CN115926041A - Network cross-linked structure hydroxyl aqueous dispersion and preparation method thereof - Google Patents
Network cross-linked structure hydroxyl aqueous dispersion and preparation method thereof Download PDFInfo
- Publication number
- CN115926041A CN115926041A CN202211252080.0A CN202211252080A CN115926041A CN 115926041 A CN115926041 A CN 115926041A CN 202211252080 A CN202211252080 A CN 202211252080A CN 115926041 A CN115926041 A CN 115926041A
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- Prior art keywords
- hydroxyl
- methacrylate
- stirring
- reaction
- formula amount
- Prior art date
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Links
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 79
- 239000006185 dispersion Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 90
- 238000004132 cross linking Methods 0.000 claims abstract description 60
- 239000003999 initiator Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 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 113
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 66
- 238000003756 stirring Methods 0.000 claims description 62
- 229910052757 nitrogen Inorganic materials 0.000 claims description 33
- 239000004593 Epoxy Substances 0.000 claims description 21
- 238000004321 preservation Methods 0.000 claims description 20
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 19
- 229920002554 vinyl polymer Polymers 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 14
- -1 hydroxyl compound Chemical class 0.000 claims description 13
- 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
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000012544 monitoring process Methods 0.000 claims description 7
- 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
- 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
- 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 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
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 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
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 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
- 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
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 2
- 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
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-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
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims 1
- 229940035437 1,3-propanediol Drugs 0.000 claims 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 14
- 239000003795 chemical substances by application Substances 0.000 abstract description 11
- 239000012948 isocyanate Substances 0.000 abstract description 8
- 150000002513 isocyanates Chemical class 0.000 abstract description 8
- 238000001035 drying Methods 0.000 abstract description 7
- 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 24
- 230000006641 stabilisation Effects 0.000 description 10
- 238000011105 stabilization Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-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
- 238000012360 testing method Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-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
- 238000009472 formulation Methods 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 241001330498 Corsia Species 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 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
- 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
- 230000007613 environmental effect Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- ZNEMGFATAVGQSF-UHFFFAOYSA-N 1-(2-amino-6,7-dihydro-4H-[1,3]thiazolo[4,5-c]pyridin-5-yl)-2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound NC=1SC2=C(CN(CC2)C(CC=2OC(=NN=2)C=2C=NC(=NC=2)NC2CC3=CC=CC=C3C2)=O)N=1 ZNEMGFATAVGQSF-UHFFFAOYSA-N 0.000 description 1
- NCXUNZWLEYGQAH-UHFFFAOYSA-N 1-(dimethylamino)propan-2-ol Chemical compound CC(O)CN(C)C NCXUNZWLEYGQAH-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
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- 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
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
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- 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
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-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
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
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- 230000004075 alteration Effects 0.000 description 1
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- 230000033228 biological regulation Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
Abstract
The invention relates to the technical field of coatings, in particular to a network cross-linked structure hydroxyl aqueous dispersion and a preparation method thereof. The solvent of the hydroxyl aqueous dispersion is large amount of water, which causes the reaction speed of crosslinking and curing of the hydroxyl aqueous dispersion and the isocyanate curing agent to be slow, and further causes the surface drying speed of a paint film to be slow. In order to solve the problems, the invention provides a hydroxyl aqueous 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 ethylenic unsaturated monomer I, an ethylenic unsaturated monomer II, an initiator and a neutralizer in an organic solvent, and then adding water for dilution, wherein the obtained hydroxyl aqueous dispersion has the network crosslinking structure, has a fast 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 more than HB in a short time.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a network cross-linked structure hydroxyl aqueous dispersion and a preparation method thereof.
Background
With the increasing awareness of environmental protection, national environmental regulations are becoming more stringent, and there is a growing call for reduced VOC use in coatings and related fields. Aqueous hydroxyl dispersions therefore hold an increasingly important position 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 aqueous dispersions in domestic and foreign markets, the performance of the hydroxyl aqueous dispersions is more different than that of solvent-based polyhydroxy resins. The first greatest difference is that the solvent of the hydroxyl aqueous dispersion is large amount of water, which results in slow reaction speed of the hydroxyl aqueous dispersion and the isocyanate curing agent in crosslinking and curing, and further results in slow surface drying speed of the paint film. The current 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 increase the glass transition temperature of the aqueous hydroxyl dispersion or to increase 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 that: the solvent of the hydroxyl aqueous dispersion is large amount of water, which causes the reaction speed of the hydroxyl aqueous dispersion and the isocyanate curing agent for crosslinking and curing to be slow, and further causes the surface drying speed of a paint film to be slow. Aiming at the problems, the invention provides a network crosslinking structure hydroxyl aqueous dispersion which is prepared by carrying out free radical copolymerization reaction on a self-crosslinking monomer containing at least two double bonds, an ethylenic unsaturated monomer I, an ethylenic 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:
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:
vinyl monomer 15-25
5-10 parts of vinyl monomer containing hydroxyl
0.5-2 parts of special functional vinyl monomer.
