1.5 hours; then, hydroxypropyl methacrylate (0.02mol, 2.88g) containing p-hydroxyanisole as a polymerization inhibitor in an amount of about 0.1wt% was added to the reaction flask, and the mixture was stirred at 80 ℃ for reaction for 1.5 hours; then adding 0.01mol (115.0 g) of hydroxyl-terminated hyperbranched polyester HyPer H304, 0.005mol (3.0 g) of hydroxyl-terminated hyperbranched polyester HyPer H201, 0.005mol (6.0 g) of hydroxyl-terminated hyperbranched polyester HyPer H202 and 0.02mol (50.0 g) of hydroxyl-terminated hyperbranched polyester HyPer H302 into a reaction bottle, and stirring and reacting for about 2 hours at 90 ℃ until isocyanate groups are completely reacted to obtain the ultraviolet-cured hyperbranched polyurethane; and cooling to 50 ℃, adding 45.0g of reactive diluent pentaerythritol triacrylate, adding triethylamine to neutralize until the pH value is 7.2, adding 400.0g of deionized water to dilute, and emulsifying at the stirring speed of 800rpm for 1.0 hour to obtain 800g of water-soluble ultraviolet-cured matte hyperbranched polyurethane acrylic resin with the solid content of about 50%.
Example 5
Dicyclohexylmethane diisocyanate (0.15mol, 39.3g), xylylene diisocyanate (0.03mol, 5.64g), polyethylene glycol having a molecular weight of 2000g/mol (0.01mol, 20.0g), polyethylene glycol having a molecular weight of 1000g/mol (0.02mol, 20.0g), dimethylolpropionic acid (0.12mol, 16.08g), ethylenediamine ethanesulfonic acid sodium (0.01mol, 1.90g), 1,2-dihydroxy-3-propanesulfonic acid sodium (0.01mol, 1.78g) and 0.045g dibutyltin diacetate were added to a reaction flask, and stirred and reacted at 65 ℃ for 1.5 hours; then, 2-hydroxybutyl methacrylate (0.005mol, 0.79g) and 4-hydroxybutyl acrylate (0.005mol, 0.72g) containing p-hydroxyanisole as a polymerization inhibitor in an amount of about 0.1wt% were added to the reaction flask, and the mixture was stirred at 75 ℃ for 2 hours; then adding 0.003mol (11.1 g) of hydroxyl-terminated hyperbranched polyester HyPer H402, 0.002mol (16.8 g) of hydroxyl-terminated hyperbranched polyester HyPer H403, 0.002mol (5.2 g) of hydroxyl-terminated hyperbranched polyester HyPer H203 and 0.003mol (2.76 g) of hydroxyl-terminated hyperbranched polyester HyPer H301 into a reaction bottle, and stirring and reacting for about 3.5 hours at 80 ℃ until isocyanate groups react completely to obtain the ultraviolet-cured hyperbranched polyurethane; and cooling to 40 ℃, adding 10.0g of reactive diluent pentaerythritol triacrylate and 15.0g of trimethylolpropane triacrylate, adding ammonia water to neutralize until the pH value is 7.0, adding 130.0g of deionized water, and emulsifying for 1.5 hours at the stirring speed of 700rpm to obtain 300g of water-soluble ultraviolet-cured matte hyperbranched polyurethane acrylic resin with the solid content of about 55 percent.
Example 6
Dicyclohexylmethane diisocyanate (0.15mol, 39.3g), lysine diisocyanate (0.03mol, 6.36g), polyethylene glycol (0.01mol, 20.0g) having a molecular weight of 2000g/mol, polytetrahydrofuran (0.02mol, 20.0g) having a molecular weight of 1000g/mol, dimethylolpropionic acid (0.12mol, 16.08g), sodium N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonate (0.02mol, 4.70g) and 0.045g of dibutyltin diacetate were added to a reaction flask, and the reaction was stirred at 65 ℃ for 1.5 hours; 2-hydroxybutyl methacrylate (0.01mol, 1.58g) containing p-hydroxyanisole in an amount of about 0.1wt% as a polymerization inhibitor was added to the reaction flask, and the mixture was stirred at 75 ℃ for 2 hours; then adding 0.003mol (25.2 g) of hydroxyl-terminated hyperbranched polyester HyPer H403, 0.004mol (10.0 g) of hydroxyl-terminated hyperbranched polyester HyPer H302 and 0.003mol (4.2 g) of hydroxyl-terminated hyperbranched polyester HyPer H401 into a reaction bottle, and stirring and reacting for about 3.5 hours at the temperature of 80 ℃ until isocyanate groups react completely to obtain the ultraviolet curing hyperbranched polyurethane; and cooling to 40 ℃, adding 20.0g of active diluent trimethylolpropane triacrylate, adding ammonia water to neutralize until the pH value is 7.0, adding 120.0g of deionized water, and emulsifying at the stirring speed of 700rpm for 1.5 hours to obtain 300g of water-soluble ultraviolet-cured matte hyperbranched polyurethane acrylic resin with the solid content of about 60%.
The particle size of the water-soluble ultraviolet-curable matte hyperbranched polyurethane acrylic resin was measured by a malvern particle sizer, and the centrifugal stability rating thereof was measured in the references Zhang Daohong, zhou Jiliang, liu Na, preparation of water-soluble bisphenol a epoxy resin emulsion, adhesion, 2008,2,30, and the results are shown in table 2. 1.0wt% of photoinitiator 1173 is added into the products prepared in examples 1-6, and the ultraviolet curing film is irradiated for about 3 minutes by a 800W mercury lamp, and the pencil hardness, the glossiness, the adhesion and the volume shrinkage rate of the ultraviolet curing film are tested according to national standards GB/T26704-2011, GB/T9754-2007, GB/T9286-2021 and GB/T24148.9-2014.
