CN115926041B - Hydroxyl water dispersion with network crosslinked structure and preparation method thereof - Google Patents
Hydroxyl water dispersion with network crosslinked structure and preparation method thereof Download PDFInfo
- Publication number
- CN115926041B CN115926041B CN202211252080.0A CN202211252080A CN115926041B CN 115926041 B CN115926041 B CN 115926041B CN 202211252080 A CN202211252080 A CN 202211252080A CN 115926041 B CN115926041 B CN 115926041B
- Authority
- CN
- China
- Prior art keywords
- parts
- hydroxyl
- reaction
- formula amount
- methacrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000006185 dispersion Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 114
- 238000004132 cross linking Methods 0.000 claims abstract description 70
- 239000003999 initiator Substances 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 4
- 238000010790 dilution Methods 0.000 claims abstract description 3
- 239000012895 dilution Substances 0.000 claims abstract description 3
- 150000003254 radicals Chemical class 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 127
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 66
- 238000003756 stirring Methods 0.000 claims description 54
- 229910052757 nitrogen Inorganic materials 0.000 claims description 33
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 238000004321 preservation Methods 0.000 claims description 22
- 239000004593 Epoxy Substances 0.000 claims description 21
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 19
- 229920002554 vinyl polymer Polymers 0.000 claims description 19
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- -1 hydroxyl compound Chemical class 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 10
- 230000003472 neutralizing effect Effects 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000012544 monitoring process Methods 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-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 4
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 4
- WQPMYSHJKXVTME-UHFFFAOYSA-N 3-hydroxypropane-1-sulfonic acid Chemical compound OCCCS(O)(=O)=O WQPMYSHJKXVTME-UHFFFAOYSA-N 0.000 claims description 3
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 3
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims description 3
- XFOFBPRPOAWWPA-UHFFFAOYSA-N 6-hydroxyhexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCO XFOFBPRPOAWWPA-UHFFFAOYSA-N 0.000 claims description 3
- OCIFJWVZZUDMRL-UHFFFAOYSA-N 6-hydroxyhexyl prop-2-enoate Chemical compound OCCCCCCOC(=O)C=C OCIFJWVZZUDMRL-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 3
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims description 3
- 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 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 2
- 239000003973 paint Substances 0.000 abstract description 17
- 239000012948 isocyanate Substances 0.000 abstract description 8
- 150000002513 isocyanates Chemical class 0.000 abstract description 8
- 238000001035 drying Methods 0.000 abstract description 6
- 230000036632 reaction speed Effects 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 15
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 4
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NCXUNZWLEYGQAH-UHFFFAOYSA-N 1-(dimethylamino)propan-2-ol Chemical compound CC(O)CN(C)C NCXUNZWLEYGQAH-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- ZUAURMBNZUCEAF-UHFFFAOYSA-N 2-(2-phenoxyethoxy)ethanol Chemical compound OCCOCCOC1=CC=CC=C1 ZUAURMBNZUCEAF-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 description 1
- RFSCGDQQLKVJEJ-UHFFFAOYSA-N 2-methylbutan-2-yl benzenecarboperoxoate Chemical compound CCC(C)(C)OOC(=O)C1=CC=CC=C1 RFSCGDQQLKVJEJ-UHFFFAOYSA-N 0.000 description 1
- FSGAMPVWQZPGJF-UHFFFAOYSA-N 2-methylbutan-2-yl ethaneperoxoate Chemical compound CCC(C)(C)OOC(C)=O FSGAMPVWQZPGJF-UHFFFAOYSA-N 0.000 description 1
- XYFRHHAYSXIKGH-UHFFFAOYSA-N 3-(5-methoxy-2-methoxycarbonyl-1h-indol-3-yl)prop-2-enoic acid Chemical compound C1=C(OC)C=C2C(C=CC(O)=O)=C(C(=O)OC)NC2=C1 XYFRHHAYSXIKGH-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the technical field of coatings, in particular to a hydroxyl water dispersion with a network crosslinking structure and a preparation method thereof. The solvent of the hydroxyl aqueous dispersion is a large amount of water, so that the reaction speed of crosslinking and curing of the hydroxyl aqueous dispersion and the isocyanate curing agent is reduced, and the surface drying speed of a paint film is reduced. In order to solve the problems, the invention provides a hydroxyl water dispersion with a network crosslinking structure, which is obtained by carrying out free radical copolymerization reaction on a self-crosslinking monomer containing at least two double bonds, an ethylenically unsaturated monomer I, an ethylenically unsaturated monomer II, an initiator and a neutralizer in an organic solvent, and then adding water for dilution, wherein the obtained hydroxyl water dispersion is of a network crosslinking structure, has a high reaction speed with an isocyanate curing agent, can improve the surface drying speed of a paint film, and can obtain the paint film with the hardness of HB or more in a short time.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a hydroxyl water dispersion with a network crosslinking structure and a preparation method thereof.
Background
With the increasing environmental awareness, the national environmental regulations are becoming stricter, and the call for reducing the use of VOCs in coatings and related fields is becoming higher. Therefore, aqueous hydroxyl dispersions are increasingly important in the coatings market.