Specifically, 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, raising the temperature of a 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 during the reaction, and when the epoxy value in the reaction system is less than 0.1, finishing the reaction to obtain the self-crosslinking monomer.
Specifically, the catalyst comprises at least one of dibutyltin dilaurate, monobutyltin oxide, dioctyltin 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 to 12 carbons and at least two hydroxyl groups includes at least one of ethylene glycol, propylene glycol, butylene glycol, 1, 3-propylene glycol, or 1, 4-butylene glycol.
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- (meth) styrene sulfonate, sodium vinyl sulfonate, sodium allyl ether hydroxypropyl sulfonate, vinyl alkoxy phosphate, and methacrylate group alkoxy phosphate.
Specifically, the vinyl monomer includes 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 azobisisobutyronitrile, azobisisoheptonitrile, 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 peroxide, tert-amyl peroxy-2-ethylhexyl peroxide and cumyl 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 aqueous hydroxyl dispersion with the network cross-linked 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, raising the temperature of a reaction system to 105-145 ℃ under the protection of nitrogen, then, dropwise adding a formula amount of ethylenically unsaturated monomer I and 65% of formula amount of initiator for 3-5h, and carrying out heat preservation stirring reaction for 30min after dropwise adding;
(2) Then, under the protection of nitrogen, beginning to dropwise add the formula amount of the ethylenically unsaturated monomer II and 34 percent of formula amount of the initiator into the reaction system in the step (1), wherein the dropwise adding time is 1-3h, after the dropwise adding is finished, keeping the temperature and stirring for reaction for 2h, then adding the rest formula amount of the initiator at one time, keeping the temperature and stirring for reaction for 30min;
(3) And then, under the protection of nitrogen, reducing the temperature of the reaction system to 80-100 ℃, then, adding the neutralizer with the formula amount at one time, stirring and reacting for 30min, dropwise adding deionized water with the formula amount of 1/2 for 15min, stirring and dispersing uniformly, reducing the temperature of the reaction system to 50-80 ℃, continuously dropwise adding the deionized water with the rest formula amount for 15min, and stirring and dispersing for 30min to obtain the hydroxyl water dispersion with the network crosslinking structure.
Advantageous effects
(1) The method adopts linear chain alcohol or branched chain alcohol containing at least two hydroxyl groups to react with glycidyl methacrylate to obtain a self-crosslinking monomer containing at least two double bonds, the self-crosslinking monomer and an ethylenic unsaturated monomer can generate chain growth, lamination and crosslinking in the solution copolymerization process to finally form the hydroxyl aqueous dispersion with a network crosslinking structure, the reaction speed of the hydroxyl aqueous dispersion with 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 more than HB can be obtained in a short time;
(2) In the process of preparing the self-crosslinking monomer, the addition amount of the glycidyl methacrylate is slightly excessive relative to the hydroxyl compound, so that part of the glycidyl methacrylate can participate in the subsequent double bond polymerization reaction, so that an epoxy group is introduced into a hydroxyl aqueous dispersion structure, and the epoxy group is introduced into the hydroxyl aqueous dispersion structure, so that the adhesion of a paint film formed by curing the hydroxyl aqueous dispersion and an isocyanate curing agent on the surface of an epoxy primer can be prevented from being reduced.
Detailed Description
Example 1
The aqueous hydroxyl dispersion with the network crosslinking structure comprises the following reaction raw materials in parts by weight:
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
5 parts of hydroxyethyl methacrylate
0.5 part 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 and 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, the mixture is stirred and reacted for 6 hours, the epoxy value in the reaction system is monitored continuously in the reaction process, and when the epoxy value in the reaction system is less than 0.1, the reaction is finished, and the self-crosslinking monomer is obtained.
