CN115433338B - Preparation method of water-soluble ultraviolet light curing matte hyperbranched polyurethane acrylic resin - Google Patents
Preparation method of water-soluble ultraviolet light curing matte hyperbranched polyurethane acrylic resin Download PDFInfo
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- CN115433338B CN115433338B CN202211216517.5A CN202211216517A CN115433338B CN 115433338 B CN115433338 B CN 115433338B CN 202211216517 A CN202211216517 A CN 202211216517A CN 115433338 B CN115433338 B CN 115433338B
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- water
- ultraviolet light
- hydroxyl
- hyperbranched
- soluble
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 56
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 56
- 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 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003085 diluting agent Substances 0.000 claims abstract description 12
- 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 10
- 230000001804 emulsifying effect Effects 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
- 238000003756 stirring Methods 0.000 claims description 23
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 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
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 6
- 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 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 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
- 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 4
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- UZMKOEWHQQPOBJ-UHFFFAOYSA-M sodium;2,3-dihydroxypropane-1-sulfonate Chemical compound [Na+].OCC(O)CS([O-])(=O)=O UZMKOEWHQQPOBJ-UHFFFAOYSA-M 0.000 claims description 4
- 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 description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003995 emulsifying agent Substances 0.000 abstract description 8
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 6
- 125000005442 diisocyanate group Chemical group 0.000 abstract description 6
- 229920000570 polyether Polymers 0.000 abstract description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract description 5
- 239000003973 paint Substances 0.000 abstract description 5
- 150000001412 amines Chemical class 0.000 abstract description 3
- 239000012948 isocyanate Substances 0.000 abstract description 3
- 150000002513 isocyanates Chemical group 0.000 abstract description 3
- 238000007865 diluting Methods 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 35
- 239000000203 mixture Substances 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- -1 hydroxyalkyl (methyl) acrylate Chemical compound 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 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 description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 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 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000011527 polyurethane coating Substances 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 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
- 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000005057 Hexamethylene diisocyanate 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
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 description 1
- QILXPCHTWXAUHE-UHFFFAOYSA-N [Na].NCCN Chemical compound [Na].NCCN QILXPCHTWXAUHE-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- NVJMGQMXNBBZIU-UHFFFAOYSA-N dibutyltin;1-dodecylsulfanyldodecane Chemical compound CCCC[Sn]CCCC.CCCCCCCCCCCCSCCCCCCCCCCCC NVJMGQMXNBBZIU-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001879 gelation Methods 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
- 239000003999 initiator Substances 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 230000010399 physical interaction Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- KCLIFOXATBWLMW-UHFFFAOYSA-M sodium;ethane-1,2-diamine;ethanesulfonate Chemical compound [Na+].NCCN.CCS([O-])(=O)=O KCLIFOXATBWLMW-UHFFFAOYSA-M 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—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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- 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
- C08G18/30—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
-
- 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
- C08G18/4009—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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- 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
- C08G18/4202—Two or more polyesters of different physical or chemical nature
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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
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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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
- C08G18/67—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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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Engineering & Computer Science (AREA)
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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 light curing matte hyperbranched polyurethane acrylic resin. The preparation process comprises the following steps: (1) The diisocyanate, polyether glycol, dimethylolpropionic acid and a difunctional reactive emulsifier are subjected to chemical reaction to synthesize an isocyanate group-terminated oligomer; (2) Sequentially reacting with (methyl) hydroxyl alkyl acrylate and hydroxyl-terminated hyperbranched polyesters with different molecular weights to obtain ultraviolet light cured hyperbranched polyurethane; (3) Adding an active diluent, neutralizing by amine, emulsifying and diluting by deionized water to obtain the water-soluble ultraviolet light 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, dilutability in water, excellent stability, excellent performance and the like, and is expected to be widely applied in the fields of water-soluble matte paint 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 light curing matte hyperbranched polyurethane acrylic resin.
