CN110317301B - Core-shell type polyurethane-acrylic emulsion and preparation method and application thereof - Google Patents
Core-shell type polyurethane-acrylic emulsion and preparation method and application thereof Download PDFInfo
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- CN110317301B CN110317301B CN201910546099.8A CN201910546099A CN110317301B CN 110317301 B CN110317301 B CN 110317301B CN 201910546099 A CN201910546099 A CN 201910546099A CN 110317301 B CN110317301 B CN 110317301B
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- China
- Prior art keywords
- acrylate
- methacrylate
- polyurethane
- core
- parts
- Prior art date
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- 239000000839 emulsion Substances 0.000 title claims abstract description 76
- 239000011258 core-shell material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000004945 emulsification Methods 0.000 title description 7
- 239000004814 polyurethane Substances 0.000 claims abstract description 72
- 229920002635 polyurethane Polymers 0.000 claims abstract description 64
- 229920006150 hyperbranched polyester Polymers 0.000 claims abstract description 61
- 239000000178 monomer Substances 0.000 claims abstract description 58
- 229920005862 polyol Polymers 0.000 claims abstract description 40
- 239000002994 raw material Substances 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000006185 dispersion Substances 0.000 claims abstract description 36
- 150000003077 polyols Chemical class 0.000 claims abstract description 35
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 34
- 239000003999 initiator Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 238000000576 coating method Methods 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- 238000004132 cross linking Methods 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 239000012948 isocyanate Substances 0.000 claims abstract description 13
- 230000000977 initiatory effect Effects 0.000 claims abstract description 8
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 8
- -1 aliphatic isocyanates Chemical class 0.000 claims description 36
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 32
- 239000004970 Chain extender Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 17
- 230000001804 emulsifying effect Effects 0.000 claims description 16
- 239000003995 emulsifying agent Substances 0.000 claims description 15
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 12
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000007334 copolymerization reaction Methods 0.000 claims description 9
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 8
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 6
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 6
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 claims description 6
- 239000005056 polyisocyanate Substances 0.000 claims description 6
- 229920001228 polyisocyanate Polymers 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 5
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229920005906 polyester polyol Polymers 0.000 claims description 5
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000007859 condensation product Substances 0.000 claims description 4
- 150000002148 esters Chemical group 0.000 claims description 4
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 claims description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 3
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-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
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- KCAMXZBMXVIIQN-UHFFFAOYSA-N octan-3-yl 2-methylprop-2-enoate Chemical compound CCCCCC(CC)OC(=O)C(C)=C KCAMXZBMXVIIQN-UHFFFAOYSA-N 0.000 claims description 3
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 claims description 3
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 2
- JPSKCQCQZUGWNM-UHFFFAOYSA-N 2,7-Oxepanedione Chemical compound O=C1CCCCC(=O)O1 JPSKCQCQZUGWNM-UHFFFAOYSA-N 0.000 claims description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 2
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 claims description 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 2
- VHNJXLWRTQNIPD-UHFFFAOYSA-N 3-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(O)CCOC(=O)C(C)=C VHNJXLWRTQNIPD-UHFFFAOYSA-N 0.000 claims description 2
- JRCGLALFKDKSAN-UHFFFAOYSA-N 3-hydroxybutyl prop-2-enoate Chemical compound CC(O)CCOC(=O)C=C JRCGLALFKDKSAN-UHFFFAOYSA-N 0.000 claims description 2
- YKXAYLPDMSGWEV-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCO YKXAYLPDMSGWEV-UHFFFAOYSA-N 0.000 claims description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 2
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 2
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 claims description 2
- WRAABIJFUKKEJQ-UHFFFAOYSA-N cyclopentyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCC1 WRAABIJFUKKEJQ-UHFFFAOYSA-N 0.000 claims description 2
- BTQLDZMOTPTCGG-UHFFFAOYSA-N cyclopentyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCC1 BTQLDZMOTPTCGG-UHFFFAOYSA-N 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- 150000005690 diesters Chemical class 0.000 claims description 2
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 2
- 150000002596 lactones Chemical class 0.000 claims description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 2
- SCZVXVGZMZRGRU-UHFFFAOYSA-N n'-ethylethane-1,2-diamine Chemical compound CCNCCN SCZVXVGZMZRGRU-UHFFFAOYSA-N 0.000 claims description 2
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 claims description 2
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 claims description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 claims description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 229940014800 succinic anhydride Drugs 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims 1
- 150000008065 acid anhydrides Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 24
- 239000002904 solvent Substances 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 229940065472 octyl acrylate Drugs 0.000 description 6
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920000178 Acrylic resin Polymers 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 5
- 125000004185 ester group Chemical group 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002981 blocking agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
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- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- XXURNZLYJUXXCF-HJWRWDBZSA-N (z)-4-octan-3-yloxy-4-oxobut-2-enoic acid Chemical compound CCCCCC(CC)OC(=O)\C=C/C(O)=O XXURNZLYJUXXCF-HJWRWDBZSA-N 0.000 description 1
- BOFGUJVLYGISIU-WAYWQWQTSA-N (z)-4-oxo-4-pentoxybut-2-enoic acid Chemical compound CCCCCOC(=O)\C=C/C(O)=O BOFGUJVLYGISIU-WAYWQWQTSA-N 0.000 description 1