At present, although the use amount of VOC is obviously reduced in the preparation and use processes of most of hydroxyl water dispersions in domestic and foreign markets, compared with solvent type polyhydroxy resins, the performance of the aqueous dispersion has a larger difference. The first difference is that the reaction speed of the hydroxyl aqueous dispersion and the isocyanate curing agent for crosslinking and curing is slow due to the fact that the solvent of the hydroxyl aqueous dispersion is a large amount of water, and the surface drying speed of a paint film is slow. A common solution to this problem is to introduce a rigid segment with a higher glass transition temperature into the molecular structure of the aqueous hydroxyl dispersion to raise the glass transition temperature of the aqueous hydroxyl dispersion or to raise the molecular weight of the aqueous hydroxyl dispersion. However, both of the above methods cause a problem that the adhesion of the obtained paint film on the surface of the epoxy primer is lowered.
Disclosure of Invention
The problems in the prior art are: the solvent of the hydroxyl aqueous dispersion is a large amount of water, so that the reaction speed of crosslinking and curing of the hydroxyl aqueous dispersion and the isocyanate curing agent is reduced, and the surface drying speed of a paint film is reduced. Aiming at the problems, the invention provides a hydroxyl water dispersion with a network crosslinking structure, which is prepared by carrying out free radical copolymerization reaction on a self-crosslinking monomer containing at least two double bonds, an ethylenically unsaturated monomer I, an ethylenically unsaturated monomer II, an initiator and a neutralizer in an organic solvent, and then adding water for dilution, wherein the dosage of reaction raw materials is as follows in parts by weight:
2-5 parts of self-crosslinking monomer
5-8 parts of organic solvent
20-30 parts of unsaturated monomer I
Initiator 0.1-3 parts
Unsaturated monomer II 7-15 parts
1-4 parts of neutralizer
30-50 parts of deionized water;
wherein, the ethylenically unsaturated monomer I comprises the following components in parts by weight:
15-25 parts of vinyl monomer
5-10 parts of vinyl monomer containing hydroxyl.
Wherein, the ethylenically unsaturated monomer II comprises the following components in parts by weight:
vinyl monomers 15-25
5-10 parts of vinyl monomer containing hydroxyl
0.5-2 parts of special functional vinyl monomer.
Specifically, the self-crosslinking monomer containing at least two double bonds, and the preparation method thereof comprises the following steps:
adding a hydroxyl compound and glycidyl methacrylate into a reaction kettle, stirring and mixing uniformly, wherein the molar ratio of the hydroxyl compound to the glycidyl methacrylate is 1:2.5-4.5, heating the reaction system to 160-180 ℃ under the protection of nitrogen, adding a catalyst, wherein the addition amount of the catalyst accounts for 0.1-1% of the weight of the hydroxyl compound, stirring and reacting for 1-6h, continuously monitoring the epoxy value in the reaction system in the reaction process, and finishing the reaction when the epoxy value in the reaction system is smaller than 0.1, thereby obtaining the self-crosslinking monomer.
Specifically, the catalyst comprises at least one of dibutyl tin dilaurate, monobutyl tin oxide, dioctyl tin dilaurate, concentrated phosphoric acid and concentrated sulfuric acid.
Specifically, the hydroxyl compound includes at least one of linear alcohols containing 2 to 12 carbons and at least two hydroxyl groups.
Specifically, the linear alcohol containing 2-12 carbons and at least two hydroxyl groups comprises at least one of ethylene glycol, propylene glycol, butanediol, 1, 3-propanediol or 1, 4-butanediol.
Specifically, the hydroxyl compound includes at least one of branched alcohols containing 2 to 12 carbons and at least two hydroxyl groups.
Specifically, the branched alcohol having 2 to 12 carbons and at least two hydroxyl groups includes at least one of trimethylolpropane, trimethylolethane or pentaerythritol.
Specifically, the hydroxyl-containing vinyl monomer comprises at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxyhexyl acrylate and hydroxyhexyl methacrylate.
Specifically, the special functional vinyl monomer comprises at least one of sodium p-styrenesulfonate, sodium vinylsulfonate, sodium allyl ether hydroxypropyl sulfonate, vinyl alkoxy phosphate and methacrylate alkoxy phosphate.
Specifically, the vinyl monomer comprises at least one of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, butyl methacrylate, isooctyl acrylate, isobornyl methacrylate, benzyl methacrylate, lauryl methacrylate and styrene.
Specifically, the initiator comprises at least one of azodiisobutyronitrile, azodiisoheptonitrile, di-tert-amyl peroxide, di-tert-butyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, tert-amyl peroxybenzoate, tert-butyl peroxyacetate, tert-amyl peroxyacetate, tert-butyl peroxy-2-ethylhexyl acid, tert-amyl peroxy-2-ethylhexyl acid and cumene peroxide.
Specifically, the neutralizing agent comprises at least one of triethanolamine, N-dimethylethanolamine, triethylamine, N-dimethylethanolamine, diethylethanolamine and N, N-dimethylisopropanolamine.
Specifically, the organic solvent comprises at least one of propylene glycol methyl ether, propylene glycol butyl ether, ethylene glycol butyl ether, propylene glycol methyl ether acetate, diethylene glycol butyl ether, diethylene glycol phenyl ether, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate and butyl acetate.