Background
Water-soluble polyurethanes are novel polyurethane systems which are water-dispersible, also known as water-dispersible polyurethanes, aqueous polyurethanes or water-based polyurethanes. The water-soluble polyurethane uses 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 paint is an environment-friendly paint which is prepared by taking water-soluble polyurethane resin as a base material and assisting other auxiliary agents, is widely used in the fields of surface coating, painting and the like, and the mechanical properties such as pencil hardness, adhesive force and the like of the obtained coating are not high due to low crosslinking density, and the crosslinking density of the water-soluble polyurethane paint modified by crosslinking can be improved, so that the water-soluble polyurethane paint has good storage stability, high mechanical property, high water resistance, excellent solvent resistance and ageing resistance, and can be used in the field of advanced coating materials. The means of crosslinking modification (acrylic acid, epoxy and the like) determines the curing form (thermocuring and photocuring) of the water-soluble polyurethane, finally influences the curing efficiency and the application field of the product, and compared with the thermocrosslinking curing, the ultraviolet curing has the excellent characteristics of high curing speed, short curing time, high efficiency, no pollution, uniform film performance and the like, and has become an important development direction of the water-soluble polyurethane coating.
Hyperbranched polymers have ellipsoidal topological structures, exhibit excellent rheological properties, low viscosity, high activity and the like, and have become a hot spot for research in the field of high polymer materials in recent years. The traditional linear polyurethane is designed into the polyurethane with the hyperbranched topological structure, so that the polyurethane has the excellent performance of the traditional polyurethane, has the excellent properties of the hyperbranched topological structure, such as a large number of active groups at the tail end, 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 a trihydroxy compound as main raw materials, the activity of three hydroxyl groups of the trihydroxy compound is similar, the water-soluble polyurethane is easy to gel in the synthesis process, the hyperbranched polyurethane with stable performance is difficult to synthesize, and the difficulty and industrialization of subsequent water-soluble modification and ultraviolet curing modification are increased; in addition, the emulsification is mainly carried out by adding an emulsifying agent, and the emulsifying agent only has physical interaction during curing, so that the mechanical property, hydrolysis resistance and solvent resistance of the product are not high. If a matte coating is to be prepared, another component, such as a matte filler, is generally required to be added, and the prepared water-soluble polyurethane resin is difficult to simultaneously exhibit the characteristics of the matte coating.
In order to solve the problems, the synthesis technology of ultraviolet light curing matte water-soluble polyurethane which has simple development process, no pollution, low cost, stable product and excellent mechanical property and can be applied industrially and in large scale is a fundamental way for solving the problems existing 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 light curing matte hyperbranched polyurethane acrylic resin.
The invention solves the technical problems with the following technical proposal:
the preparation method of the water-soluble ultraviolet light curing matte hyperbranched polyurethane acrylic resin comprises the following specific processes:
(1) Adding diisocyanate, polyether glycol, dimethylolpropionic acid, a difunctional reactive emulsifier and a catalyst into a reaction bottle, and stirring and reacting for 1-3 hours at 40-80 ℃ to obtain an oligomer with isocyanate groups at two ends;
(2) Adding hydroxyalkyl (methyl) 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 the isocyanate groups react completely, and obtaining the ultraviolet light curing hyperbranched polyurethane, wherein the synthetic principle reaction formula is as follows:
Reactive ultraviolet light curing hyperbranched polyurethane containing emulsifier
(4) Cooling to 30-50 ℃, adding an active diluent into the mixture, adding an amine neutralizer into the mixture to neutralize the mixture to a pH value of 6.8-7.5, adding deionized water into the mixture, and emulsifying the mixture for 0.5-2 hours under the condition that the stirring speed is 500-1000rpm to obtain the water-soluble ultraviolet light curing matte hyperbranched polyurethane acrylic resin with the solid content of 40-60%;
The (methyl) acrylic acid hydroxyalkyl ester is acrylic acid hydroxyalkyl ester and/or methacrylic acid hydroxyalkyl ester.
Further, the catalyst is one or more of dibutyl tin dilaurate, dibutyl tin diacetate and stannous octoate, and the dosage is 0.05-0.5% of the total mass of diisocyanate, preferably 0.05-0.2%.
Further, the molar ratio of diisocyanate, polyether glycol, dimethylolpropionic acid, difunctional reactive emulsifier, hydroxyalkyl (meth) acrylate and 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 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).