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- AYAUWVRAUCDBFR-ARJAWSKDSA-N (z)-4-oxo-4-propoxybut-2-enoic acid Chemical compound CCCOC(=O)\C=C/C(O)=O AYAUWVRAUCDBFR-ARJAWSKDSA-N 0.000 description 1
- VNMOIBZLSJDQEO-UHFFFAOYSA-N 1,10-diisocyanatodecane Chemical compound O=C=NCCCCCCCCCCN=C=O VNMOIBZLSJDQEO-UHFFFAOYSA-N 0.000 description 1
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 1
- OHTRJOZKRSVAOX-UHFFFAOYSA-N 1,3-diisocyanato-2-methylcyclohexane Chemical compound CC1C(N=C=O)CCCC1N=C=O OHTRJOZKRSVAOX-UHFFFAOYSA-N 0.000 description 1
- GNQKHBSIBXSFFD-UHFFFAOYSA-N 1,3-diisocyanatocyclohexane Chemical compound O=C=NC1CCCC(N=C=O)C1 GNQKHBSIBXSFFD-UHFFFAOYSA-N 0.000 description 1
- ROHUXHMNZLHBSF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCC(CN=C=O)CC1 ROHUXHMNZLHBSF-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- OUJCKESIGPLCRN-UHFFFAOYSA-N 1,5-diisocyanato-2,2-dimethylpentane Chemical compound O=C=NCC(C)(C)CCCN=C=O OUJCKESIGPLCRN-UHFFFAOYSA-N 0.000 description 1
- AHBNSOZREBSAMG-UHFFFAOYSA-N 1,5-diisocyanato-2-methylpentane Chemical compound O=C=NCC(C)CCCN=C=O AHBNSOZREBSAMG-UHFFFAOYSA-N 0.000 description 1
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 description 1
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 description 1
- VZDIRINETBAVAV-UHFFFAOYSA-N 2,4-diisocyanato-1-methylcyclohexane Chemical compound CC1CCC(N=C=O)CC1N=C=O VZDIRINETBAVAV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- LZDXRPVSAKWYDH-UHFFFAOYSA-N 2-ethyl-2-(prop-2-enoxymethyl)propane-1,3-diol Chemical compound CCC(CO)(CO)COCC=C LZDXRPVSAKWYDH-UHFFFAOYSA-N 0.000 description 1
- ZDKYYMRLZONTFK-UHFFFAOYSA-N 3,4-bis(isocyanatomethyl)bicyclo[2.2.1]heptane Chemical compound C1CC2(CN=C=O)C(CN=C=O)CC1C2 ZDKYYMRLZONTFK-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- XLYMOEINVGRTEX-ARJAWSKDSA-N Ethyl hydrogen fumarate Chemical compound CCOC(=O)\C=C/C(O)=O XLYMOEINVGRTEX-ARJAWSKDSA-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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical class NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- MWJNGKOBSUBRNM-FPLPWBNLSA-N dibutan-2-yl (z)-but-2-enedioate Chemical compound CCC(C)OC(=O)\C=C/C(=O)OC(C)CC MWJNGKOBSUBRNM-FPLPWBNLSA-N 0.000 description 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- QMCVOSQFZZCSLN-QXMHVHEDSA-N dihexyl (z)-but-2-enedioate Chemical compound CCCCCCOC(=O)\C=C/C(=O)OCCCCCC QMCVOSQFZZCSLN-QXMHVHEDSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 description 1
- NFCMRHDORQSGIS-KTKRTIGZSA-N dipentyl (z)-but-2-enedioate Chemical compound CCCCCOC(=O)\C=C/C(=O)OCCCCC NFCMRHDORQSGIS-KTKRTIGZSA-N 0.000 description 1
- FNMTVMWFISHPEV-WAYWQWQTSA-N dipropan-2-yl (z)-but-2-enedioate Chemical compound CC(C)OC(=O)\C=C/C(=O)OC(C)C FNMTVMWFISHPEV-WAYWQWQTSA-N 0.000 description 1
- DSTWFRCNXMNXTR-WAYWQWQTSA-N dipropyl (z)-but-2-enedioate Chemical compound CCCOC(=O)\C=C/C(=O)OCCC DSTWFRCNXMNXTR-WAYWQWQTSA-N 0.000 description 1
- MSVGHYYKWDQHFV-FPLPWBNLSA-N ditert-butyl (z)-but-2-enedioate Chemical compound CC(C)(C)OC(=O)\C=C/C(=O)OC(C)(C)C MSVGHYYKWDQHFV-FPLPWBNLSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- VGGRCVDNFAQIKO-UHFFFAOYSA-N formic anhydride Chemical compound O=COC=O VGGRCVDNFAQIKO-UHFFFAOYSA-N 0.000 description 1
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- DUDXQIXWPJMPRQ-UHFFFAOYSA-N isocyanatomethylcyclohexane Chemical compound O=C=NCC1CCCCC1 DUDXQIXWPJMPRQ-UHFFFAOYSA-N 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000768 polyamine Chemical class 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000379 polypropylene carbonate Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses a core-shell polyurethane-acrylic emulsion, wherein the raw materials of the polyurethane-acrylic emulsion comprise hyperbranched polyester modified polyurethane aqueous dispersion serving as a core structure, an acrylate pre-emulsified monomer mixture serving as a shell structure and an initiator aqueous solution for initiating a crosslinking bonding reaction between the shell structure and the core structure; the raw material components of the hyperbranched polyester modified polyurethane aqueous dispersion comprise polyfunctional isocyanate, polymer polyol and hyperbranched polyester with carboxyl groups; the invention also relates to the preparation and application of the core-shell polyurethane-acrylic emulsion, which can obviously improve the mechanical strength and hardness of the aqueous polyurethane chain segment in the polyurethane-acrylic emulsion, thereby further improving the water resistance and solvent resistance of the aqueous polyurethane chain segment and simultaneously obviously improving the defects of high viscosity and low brittleness of the acrylate chain segment in the polyurethane-acrylic emulsion; the coating is applied as a raw material for preparing the coating, and can effectively improve the physical and mechanical properties, water resistance, solvent resistance, film forming property and weather resistance of the coating.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a core-shell type polyurethane-acrylic emulsion, and a preparation method and application thereof.
Background
As is well known, the waterborne polyurethane has excellent film forming property, and a coating film prepared from the waterborne polyurethane has the advantages of excellent elasticity, glossiness, wear resistance, low-temperature impact resistance, small temperature-dependent change of hardness and the like, but has defects in hardness, water resistance, alcohol resistance and the like. In the case of acrylic resin, the coating film has excellent weather resistance and can provide excellent hardness performance and excellent water resistance and alcohol resistance, but the acrylic resin has the defects of high viscosity and low brittleness, so that the acrylic resin is sensitive to temperature change. Therefore, in the prior art, the acrylic resin is usually adopted to modify the waterborne polyurethane, and the obtained modified product has the advantages of two resins, so that the performance complementation is achieved. The modified product is applied to traditional coatings, usually aqueous polyurethane and aqueous acrylic resin are added into a coating system by means of material blending, however, because of the difference of physical properties between the two resins, compatibility problems exist between the two resins in the coating, and thus the stability of the coating system is poor. For the waterborne polyurethane-acrylic acid copolymer, the copolymerization system connects two resins together through chemical bonds in the preparation process, so that the compatibility between the two resins can be greatly improved, and the stability of a coating system can be improved.