The preparation method of the aqueous hydroxyl dispersion with the network crosslinking structure comprises the following steps:
(1) Adding an organic solvent and a self-crosslinking monomer in a formula amount into a reaction kettle, raising the temperature of a reaction system to 105 ℃ under the protection of nitrogen, then, dropwise adding an ethylenically unsaturated monomer I in a formula amount and an initiator in a formula amount of 65% for 3 hours, and carrying out heat preservation stirring reaction for 30min after dropwise adding;
(2) Then, under the protection of nitrogen, beginning to dropwise add the formula amount of the ethylenically unsaturated monomer II and 34% of the formula amount of the initiator into the reaction system in the step (1), wherein the dropwise adding time is 1h, after the dropwise adding is finished, stirring and reacting for 2h under heat preservation, then adding the rest formula amount of the initiator at one time, and stirring and reacting for 30min under heat preservation;
(3) And then, under the protection of nitrogen, reducing the temperature of the reaction system to 80 ℃, then, adding the neutralizer with the formula amount at one time, stirring and reacting for 30min, dropwise adding deionized water with the formula amount of 1/2, wherein the dropwise adding time is 15min, stirring and dispersing uniformly, reducing the temperature of the reaction system to 50 ℃, continuously dropwise adding the deionized water with the rest formula amount, wherein the dropwise adding time is 15min, and stirring and dispersing for 30min to obtain the hydroxyl water dispersion with the network crosslinking structure.
Example 2
The aqueous hydroxyl dispersion with the network crosslinking structure comprises the following reaction raw materials in parts by weight:
the ethylenically unsaturated monomer I comprises the following components in parts by weight:
15 portions of n-butyl acrylate
5 parts of hydroxyethyl acrylate.
The ethylenically unsaturated monomer II comprises the following components in parts by weight;
5 parts of isooctyl acrylate
2 parts of hydroxybutyl acrylate
1 part of sodium p- (methyl) styrene sulfonate.
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, raising the temperature of a reaction system to 180 ℃ under the protection of nitrogen, adding 1g of monobutyl tin oxide, stirring and reacting for 1 hour, continuously monitoring the epoxy value in the reaction system during the reaction process, and obtaining the self-crosslinking monomer after the reaction is finished when the epoxy value in the reaction system is less than 0.1.
The preparation method of the aqueous hydroxyl dispersion with the network crosslinking structure comprises the following steps:
(1) Adding an organic solvent and a self-crosslinking monomer in a formula amount into a reaction kettle, raising the temperature of a reaction system to 145 ℃ under the protection of nitrogen, then dropwise adding an ethylenically unsaturated monomer I in a formula amount and an initiator in a formula amount of 65% for 5 hours, and carrying out heat preservation stirring reaction for 30min after dropwise adding;
(2) Then, under the protection of nitrogen, beginning to dropwise add the formula amount of the ethylenically unsaturated monomer II and 34% of the formula amount of the initiator into the reaction system in the step (1), wherein the dropwise adding time is 3 hours, after the dropwise adding is finished, stirring and reacting for 2 hours under heat preservation, then adding the rest formula amount of the initiator at one time, and stirring and reacting for 30 minutes under heat preservation;
(3) And then, under the protection of nitrogen, reducing the temperature of the reaction system to 80 ℃, then, adding a neutralizing agent in a formula amount at one time, stirring and reacting for 30min, dropwise adding deionized water in a formula amount of 1/2, wherein the dropwise adding time is 15min, stirring and dispersing uniformly, reducing the temperature of the reaction system to 50 ℃, continuously dropwise adding deionized water in the rest formula amount, wherein the dropwise adding time is 15min, and stirring and dispersing for 30min to obtain the network cross-linked structure hydroxyl aqueous dispersion.
Example 3
The aqueous hydroxyl dispersion with the network cross-linking structure comprises the following reaction raw materials in parts by weight:
the ethylenically unsaturated monomer I comprises the following components in parts by weight:
20 parts of methyl methacrylate
8 parts of hydroxyethyl acrylate.
The ethylenically unsaturated monomer II comprises the following components in parts by weight;
15 parts of ethyl methacrylate
6 parts of hydroxyethyl methacrylate
2 parts of vinyl alkoxy phosphate.
The self-crosslinking monomer is prepared by the following steps:
adding 41g of butanediol and 142g of glycidyl methacrylate into a reaction kettle, stirring and mixing uniformly, raising the temperature of a reaction system to 130 ℃ under the protection of nitrogen, adding 0.2g of dioctyltin dilaurate, stirring and reacting for 6 hours, continuously monitoring the epoxy value in the reaction system during the reaction process, and when the epoxy value in the reaction system is less than 0.1, finishing the reaction to obtain the self-crosslinking monomer.
The preparation method of the aqueous hydroxyl dispersion with the network cross-linked structure comprises the following steps:
(1) Adding an organic solvent and a self-crosslinking monomer in a formula amount into a reaction kettle, heating the temperature of a reaction system to 135 ℃ under the protection of nitrogen, then dropwise adding an ethylenically unsaturated monomer I in a formula amount and an initiator in a formula amount of 65% for 4 hours, and carrying out heat preservation stirring reaction for 30min after dropwise adding;
(2) Then, under the protection of nitrogen, beginning to dropwise add the formula amount of the ethylenically unsaturated monomer II and 34% of the formula amount of the initiator into the reaction system in the step (1), wherein the dropwise adding time is 2 hours, after the dropwise adding is finished, stirring and reacting for 2 hours under heat preservation, then adding the rest formula amount of the initiator at one time, and stirring and reacting for 30 minutes under heat preservation;
(3) And then, under the protection of nitrogen, reducing the temperature of the reaction system to 90 ℃, then, adding the neutralizer with the formula amount at one time, stirring and reacting for 30min, dropwise adding deionized water with the formula amount of 1/2, wherein the dropwise adding time is 15min, stirring and dispersing uniformly, reducing the temperature of the reaction system to 80 ℃, continuously dropwise adding the deionized water with the rest formula amount, wherein the dropwise adding time is 15min, and stirring and dispersing for 30min to obtain the network cross-linked structure hydroxyl aqueous dispersion.
Example 4
The aqueous hydroxyl dispersion with the network crosslinking structure comprises the following reaction raw materials in parts by weight:
the ethylenically unsaturated monomer I comprises the following components in parts by weight:
18 parts of methyl methacrylate
6 parts of hydroxyethyl acrylate.
The ethylenically unsaturated monomer II comprises the following components in parts by weight;
22 portions of ethyl methacrylate
7 parts of hydroxyethyl methacrylate
0.8 part of methacrylate alkoxyl 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, raising the temperature of a 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 during the reaction process, and when the epoxy value in the reaction system is less than 0.1, finishing the reaction to obtain the self-crosslinking monomer.
The preparation method of the aqueous hydroxyl dispersion with the network crosslinking structure comprises the following steps:
(1) Adding an organic solvent and a self-crosslinking monomer in a formula amount into a reaction kettle, raising the temperature of a reaction system to 145 ℃ under the protection of nitrogen, then dropwise adding an ethylenically unsaturated monomer I in a formula amount and an initiator in a formula amount of 65% for 3 hours, and carrying out heat preservation stirring reaction for 30min after dropwise adding;
(2) Then, under the protection of nitrogen, beginning to dropwise add the formula amount of the ethylenically unsaturated monomer II and 34% of the formula amount of the initiator into the reaction system in the step (1), wherein the dropwise adding time is 1h, after the dropwise adding is finished, stirring and reacting for 2h under heat preservation, then adding the rest formula amount of the initiator at one time, and stirring and reacting for 30min under heat preservation;
(3) And then, under the protection of nitrogen, reducing the temperature of the reaction system to 90 ℃, then, adding the neutralizer with the formula amount at one time, stirring and reacting for 30min, dropwise adding deionized water with the formula amount of 1/2, wherein the dropwise adding time is 15min, stirring and dispersing uniformly, reducing the temperature of the reaction system to 60 ℃, continuously dropwise adding the deionized water with the rest formula amount, wherein the dropwise adding time is 15min, and stirring and dispersing for 30min to obtain the network cross-linked structure hydroxyl aqueous dispersion.
Example 5
The aqueous hydroxyl dispersion with the network cross-linking structure comprises the following reaction raw materials in parts by weight:
the ethylenically unsaturated monomer I comprises the following components in parts by weight:
23 parts of isooctyl acrylate
6 parts of hydroxypropyl methacrylate.
The ethylenically unsaturated monomer II comprises the following components in parts by weight;
18 parts of isobornyl methacrylate
9 portions of hydroxybutyl acrylate
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, raising the temperature of a 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 during the reaction process, and when the epoxy value in the reaction system is less than 0.1, finishing the reaction to obtain the self-crosslinking monomer.
The preparation method of the aqueous hydroxyl dispersion with the network crosslinking structure comprises the following steps:
(1) Adding an organic solvent and a self-crosslinking monomer in a formula amount into a reaction kettle, raising the temperature of a reaction system to 145 ℃ under the protection of nitrogen, then dropwise adding an ethylenically unsaturated monomer I in a formula amount and an initiator in a formula amount of 65% for 4 hours, and carrying out heat preservation stirring reaction for 30min after dropwise adding;
(2) Then, under the protection of nitrogen, beginning to dropwise add the formula amount of the ethylenically unsaturated monomer II and 34% of the formula amount of the initiator into the reaction system in the step (1), wherein the dropwise adding time is 1h, after the dropwise adding is finished, stirring and reacting for 2h under heat preservation, then adding the rest formula amount of the initiator at one time, and stirring and reacting for 30min under heat preservation;
(3) And then, under the protection of nitrogen, reducing the temperature of the reaction system to 100 ℃, then, adding a neutralizing agent in a formula amount at one time, stirring and reacting for 30min, dropwise adding deionized water in a formula amount of 1/2, wherein the dropwise adding time is 15min, stirring and dispersing uniformly, reducing the temperature of the reaction system to 50 ℃, continuously dropwise adding deionized water in the rest formula amount, wherein the dropwise adding time is 15min, and stirring and dispersing for 30min to obtain the network cross-linked structure hydroxyl aqueous dispersion.
Example 6
The aqueous hydroxyl dispersion with the network crosslinking structure comprises the following reaction raw materials in parts by weight:
the ethylenically unsaturated monomer I comprises the following components in parts by weight:
21 parts of n-butyl acrylate
And 7 parts of hydroxyhexyl acrylate.
The ethylenically unsaturated monomer II comprises the following components in parts by weight;
18 portions of styrene
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, raising the temperature of a 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 during the reaction process, and when the epoxy value in the reaction system is less than 0.1, finishing the reaction to obtain the self-crosslinking monomer.
The preparation method of the aqueous hydroxyl dispersion with the network crosslinking structure comprises the following steps:
(1) Adding an organic solvent and a self-crosslinking monomer in a formula amount into a reaction kettle, raising the temperature of a reaction system to 145 ℃ under the protection of nitrogen, then dropwise adding an ethylenically unsaturated monomer I in a formula amount and an initiator in a formula amount of 65% for 4 hours, and carrying out heat preservation stirring reaction for 30min after dropwise adding;
(2) Then, under the protection of nitrogen, beginning to dropwise add the formula amount of the ethylenically unsaturated monomer II and 34% of the formula amount of the initiator into the reaction system in the step (1), wherein the dropwise adding time is 1h, after the dropwise adding is finished, stirring and reacting for 2h under heat preservation, then adding the rest formula amount of the initiator at one time, and stirring and reacting for 30min under heat preservation;
(3) And then, under the protection of nitrogen, reducing the temperature of the reaction system to 85 ℃, then, adding the neutralizer with the formula amount at one time, stirring and reacting for 30min, dropwise adding deionized water with the formula amount of 1/2, wherein the dropwise adding time is 15min, stirring and dispersing uniformly, reducing the temperature of the reaction system to 65 ℃, continuously dropwise adding the deionized water with the rest formula amount, wherein the dropwise adding time is 15min, and stirring and dispersing for 30min to obtain the network cross-linked structure hydroxyl aqueous dispersion.
Comparative example 1 the same as example 1 except that comparative example 1 did not add a self-crosslinking monomer during the preparation of the aqueous hydroxyl dispersion.
Comparative example 2 the same as example 1 except that in comparative example 2, the self-crosslinking monomer was not added during the preparation of the aqueous hydroxyl dispersion, and the self-crosslinking monomer was replaced with an equimolar amount of glycidyl methacrylate.