Further, the polyether glycol is one or more of commercial polytetrahydrofuran, polypropylene glycol and polyethylene glycol, and the number average molecular weight of the polyether glycol is 400-20000g/mol.
Further, the difunctional reactive emulsifier is one or more of sodium 1, 2-dihydroxy-3-propane sulfonate, sodium ethylenediamine ethanesulfonate, sodium N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonate and sodium N, N-bis (2-hydroxypropyl) -2-aminoethanesulfonate.
Still 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), 2-hydroxybutyl methacrylate (HBMA).
Further, 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 H of Wuhan hyperbranched resin science and technology Co., ltd, the hydroxyl-terminated hyperbranched polyester has a number average molecular weight of 500-11500 g/mol and a hydroxyl value of 160-670 mgKOH/g; among them, the high molecular weight hydroxyl-terminated hyperbranched polyesters are HyPer H, hyPer H, 204, hyPer H, 303, hyPer H, hyPer H, 402 and HyPer H, 403, and the others are low molecular weight hydroxyl-terminated hyperbranched polyesters. Their properties are shown in Table 1.
TABLE 1 Properties of hydroxyl terminated hyperbranched polyesters
Further, the reactive diluent is one or more of (methyl) acrylic ester with three functionalities and above, and the dosage is 2-20% of the total mass of the final water-soluble ultraviolet light curing matte hyperbranched polyurethane acrylic resin.
Still 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 product in the prior art, the water-soluble ultraviolet light curing matte hyperbranched polyurethane acrylic resin prepared by the invention has the following advantages:
(1) Firstly synthesizing an oligomer of isocyanate, and then modifying by using hydroxyl-terminated hyperbranched polyester, wherein the whole process does not involve the reaction between polyfunctional groups, so that the gelation 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, and the prepared hyperbranched polyurethane has low viscosity, small particle size and high solid content, does not use an organic solvent in the reaction process, can reduce the pollution of the organic solvent in the traditional coating, reduces the complicated process of removing the organic solvent, and reduces the production cost;
(3) The hyperbranched topological structure can effectively improve the leveling property of the coating, and the thin coating can be prepared under the condition of no addition of an organic solvent;
(4) In the system, the polyfunctional reactive diluent can be crosslinked with (methyl) acrylate groups on the surface of 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 solidification, 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, prepares two water-soluble polyurethane coatings with larger particle size difference by a simple one-pot method, realizes the matte function of the coating, and has higher stability and simpler method than the coating prepared by the traditional technology of externally adding matte agents and the like;
(7) The advantages of the coating prepared by the invention such as hyperbranched topological structure, ultraviolet curing and matte are integrated, and are not reported in the literature;
(8) The process is simple, the emulsifying rotating speed is low, the performance is excellent, and the method is favorable for industrial application.
Drawings
Fig. 1 is a particle size distribution diagram of a water-soluble uv-curable matte hyperbranched polyurethane acrylic resin prepared in example 5.
Detailed Description
The following is a further description of embodiments of the invention, in conjunction with examples. The description of these embodiments is provided to assist understanding of the present invention, but is not intended to limit the present invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
In all of the following examples:
the hydroxyl-terminated hyperbranched polyesters used were all purchased from the chemical company of the martial arts, 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 (0.1 mol,17.4 g), polyethylene glycol having a molecular weight of 400g/mol (0.03 mol,12.0 g), dimethylolpropionic acid (0.05 mol,6.7 g), sodium 1, 2-dihydroxy-3-propanesulfonate (0.01 mol,1.78 g) and 0.02g dibutyltin dilaurate were added to a reaction flask and reacted under stirring at 40℃for 3 hours; then, hydroxyethyl acrylate (0.01 mol,1.16 g) containing about 0.1wt% of a polymerization inhibitor p-hydroxyanisole 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 H and 0.002mol (1.0 g) of hydroxyl-terminated hyperbranched polyester HyPer H101 into a reaction bottle, stirring and reacting for about 4 hours at 50 ℃ until the isocyanate groups react completely, thus obtaining ultraviolet curing hyperbranched polyurethane; cooling to 30 ℃, adding 5.0g of trimethylolpropane triacrylate serving as an active diluent, 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 of stirring speed of 500rpm to obtain 180g of water-soluble ultraviolet light curing matte hyperbranched polyurethane acrylic resin with the solid content of about 50%.