There are many technical disclosures on the chemical bond between the two resins: for example, Chinese patent No. CN109162123A discloses an anionic polyurethane modified polyacrylate emulsion with a cross-linked core-shell structure and a preparation method thereof. The preparation method described in this patent comprises the following steps: 1) in the presence of a polyurethane catalyst, preparing a PU (polyurethane) active prepolymer by using polyester glycol, poly (butadiene) glycol, isophorone diisocyanate, dimethylolpropionic acid, trimethylolpropane monoallyl ether, 1, 4-butanediol, polyethylene glycol monomethyl ether and hydroxyethyl methacrylate as raw materials, and mixing the PU active prepolymer, part of polyacrylate monomer raw materials, part of an emulsifier, triethylamine and water to prepare a PU active prepolymer emulsion; (2) mixing the rest of polyacrylate monomer raw material, the rest of emulsifier and water, stirring and emulsifying to obtain PA pre-emulsion, performing pre-polymerization reaction on the PA pre-emulsion in the presence of an initiator, and then adding the PU active prepolymer emulsion to perform polymerization reaction to obtain a final product; by analyzing the PU active prepolymer emulsion in the patent, the molecular structure of the PU active prepolymer is a linear structure, and the molecules of the PU active prepolymer before emulsification do not contain isocyanate groups any more, so that the PU active prepolymer can not be further crosslinked and chain extended to form an internal crosslinking structure in the dispersing process.
For example, Chinese patent with publication number CN109734846A discloses a core-shell type waterborne polyurethane/acrylate composite emulsion, a preparation method thereof and a damping coating. The preparation method described in this patent comprises the following steps: 1) mixing oligomer dihydric alcohol, polyisocyanate, a micromolecule alcohol chain extender, a hydrophilic chain extender, a micromolecule cross-linking agent, an organic solvent and a catalyst, and carrying out polycondensation reaction to obtain an isocyanate-terminated polyurethane prepolymer; 2) mixing the isocyanate-terminated polyurethane prepolymer obtained in the step 1) with a blocking agent to perform a polycondensation reaction to obtain a waterborne polyurethane prepolymer; 3) mixing the waterborne polyurethane prepolymer with part of acrylate monomers and a salt forming agent to perform a neutralization reaction to obtain a waterborne polyurethane emulsion; 4) and mixing the aqueous polyurethane emulsion with the rest acrylate monomer, an emulsifier, a cross-linking agent, an initiator and water to perform free radical emulsion polymerization reaction to obtain the core-shell aqueous polyurethane/acrylate composite emulsion. Wherein the end capping agent comprises one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate; by analyzing the waterborne polyurethane prepolymer prepared in the embodiment, the molecular structure of the waterborne polyurethane prepolymer is linear, and the molecules of the prepolymer before emulsification do not contain isocyanate groups any more, so that the prepolymer cannot be further crosslinked and extended in a dispersing process to form an internal crosslinking structure.
For example, Chinese patent with publication number CN109321077A discloses a preparation method of aqueous polyurethane/acrylate composite emulsion. The method comprises the steps of polymerizing polyether polyol, polyisocyanate monomers, castor oil and a hydrophilic chain extender step by step according to a certain proportion, adding a blocking agent for blocking to prepare a blocked anionic waterborne polyurethane emulsion, and then adding an acrylate monomer for continuous polymerization with styrene to form a core-shell waterborne polyurethane/acrylate composite emulsion; by analyzing the waterborne polyurethane prepolymer prepared in the embodiment, the molecular structure of the waterborne polyurethane prepolymer is linear, and the molecules of the prepolymer before emulsification do not contain isocyanate groups any more, so that the prepolymer cannot be further crosslinked and extended in a dispersing process to form an internal crosslinking structure.
For example, Chinese patent with publication No. CN108017761A discloses an acrylic monomer modified polyurethane emulsion, its preparation method and its application. The method comprises the following steps of 1) carrying out prepolymerization reaction on polyol and polyisocyanate, then adding a chain extender containing a hydrophilic group, and after the reaction is finished, adding a blocking agent and a catalyst to carry out blocking reaction; 2) adding an acrylic monomer and an optional functional monomer into the reactant mixture obtained in the step 1), adding a neutralizing agent, and then adding water for emulsification to obtain a polyurethane prepolymer emulsion containing the acrylic monomer and the optional functional monomer; 3) taking out part of the polyurethane prepolymer emulsion obtained in the step 2), adding part of the initiator, carrying out polymerization reaction, taking the obtained polymerization reaction mixture as a seed solution, and then dropwise adding the rest of the polyurethane prepolymer emulsion and the rest of the initiator into the seed solution to carry out seed emulsion polymerization reaction; by analyzing the waterborne polyurethane prepolymer prepared in the embodiment, the molecular structure of the waterborne polyurethane prepolymer is linear, and the molecules of the prepolymer before emulsification do not contain isocyanate groups any more, so that the prepolymer cannot be further crosslinked and extended in a dispersing process to form an internal crosslinking structure.
For example, Chinese patent with publication number CN108164650A discloses an alkenyl non-ionic waterborne polyurethane modified acrylate emulsion and a preparation method thereof. Firstly, preparing a double-bond-containing nonionic aqueous polyurethane monomer by using terminal alkenyl polyglycol ether, diisocyanate, micromolecular dihydric alcohol and micromolecular trihydric alcohol as raw materials, and then carrying out emulsion polymerization on an acrylate monomer and the prepared terminal alkenyl nonionic aqueous polyurethane monomer to obtain an aqueous polyurethane modified acrylate emulsion; in the patent, micromolecular trihydric alcohol is used as an internal crosslinking component in the prepolymerization process, and finally the prepolymer is terminated by terminal alkenyl polyglycol ether to obtain the nonionic polyurethane prepolymer emulsion with the internal crosslinking structure.
For example, Chinese patent publication No. CN108264614A discloses a polyurethane-acrylic acid composite emulsion composition and a preparation method thereof. The method takes isocyanate prepolymer, polyester polyol, hydrophilic chain extender, short chain extender, post chain extender, neutralizer and acrylic monomer as main raw materials to prepare the polyurethane-acrylic acid composite emulsion. During film formation, the polyurethane has good film forming property through a core-shell crosslinking structure between the polyurethane and the acrylic acid, and the temperature resistance and the compatibility are improved; the patent firstly synthesizes prepolymer with isocyanate groups, and then uses a post-chain extender to ensure that the final polyurethane aqueous dispersion obtains an internal crosslinking structure when the prepolymer is dispersed in water; by analyzing the examples, the post-chain extender used was selected from ethylenediamine, divinyltriamine, trivinyltetramine, adipic dihydrazide, polyamine compounds all of which are small molecules.
From the above, in the prior art, there are many preparation methods for preparing polyurethane-acrylic acid emulsion for improving the bonding between polyurethane and acrylic acid, and then these methods basically adopt prepolymer fluids of linear high polymer melt and concentrated solution, these fluids do not obey newton's law, and have high viscosity, poor fluidity and film forming property, and still have many problems, so there is an urgent need to seek technical solution for improvement.