TABLE 2 Properties and Properties of water-soluble UV-curable matte hyperbranched polyurethane acrylic resin
As can be seen from table 2, the water-soluble ultraviolet-curable matte hyperbranched polyurethane acrylic resin prepared by the present invention has excellent stability, high hardness, strong adhesion, high gloss, and low volume shrinkage, and as can be seen from the particle size distribution diagram (fig. 1) of the water-soluble ultraviolet-curable matte hyperbranched polyurethane acrylic resin prepared in example 5, the particle size distribution is an obvious bimodal distribution, which is beneficial to producing a matte effect.
Claims (10)
1. A preparation method of water-soluble ultraviolet-curing matte hyperbranched polyurethane acrylic resin comprises the following specific steps:
(1) Adding diisocyanate, polyether diol, dimethylolpropionic acid, a bifunctional reactive emulsifier and a catalyst into a reaction bottle, and stirring and reacting for 1-3 hours at the temperature of 40-80 ℃ to obtain an oligomer with isocyanate groups at two ends;
(2) Adding hydroxyalkyl (meth) acrylate containing 0.1wt% of polymerization inhibitor p-hydroxyanisole into a reaction bottle, and stirring and reacting for 1-3 hours at 50-90 ℃ to obtain an oligomer with one end of isocyanate group and one end of acrylate group;
(3) Adding two hydroxyl-terminated hyperbranched polyesters with different molecular weights into a reaction bottle, and stirring and reacting for 2-4 hours at 50-90 ℃ until isocyanate groups react completely to obtain ultraviolet-cured hyperbranched polyurethane;
(4) Cooling to 30-50 ℃, adding an active diluent, adding an amine neutralizer to neutralize until the pH value is 6.8-7.5, adding deionized water, and emulsifying for 0.5-2 hours under the condition that the stirring speed is 500-1000rpm to obtain the water-soluble ultraviolet-cured matte hyperbranched polyurethane acrylic resin with the solid content of 40-60%;
the hydroxyalkyl (meth) acrylate is a hydroxyalkyl acrylate and/or a hydroxyalkyl methacrylate.
2. The method of claim 1, wherein: the catalyst is one or more of dibutyltin dilaurate, dibutyltin didodecyl sulfide, dibutyltin diacetate and stannous octoate, and the using amount of the catalyst is 0.05-0.5% of the total mass of diisocyanate.
3. The method of claim 1, wherein: the mole ratio of the diisocyanate, the polyether diol, the dimethylolpropionic acid, the bifunctional reactive emulsifier, the (methyl) acrylic acid hydroxyalkyl ester and the hydroxyl-terminated hyperbranched polyester is (1.0-2.0): (0.1-0.5): (0.5-1.2): (0.1-0.5): (0.01-0.6): (0.01-0.6), wherein the two hydroxyl-terminated hyperbranched polyesters with different molecular weights are high-molecular-weight hydroxyl-terminated hyperbranched polyester and low-molecular-weight hydroxyl-terminated hyperbranched polyester, and the molar ratio of the high-molecular-weight hydroxyl-terminated hyperbranched polyester to the low-molecular-weight hydroxyl-terminated hyperbranched polyester is 1.0: (0.2-4.0).
4. The method of claim 1, wherein: the diisocyanate is one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 1,6-Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (HMDI), lysine Diisocyanate (LDI) and Xylylene Diisocyanate (XDI).
5. The production method according to claim 1, characterized in that: the polyether diol is one or more of polytetrahydrofuran, polypropylene glycol and polyethylene glycol, and the number average molecular weight of the polyether diol is 400-20000g/mol.
6. The method of claim 1, wherein: the bifunctionality reaction type emulsifier is one or more of 1,2-dihydroxy-3-propane sodium sulfonate, ethylenediamine ethanesodium sulfonate, N-bis (2-hydroxyethyl) -2-aminoethyl sodium sulfonate and 1,2-dihydroxy anthraquinone-3-sodium sulfonate.
7. The method of claim 1, wherein: the hydroxyalkyl (meth) acrylate is one or more of hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), hydroxyethyl methacrylate (HEMA), hydroxypropyl methacrylate (HPMA), 4-hydroxybutyl acrylate (HBA) and 2-hydroxybutyl methacrylate (HBMA).
8. The method of claim 1, wherein: the hydroxyl-terminated hyperbranched polyester is one or more of HyPer H101, hyPer H102, hyPer H103, hyPer H104, hyPer H201, hyPer H202, hyPer H203, hyPer H204, hyPer H301, hyPer H302, hyPer H303, hyPer H304, hyPer H401, hyPer H402 and HyPer H403 of Wuhan hyperbranched resin science and technology Limited, the number-average molecular weight of the hydroxyl-terminated hyperbranched polyester is 500-11500 g/mol, and the hydroxyl value is 160-670 mgKOH/g; among the hydroxyl-terminated hyperbranched polyesters, hyPer H104, hyPer H204, hyPer H303, hyPer H304, hyPer H402 and HyPer H403 are high molecular weight hydroxyl-terminated hyperbranched polyesters, and the others are low molecular weight hydroxyl-terminated hyperbranched polyesters.
9. The method of claim 1, wherein: the reactive diluent is one or more of (methyl) acrylic ester with more than three functionality degrees, and the using amount of the reactive diluent is 5-20% of the total mass of the emulsion.
10. The method of claim 1, wherein: the amine neutralizer is one or more of triethanolamine, diethanolamine, methyldiethanolamine, N-dimethylethanolamine, triethylamine and ammonia water.
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