Specifically, the preparation method of the hydroxyl water dispersion with the network crosslinking structure comprises the following steps:
(1) Adding a formula amount of organic solvent and a formula amount of self-crosslinking monomer into a reaction kettle, heating the reaction system to 105-145 ℃ under the protection of nitrogen, beginning to dropwise add a formula amount of ethylenically unsaturated monomer I and 65% of formula amount of initiator, keeping the temperature and stirring for reaction for 30min after the dropwise addition is completed, wherein the dropwise addition time is 3-5 h;
(2) Then, under the protection of nitrogen, dripping the formula amount of the ethylenically unsaturated monomer II and 34% formula amount of the initiator into the reaction system in the step (1) for 1-3h, carrying out heat preservation and stirring reaction for 2h after dripping, then adding the rest formula amount of the initiator at one time, and carrying out heat preservation and stirring reaction for 30min;
(3) Then, under the protection of nitrogen, the temperature of the reaction system is reduced to 80-100 ℃, at this time, the neutralizing agent with the formula amount is added at one time, the mixture is stirred and reacts for 30min, the deionized water with the formula amount of 1/2 is added dropwise, the dripping time is 15min, after stirring and dispersing uniformly, the temperature of the reaction system is reduced to 50-80 ℃, the deionized water with the residual formula amount is continuously added dropwise, the dripping time is 15min, and the network crosslinking structure hydroxyl water dispersion is obtained after stirring and dispersing for 30 min.
Advantageous effects
(1) The invention adopts the straight chain alcohol or branched chain alcohol containing at least two hydroxyl groups to react with glycidyl methacrylate to obtain the self-crosslinking monomer containing at least two double bonds, the self-crosslinking monomer and the ethylenically unsaturated monomer can generate chain growth, lamination and crosslinking in the solution copolymerization process to finally form the hydroxyl water dispersion of a network crosslinking structure, the reaction speed of the hydroxyl water dispersion of the network crosslinking structure and an isocyanate curing agent is higher, the surface drying speed of a paint film can be improved, and the paint film with the hardness of HB or more can be obtained in a short time;
(2) In the process of preparing the self-crosslinking monomer, the adding amount of the glycidyl methacrylate is slightly excessive relative to the hydroxyl compound, so that part of glycidyl methacrylate can participate in the subsequent double bond polymerization reaction, epoxy groups can be conveniently introduced into the hydroxyl water dispersion structure, and the epoxy groups introduced into the hydroxyl water dispersion structure can prevent the adhesive force of a paint film formed by curing the hydroxyl water dispersion and the isocyanate curing agent on the surface of the epoxy primer from being reduced.
Detailed Description
Example 1
The hydroxyl water dispersion with the network crosslinking structure comprises the following reaction raw materials in parts by weight:
3 parts of self-crosslinking monomer
Ethylene glycol butyl ether 7 parts
Unsaturated monomer I30 parts
0.8 part of azobisisobutyronitrile
Unsaturated monomer II 15 parts
Triethanolamine 4 parts
50 parts of deionized water;
wherein, the ethylenically unsaturated monomer I comprises the following components in parts by weight:
25 parts of methyl methacrylate
5 parts of hydroxyethyl acrylate.
Wherein, the ethylenically unsaturated monomer II comprises the following components in parts by weight:
10 parts of ethyl methacrylate
Hydroxyethyl methacrylate 5 parts
0.5 parts of sodium vinylsulfonate.
The self-crosslinking monomer is prepared by the following steps:
36g of 1, 4-butanediol and 142g of glycidyl methacrylate are added into a reaction kettle to be stirred and mixed uniformly, the temperature of a reaction system is raised to 170 ℃ under the protection of nitrogen, 0.4g of dibutyltin dilaurate is added, stirring is carried out for 6 hours, the epoxy value in the reaction system is continuously monitored in the reaction process, and when the epoxy value in the reaction system is smaller than 0.1, the reaction is finished, so that the self-crosslinking monomer is obtained.
The preparation method of the network crosslinked hydroxyl water dispersion comprises the following steps:
(1) Adding a formula amount of organic solvent and a formula amount of self-crosslinking monomer into a reaction kettle, heating the reaction system to 105 ℃ under the protection of nitrogen, then beginning to dropwise add a formula amount of ethylenically unsaturated monomer I and 65% of formula amount of initiator, wherein the dropwise adding time is 3h, and carrying out heat preservation and stirring reaction for 30min after the dropwise adding is finished;
(2) Then, under the protection of nitrogen, dripping the formula amount of the ethylenically unsaturated monomer II and 34% formula amount of the initiator into the reaction system in the step (1) for 1h, and after dripping, carrying out heat preservation and stirring reaction for 2h, then adding the rest formula amount of the initiator at one time, and carrying out heat preservation and stirring reaction for 30min;
(3) Then, under the protection of nitrogen, the temperature of the reaction system is reduced to 80 ℃, at this time, the neutralizing agent with the formula amount is added at one time, the mixture is stirred and reacts for 30 minutes, the deionized water with the formula amount of 1/2 is dripped, the dripping time is 15 minutes, after stirring and dispersing uniformly, the temperature of the reaction system is reduced to 50 ℃, the deionized water with the residual formula amount is continuously dripped, the dripping time is 15 minutes, and the network crosslinking structure hydroxyl water dispersion is obtained after stirring and dispersing for 30 minutes.
Example 2
The hydroxyl water dispersion with the network crosslinking structure comprises the following reaction raw materials in parts by weight:
5 parts of self-crosslinking monomer
Propylene glycol butyl ether 5 parts
20 parts of ethylenically unsaturated monomers I
Azodiisobutyronitrile 0.1 part
Ethylenically unsaturated monomer II 7 parts
Diethyl ethanolamine 1 part
And 35 parts of deionized water.
The ethylenically unsaturated monomer I comprises the following components in parts by weight:
15 parts of n-butyl acrylate
5 parts of hydroxyethyl acrylate.
The ethylenically unsaturated monomer II comprises the following components in parts by weight;
isooctyl acrylate 5 parts
2 parts of hydroxybutyl acrylate
1 part of sodium p-styrenesulfonate.