Disclosure of Invention
In view of the above, the present invention provides a core-shell type polyurethane-acrylic emulsion and a preparation method thereof, which can significantly improve the mechanical strength and hardness of a water polyurethane chain segment in the polyurethane-acrylic emulsion, thereby further improving the water resistance and solvent resistance of the water polyurethane chain segment, and at the same time, can significantly improve the defects of high viscosity and low brittleness of an acrylate chain segment in the polyurethane-acrylic emulsion.
The invention also aims to provide application of the core-shell type polyurethane-acrylic emulsion, wherein the core-shell type polyurethane-acrylic emulsion is used as a raw material for preparing the coating, so that the physical and mechanical properties, water resistance, solvent resistance, film forming property and weather resistance of the coating can be effectively improved.
The technical scheme adopted by the invention is as follows:
the raw materials of the polyurethane-acrylic emulsion comprise hyperbranched polyester modified polyurethane aqueous dispersion serving as a core structure, acrylate pre-emulsified monomer mixture serving as a shell structure and initiator aqueous solution for initiating a cross-linking bonding reaction between the shell structure and the core structure; the hyperbranched polyester modified polyurethane aqueous dispersion comprises raw material components of polyfunctional isocyanate, polymer polyol and hyperbranched polyester with carboxyl groups.
Preferably, the hyperbranched polyester modified polyurethane aqueous dispersion comprises the following raw material components:
preferably, the raw materials of the acrylate pre-emulsified monomer mixture comprise the following raw material components:
preferably, the initiator aqueous solution comprises 1-10 parts of initiator and 10-50 parts of pure water, wherein persulfate is adopted as the initiator.
Preferably, the functionality of the isocyanate group in the polyfunctional isocyanate is at least 2, and is selected from at least one of polyfunctional aliphatic isocyanate and polyfunctional alicyclic isocyanate;
the polymer polyol is at least one of polyester polyol, polyether polyol and polycarbonate polyol, wherein the polyester polyol is formed by condensation of dibasic acid and dihydric alcohol or ring-opening polymerization of lactone; the polyether polyol is polyether polyol containing at least one repeating unit of ethylene oxide, propylene oxide and butylene oxide; the polycarbonate polyol is an oligomer containing at least two terminal hydroxyl carbonic ester structures and is obtained by performing ester exchange reaction on carbonic diester and dihydric alcohol; the molecular weight range of the polymer polyol is 500-5000g/mol, and the hydroxyl value range is 10-250mg KOH/g;
the hydrophilic chain extender is selected from at least one of 2, 2-dimethylolpropionic acid, 2-dimethylolbutyric acid and N-sulfoacid ethylethylenediamine;
the general chain extender is selected from at least one of dihydric alcohol and diamine;
the functional dihydric alcohol containing the carbon-carbon double bond is selected from one of the following structures:
wherein m + n is 2, and m and n are integers;
the organic metal catalyst is at least one of organic tin, organic bismuth and organic zirconium metal compound;
the organic solvent is at least one selected from aliphatic ketones;
the organic amine neutralizer is selected from at least one of aliphatic tertiary amines;
the hyperbranched polyester with carboxyl groups is selected from one of the following structures:
wherein o and p are positive integers, and o + p is less than or equal to 80; wherein,
is the backbone of the hyperbranched hydroxy polyester, R1Is the residual alkyl group of anhydride molecule after removing anhydride group, wherein the anhydride is selected from hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and tetrahydrophthalic anhydrideAt least one of formic anhydride, methyl tetrahydrophthalic anhydride, phthalic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, and trimellitic anhydride.
Preferably, the monomer containing a carbon-carbon double bond and capable of undergoing copolymerization is selected from at least one of styrene, methyl styrene, allyl alcohol, vinyl versatate, monomethyl maleate, monoethyl maleate, mono-n-propyl maleate, mono-isopropyl maleate, mono-n-butyl maleate, mono-sec-butyl maleate, mono-tert-butyl maleate, monopentyl maleate, monohexyl maleate, mono-ethylhexyl maleate, bis-methyl maleate, bis-ethyl maleate, bis-n-propyl maleate, bis-isopropyl maleate, bis-n-butyl maleate, bis-sec-butyl maleate, bis-tert-butyl maleate, bis-pentyl maleate, bis-hexyl maleate, and bis-ethylhexyl maleate, and may also be selected from other monomers containing a carbon-carbon double bond and capable of undergoing copolymerization known to those skilled in the art.
Preferably, the derivative of the acrylate and/or methacrylate monomer is selected from at least one of alkyl acrylate, alkyl methacrylate, cycloalkyl acrylate, cycloalkyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate;
the emulsifier is selected from at least one of anionic emulsifiers.
Preferably, the derivative of the acrylate and/or methacrylate monomer is methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, pentyl acrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, 3, 5-trimethylhexyl acrylate, 3, 5-trimethylhexyl methacrylate, octadecyl acrylate, octadecyl methacrylate, dodecyl acrylate, dodecyl methacrylate, cyclopentyl acrylate, methyl methacrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, pentyl acrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate, ethylhexyl acrylate, hexyl acrylate, octyl acrylate, hexyl acrylate, octyl acrylate, hexyl acrylate, octyl acrylate, hexyl methacrylate, hexyl acrylate, dodecyl methacrylate, hexyl acrylate, octyl acrylate, hexyl acrylate, dodecyl methacrylate, hexyl acrylate, octyl acrylate, hexyl acrylate, dodecyl methacrylate, octyl acrylate, hexyl, At least one of cyclopentyl methacrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, a condensation product of acrylic acid and glycidyl versatate, a condensation product of methacrylic acid and glycidyl versatate, acrylic acid, and methacrylic acid;
the lipophilic group in the emulsifier adopts at least one of straight-chain alkyl with 11-17 carbon atoms and aromatic alkyl with 3-8 carbon atoms, and the hydrophilic group adopts at least one of phosphate, carboxylate, sulfate and sulfonate.
Preferably, the polyfunctional aliphatic isocyanate is selected from the group consisting of 1, 4-diisocyanatobutane, 1, 6-diisocyanatohexane, 2-methyl-1, 5-diisocyanatopentane, 1, 5-diisocyanato-2, 2-dimethyl-pentane, 2, 4-trimethyl-1, 6-diisocyanatohexane, 2,4, 4-trimethyl-1, 6-diisocyanatohexane, 1, 10-diisocyanatodecane, 1, 3-diisocyanatocyclohexane, 1, 4-diisocyanatocyclohexane, 2, 6-diisocyanato-1-methylcyclohexane, 2, 4-diisocyanato-1-methylcyclohexane, 1, 3-bis- (isocyanatomethyl) cyclohexane, at least one of 1, 4-bis- (isocyanatomethyl) cyclohexane, isophorone diisocyanate, 2,4 '-diisocyanatodicyclohexylmethane, 4' -diisocyanatodicyclohexylmethane, 1-isocyanato-1-methyl-4 (3) isocyanatomethylcyclohexane, bis (isocyanatomethyl) -norbornane, and/or trimers, pentamers, and multimers formed from the above aliphatic diisocyanate monomers, alicyclic diisocyanate monomers, may be selected from other polyfunctional aliphatic isocyanates known to those skilled in the art.
Preferably, the polymer polyol is at least one selected from the group consisting of polytetrahydrofuran polyol, polyethylene oxide polyol, polypropylene oxide polyol, polytetrahydrofuran-ethylene oxide polyol, polytetrahydrofuran-propylene oxide polyol, polyethylene oxide-propylene oxide polyol, polytetrahydrofuran-ethylene oxide-propylene oxide polyol, polyhexamethylene adipate polyol, polytetramethylene adipate polyol, polyethylene adipate polyol, neopentyl adipate polyol, polyhexamethylene phthalate polyol, polycaprolactone polyol, polyethylene carbonate polyol, polypropylene carbonate polyol, and other polymer polyols known to those skilled in the art.
Preferably, the general chain extender is selected from at least one of ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, ethylene diamine, propylene diamine, butylene diamine, and hexamethylene diamine, and may also be selected from other general chain extenders known to those skilled in the art.
Preferably, the organometallic catalyst is selected from at least one of dibutyltin oxide, dibutyltin dilaurate, dioctyltin oxide, stannous octoate, bismuth acetate, bismuth octoate, and zirconium acetylacetonate, and may be selected from other organometallic catalysts known to those skilled in the art.
Preferably, the organic solvent is selected from at least one of acetone, butanone, methyl isobutyl ketone and methyl amyl ketone, and can also be selected from other organic solvents known to those skilled in the art.
Preferably, the organic amine neutralizer is at least one selected from triethylamine, tributylamine, N-dimethylbenzylamine, and triisopropylamine, and may be selected from other organic amine neutralizers known to those skilled in the art.
Preferably, the preparation method of the core-shell type polyurethane-acrylic emulsion comprises the following steps:
s10), preparing the hyperbranched polyester modified polyurethane aqueous dispersion, wherein the operation steps comprise: firstly, preparing an isocyanate-terminated polyurethane prepolymer, neutralizing carboxyl in the isocyanate-terminated polyurethane prepolymer into salt, and then adding the neutralized isocyanate-terminated polyurethane prepolymer into pure water in which hyperbranched polyester with carboxyl groups is dissolved to perform dispersion chain extension reaction to obtain a hyperbranched polyester modified polyurethane aqueous dispersion;
s20), preparing an acrylate pre-emulsified monomer mixture, and the operation steps comprise: pre-emulsifying monomers which contain carbon-carbon double bonds and can undergo copolymerization reaction, derivatives of acrylate and/or methacrylate monomers, an emulsifier and pure water to obtain an acrylate pre-emulsified monomer mixture;
s30), dissolving an initiator in pure water to obtain an initiator aqueous solution;
s40), dropwise adding the acrylic ester pre-emulsified monomer mixture obtained in the step S20) and the initiator aqueous solution obtained in the step S30) into the hyperbranched polyester modified polyurethane aqueous dispersion obtained in the step S10), and reacting the acrylic ester pre-emulsified monomer mixture with the hyperbranched polyester modified polyurethane aqueous dispersion under the initiation action of the initiator aqueous solution to obtain the core-shell polyurethane-acrylic emulsion; the step S10), the step S20) and the step S30) are carried out simultaneously or sequentially.
Preferably, the operation procedure of step S10) is: carrying out prepolymerization reaction on 20-50 parts of polyisocyanate, 30-70 parts of polymer polyol, 5-15 parts of hydrophilic chain extender, 5-10 parts of general chain extender, 2-5 parts of functional dihydric alcohol containing carbon-carbon double bonds, 0.1-1 part of organic metal catalyst and 10-30 parts of organic solvent as raw materials to obtain an isocyanate-terminated polyurethane prepolymer, wherein the reaction temperature is 70-90 ℃, and the reaction time is 4-8 hours; then 5-15 parts of organic amine neutralizer is adopted to neutralize carboxyl in the isocyanate-terminated polyurethane prepolymer to form salt; finally, adding the neutralized isocyanate-terminated polyurethane prepolymer into 400 parts of pure water containing 200-400 parts of hyperbranched polyester with carboxyl groups dissolved therein for carrying out dispersion chain extension reaction at the temperature of 25-50 ℃ for 0.5-1.5h to obtain hyperbranched polyester modified polyurethane aqueous dispersion;
the operation process of the step S20) is as follows: pre-emulsifying 25-200 parts of monomer which contains carbon-carbon double bond and can carry out copolymerization reaction, 80-350 parts of derivative of acrylate and/or methacrylate monomer, 0.5-5 parts of emulsifier and 100-300 parts of pure water, wherein the pre-emulsifying rotation speed is 500-2000rpm, and the pre-emulsifying time is 5-20min, so as to obtain an acrylate pre-emulsifying monomer mixture;
the operation process of the step S30) is as follows: dissolving 1-10 parts of initiator in 10-50 parts of pure water to obtain an initiator aqueous solution;
in the step S40), the reaction temperature is 70-90 ℃ and the reaction time is 4-10 h.
Preferably, the core-shell type polyurethane-acrylic emulsion is used as a raw material for preparing a coating.