Comparative example 3 the same as example 1 except that comparative example 3 did not add a self-crosslinking monomer during the preparation of the aqueous hydroxyl dispersion, it replaced the self-crosslinking monomer with an equimolar amount of compound a, prepared according to the following procedure:
36g of 1, 4-butanediol and 214g of glycidyl versatate are added into a reaction kettle and 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, the mixture is stirred and reacted for 6 hours, the epoxy value in the reaction system is monitored continuously in the reaction process, and when the epoxy value in the reaction system is less than 0.1, the reaction is finished to obtain the compound A.
Comparative example 4 the same as example 1 except that the amount of the initiator used in the reaction raw materials used in the preparation of the aqueous hydroxyl group dispersion was reduced by half in comparative example 4.
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 relevant performance tests, the results of which are shown in Table 1.
The storage stability of the aqueous hydroxyl dispersion was tested by placing the aqueous hydroxyl dispersion in an oven at 50 ℃ for 30 days and observing whether the physical state of the dispersion had changed (e.g., whether delamination, cloudiness, etc.) or not.
TABLE 1
| Test item | Appearance of the emulsion | Solid content (%) | Viscosity (25 ℃, mPa. Multidot.s) | Hydroxyl group content (%) | pH value | Storage stability |
| Example 1 | Milky white blue light | 48.5 | 3200 | 2.4 | 8.1 | Stabilization |
| Example 2 | Milky white blue light | 46.5 | 1800 | 3.0 | 7.8 | Stabilization |
| Example 3 | Milky white blue light | 46.8 | 2400 | 5.1 | 7.6 | Stabilization of |
| Example 4 | Milky white blue light | 45.5 | 2700 | 4.5 | 7.5 | Stabilization |
| Example 5 | Milky white blue light | 45.5 | 2500 | 4.2 | 7.8 | Stabilization of |
| Example 6 | Milky white blue light | 46.5 | 2400 | 1.7 | 8.0 | Stabilization |
| Comparative example 1 | Milky white blue light | 48.6 | 5500 | 2.4 | 7.4 | Stabilization of |
| Comparative example 2 | Milky white blue light | 48.5 | 7500 | 2.4 | 7.6 | Stabilization of |
| Comparative example 3 | Milky white blue light | 48.1 | 3500 | 2.4 | 7.5 | Stabilization |
| Comparative example 4 | Milky white blue light | 47.6 | 3250 | 2.4 | 7.8 | Stabilization of |
Applications of
The hydroxyl aqueous dispersions obtained in examples 1 to 6 and comparative examples 1 to 4 were prepared into a topcoat according to the following formulation in parts by weight, and were respectively coated on the surface of a sandblasted steel plate having a cured surface with a 45 μm thick primer of the paraglider technology XF44-33 epoxy, after the topcoat was cured to form a paint film with a thickness of 25 ± 2 μm, the paint film was tested for its relevant properties, the specific test results are shown in table 2, and the specific formulation of the topcoat is as follows:
and (2) component A:
and B component:
20 parts of Corsia 2655 isocyanate curing agent
6 parts of propylene glycol monomethyl ether acetate.
Wherein, the mass ratio of the component A to the component B in the embodiment 1 is 9;
mass ratio of the a component to the B component in example 2 7
Mass ratio of the a component to the B component in example 3 was 4.5
Mass ratio of the a component to the B component in example 4 was 5.5
Mass ratio of a component a to B component in example 5 5.7
Mass ratio of a component a to B component in example 6 11
Mass ratio of the a component to the B component in comparative example 19
Mass ratio of the a component to the B component in comparative example 2 9
Mass ratio of the a component to the B component in comparative example 39
Mass ratio of a component a to B component in comparative example 4 9
The formulation of the topcoat of comparative example 5 was as follows:
the component A comprises:
and B component:
20 parts of Corsia 2655 isocyanate curing agent
6 parts of propylene glycol methyl ether acetate.
The mass ratio of the component A to the component B is 9.
Wherein the adhesion is tested according to the paint film adhesion test of GB/T1720-1979 (1989).
The pencil hardness of the paint film reaching HB pencil hardness is tested every 5min according to GB/T6739-1996.
The surface drying speed of the paint film is tested according to GB/T1728-2020.