The self-crosslinking monomer is prepared by the following steps:
adding 35.5g of pentaerythritol and 142g of glycidyl methacrylate into a reaction kettle, stirring and mixing uniformly, heating the reaction system to 180 ℃ under the protection of nitrogen, adding 1g of monobutyl tin oxide, stirring and reacting for 1h, continuously monitoring the epoxy value in the reaction system in the reaction process, and ending the reaction when the epoxy value in the reaction system is less than 0.1, thus obtaining the self-crosslinking monomer.
The preparation method of the network crosslinked hydroxyl water dispersion comprises the following steps:
(1) Adding a formula amount of organic solvent and a formula amount of self-crosslinking monomer into a reaction kettle, heating the reaction system to 145 ℃ under the protection of nitrogen, then beginning to dropwise add a formula amount of ethylenically unsaturated monomer I and 65% of formula amount of initiator, wherein the dropwise adding time is 5h, and carrying out heat preservation and stirring reaction for 30min after the dropwise adding is finished;
(2) Then, under the protection of nitrogen, dripping the formula amount of the ethylenically unsaturated monomer II and 34% formula amount of the initiator into the reaction system in the step (1) for 3 hours, and after dripping, carrying out heat preservation and stirring reaction for 2 hours, then adding the rest formula amount of the initiator at one time, and carrying out heat preservation and stirring reaction for 30 minutes;
(3) Then, under the protection of nitrogen, the temperature of the reaction system is reduced to 80 ℃, at this time, the neutralizing agent with the formula amount is added at one time, the mixture is stirred and reacts for 30 minutes, the deionized water with the formula amount of 1/2 is dripped, the dripping time is 15 minutes, after stirring and dispersing uniformly, the temperature of the reaction system is reduced to 50 ℃, the deionized water with the residual formula amount is continuously dripped, the dripping time is 15 minutes, and the network crosslinking structure hydroxyl water dispersion is obtained after stirring and dispersing for 30 minutes.
Example 3
The hydroxyl water dispersion with the network crosslinking structure comprises the following reaction raw materials in parts by weight:
self-crosslinking monomer 2 parts
Ethylene glycol butyl ether 7 parts
Ethylenically unsaturated monomer I25 parts
0.5 part of azobisisobutyronitrile
8 parts of olefinically unsaturated monomers II
Triethanolamine 2 parts
50 parts of deionized water.
The ethylenically unsaturated monomer I comprises the following components in parts by weight:
methyl methacrylate 20 parts
8 parts of hydroxyethyl acrylate.
The ethylenically unsaturated monomer II comprises the following components in parts by weight;
15 parts of ethyl methacrylate
Hydroxyethyl methacrylate 6 parts
2 parts of vinyl alkoxy phosphate.
The self-crosslinking monomer is prepared by the following steps:
41g of butanediol and 142g of glycidyl methacrylate are added into a reaction kettle to be stirred and mixed uniformly, the temperature of a reaction system is raised to 130 ℃ under the protection of nitrogen, 0.2g of dioctyl tin dilaurate is added to be stirred and reacted for 6 hours, the epoxy value in the reaction system is continuously monitored in the reaction process, and when the epoxy value in the reaction system is smaller than 0.1, the reaction is finished, so that the self-crosslinking monomer is obtained.
The preparation method of the network crosslinked hydroxyl water dispersion comprises the following steps:
(1) Adding a formula amount of organic solvent and a formula amount of self-crosslinking monomer into a reaction kettle, heating the reaction system to 135 ℃ under the protection of nitrogen, then beginning to dropwise add a formula amount of ethylenically unsaturated monomer I and 65% of formula amount of initiator, wherein the dropwise adding time is 4 hours, and carrying out heat preservation and stirring reaction for 30 minutes after the dropwise adding is finished;
(2) Then, under the protection of nitrogen, dripping the formula amount of the ethylenically unsaturated monomer II and 34% formula amount of the initiator into the reaction system in the step (1) for 2 hours, and after dripping, carrying out heat preservation and stirring reaction for 2 hours, then adding the rest formula amount of the initiator at one time, and carrying out heat preservation and stirring reaction for 30 minutes;
(3) Then, under the protection of nitrogen, the temperature of the reaction system is reduced to 90 ℃, at this time, the neutralizing agent with the formula amount is added at one time, the mixture is stirred and reacts for 30 minutes, the deionized water with the formula amount of 1/2 is dripped, the dripping time is 15 minutes, after stirring and dispersing uniformly, the temperature of the reaction system is reduced to 80 ℃, the deionized water with the residual formula amount is continuously dripped, the dripping time is 15 minutes, and the network crosslinking structure hydroxyl water dispersion is obtained after stirring and dispersing for 30 minutes.
Example 4
The hydroxyl water dispersion with the network crosslinking structure comprises the following reaction raw materials in parts by weight:
3 parts of self-crosslinking monomer
Propylene glycol methyl ether acetate 8 parts
Ethylenically unsaturated monomer I24 parts
0.3 part of azobisisobutyronitrile
10 parts of olefinically unsaturated monomers II
Triethanolamine 2 parts
30 parts of deionized water.
The ethylenically unsaturated monomer I comprises the following components in parts by weight:
methyl methacrylate 18 parts
6 parts of hydroxyethyl acrylate.
The ethylenically unsaturated monomer II comprises the following components in parts by weight;
ethyl methacrylate 22 parts
Hydroxyethyl methacrylate 7 parts
0.8 parts of methacrylate alkoxy phosphate.