The hyperbranched polyester component adopted by the invention has a compact molecular structure and a spherical three-dimensional spatial structure, the applicant surprisingly discovers that the hyperbranched polyester usually shows Newtonian fluid behavior, so that the hyperbranched polyester has low viscosity, good fluidity and film forming property, and the highly branched structure of the hyperbranched polyester can embed ester groups in molecular chains, so that the direct contact between the ester groups and water in the air can be effectively prevented, the hydrolysis probability of the ester groups is reduced, the characteristics can simultaneously and obviously improve the relevant characteristics of a waterborne polyurethane chain segment and an acrylate chain segment in polyurethane-acrylic emulsion, and after retrieval, technical disclosure or technical inspiration is not discovered and proposed to apply the hyperbranched polyester component as a raw material for preparing the polyurethane-acrylic emulsion and can simultaneously bring about remarkable technical effects in various aspects, the applicant creatively takes the hyperbranched polyester component as a key raw material component for preparing the core-shell type polyurethane-acrylic emulsion, and obtains remarkable technical effects in various aspects at the same time, specifically:
1. according to the core-shell polyurethane-acrylic emulsion provided by the invention, when the hyperbranched polyester is grafted to a polyurethane molecular chain in the process of preparing the hyperbranched polyester modified polyurethane aqueous dispersion, an internal crosslinking structure can be formed, and the mechanical strength and hardness of a waterborne polyurethane chain segment can be obviously improved, so that the water resistance and solvent resistance of the waterborne polyurethane chain segment in the core-shell polyurethane-acrylic emulsion are further improved;
2. due to the introduction of the hyperbranched polyester component into the core-shell polyurethane-acrylic emulsion provided by the invention, the soft segment of the hyperbranched polyester has good flexibility and film-forming property, so that the defects of high viscosity and low brittleness of an acrylate chain segment in the polyurethane-acrylic emulsion can be obviously improved;
3. according to the core-shell polyurethane-acrylic emulsion containing the hyperbranched polyester soft segment, due to the special structure of the hyperbranched polyester, the highly branched structure can embed ester groups in molecular chains, so that hydrolysis of ester bonds can be effectively inhibited;
4. the invention further preferably provides that the core-shell type polyurethane-acrylic emulsion provided by the invention is used as a raw material for preparing the coating, and the water resistance, solvent resistance, flexibility, film forming property and weather resistance of a coating film can be obviously improved.
Detailed Description
The embodiment of the invention discloses a core-shell polyurethane-acrylic emulsion, wherein the raw materials of the polyurethane-acrylic emulsion comprise hyperbranched polyester modified polyurethane aqueous dispersion serving as a core structure, an acrylate pre-emulsified monomer mixture serving as a shell structure and an initiator aqueous solution for initiating a cross-linking bonding reaction between the shell structure and the core structure; the hyperbranched polyester modified polyurethane aqueous dispersion comprises raw material components of polyfunctional isocyanate, polymer polyol and hyperbranched polyester with carboxyl groups.
The embodiment of the invention also discloses a preparation method of the core-shell type polyurethane-acrylic emulsion, which comprises the following steps: s10), preparing the hyperbranched polyester modified polyurethane aqueous dispersion, wherein the operation steps comprise: firstly, preparing an isocyanate-terminated polyurethane prepolymer, neutralizing carboxyl in the isocyanate-terminated polyurethane prepolymer into salt, and then adding the neutralized isocyanate-terminated polyurethane prepolymer into pure water in which hyperbranched polyester with carboxyl groups is dissolved to perform dispersion chain extension reaction to obtain a hyperbranched polyester modified polyurethane aqueous dispersion; s20), preparing an acrylate pre-emulsified monomer mixture, and the operation steps comprise: pre-emulsifying monomers which contain carbon-carbon double bonds and can undergo copolymerization reaction, derivatives of acrylate and/or methacrylate monomers, an emulsifier and pure water to obtain an acrylate pre-emulsified monomer mixture; s30), dissolving an initiator in pure water to obtain an initiator aqueous solution; s40), dropwise adding the acrylic ester pre-emulsified monomer mixture obtained in the step S20) and the initiator aqueous solution obtained in the step S30) into the hyperbranched polyester modified polyurethane aqueous dispersion obtained in the step S10), and reacting the acrylic ester pre-emulsified monomer mixture with the hyperbranched polyester modified polyurethane aqueous dispersion under the initiation action of the initiator aqueous solution to obtain a core-shell polyurethane-acrylic emulsion; step S10), step S20) and step S30) are performed simultaneously or sequentially.
The embodiment of the invention also discloses application of the core-shell type polyurethane-acrylic emulsion, wherein the core-shell type polyurethane-acrylic emulsion is used as a raw material for preparing the coating.
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
Various aspects of the present invention will be described in detail below, and various starting materials of the present invention are commercially available unless otherwise specified; or prepared according to conventional methods in the art. Unless defined or stated otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention.
The experimental procedures, in which specific conditions are not specified, in the following examples are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers. Unless otherwise indicated, all parts are parts by weight and all percentages are percentages by weight.
Example 1: preparation of hyperbranched polyesters with carboxyl groups HPPE (I)
354.8g of Boltorn H40 and 74g of hexahydrophthalic anhydride were charged in a 1L reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube and a reflux condenser, and then the reaction system was warmed to 130 ℃. After the reaction temperature is constant, continuously preserving the heat for 4-5h at the temperature, sampling every 1h during the period to measure the acid value, and cooling the reaction system to 100 ℃ when the measured value of the acid value (63mgKOH/g) reaches the theoretical value (62.8 mgKOH/g); and finally, 48g of triethylamine and 595g of pure water are added to obtain the hyperbranched polyester with the carboxyl groups, the solid content of which is 40 percent.
Example 2: preparation of hyperbranched polyesters with carboxyl groups HPPE (II)
354.8g of Boltorn H40 and 98.6g of hexahydrophthalic anhydride were charged in a 1L reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube and a reflux condenser, and then the reaction system was warmed to 130 ℃. After the reaction temperature is constant, continuously preserving the heat for 4-5h at the temperature, sampling every 1h during the period to measure the acid value, and cooling the reaction system to 100 ℃ when the measured value of the acid value (79mgKOH/g) reaches the theoretical value (79.2 mgKOH/g); finally, 52g of triethylamine and 400g of pure water are added to obtain the hyperbranched polyester with the carboxyl groups and the solid content of which is 50 percent.
Examples 3 to 8: preparation of core-shell polyurethane-acrylic emulsion
S10), carrying out prepolymerization reaction on 20-50 parts of polyisocyanate, 30-70 parts of polymer polyol, 5-15 parts of hydrophilic chain extender, 5-10 parts of general chain extender, 2-5 parts of functional dihydric alcohol containing carbon-carbon double bonds, 0.1-1 part of organic metal catalyst and 10-30 parts of organic solvent as raw materials to obtain an isocyanate-terminated polyurethane prepolymer, wherein the reaction temperature is 70-90 ℃, and the reaction time is 4-8 h; then 5-15 parts of organic amine neutralizer is adopted to neutralize carboxyl in the isocyanate-terminated polyurethane prepolymer to form salt; finally, adding the neutralized isocyanate-terminated polyurethane prepolymer into 400 parts of pure water containing 200-400 parts of hyperbranched polyester with carboxyl groups dissolved therein for carrying out dispersion chain extension reaction at the temperature of 25-50 ℃ for 0.5-1.5h to obtain hyperbranched polyester modified polyurethane aqueous dispersion;
s20), pre-emulsifying 25-200 parts of monomer which contains carbon-carbon double bond and can carry out copolymerization reaction, 80-350 parts of derivative of acrylate and/or methacrylate monomer, 0.5-5 parts of emulsifier and 100-300 parts of pure water, wherein the pre-emulsifying rotating speed is 500-2000rpm, and the pre-emulsifying time is 5-20min, so as to obtain an acrylate pre-emulsifying monomer mixture;
s30), dissolving 1-10 parts of initiator in 10-50 parts of pure water to obtain an initiator aqueous solution;
s40), dropwise adding the acrylic ester pre-emulsified monomer mixture obtained in the step S20) and the initiator aqueous solution obtained in the step S30) into the hyperbranched polyester modified polyurethane aqueous dispersion obtained in the step S10), and reacting the acrylic ester pre-emulsified monomer mixture with the hyperbranched polyester modified polyurethane aqueous dispersion under the initiation action of the initiator aqueous solution, wherein the reaction temperature is 70-90 ℃, and the reaction time is 4-10 hours, so as to finally obtain the core-shell polyurethane-acrylic emulsion; in the present embodiment, step S10) is performed first, and step S20) and step S30) are performed simultaneously; in other embodiments, step S10), step S20), and step S30) may be performed simultaneously or may be performed in a sequential order as needed, and this embodiment is not particularly limited thereto.
The specific raw material components and their parts by weight in examples 3-4 can be directly referred to in table 1 below; the specific raw material components and their parts by weight in examples 5-6 can be directly seen in table 2 below: the specific raw material components and their parts by weight in examples 7-8 can be directly seen in table 3 below:
TABLE 1 data tables for the specific raw material components and parts by weight thereof in examples 3-4
TABLE 2 data tables for the specific raw material components and their parts by weight in examples 5-6
TABLE 3 tables for the specific raw material components and parts by weight thereof in examples 7 to 8
Example 9: the core-shell type polyurethane-acrylic emulsions prepared according to the above examples 3 to 8 were used as raw materials for preparing paints, respectively.
Comparative example: the invention also provides a comparative example, which adopts the anionic polyurethane modified polyacrylate emulsion with the cross-linked core-shell structure disclosed in CN109162123A as a raw material for preparing the coating.
Example 9 also shows the coating prepared by respectively using examples 3-8 as the raw material of the coating and the coating prepared by using comparative example as the raw material of the coating, wherein the other components and the preparation methods used in the coatings of examples 3-8 and comparative example are completely the same and are known technologies, and the application performs film coating on the coatings and performs the following comparative tests on the film coatings, and the results are shown in the following table 4:
TABLE 4 comparison of the effects of the coating film applications of examples 3 to 8 and comparative examples
Thus, it is suggested by table 4 above that the embodiments of the present invention have the following technical effects:
1. according to the core-shell polyurethane-acrylic emulsion provided by the invention, when the hyperbranched polyester is grafted to a polyurethane molecular chain in the process of preparing the hyperbranched polyester modified polyurethane aqueous dispersion, an internal crosslinking structure can be formed, and the mechanical strength and hardness of a waterborne polyurethane chain segment can be obviously improved, so that the water resistance and solvent resistance of the waterborne polyurethane chain segment in the core-shell polyurethane-acrylic emulsion are further improved;
2. due to the introduction of the hyperbranched polyester component into the core-shell polyurethane-acrylic emulsion provided by the invention, the soft segment of the hyperbranched polyester has good flexibility and film-forming property, so that the defects of high viscosity and low brittleness of an acrylate chain segment in the polyurethane-acrylic emulsion can be obviously improved;
3. according to the core-shell polyurethane-acrylic emulsion containing the hyperbranched polyester soft segment, due to the special structure of the hyperbranched polyester, the highly branched structure can embed ester groups in molecular chains, so that hydrolysis of ester bonds can be effectively inhibited;
4. the core-shell polyurethane-acrylic emulsion is used as a raw material for preparing the coating, and the water resistance, solvent resistance, flexibility, film forming property and weather resistance of the coating can be obviously improved.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the invention and are not to be construed as limiting the embodiments of the present invention, and that various other changes and modifications may be made by those skilled in the art based on the above description. All documents mentioned in this application are incorporated by reference into this application as if each were individually incorporated by reference.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (9)
1. The core-shell polyurethane-acrylic emulsion is characterized in that raw materials of the polyurethane-acrylic emulsion comprise hyperbranched polyester modified polyurethane aqueous dispersion serving as a core structure, an acrylate pre-emulsified monomer mixture serving as a shell structure and an initiator aqueous solution for initiating a crosslinking bonding reaction between the shell structure and the core structure; the raw material components of the hyperbranched polyester modified polyurethane aqueous dispersion comprise polyfunctional isocyanate, polymer polyol and hyperbranched polyester with carboxyl groups; the hyperbranched polyester modified polyurethane aqueous dispersion comprises the following raw material components:
2. the core-shell polyurethane-acrylic emulsion of claim 1, wherein the raw materials of the acrylate pre-emulsified monomer mixture comprise the following raw material components:
3. the core-shell polyurethane-acrylic emulsion according to claim 1 or 2, wherein the aqueous initiator solution comprises 1 to 10 parts of initiator and 10 to 50 parts of pure water, wherein the initiator is persulfate.
4. The core-shell polyurethane-acrylic emulsion of claim 1 wherein the polyfunctional isocyanate has an isocyanate group functionality of at least 2 and is selected from at least one of polyfunctional aliphatic isocyanates and polyfunctional cycloaliphatic isocyanates;
the polymer polyol is at least one of polyester polyol, polyether polyol and polycarbonate polyol, wherein the polyester polyol is formed by condensation of dibasic acid and dihydric alcohol or ring-opening polymerization of lactone; the polyether polyol is polyether polyol containing at least one repeating unit of ethylene oxide, propylene oxide and butylene oxide; the polycarbonate polyol is an oligomer containing at least two terminal hydroxyl carbonic ester structures and is obtained by performing ester exchange reaction on carbonic diester and dihydric alcohol; the molecular weight range of the polymer polyol is 500-5000g/mol, and the hydroxyl value range is 10-250mg KOH/g;
the hydrophilic chain extender is selected from at least one of 2, 2-dimethylolpropionic acid, 2-dimethylolbutyric acid and N-sulfoacid ethylethylenediamine;
the general chain extender is selected from at least one of dihydric alcohol and diamine;
the functional dihydric alcohol containing the carbon-carbon double bond is selected from one of the following structures:
wherein m + n is 2, and m and n are integers;
the organic metal catalyst is at least one of organic tin, organic bismuth and organic zirconium metal compound;
the organic solvent is at least one selected from aliphatic ketones;
the organic amine neutralizer is selected from at least one of aliphatic tertiary amines;
the hyperbranched polyester with carboxyl groups is selected from one of the following structures:
wherein o and p are positive integers, and o + p is less than or equal to 80; wherein,
is the backbone of the hyperbranched hydroxy polyester, R1For alkyl radicals remaining in the anhydride molecule after removal of the anhydride groupsAnd the acid anhydride is at least one selected from hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, phthalic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride and trimellitic anhydride.