TABLE 2
| Test item | Adhesion (grade) | Speed of surface drying (min) | Pencil hardness time (min) to HB |
| Example 1 | 0 | 28 | 55 |
| Example 2 | 0 | 29 | 53 |
| Example 3 | 0 | 31 | 53 |
| Example 4 | 0 | 27 | 58 |
| Example 5 | 0 | 28 | 49 |
| Example 6 | 0 | 29 | 54 |
| Comparative example 1 | 1 | 42 | 78 |
| Comparative example 2 | 2 | 47 | 75 |
| Comparative example 3 | 1 | 50 | 80 |
| Comparative example 4 | 2 | 50 | 76 |
| Comparative example 5 | 1 | 45 | 85 |
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The network crosslinking structure hydroxyl aqueous dispersion is characterized by being prepared by carrying out free radical copolymerization reaction on a self-crosslinking monomer containing at least two double bonds, an ethylenic unsaturated monomer I, an ethylenic unsaturated monomer II, an initiator and a neutralizer in an organic solvent, and then adding water for dilution, wherein the using amount of reaction raw materials in parts by weight is as follows:
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:
vinyl monomer 15-25
5-10 parts of vinyl monomer containing hydroxyl
0.5-2 parts of special functional vinyl monomer.
2. The aqueous hydroxyl dispersion with a network crosslinking structure of claim 1, wherein the self-crosslinking monomer containing at least two double bonds is prepared by 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, raising the temperature of a 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 during the reaction, and when the epoxy value in the reaction system is less than 0.1, finishing the reaction to obtain the self-crosslinking monomer.
3. The aqueous hydroxyl dispersion with a network cross-linked structure according to claim 2, wherein the hydroxyl compound comprises at least one of linear alcohols containing 2 to 12 carbons and at least two hydroxyl groups.
4. The aqueous hydroxyl dispersion with a network cross-linked structure of claim 3, wherein the linear alcohol containing 2 to 12 carbons and at least two hydroxyl groups comprises at least one of ethylene glycol, propylene glycol, butylene glycol, 1, 3-propanediol, or 1, 4-butanediol.
5. The aqueous hydroxyl dispersion with a network cross-linked structure according to claim 2, wherein the hydroxyl compound comprises at least one of branched alcohols containing 2 to 12 carbons and at least two hydroxyl groups.
6. The aqueous hydroxyl dispersion with a network cross-linked structure according to claim 5, wherein the branched alcohol having 2 to 12 carbons and at least two hydroxyl groups comprises at least one of trimethylolpropane, trimethylolethane or pentaerythritol.
7. The aqueous hydroxyl dispersion with a network cross-linked structure as claimed in claim 1, wherein the vinyl monomer containing hydroxyl group comprises at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxyhexyl acrylate and hydroxyhexyl methacrylate.
8. The aqueous hydroxyl dispersion according to claim 1, wherein the special functional vinyl monomer comprises at least one of sodium p- (meth) styrene sulfonate, sodium vinyl sulfonate, sodium allyl ether hydroxypropyl sulfonate, vinyl alkoxy phosphate, and methacrylate alkoxy phosphate.
9. The aqueous hydroxyl dispersion according to claim 1, wherein 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.
10. An aqueous dispersion of hydroxyl groups with a network cross-linked structure according to any of claims 1 to 9, characterized in that it is prepared by a process comprising the following steps:
(1) Adding an organic solvent and a self-crosslinking monomer in a formula amount into a reaction kettle, raising the temperature of a reaction system to 105-145 ℃ under the protection of nitrogen, then dropwise adding an ethylenically unsaturated monomer I in a formula amount and an initiator in a formula amount of 65% for 3-5h, and carrying out heat preservation stirring reaction for 30min after dropwise adding;
(2) Then, under the protection of nitrogen, beginning to dropwise add the formula amount of the ethylenically unsaturated monomer II and 34 percent of the formula amount of the initiator into the reaction system in the step (1), wherein the dropwise adding time is 1-3h, after the dropwise adding is finished, keeping the temperature, stirring and reacting for 2h, then adding the rest formula amount of the initiator at one time, keeping the temperature, stirring and reacting for 30min;
(3) And then, under the protection of nitrogen, reducing the temperature of the reaction system to 80-100 ℃, then, adding the neutralizer with the formula amount at one time, stirring and reacting for 30min, dropwise adding deionized water with the formula amount of 1/2 for 15min, stirring and dispersing uniformly, reducing the temperature of the reaction system to 50-80 ℃, continuously dropwise adding the deionized water with the rest formula amount for 15min, and stirring and dispersing for 30min to obtain the hydroxyl water dispersion with the network crosslinking structure.
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