The self-crosslinking monomer is prepared by the following steps:
adding 25g of ethylene glycol and 142g of glycidyl methacrylate into a reaction kettle, stirring and mixing uniformly, heating the reaction system to 145 ℃ under the protection of nitrogen, adding 0.4g of concentrated phosphoric acid, stirring and reacting for 2 hours, continuously monitoring the epoxy value in the reaction system in the reaction process, and ending the reaction when the epoxy value in the reaction system is less than 0.1, thereby obtaining the self-crosslinking monomer.
The preparation method of the network crosslinked hydroxyl water dispersion comprises the following steps:
(1) Adding a formula amount of organic solvent and a formula amount of self-crosslinking monomer into a reaction kettle, heating the reaction system to 145 ℃ under the protection of nitrogen, then beginning to dropwise add a formula amount of ethylenically unsaturated monomer I and 65% of formula amount of initiator, wherein the dropwise adding time is 3h, and carrying out heat preservation and stirring reaction for 30min after the dropwise adding is finished;
(2) Then, under the protection of nitrogen, dripping the formula amount of the ethylenically unsaturated monomer II and 34% formula amount of the initiator into the reaction system in the step (1) for 1h, and after dripping, carrying out heat preservation and stirring reaction for 2h, then adding the rest formula amount of the initiator at one time, and carrying out heat preservation and stirring reaction for 30min;
(3) Then, under the protection of nitrogen, the temperature of the reaction system is reduced to 90 ℃, at this time, the neutralizing agent with the formula amount is added at one time, the mixture is stirred and reacts for 30 minutes, the deionized water with the formula amount of 1/2 is dripped, the dripping time is 15 minutes, after stirring and dispersing uniformly, the temperature of the reaction system is reduced to 60 ℃, the deionized water with the residual formula amount is continuously dripped, the dripping time is 15 minutes, and the network crosslinking structure hydroxyl water dispersion is obtained after stirring and dispersing for 30 minutes.
Example 5
The hydroxyl water dispersion with the network crosslinking structure comprises the following reaction raw materials in parts by weight:
4 parts of self-crosslinking monomer
5-8 parts of dimethylbenzene
Ethylenically unsaturated monomer I25 parts
Benzoyl peroxide 0.5 parts
12 parts of olefinically unsaturated monomers II
N-dimethylethanolamine 3 parts
50 parts of deionized water.
The ethylenically unsaturated monomer I comprises the following components in parts by weight:
isooctyl acrylate 23 parts
6 parts of hydroxypropyl methacrylate.
The ethylenically unsaturated monomer II comprises the following components in parts by weight;
isobornyl methacrylate 18 parts
Hydroxy butyl acrylate 9 parts
1.2 parts of sodium allyl ether hydroxypropyl sulfonate.
The self-crosslinking monomer is prepared by the following steps:
adding 25g of propylene glycol and 142g of glycidyl methacrylate into a reaction kettle, stirring and mixing uniformly, heating the reaction system to 130 ℃ under the protection of nitrogen, adding 1.1g of concentrated sulfuric acid, stirring and reacting for 2 hours, continuously monitoring the epoxy value in the reaction system in the reaction process, and ending the reaction when the epoxy value in the reaction system is less than 0.1, thereby obtaining the self-crosslinking monomer.
The preparation method of the network crosslinked hydroxyl water dispersion comprises the following steps:
(1) Adding a formula amount of organic solvent and a formula amount of self-crosslinking monomer into a reaction kettle, heating the reaction system to 145 ℃ under the protection of nitrogen, then beginning to dropwise add a formula amount of ethylenically unsaturated monomer I and 65% of formula amount of initiator, wherein the dropwise adding time is 4 hours, and carrying out heat preservation and stirring reaction for 30 minutes after the dropwise adding is finished;
(2) Then, under the protection of nitrogen, dripping the formula amount of the ethylenically unsaturated monomer II and 34% formula amount of the initiator into the reaction system in the step (1) for 1h, and after dripping, carrying out heat preservation and stirring reaction for 2h, then adding the rest formula amount of the initiator at one time, and carrying out heat preservation and stirring reaction for 30min;
(3) Then, under the protection of nitrogen, the temperature of the reaction system is reduced to 100 ℃, at this time, the neutralizing agent with the formula amount is added at one time, the mixture is stirred and reacts for 30 minutes, the deionized water with the formula amount of 1/2 is dripped, the dripping time is 15 minutes, after stirring and dispersing uniformly, the temperature of the reaction system is reduced to 50 ℃, the deionized water with the residual formula amount is continuously dripped, the dripping time is 15 minutes, and the network crosslinking structure hydroxyl water dispersion is obtained after stirring and dispersing for 30 minutes.
Example 6
The hydroxyl water dispersion with the network crosslinking structure comprises the following reaction raw materials in parts by weight:
3 parts of self-crosslinking monomer
Propylene glycol butyl ether 6 parts
26 parts of ethylenically unsaturated monomers I
0.5 part of tert-butyl peroxy-2-ethylhexyl acid
9 parts of olefinically unsaturated monomers II
2 parts of N, N-dimethyl isopropanolamine
40 parts of deionized water.
The ethylenically unsaturated monomer I comprises the following components in parts by weight:
21 parts of n-butyl acrylate
7 parts of hydroxyhexyl acrylate.
The ethylenically unsaturated monomer II comprises the following components in parts by weight;
styrene 18 parts
6 parts of hydroxy hexyl methacrylate
3 parts of sodium vinylsulfonate.