5. The core-shell polyurethane-acrylic emulsion of claim 2, wherein the derivative of the acrylate and/or methacrylate monomer is selected from at least one of alkyl acrylate, alkyl methacrylate, cycloalkyl acrylate, cycloalkyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate;
the emulsifier is selected from at least one of anionic emulsifiers.
6. The core-shell polyurethane-acrylic emulsion of claim 5, wherein the derivative of the acrylate and/or methacrylate monomer is methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, pentyl acrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, 3, 5-trimethylhexyl acrylate, 3, 5-trimethylhexyl methacrylate, octadecyl acrylate, octadecyl methacrylate, ethyl acrylate, propyl methacrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, butyl acrylate, pentyl acrylate, hexyl methacrylate, hexyl acrylate, ethylhexyl methacrylate, ethyl methacrylate, hexyl methacrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, dodecyl methacrylate, cyclopentyl acrylate, cyclopentyl methacrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, a condensation product of acrylic acid with glycidyl versatate, a condensation product of methacrylic acid with glycidyl versatate, a salt of acrylic acid with a salt of methacrylic acid with glycidyl versatate, a salt of methacrylic acid with a salt of methacrylic acid, a salt of methacrylic acid with glycidyl versatate, a salt of methacrylic acid with a salt of methacrylic acid, a salt of glycidyl ester, a salt of methacrylic acid, a salt of methacrylic acid, a compound of a compound, at least one of acrylic acid and methacrylic acid;
the lipophilic group in the emulsifier adopts at least one of straight-chain alkyl with 11-17 carbon atoms and aromatic alkyl with 3-8 carbon atoms, and the hydrophilic group adopts at least one of phosphate, carboxylate, sulfate and sulfonate.
7. A process for preparing the core-shell polyurethane-acrylic emulsion of any of claims 1 to 6, comprising the steps of:
s10), preparing the hyperbranched polyester modified polyurethane aqueous dispersion, wherein the operation steps comprise: firstly, preparing an isocyanate-terminated polyurethane prepolymer, neutralizing carboxyl in the isocyanate-terminated polyurethane prepolymer into salt, and then adding the neutralized isocyanate-terminated polyurethane prepolymer into pure water in which hyperbranched polyester with carboxyl groups is dissolved to perform dispersion chain extension reaction to obtain a hyperbranched polyester modified polyurethane aqueous dispersion;
s20), preparing an acrylate pre-emulsified monomer mixture, and the operation steps comprise: pre-emulsifying monomers which contain carbon-carbon double bonds and can undergo copolymerization reaction, derivatives of acrylate and/or methacrylate monomers, an emulsifier and pure water to obtain an acrylate pre-emulsified monomer mixture;
s30), dissolving an initiator in pure water to obtain an initiator aqueous solution;
s40), dropwise adding the acrylic ester pre-emulsified monomer mixture obtained in the step S20) and the initiator aqueous solution obtained in the step S30) into the hyperbranched polyester modified polyurethane aqueous dispersion obtained in the step S10), and reacting the acrylic ester pre-emulsified monomer mixture with the hyperbranched polyester modified polyurethane aqueous dispersion under the initiation action of the initiator aqueous solution to obtain the core-shell polyurethane-acrylic emulsion; the step S10), the step S20) and the step S30) are carried out simultaneously or sequentially.
8. The method for preparing the core-shell type polyurethane-acrylic emulsion according to claim 7, wherein the operation process of step S10) is: carrying out prepolymerization reaction on 20-50 parts of polyisocyanate, 30-70 parts of polymer polyol, 5-15 parts of hydrophilic chain extender, 5-10 parts of general chain extender, 2-5 parts of functional dihydric alcohol containing carbon-carbon double bonds, 0.1-1 part of organic metal catalyst and 10-30 parts of organic solvent as raw materials to obtain an isocyanate-terminated polyurethane prepolymer, wherein the reaction temperature is 70-90 ℃, and the reaction time is 4-8 hours; then 5-15 parts of organic amine neutralizer is adopted to neutralize carboxyl in the isocyanate-terminated polyurethane prepolymer to form salt; finally, adding the neutralized isocyanate-terminated polyurethane prepolymer into 400 parts of pure water containing 200-400 parts of hyperbranched polyester with carboxyl groups dissolved therein for carrying out dispersion chain extension reaction at the temperature of 25-50 ℃ for 0.5-1.5h to obtain hyperbranched polyester modified polyurethane aqueous dispersion;
the operation process of the step S20) is as follows: pre-emulsifying 25-200 parts of monomer which contains carbon-carbon double bond and can carry out copolymerization reaction, 80-350 parts of derivative of acrylate and/or methacrylate monomer, 0.5-5 parts of emulsifier and 100-300 parts of pure water, wherein the pre-emulsifying rotation speed is 500-2000rpm, and the pre-emulsifying time is 5-20min, so as to obtain an acrylate pre-emulsifying monomer mixture;
the operation process of the step S30) is as follows: dissolving 1-10 parts of initiator in 10-50 parts of pure water to obtain an initiator aqueous solution;
in the step S40), the reaction temperature is 70-90 ℃ and the reaction time is 4-10 h.
9. Use of the core-shell polyurethane-acrylic emulsion according to any of claims 1 to 6 as a starting material for the preparation of coatings.
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| CN111690097B (en) * | 2020-06-09 | 2023-05-23 | 常熟巴德富科技有限公司 | Core-shell type polyester-acrylic emulsion and preparation method and application thereof |
| CN114276498A (en) * | 2022-01-06 | 2022-04-05 | 安徽红太阳新材料有限公司 | Modified polyacrylate emulsion and coating composed of same |
| CN117203258A (en) * | 2022-08-11 | 2023-12-08 | 摩珈(上海)生物科技有限公司 | Modified bio-based waterborne polyurethane and preparation method and application thereof |
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