Example 2
Diphenylmethane diisocyanate (0.2 mol,50.0 g), polytetrahydrofuran (0.05 mol,50.0 g) having a molecular weight of 1000g/mol, dimethylolpropionic acid (0.12 mol,16.08 g), sodium ethylenediamine-based ethanesulfonate (0.02 mol,3.80 g) and 0.025g of dibutyltin dilauryl sulfide were charged into a reaction flask, and reacted under stirring at 60℃for 2 hours; then, hydroxypropyl acrylate (0.01 mol,1.30 g) containing about 0.1wt% of the polymerization inhibitor p-hydroxyanisole was added to the reaction flask, and the mixture was stirred at 70℃for 2 hours; then adding 0.002mol (10.8 g) of hydroxyl-terminated hyperbranched polyester HyPer H and 0.008mol (8.8 g) of hydroxyl-terminated hyperbranched polyester HyPer H to a reaction bottle, stirring and reacting for about 3 hours at 70 ℃ until the isocyanate groups are reacted completely, thus obtaining ultraviolet curing hyperbranched polyurethane; cooling to 40 ℃, adding 48.0g of active diluent pentaerythritol triacrylate, adding methyl diethanolamine to neutralize to pH value of 7.0, adding 300.0g of deionized water to dilute, and emulsifying for 1 hour under the condition of stirring speed of 700rpm to obtain 500g of water-soluble ultraviolet light curing matte hyperbranched polyurethane acrylic resin with solid content of about 40%.
Example 3
Isophorone diisocyanate (0.18 mol,40.0 g), polyethylene glycol with a molecular weight of 6000g/mol (0.01 mol,60.0 g), dimethylolpropionic acid (0.06 mol,8.04 g), sodium N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonate (0.05 mol,11.75 g) and 0.025g dibutyltin diacetate were added to a reaction flask, and stirred at 80℃for 1 hour; then, hydroxyethyl methacrylate (0.06 mol,7.80 g) containing about 0.1wt% of the polymerization inhibitor p-hydroxyanisole was added to the reaction flask, and the mixture was stirred at 90℃for 1 hour; then adding 0.05mol (275.0 g) of hydroxyl-terminated hyperbranched polyester HyPer H and 0.01mol (24.0 g) of hydroxyl-terminated hyperbranched polyester HyPer H and 103 into a reaction bottle, stirring and reacting for about 2 hours at 90 ℃ until the isocyanate groups react completely, thus obtaining ultraviolet curing hyperbranched polyurethane; cooling to 50 ℃, adding 100.0g of active diluent pentaerythritol triacrylate, adding N, N-dimethylethanolamine to neutralize to pH value of 7.5, adding 350.0g of deionized water to dilute, and emulsifying for 0.5 hours under the condition of stirring speed of 1000rpm to obtain 900g of water-soluble ultraviolet light curing matte hyperbranched polyurethane acrylic resin with solid content of about 60%.
Example 4
1, 6-Hexamethylene diisocyanate (0.15 mol,25.2 g), polypropylene glycol (0.01 mol,200.0 g) with a molecular weight of 20000g/mol, dimethylolpropionic acid (0.1 mol,13.4 g), sodium N, N-bis (2-hydroxypropyl) -2-aminoethanesulfonate (0.02 mol,5.26 g) and 0.025g stannous octoate were added to the reaction flask, and the mixture was stirred at 60℃for 1.5 hours; subsequently, hydroxypropyl methacrylate (0.02 mol,2.88 g) containing about 0.1wt% of p-hydroxyanisole as a polymerization inhibitor was added to the reaction flask, and the mixture was stirred at 80℃for 1.5 hours; then adding 0.01mol (115.0 g) of hydroxyl-terminated hyperbranched polyester HyPer H304,304, 0.005mol (3.0 g) of hydroxyl-terminated hyperbranched polyester HyPer H201,201, 0.005mol (6.0 g) of hydroxyl-terminated hyperbranched polyester HyPer H202,202 and 0.02mol (50.0 g) of hydroxyl-terminated hyperbranched polyester HyPer H302,302 into a reaction bottle, stirring and reacting for about 2 hours at 90 ℃ until the isocyanate groups are reacted completely, thus obtaining ultraviolet light cured hyperbranched polyurethane; cooling to 50 ℃, adding 45.0g of active diluent pentaerythritol triacrylate, adding triethylamine to neutralize to pH value of 7.2, adding 400.0g of deionized water to dilute, and emulsifying for 1.0 hour under the condition of stirring speed of 800rpm to obtain 800g of water-soluble ultraviolet light curing matte hyperbranched polyurethane acrylic resin with solid content of about 50%.
Example 5
Dicyclohexylmethane diisocyanate (0.15 mol,39.3 g), xylylene diisocyanate (0.03 mol,5.64 g), polyethylene glycol having a molecular weight of 2000g/mol (0.01 mol,20.0 g), polyethylene glycol having a molecular weight of 1000g/mol (0.02 mol,20.0 g), dimethylolpropionic acid (0.12 mol,16.08 g), sodium ethylenediamine-ethanesulfonate (0.01 mol,1.90 g), sodium 1, 2-dihydroxy-3-propanesulfonate (0.01 mol,1.78 g) and dibutyltin diacetate (0.045 g) were added to a reaction flask, and the mixture was stirred at 65℃for 1.5 hours; then, 2-hydroxybutyl methacrylate (0.005 mol,0.79 g) containing about 0.1wt% of p-hydroxyanisole as a polymerization inhibitor and 4-hydroxybutyl acrylate (0.005 mol,0.72 g) were added to the reaction flask, and reacted under stirring at 75℃for 2 hours; then adding 0.003mol (11.1 g) of hydroxyl-terminated hyperbranched polyester HyPer H402,402, 0.002mol (16.8 g) of hydroxyl-terminated hyperbranched polyester HyPer H403,403, 0.002mol (5.2 g) of hydroxyl-terminated hyperbranched polyester HyPer H203,203 and 0.003mol (2.76 g) of hydroxyl-terminated hyperbranched polyester HyPer H301,301 into a reaction bottle, stirring and reacting at 80 ℃ for about 3.5 hours until the isocyanate groups are reacted completely, thus obtaining ultraviolet light cured hyperbranched polyurethane; cooling to 40 ℃, adding 10.0g of active diluent pentaerythritol triacrylate and 15.0g of trimethylolpropane triacrylate, adding ammonia water to neutralize to pH value of 7.0, adding 130.0g of deionized water, and emulsifying for 1.5 hours under the condition of stirring speed of 700rpm to obtain 300g of water-soluble ultraviolet light curing matte hyperbranched polyurethane acrylic resin with solid content of about 55%.
Example 6
Dicyclohexylmethane diisocyanate (0.15 mol,39.3 g), lysine diisocyanate (0.03 mol,6.36 g), polyethylene glycol having a molecular weight of 2000g/mol (0.01 mol,20.0 g), polytetrahydrofuran having a molecular weight of 1000g/mol (0.02 mol,20.0 g), dimethylolpropionic acid (0.12 mol,16.08 g), sodium N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonate (0.02 mol,4.70 g) and dibutyltin diacetate were added to a reaction flask, and reacted under stirring at 65℃for 1.5 hours; then, 2-hydroxybutyl methacrylate (0.01 mol,1.58 g) containing about 0.1wt% of p-hydroxyanisole 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 H and 0.003mol (4.2 g) of hydroxyl-terminated hyperbranched polyester HyPer H401 into a reaction bottle, stirring and reacting at 80 ℃ for about 3.5 hours until the isocyanate groups are reacted completely, and obtaining ultraviolet light curing hyperbranched polyurethane; cooling to 40 ℃, adding 20.0g of trimethylolpropane triacrylate serving as an active diluent, adding ammonia water to neutralize to a pH value of 7.0, adding 120.0g of deionized water, and emulsifying for 1.5 hours under the condition of a stirring rate of 700rpm to obtain 300g of water-soluble ultraviolet light curing matte hyperbranched polyurethane acrylic resin with a solid content of about 60%.
The particle size of the water-soluble ultraviolet light curing matte hyperbranched polyurethane acrylic resin was tested by a Markov particle sizer, and the test of the centrifugal stability grade of the resin is described in reference Zhang Daohong, zhou Jiliang and Liu Na, the preparation, bonding and 2008,2,30 of the water-soluble bisphenol A type epoxy resin emulsion are shown in the table 2. The photo-initiator 1173 accounting for 1.0wt% of the mass of the products prepared in the examples 1 to 6 is respectively added, and then the ultraviolet curing film is irradiated for 3 minutes at a mercury lamp of 800W, and the pencil hardness, the glossiness, the adhesive force and the volume shrinkage rate of the ultraviolet curing film are respectively tested according to the national standards GB/T26704-2011, GB/T9754-2007, GB/T9286-2021 and GB/T24148.9-2014.
Table 2 properties and performance of water-soluble uv-curable matte hyperbranched polyurethane acrylic resin
As can be seen from Table 2, the water-soluble ultraviolet light curing matte hyperbranched polyurethane acrylic resin prepared by the invention has excellent stability, high hardness, strong adhesive force, high glossiness and low volume shrinkage, and the particle size distribution diagram (figure 1) of the water-soluble ultraviolet light curing matte hyperbranched polyurethane acrylic resin prepared by the invention is a remarkable bimodal distribution, which is beneficial to generating a matte effect.
Claims (1)
1. The preparation method of the water-soluble ultraviolet light curing matte hyperbranched polyurethane acrylic resin is characterized by comprising the following steps of:
0.15mol of dicyclohexylmethane diisocyanate, 0.03mol of xylylene diisocyanate, 0.01mol of polyethylene glycol with a molecular weight of 2000g/mol, 0.02mol of polyethylene glycol with a molecular weight of 1000g/mol, 0.12mol of dimethylolpropionic acid, 0.01mol of sodium ethylenediamine-ethanesulfonate, 0.01mol of sodium 1, 2-dihydroxy-3-propanesulfonate and 0.045g of dibutyltin diacetate are added into a reaction flask, and stirred at 65 ℃ for reaction for 1.5 hours; then adding 0.005mol of 2-hydroxybutyl methacrylate containing about 0.1wt% of p-hydroxyanisole inhibitor and 0.005mol of 4-hydroxybutyl acrylate into a reaction bottle, and stirring and reacting for 2 hours at 75 ℃; then adding 0.003mol of hydroxyl-terminated hyperbranched polyester HyPer H to 402, 0.002mol of hydroxyl-terminated hyperbranched polyester HyPer H to 403, 0.002mol of hydroxyl-terminated hyperbranched polyester HyPer H to 203 and 0.003mol of hydroxyl-terminated hyperbranched polyester HyPer H to 301 into a reaction bottle, stirring and reacting at 80 ℃ for about 3.5 hours until the isocyanate groups react completely, and obtaining ultraviolet light curing hyperbranched polyurethane; cooling to 40 ℃, adding 10.0g of active diluent pentaerythritol triacrylate and 15.0g of trimethylolpropane triacrylate, adding ammonia water to neutralize to pH value of 7.0, adding 130.0g of deionized water, and emulsifying for 1.5 hours under the condition of stirring speed of 700rpm to obtain the water-soluble ultraviolet light curing matte hyperbranched polyurethane acrylic resin with solid content of about 55%.
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| CN110078868A (en) * | 2019-05-08 | 2019-08-02 | 广东伟明涂料有限公司 | A kind of synthetic method of silane-modified water-borne polyurethane-acrylate resin |
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| CN107266654A (en) * | 2017-06-16 | 2017-10-20 | 徐州佑季化工材料有限公司 | A kind of ultraviolet light solidification hyper-branched polyester polyurethane acrylate resin and preparation method thereof |
| CN110078868A (en) * | 2019-05-08 | 2019-08-02 | 广东伟明涂料有限公司 | A kind of synthetic method of silane-modified water-borne polyurethane-acrylate resin |
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