The self-crosslinking monomer is prepared by the following steps:
adding 33.5g of trimethylolpropane and 142g of glycidyl methacrylate into a reaction kettle, stirring and mixing uniformly, heating the reaction system to 130 ℃ under the protection of nitrogen, adding 0.4g of dibutyltin dilaurate, stirring and reacting for 2 hours, continuously monitoring the epoxy value in the reaction system in the reaction process, and ending the reaction when the epoxy value in the reaction system is less than 0.1, thereby obtaining the self-crosslinking monomer.
The preparation method of the network crosslinked hydroxyl water dispersion comprises the following steps:
(1) Adding a formula amount of organic solvent and a formula amount of self-crosslinking monomer into a reaction kettle, heating the reaction system to 145 ℃ under the protection of nitrogen, then beginning to dropwise add a formula amount of ethylenically unsaturated monomer I and 65% of formula amount of initiator, wherein the dropwise adding time is 4 hours, and carrying out heat preservation and stirring reaction for 30 minutes after the dropwise adding is finished;
(2) Then, under the protection of nitrogen, dripping the formula amount of the ethylenically unsaturated monomer II and 34% formula amount of the initiator into the reaction system in the step (1) for 1h, and after dripping, carrying out heat preservation and stirring reaction for 2h, then adding the rest formula amount of the initiator at one time, and carrying out heat preservation and stirring reaction for 30min;
(3) Then, under the protection of nitrogen, the temperature of the reaction system is reduced to 85 ℃, at this time, the neutralizing agent with the formula amount is added at one time, the mixture is stirred and reacts for 30 minutes, the deionized water with the formula amount of 1/2 is dripped, the dripping time is 15 minutes, after stirring and dispersing uniformly, the temperature of the reaction system is reduced to 65 ℃, the deionized water with the residual formula amount is continuously dripped, the dripping time is 15 minutes, and after stirring and dispersing for 30 minutes, the network crosslinking structure hydroxyl water dispersion is obtained.
Comparative example 1 the same as example 1, except that comparative example 1 was not added with self-crosslinking monomer during the preparation of the aqueous hydroxyl dispersion.
Comparative example 2 the same as example 1 was different in that in comparative example 2 no self-crosslinking monomer was added during the preparation of the aqueous hydroxyl dispersion, which replaced the self-crosslinking monomer with an equimolar amount of glycidyl methacrylate.
Comparative example 3 the same as example 1, except that comparative example 3 was not added with self-crosslinking monomer during the preparation of the aqueous hydroxyl dispersion, it replaced the self-crosslinking monomer with an equivalent molar amount of compound a prepared according to the following procedure:
36g of 1, 4-butanediol and 214g of tertiary glycidyl ester are added into a reaction kettle to be stirred and mixed uniformly, the temperature of a reaction system is raised to 170 ℃ under the protection of nitrogen, 0.4g of dibutyltin dilaurate is added, stirring is carried out for 6 hours, the epoxy value in the reaction system is continuously monitored in the reaction process, and when the epoxy value in the reaction system is smaller than 0.1, the reaction is finished, so that the compound A is obtained.
Comparative example 4 the same as example 1 was carried out, except that comparative example 4 was reduced by half in the amount of initiator in the reaction raw material used in the preparation of the aqueous hydroxyl group dispersion.
Evaluation of Performance
The aqueous hydroxyl dispersions obtained in examples 1 to 6 according to the invention and comparative examples 1 to 4 were subjected to the relevant performance tests, the specific test results being shown in Table 1.
Among them, the storage stability test of the aqueous hydroxyl dispersion is to put the aqueous hydroxyl dispersion in an oven at 50 ℃ and stand for 30d at constant temperature, and observe whether there is a change in the physical state of the dispersion (e.g., whether delamination, turbidity, etc. occur).
TABLE 1
Application of
The aqueous hydroxyl dispersions obtained in examples 1 to 6 and comparative examples 1 to 4 were prepared as a top-coat paint in parts by weight as follows, and coated on the surface of a sandblasted steel sheet having a surface cured with a XF44-33 epoxy primer of a thickness of 45 μm, respectively, and after the top-coat paint was cured to form a paint film having a film thickness of 25.+ -. 2. Mu.m, the paint film was subjected to a relevant performance test, the specific test results are shown in Table 2, and the specific formulation of the top-coat paint is as follows:
and (3) a component A:
60 parts of aqueous hydroxyl dispersion
Wetting agent TEGO 270.2 parts
Defoaming agent BYK-024 0.2 parts
Dispersant BYK-190.1 part
38.5 parts of water
And the component B comprises the following components:
colorgea 2655 isocyanate curing agent 20 parts
6 parts of propylene glycol methyl ether acetate.
Wherein, the mass ratio of the component A to the component B in the embodiment 1 is 9:1;
the mass ratio of the A component to the B component in example 2 is 7:1
The mass ratio of the A component to the B component in example 3 was 4.5:1
The mass ratio of the A component to the B component in example 4 was 5.5:1
The mass ratio of the A component to the B component in example 5 was 5.7:1
The mass ratio of the A component to the B component in example 6 is 11:1
The mass ratio of the A component to the B component in comparative example 1 was 9:1
The mass ratio of the A component to the B component in comparative example 2 was 9:1
The mass ratio of the A component to the B component in comparative example 3 was 9:1
The mass ratio of the A component to the B component in comparative example 4 was 9:1
The topcoat formulation of comparative example 5 is as follows:
and (3) a component A:
1123 60 parts of aqueous acrylic resin dispersion ACUST
Wetting agent TEGO 270.2 parts
Defoaming agent BYK-024 0.2 parts
Dispersant BYK-190.1 part
38.5 parts of water
And the component B comprises the following components:
colorgea 2655 isocyanate curing agent 20 parts
6 parts of propylene glycol methyl ether acetate.
The mass ratio of the component A to the component B is 9:1.
The adhesion was tested according to the paint film adhesion test of GB/T1720-1979 (1989).
The time for the paint film to reach HB pencil hardness was measured by measuring pencil hardness every 5 minutes according to GB/T6739-1996.
The surface drying speed of the paint film was measured according to GB/T1728-2020.
TABLE 2
The present invention is not limited to the above embodiments, but is capable of modification and variation in detail, and other modifications and variations can be made by those skilled in the art without departing from the scope of the present invention.
Claims (2)
1. The hydroxyl water dispersion with a network crosslinking structure is characterized by being prepared by carrying out free radical copolymerization reaction on a self-crosslinking monomer containing at least two double bonds, an ethylenically unsaturated monomer I, an ethylenically unsaturated monomer II, an initiator and a neutralizer in an organic solvent, and then adding water for dilution, wherein the reaction raw materials are in use in parts by weight as follows:
2-5 parts of self-crosslinking monomer;
5-8 parts of an organic solvent;
20-30 parts of unsaturated monomer I;
0.1-3 parts of initiator;
7-15 parts of unsaturated monomer II;
1-4 parts of neutralizing agent;
30-50 parts of deionized water;
wherein, the ethylenically unsaturated monomer I comprises the following components in parts by weight:
15-25 parts of vinyl monomer;
5-10 parts of hydroxyl-containing vinyl monomer;
wherein, the ethylenically unsaturated monomer II comprises the following components in parts by weight:
15-25 of vinyl monomers;
5-10 parts of hydroxyl-containing vinyl monomer;
0.5-2 parts of special functional vinyl monomer;
the preparation method of the self-crosslinking monomer containing at least two double bonds comprises the following steps:
adding a hydroxyl compound and glycidyl methacrylate into a reaction kettle, stirring and mixing uniformly, wherein the molar ratio of the hydroxyl compound to the glycidyl methacrylate is 1:2.5-4.5, under the protection of nitrogen, heating the reaction system to 160-180 ℃, adding a catalyst, wherein the addition amount of the catalyst accounts for 0.1-1% of the weight of the hydroxyl compound, stirring and reacting for 1-6h, continuously monitoring the epoxy value in the reaction system in the reaction process, and when the epoxy value in the reaction system is less than 0.1, ending the reaction to obtain a self-crosslinking monomer;
the hydroxyl compound includes at least one of linear alcohols containing 2 to 12 carbons and at least two hydroxyl groups;
the linear alcohol containing 2-12 carbons and at least two hydroxyl groups comprises at least one of ethylene glycol, propylene glycol and butanediol;
or the hydroxyl compound comprises at least one of branched alcohols containing 2 to 12 carbons and at least two hydroxyl groups;
the branched alcohol containing 2-12 carbons and at least two hydroxyl groups includes at least one of trimethylolpropane, trimethylolethane or pentaerythritol;
the hydroxyl-containing vinyl monomer comprises at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxyhexyl acrylate and hydroxyhexyl methacrylate;
the special functional vinyl monomer comprises at least one of sodium p-styrenesulfonate, sodium vinylsulfonate, sodium allyl ether hydroxypropyl sulfonate, vinyl alkoxy phosphate and methacrylate alkoxy phosphate;
the vinyl monomer comprises at least one of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, butyl methacrylate, isooctyl acrylate, isobornyl methacrylate, benzyl methacrylate, lauryl methacrylate and styrene.
2. The aqueous dispersion of hydroxyl groups of network cross-linked structure according to claim 1, wherein the preparation method comprises the following steps:
(1) Adding a formula amount of organic solvent and a formula amount of self-crosslinking monomer into a reaction kettle, heating the reaction system to 105-145 ℃ under the protection of nitrogen, beginning to dropwise add a formula amount of ethylenically unsaturated monomer I and 65% of formula amount of initiator, keeping the temperature and stirring for reaction for 30min after the dropwise addition is completed, wherein the dropwise addition time is 3-5 h;
(2) Then, under the protection of nitrogen, dripping the formula amount of the ethylenically unsaturated monomer II and 34% formula amount of the initiator into the reaction system in the step (1) for 1-3h, carrying out heat preservation and stirring reaction for 2h after dripping, then adding the rest formula amount of the initiator at one time, and carrying out heat preservation and stirring reaction for 30min;
(3) Then, under the protection of nitrogen, the temperature of the reaction system is reduced to 80-100 ℃, at this time, the neutralizing agent with the formula amount is added at one time, the mixture is stirred and reacts for 30min, the deionized water with the formula amount of 1/2 is added dropwise, the dripping time is 15min, after stirring and dispersing uniformly, the temperature of the reaction system is reduced to 50-80 ℃, the deionized water with the residual formula amount is continuously added dropwise, the dripping time is 15min, and the network crosslinking structure hydroxyl water dispersion is obtained after stirring and dispersing for 30 min.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211252080.0A CN115926041B (en) | 2022-10-13 | 2022-10-13 | Hydroxyl water dispersion with network crosslinked structure and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211252080.0A CN115926041B (en) | 2022-10-13 | 2022-10-13 | Hydroxyl water dispersion with network crosslinked structure and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN115926041A CN115926041A (en) | 2023-04-07 |
CN115926041B true CN115926041B (en) | 2024-03-26 |
Family
ID=86556549
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202211252080.0A Active CN115926041B (en) | 2022-10-13 | 2022-10-13 | Hydroxyl water dispersion with network crosslinked structure and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115926041B (en) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106854285A (en) * | 2016-12-22 | 2017-06-16 | 徐州海太新材料科技有限公司 | A kind of water-based hydroxyl acrylic acid dispersion and preparation method thereof |
CN107163177A (en) * | 2017-05-02 | 2017-09-15 | 广东拓普合成科技股份有限公司 | A kind of quick-dry type Hydroxylated acrylic resin aqueous dispersion of working life length and preparation method thereof |
CN111116812A (en) * | 2019-12-23 | 2020-05-08 | 上海金力泰化工股份有限公司 | Aqueous polyacrylate dispersoid containing hydroxyl and preparation method thereof |
CN112341566A (en) * | 2020-11-23 | 2021-02-09 | 广州冠志新材料科技有限公司 | Sulfonic acid type hydroxyl acrylic resin aqueous dispersion and preparation method thereof |
CN113817308A (en) * | 2021-08-30 | 2021-12-21 | 无锡洪汇新材料科技股份有限公司 | Polyhydroxy aqueous dispersion and preparation method thereof |
CN115160511A (en) * | 2022-07-14 | 2022-10-11 | 无锡洪汇新材料科技股份有限公司 | Hydroxyl-containing aqueous resin dispersion and preparation method thereof |
-
2022
- 2022-10-13 CN CN202211252080.0A patent/CN115926041B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106854285A (en) * | 2016-12-22 | 2017-06-16 | 徐州海太新材料科技有限公司 | A kind of water-based hydroxyl acrylic acid dispersion and preparation method thereof |
CN107163177A (en) * | 2017-05-02 | 2017-09-15 | 广东拓普合成科技股份有限公司 | A kind of quick-dry type Hydroxylated acrylic resin aqueous dispersion of working life length and preparation method thereof |
CN111116812A (en) * | 2019-12-23 | 2020-05-08 | 上海金力泰化工股份有限公司 | Aqueous polyacrylate dispersoid containing hydroxyl and preparation method thereof |
CN112341566A (en) * | 2020-11-23 | 2021-02-09 | 广州冠志新材料科技有限公司 | Sulfonic acid type hydroxyl acrylic resin aqueous dispersion and preparation method thereof |
CN113817308A (en) * | 2021-08-30 | 2021-12-21 | 无锡洪汇新材料科技股份有限公司 | Polyhydroxy aqueous dispersion and preparation method thereof |
CN115160511A (en) * | 2022-07-14 | 2022-10-11 | 无锡洪汇新材料科技股份有限公司 | Hydroxyl-containing aqueous resin dispersion and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
夏宇正,陈晓农.《精细高分子化工及应用》.化学工业出版社,2000,(第1版),121. * |
Also Published As
Publication number | Publication date |
---|---|
CN115926041A (en) | 2023-04-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4880889A (en) | Hydroxylic acrylate copolymer process for its preparation, and coating agent based on the acrylate | |
CN107805291B (en) | Aqueous hydroxy acrylic acid dispersion and preparation method thereof | |
CN109054570B (en) | Environment-friendly high-strength elastic coating and preparation method thereof | |
CN109867743B (en) | Room-temperature self-crosslinking water-based acrylic resin dispersion and preparation method thereof | |
CN109337487B (en) | Water-based acrylic amino baking paint | |
CN113968931B (en) | High-adhesion water-based acrylic resin and preparation method thereof | |
US4312797A (en) | Aqueous coating composition | |
CN114316854B (en) | Acrylic acid adhesive with high solid content and low viscosity and preparation method thereof | |
CN114891160A (en) | Asparagus resin and epoxy resin modified waterborne hydroxyl acrylic resin and preparation method and application thereof | |
CN109503738B (en) | Phosphoric acid modified polyisoprene rubber, polyisoprene rubber modified acrylate resin dispersion, preparation method and application | |
CN109517512B (en) | High-solid-content two-component coating and application thereof | |
CN115926041B (en) | Hydroxyl water dispersion with network crosslinked structure and preparation method thereof | |
CN111807961B (en) | High-hydroxyl acrylic emulsion with quick drying and long pot life and synthesis method thereof | |
CN111116831B (en) | Preparation method of hydroxyl acrylic emulsion | |
CN110922540B (en) | Polyether amine derivative modified waterborne acrylic resin and preparation method thereof | |
CN114989362B (en) | Functional polyfunctional siloxane prepolymer acrylate emulsion and preparation method thereof | |
AU2006302124B2 (en) | High temperature polymerization process for making branched acrylic polymers, caprolactone-modified branched acrylic polymers, and uses thereof | |
US4357455A (en) | Process for the preparation of copolymers containing hydroxyl groups and the use thereof | |
CN113321777A (en) | Epoxy graft modified water-based acrylic resin and preparation method thereof | |
CN114891166A (en) | Organic silicon oil composite acrylic latex and preparation method thereof | |
TW200526747A (en) | Fast drying coating composition comprising an unsaturated hydroxydiester | |
CN114621385A (en) | High-distinctness of image waterborne acrylic resin and preparation method thereof | |
CN113121744B (en) | Rapid crosslinking and curing water-based polyacrylate and preparation method thereof | |
CN112876599B (en) | Preparation process of solid acrylic resin suitable for UV (ultraviolet) photocuring system | |
CN116716066B (en) | Anti-corrosion acid-resistant acrylic resin adhesive and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |