CN106634548B - A kind of polyurethane/acrylate hybridisation emulsion and preparation method thereof - Google Patents
A kind of polyurethane/acrylate hybridisation emulsion and preparation method thereof Download PDFInfo
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- CN106634548B CN106634548B CN201611163171.1A CN201611163171A CN106634548B CN 106634548 B CN106634548 B CN 106634548B CN 201611163171 A CN201611163171 A CN 201611163171A CN 106634548 B CN106634548 B CN 106634548B
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- acrylate
- polyurethane
- methyl
- reaction
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 74
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 72
- 239000000839 emulsion Substances 0.000 title claims abstract description 37
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 35
- 238000009396 hybridization Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000004945 emulsification Methods 0.000 title description 3
- 239000000178 monomer Substances 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- -1 acrylic ester Chemical class 0.000 claims abstract description 39
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 33
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000003999 initiator Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims description 36
- 229920002521 macromolecule Polymers 0.000 claims description 32
- 239000004530 micro-emulsion Substances 0.000 claims description 32
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 18
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 11
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 10
- 238000009413 insulation Methods 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 239000004970 Chain extender Substances 0.000 claims description 9
- 150000001450 anions Chemical class 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000006392 deoxygenation reaction Methods 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 9
- 125000002348 vinylic group Chemical group 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 claims description 8
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000006386 neutralization reaction Methods 0.000 claims description 8
- 229920001610 polycaprolactone Polymers 0.000 claims description 8
- 239000004632 polycaprolactone Substances 0.000 claims description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 8
- 235000019394 potassium persulphate Nutrition 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
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 7
- 125000005442 diisocyanate group Chemical group 0.000 claims description 7
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- 150000002923 oximes Chemical class 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 6
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 6
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 claims description 6
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 150000002009 diols Chemical class 0.000 claims description 5
- 239000007858 starting material Substances 0.000 claims description 5
- YXYZMHGSOKYZAF-UHFFFAOYSA-M [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C Chemical compound [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C YXYZMHGSOKYZAF-UHFFFAOYSA-M 0.000 claims description 4
- OVAJTCYOCUQIRF-UHFFFAOYSA-N [Na].NC=1C(=C(C=CC1)S(=O)(=O)O)N Chemical compound [Na].NC=1C(=C(C=CC1)S(=O)(=O)O)N OVAJTCYOCUQIRF-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 230000002459 sustained effect Effects 0.000 claims description 4
- 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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 3
- GUHRAJHKEBMTIG-UHFFFAOYSA-N [Na].NCCNC(C)S(=O)(=O)O Chemical compound [Na].NCCNC(C)S(=O)(=O)O GUHRAJHKEBMTIG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 229940051250 hexylene glycol Drugs 0.000 claims description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N hexylene glycol Natural products CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- KKVTYAVXTDIPAP-UHFFFAOYSA-M sodium;methanesulfonate Chemical compound [Na+].CS([O-])(=O)=O KKVTYAVXTDIPAP-UHFFFAOYSA-M 0.000 claims description 3
- VIFFNYAVJACGFW-UHFFFAOYSA-N 2-butylhexanoic acid;tin Chemical compound [Sn].CCCCC(C(O)=O)CCCC VIFFNYAVJACGFW-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000004643 cyanate ester Substances 0.000 claims 2
- 150000001913 cyanates Chemical class 0.000 claims 2
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- USUBUUXHLGKOHN-UHFFFAOYSA-N methyl 2-methylidenehexanoate Chemical compound CCCCC(=C)C(=O)OC USUBUUXHLGKOHN-UHFFFAOYSA-N 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- 239000006210 lotion Substances 0.000 abstract description 12
- 230000000903 blocking effect Effects 0.000 abstract description 3
- 229920001577 copolymer Polymers 0.000 abstract description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000000977 initiatory effect Effects 0.000 abstract description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 230000003750 conditioning effect Effects 0.000 description 5
- 239000006071 cream Substances 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- NIHJEJFQQFQLTK-UHFFFAOYSA-N butanedioic acid;hexanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCCCC(O)=O NIHJEJFQQFQLTK-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 3
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000005395 methacrylic acid group Chemical class 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QSLPNSWXUQHVLP-UHFFFAOYSA-N $l^{1}-sulfanylmethane Chemical compound [S]C QSLPNSWXUQHVLP-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 1
- VXTMLLAYZATZIB-UHFFFAOYSA-N 3,3-dihydroxy-2-methylbutanoic acid Chemical group OC(=O)C(C)C(C)(O)O VXTMLLAYZATZIB-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 241000165940 Houjia Species 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000007957 coemulsifier Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000004672 propanoic acids Chemical class 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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Abstract
The invention discloses a kind of polyurethane/acrylate hybridisation emulsions and preparation method thereof.The present invention uses chain tra nsfer catalysis method, using water as continuous phase, vinyl-based hydrophilic monomer is reaction object, divalent cobalt is catalyst, the water-wet side strand that unsaturated double-bond is contained in end is prepared by solution polymerization process, being subject to vinyl oleophylic monomer, the reaction was continued, and the amphipathic copolymer of block that end retains double bond is made.Then it is added in the ethenyl blocking polyurethane macromolecular performed polymer that inert acrylate is continuous phase, initiator initiation polymerizable macromolecular surfactant, acrylic ester monomer and polyurethane macromolecular mixing is added to be copolymerized, in reaction process, polymerisable emulsifier is coated and fixed by double bond on emulsion colloidal surface, lotion avoids migration of this kind of emulsifier to surface in the drying process in this way, ensure that this kind of lotion has good waterproof performance.
Description
[technical field]
The present invention relates to the preparation technical field of polyurethane, in particular to a kind of polyurethane/acrylate hybridisation emulsion and
Preparation method.
[background technique]
With sound and people's environmental consciousness the reinforcement of environmentally friendly laws and regulations, the use scope of solvent based coating is limited
System, the research of water paint are paid more and more attention.Aqueous polyurethane is a kind of film-forming resin haveing excellent performance, the 1970s
The self-emulsifying preparation method of polyaminoester emulsion is developed, current research focuses mostly on to be modified in it, wherein acrylate modified
Polyurethane is most common.The aqueous polyurethane-acrylate (PUA) of copolymerization method preparation fully utilizes the excellent weather resistance and hard of acrylate
The advantages of good and polyurethane wear resistant, excellent in mechanical performance, overcome acrylate hot sticky cold crisp and Water-resistance of Waterborne Polyurethane it is poor,
The low disadvantage of solid content.But PUA lotion be used as high-grade Coating base water resistance, in terms of still have deficiency.
[summary of the invention]
It is an object of the invention in place of overcome the deficiencies in the prior art, provide a kind of macromolecular polymerisable emulsifier and its
Preparation method.The present invention effectively improves the solid content of microemulsion, improves the curing rate of film, and synthesis improves the water-fast of film
The performances such as property, chemical-resistant, to compare favourably with solvent based coating.
In order to achieve the above objectives, the technical solution adopted by the present invention is that:
A kind of polyurethane/acrylate hybridisation emulsion, the raw material including following parts by weight:
0.5~2 part of polymerizable macromolecule emulsifier, 5~20 parts of acrylic ester monomers, 10~18 parts of aqueous polyurethanes are micro-
Lotion, 0.1~0.3 part of water soluble starter are dissolved in manufactured initiator solution in 5~10 parts of water；
The polymerizable macromolecule emulsifier includes the raw material of following parts by weight: 50~120 parts of water, and 0.01~0.1 part
Divalent cobalt class catalyst, 0.1~0.5 part of water soluble starter, 50~100 parts of vinyl hydrophilic monomers, 100~150 parts of second
Alkenyl oleophylic monomer；The polymerizable macromolecule emulsifier the preparation method comprises the following steps:
50~120 parts of water, 0.01~0.1 part of divalent cobalt and 0.1~0.5 part are added into the reactor equipped with blender
Aqueous initiator after being sufficiently stirred, with freeze-thaw pump circulation method to system deoxygenation, fills guarantor to carrying out vacuumizing in flask later
Protect gas；Then it keeps the temperature at 65-85 DEG C, vinyl hydrophilic monomer is at the uniform velocity added dropwise in reactor, continue after being added dropwise anti-
It answers 0.5~1.5 hour, then disposably puts into 100~150 parts of vinyl oleophylic monomers into flask, sustained response to termination, it
Cooling immediately stops reaction afterwards, and product drying for standby under room temperature in vacuum conditions obtains polymerizable macromolecule emulsifier.
The aqueous polyurethane microemulsion includes the raw material of following parts by weight: 15~30 parts of inertia vinyl monomers, 7~
18 parts of polymer polyatomic alcohols, 5~15 parts of diisocyanate cpds, 2~8 parts of anion mixing hydrophilic chain extenders and 0.10~
0.35 part of catalyst, the hydrophilic vinylic monomer of 2~9 parts of hydroxyls or amino, 1.5~9.6 parts of bases salt forming agent, 50~
80 parts of deionized water.The Polyurethane Microemulsion the preparation method comprises the following steps:
15~30 parts of inertia vinyl monomers, 7~18 parts of polymer polyatomic alcohols, 5~15 parts are added into dry reactor
Diisocyanate cpd, 2~8 parts of anion mixing hydrophilic chain extenders and 0.10~0.35 part of catalyst, reaction temperature are constant
It is 75~85 DEG C, the reaction time is 2~4 hours；The hydrophilic vinylic monomer that 2~9 parts of hydroxyls or amino are added is sealed
End insulation reaction 0.5~1 hour, adds 2.3~9.6 parts of bases salt forming agents and carries out neutralization reaction, be eventually adding deionization
Dispersion is sufficiently stirred to get Polyurethane Microemulsion in water；
The divalent cobalt class catalyst is that cobalt II oxime is fluorinated boron complex；
The water soluble starter is one or more of ammonium persulfate, potassium peroxydisulfate and sodium peroxydisulfate；
The catalyst is dibutyl tin dilaurate, stannous octoate or di-n-butylacetic acid tin.
The vinyl hydrophilic monomer is acrylic acid, methacrylic acid, 2- acrylamide-2-methyl propane sulfonic, methyl sulphur
The mixture that one or more of sour sodium, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride arbitrarily match；
The vinyl oleophylic monomer is methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, propylene
Sour pentyl ester, Hexyl 2-propenoate, Isooctyl acrylate monomer, methyl methacrylate, ethyl methacrylate, propyl methacrylate,
One of butyl methacrylate, pentylmethacrylate, hexyl methacrylate, isooctyl methacrylate and styrene
Or the two or more mixtures arbitrarily matched.
The acrylic ester monomer is methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, propylene
Sour pentyl ester, Hexyl 2-propenoate, Isooctyl acrylate monomer, methyl methacrylate, ethyl methacrylate, propyl methacrylate,
Butyl methacrylate, pentylmethacrylate, hexyl methacrylate, isooctyl methacrylate and Glycidyl methacrylate
The mixture that one or more of glyceride arbitrarily matches.
The inertia vinyl monomer is (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid fourth
Ester, (methyl) Hexyl 2-propenoate, (methyl) n-octyl, (methyl) 2-EHA, styrene, Alpha-Methyl benzene
One of ethylene, two or more mixture arbitrarily matched；
The polymer polyatomic alcohol is polyadipate hexylene glycol ester of the molecular weight between 1000~2000, polyadipate
The mixing that one or both of butanediol ester, polycaprolactone glycol, polycarbonate glycol, polytetrahydrofuran diol arbitrarily match
Object；
The diisocyanate cpd is that hexamethylene diisocyanate, isophorone diisocyanate, toluene two are different
The mixture that one or both of cyanate, methyl diphenylene diisocyanate arbitrarily match.
The anion mixing hydrophilic chain extender is dihydromethyl propionic acid, one or two kinds of and dihydroxy in dimethylolpropionic acid
What one or more of base propanesulfonate, 2- aminoethylamino ethanesulfonic acid sodium and diamino benzene sulfonic acid sodium arbitrarily matched
Mixture；
The hydrophilic vinylic monomer of the hydroxyl or amino is hydroxy-ethyl acrylate, hydroxypropyl acrylate, acryloyl
One or both of amine, hydroxyethyl methacrylate, hydroxy propyl methacrylate, hydroxymethyl acrylamide arbitrarily match mixed
Close object；
The bases salt forming agent is ammonium hydroxide or triethylamine.
A kind of preparation method of polyurethane/acrylate hybridisation emulsion, comprising the following steps:
Step 1) prepares polymerizable macromolecule emulsifier:
50~120 parts of water, 0.01~0.1 part of divalent cobalt and 0.1~0.5 part are added into the reactor equipped with blender
Aqueous initiator after being sufficiently stirred, with freeze-thaw pump circulation method to system deoxygenation, fills guarantor to carrying out vacuumizing in flask later
Protect gas；Then it keeps the temperature at 65-85 DEG C, vinyl hydrophilic monomer is at the uniform velocity added dropwise in reactor, continue after being added dropwise anti-
It answers 0.5~1.5 hour, then disposably puts into 100~150 parts of vinyl oleophylic monomers into flask, sustained response to termination, it
Cooling immediately stops reaction afterwards, and product drying for standby under room temperature in vacuum conditions obtains polymerizable macromolecule emulsifier；
Step 2) prepares Polyurethane Microemulsion:
15~30 parts of inertia vinyl monomers, 7~18 parts of polymer polyatomic alcohols, 5~15 parts are added into dry reactor
Diisocyanate cpd, 2~8 parts of anion mixing hydrophilic chain extenders and 0.10~0.35 part of catalyst, reaction temperature are constant
It is 75~85 DEG C, the reaction time is 2~4 hours；The hydrophilic vinylic monomer that 2~9 parts of hydroxyls or amino are added is sealed
End insulation reaction 0.5~1 hour, adds 2.3~9.6 parts of bases salt forming agents and carries out neutralization reaction, be eventually adding deionization
Dispersion is sufficiently stirred to get Polyurethane Microemulsion in water；
Step 3) prepares hybridisation emulsion:
Under conditions of temperature is 75~85 DEG C, 10~18 parts of Polyurethane Microemulsions, 0.5~2 are added into drying receptacle
Part polymerizable macromolecule emulsifier, is then dissolved in manufactured initiator solution in 5~10 parts of water for 0.1~0.3 part of initiator
It is uniformly added dropwise in reactor in 1~3 hour with 5~20 parts of acrylic ester monomers, after being added dropwise, continues insulation reaction
To termination, taking-up is cooled to room temperature, and adjusting pH is alkalinity to get polyurethane/acrylate hybridisation emulsion.
Compared with prior art, the invention has the following beneficial technical effects:
It with a kind of polymerizable amphipathic nature block polymer is big point that the present invention, which is a kind of polyurethane/acrylate hybridisation emulsion,
Sub- emulsifier is equipped with polyurethane/acrylate hybridisation emulsion made of Polyurethane Microemulsion using water as decentralized medium.The present invention
By a kind of polymerizable macromolecule emulsifier, waterborne PUA is further changed using the double bond of macromolecule and end reactable
Property, to significantly improve water resistance, the solvent resistance of waterborne PUA film.It is demonstrated experimentally that polymerisable macromolecule prepared by the present invention
Emulsifier terminal double bond retains, the amphipathic nature block polymer of structure-controllable, for being used as polymerisable macromolecule in emulsion polymerization
Emulsifier.And hybridisation emulsion average grain diameter prepared by the present invention is 88.2nm, and uniform particle sizes, product stability is good.Relative to
The solid content of existing PUA lotion, this product is high, and the curing rate of film is fast, ambient temperature curable, zero free TDI, VOC free, tool
Have the advantages that nontoxic, safety, water resistance, chemicals-resistant and solvent-resisting are good；It can compare favourably with solvent based coating.This lotion is available
In surface coverings such as woodenware, paper, metals.
The present invention is a kind of preparation method of polyurethane/acrylate hybridisation emulsion, and inert acrylate is continuous
In the ethenyl blocking polyurethane macromolecular performed polymer of phase, initiator is added and causes polymerizable macromolecular surfactant, propylene
Esters of gallic acid monomer and the mixing of polyurethane (PU) macromolecular are copolymerized, and in reaction process, polymerisable emulsifier is coated by double bond
It is fixed on emulsion colloidal surface, such lotion avoids migration of this kind of emulsifier to surface in the drying process, protects
This kind of lotion has been demonstrate,proved with good waterproof performance.Key, which is to be catalyzed by chain tra nsfer, reacts, and polymer high score is effectively reduced
The molecular weight and molecular weight distribution of son, and retain the double bond for subsequent reactions in molecule chain end, obtain the two of structure-controllable
Parent's property block copolymer, for being used as polymerizable macromolecule emulsifier in emulsion polymerization.Preparing polyurethane/acrylate hydridization
It is not required to effectively improve consolidating for microemulsion by any small-molecular emulsifier, the introducing of polymerizable macromolecule emulsifier and contain when lotion
Amount improves the curing rate of film, and synthesis improves the performances such as water resistance, the chemical-resistant of film, to apply with solvent type
Material compares favourably.
Wherein, the preparation of polymerizable macromolecule emulsifier is using water as continuous phase, and vinyl-based hydrophilic monomer is reaction pair
As divalent cobalt is catalyst, prepares the water-wet side strand that unsaturated double-bond is contained in end, Zhi Houjia by solution polymerization process
With vinyl oleophylic monomer, the reaction was continued, and after completion of the reaction, the block of vacuum drying at room temperature, obtained end reservation double bond is amphipathic
Copolymer, i.e., required polymerizable macromolecule emulsifier.
The preparation of Waterborne Polyurethane Prepolymer is using inertia mixture of vinyl monomer as continuous phase, in the effect of catalyst
The lower polymerization for carrying out polymer polyatomic alcohol, anion mixing hydrophilic chain extender and diisocyanate cpd obtains isocyanates
It is reacted with the hydrophilic vinylic monomer of hydroxyl or amino and the poly- ammonia containing vinyl is made by the polyurethane molecular chain of sealing end
Ester performed polymer.Then it is neutralized with bases salt forming agent, water dispersion obtains Polyurethane Microemulsion.
[Detailed description of the invention]
Fig. 1 is that the laser Raman spectroscopy of polymerizable macromolecule emulsifier of the present invention characterizes；
Fig. 2 is the grain size distribution of polyurethane/acrylate hybridisation emulsion of the present invention.
[specific embodiment]
The invention will be described in further detail combined with specific embodiments below: (being in parts by weight below)
Embodiment 1:
Under conditions of temperature is 85 DEG C, 10 parts of Polyurethane Microemulsions, the polymerizable cream of macromolecular are added in drying receptacle
0.5 part of agent, then by ammonium persulfate aqueous solution (0.1 part of ammonium persulfate is dissolved in 5 parts of water) and 8 parts of acrylic ester monomers from
Two sides are uniformly added dropwise in reactor in 2 hours, after being added dropwise, are continued insulation reaction 1.5 hours, taking-up is cooled to room
Temperature is used for polyurethane/acrylate hybridisation emulsion for 7 with ammonia water conditioning system pH to get a kind of polymerizable macromolecule emulsifier.
Wherein, the preparation process of macromolecular polymerisable emulsifier is as follows:
A certain amount of 60 parts of water is added in reactor equipped with blender, 0.01 part of cobalt II oxime is fluorinated boron complex and 0.3
Part potassium peroxydisulfate, after being sufficiently stirred, with freeze-thaw pump circulation method to system deoxygenation, later to carrying out vacuum nitrogen filling in flask
Gas operation, is repeated 6 times, and then keeps 65 DEG C of constant temperature, 80 parts of methacrylic acids in being at the uniform velocity added dropwise in reactor in 1 hour,
The reaction was continued 1 hour after being added dropwise, and 100 parts of butyl acrylates are once put into flask, and reaction continues 2 hours again, Zhi Houli
I.e. cooling stops reaction, and polymerizable macromolecule emulsifier is made in product drying for standby under room temperature in vacuum conditions.
Wherein, the preparation process of Polyurethane Microemulsion is as follows:
Firstly, mixture (the mass ratio of 15 parts of methyl methacrylates and butyl acrylate is added into dry reactor
For 5:1), 10 parts of polycaprolactone diolss (molecular weight 1000), 10 parts of isophorone diisocyanate, 2 parts of dihydroxymethyl fourths
Acid and 0.1 part of catalyst, constant reaction temperature is 80 DEG C, and the reaction time is 3 hours；Then, be added 3 parts of hydroxy-ethyl acrylates into
Row sealing end, reacts 0.5 hour, and system temperature remains 80 DEG C, adds 1.5 parts of triethylamine, after neutralization reaction 30 minutes, and
60 parts of deionized water is dispersed with stirring 30 minutes, and constant temperature is 80 DEG C to get Polyurethane Microemulsion.
Embodiment 2:
Under conditions of temperature is 75 DEG C, 10 parts of Polyurethane Microemulsions, the polymerizable cream of macromolecular are added in drying receptacle
1 part of agent, then by persulfate aqueous solution (0.15 part of potassium peroxydisulfate is dissolved in 5 parts of water) and 5 parts of acrylic ester monomers from
Two sides are uniformly added dropwise in reactor in 2 hours, after being added dropwise, are continued insulation reaction 1.5 hours, taking-up is cooled to room
Temperature is used for polyurethane/acrylate hybridisation emulsion for 7 with ammonia water conditioning system pH to get a kind of polymerizable macromolecule emulsifier.
Wherein, the preparation process of macromolecular polymerisable emulsifier is as follows:
A certain amount of 60 parts of water is added in reactor equipped with blender, 0.01 part of cobalt II oxime is fluorinated boron complex and 0.3
Part ammonium persulfate, after being sufficiently stirred, with freeze-thaw pump circulation method to system deoxygenation, later to carrying out vacuum nitrogen filling in flask
Gas operation, is repeated 6 times, and then keeps 70 DEG C of constant temperature, 80 parts of methacrylic acids in being at the uniform velocity added dropwise in reactor in 1 hour,
The reaction was continued 1 hour after being added dropwise, and 120 parts of butyl acrylates are once put into flask, and reaction continues 2 hours again, Zhi Houli
I.e. cooling stops reaction, and polymerizable macromolecule emulsifier is made in product drying for standby under room temperature in vacuum conditions.
Wherein, the preparation process of Polyurethane Microemulsion is as follows:
Gather in oneself firstly, 12 parts of styrene are added into dry reactor with butyl acrylate (mass ratio 5:4), 10 parts
Ester dihydric alcohol (molecular weight 1000), 12 parts of isophorone diisocyanate, 2 parts of dimethylolpropionic acids and 0.1 part of catalyst, instead
Answering temperature constant is 70 DEG C, and the reaction time is 3 hours；Then, 3 parts of hydroxy-ethyl acrylates are added to be blocked, reaction 0.5 is small
When, system temperature remains 80 DEG C, 1.5 parts of triethylamine is added, after neutralization reaction 30 minutes and 50 parts of deionized water,
It is dispersed with stirring 30 minutes, constant temperature is 80 DEG C to get Polyurethane Microemulsion.
Embodiment 3:
Under conditions of temperature is 80 DEG C, 10 parts of Polyurethane Microemulsions, the polymerizable cream of macromolecular are added in drying receptacle
0.5 part of agent, then by potassium peroxydisulfate (0.1 part of potassium peroxydisulfate is dissolved in 5 parts of water) and 15 parts of acrylic ester monomers from two sides
It being uniformly added dropwise in reactor in 2 hours, after being added dropwise, continues insulation reaction 1.5 hours, taking-up is cooled to room temperature, with
Ammonia water conditioning system pH is used for polyurethane/acrylate hybridisation emulsion for 7 to get a kind of polymerizable macromolecule emulsifier.
Wherein, the preparation process of macromolecular polymerisable emulsifier is as follows:
A certain amount of 60 parts of water is added in reactor equipped with blender, 0.03 part of cobalt II oxime is fluorinated boron complex and 0.3
Part ammonium persulfate, after being sufficiently stirred, with freeze-thaw pump circulation method to system deoxygenation, later to carrying out vacuum nitrogen filling in flask
Gas operation, is repeated 6 times, and then keeps 80 DEG C of constant temperature, and 60 parts of methylpropene sodium sulfonates are in being at the uniform velocity added dropwise to reactor in 1 hour
Interior, the reaction was continued 1 hour after being added dropwise, and 100 parts of butyl methacrylates are once put into flask, and reaction continues 2 hours again,
Cooling immediately stops reaction later, and polymerizable macromolecule emulsifier is made in product drying for standby under room temperature in vacuum conditions.
Wherein, the preparation process of Polyurethane Microemulsion is as follows:
Firstly, mixture (the mass ratio of 15 parts of methyl methacrylates and butyl acrylate is added into dry reactor
For 5:1), 10 parts of polycaprolactone diolss (molecular weight 1000), 10 parts of isophorone diisocyanate, 2 parts of dihydroxymethyl fourths
Acid and 0.1 part of catalyst, constant reaction temperature is 80 DEG C, and the reaction time is 3 hours；Then, be added 3 parts of hydroxy-ethyl acrylates into
Row sealing end, reacts 0.5 hour, and system temperature remains 80 DEG C, adds 1.5 parts of triethylamine, after neutralization reaction 30 minutes, and
60 parts of deionized water is dispersed with stirring 30 minutes, and constant temperature is 80 DEG C to get Polyurethane Microemulsion.
Embodiment 4:
Under conditions of temperature is 80 DEG C, 15 parts of Polyurethane Microemulsions, the polymerizable cream of macromolecular are added in drying receptacle
1 part of agent, then by sodium persulfate aqueous solution (0.2 part of sodium peroxydisulfate is dissolved in 8 parts of water) and 10 parts of acrylic ester monomers from
Two sides are uniformly added dropwise in reactor in 1 hour, after being added dropwise, are continued insulation reaction 1 hour, and taking-up is cooled to room temperature,
Polyurethane/acrylate hybridisation emulsion is used for get a kind of polymerizable macromolecule emulsifier with ammonia water conditioning system pH for 8.
Wherein, the preparation process of macromolecular polymerisable emulsifier is as follows:
A certain amount of 50 parts of water is added in reactor equipped with blender, 0.01 part of cobalt II oxime is fluorinated boron complex and 0.1
Part potassium peroxydisulfate, after being sufficiently stirred, with freeze-thaw pump circulation method to system deoxygenation, later to carrying out vacuum nitrogen filling in flask
Gas operation, is repeated 6 times, and then keeps 85 DEG C of constant temperature, 50 parts of acrylic acid and 2- acrylamide-2-methyl propane sulfonic arbitrary proportion
Mixture in 0.5 hour in being at the uniform velocity added dropwise in reactor, and the reaction was continued 0.5 hour after being added dropwise, and once throws in flask
Enter the mixture of 120 parts of methyl methacrylates and ethyl acrylate arbitrary proportion, reaction continues 2.5 hours again, immediately later
Cooling stops reaction, and polymerizable macromolecule emulsifier is made in product drying for standby under room temperature in vacuum conditions.
Wherein, the preparation process of Polyurethane Microemulsion is as follows:
Firstly, 20 parts of methyl methacrylates and butyl acrylate (mass ratio 5:1), 7 are added into dry reactor
Part polyadipate hexylene glycol ester and poly adipate succinic acid ester mixture (molecular weight 2000), 5 parts of hexa-methylene diisocyanates
Ester and isophorone diisocyanate, 5 parts of dihydromethyl propionic acids and dihydroxy propanesulfonate mixture and 0.2 part of catalyst, instead
Answering temperature constant is 80 DEG C, and the reaction time is 2 hours；Then, 2 parts of hydroxyethyl methacrylates and methacrylic acid hydroxypropyl is added
Ester is blocked, and is reacted 0.8 hour, and system temperature remains 85 DEG C, adds 1.5 parts of ammonium hydroxide, neutralization reaction after twenty minutes,
It with 50 parts of deionized water, is dispersed with stirring 10 minutes, constant temperature is 80 DEG C to get Polyurethane Microemulsion.
Embodiment 5:
Under conditions of temperature is 80 DEG C, 18 parts of Polyurethane Microemulsions, the polymerizable cream of macromolecular are added in drying receptacle
2 parts of agent, then by ammonium persulfate aqueous solution (0.3 part of ammonium persulfate is dissolved in 10 parts of water) and 20 parts of acrylic ester monomers from
Two sides are uniformly added dropwise in reactor in 3 hours, after being added dropwise, are continued insulation reaction 2 hours, and taking-up is cooled to room temperature,
Polyurethane/acrylate hybridisation emulsion is used for get a kind of polymerizable macromolecule emulsifier with ammonia water conditioning system pH for 8.
Wherein, the preparation process of macromolecular polymerisable emulsifier is as follows:
A certain amount of 120 parts of water is added in reactor equipped with blender, 0.1 part of cobalt II oxime is fluorinated boron complex and 0.5
Part sodium peroxydisulfate, after being sufficiently stirred, with freeze-thaw pump circulation method to system deoxygenation, later to carrying out vacuum nitrogen filling in flask
Gas operation, is repeated 6 times, and then keeps 75 DEG C of constant temperature, 80 parts of acrylic acid, 2- acrylamide-2-methyl propane sulfonic, sodium methanesulfonate
With MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride mixture in being at the uniform velocity added dropwise in reactor in 1.5 hours, it is added dropwise
The reaction was continued afterwards 1.5 hours, and 150 parts of butyl acrylates, amyl acrylate, hexyl methacrylate, first are once put into flask
The mixture of base Isooctyl acrylate monomer and styrene, reaction continue 3 hours again, and cooling stops reaction immediately later, and product is in room
Polymerizable macromolecule emulsifier is made in drying for standby under warm vacuum condition.
Wherein, the preparation process of Polyurethane Microemulsion is as follows:
Firstly, 30 parts of methyl methacrylates and butyl acrylate (mass ratio 5:1), 18 are added into dry reactor
Mixture (molecular weight 1500), the 15 parts of toluene di-isocyanate(TDI)s and two of part poly adipate succinic acid ester and polycaprolactone glycol
The mixture of methylenebis phenyl isocyanate, the mixture of 8 parts of dimethylolpropionic acids and diamino benzene sulfonic acid sodium and 0.35 part are urged
Agent, constant reaction temperature is 80 DEG C, and the reaction time is 4 hours；Then, 9 parts of hydroxy propyl methacrylates and methylol is added
The mixture of acrylamide is blocked, and is reacted 1 hour, system temperature remains 80 DEG C, adds 1.5 parts of triethylamine；In
After with reaction 30 minutes and 80 parts of deionized water, it is dispersed with stirring 30 minutes, constant temperature is 80 DEG C to get Polyurethane Microemulsion；
The inertia vinyl monomer is the mixture of methyl methacrylate and butyl acrylate, wherein metering system
The mass ratio of sour methyl esters and butyl acrylate is 5:1；The polymer polyatomic alcohol is that (molecular weight is polycaprolactone diols
1000)；The diisocyanate cpd is isophorone diisocyanate；The anion mixing hydrophilic chain extender is dihydroxy
Methylbutanoic acid,；The hydrophilic vinylic monomer of the hydroxyl or amino is hydroxy-ethyl acrylate；The bases salt forming agent is three
Ethamine；The initiator is potassium peroxydisulfate.
Methacrylic acid in embodiment 1 can also be acrylic acid, methacrylic acid, 2- acrylamide -2- methyl-prop sulphur
The mixture that one or more of acid, sodium methanesulfonate, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride arbitrarily match；
Butyl acrylate in embodiment 1 can also be, methyl acrylate, ethyl acrylate, propyl acrylate, acrylic acid
Butyl ester, amyl acrylate, Hexyl 2-propenoate, Isooctyl acrylate monomer, methyl methacrylate, ethyl methacrylate, methyl-prop
Olefin(e) acid propyl ester, butyl methacrylate, pentylmethacrylate, hexyl methacrylate, isooctyl methacrylate and benzene second
The mixture that one or more of alkene arbitrarily matches.
Acrylic ester monomer in embodiment 1 is methyl acrylate, ethyl acrylate, propyl acrylate, acrylic acid fourth
Ester, amyl acrylate, Hexyl 2-propenoate, Isooctyl acrylate monomer, methyl methacrylate, ethyl methacrylate, metering system
Propyl propionate, butyl methacrylate, pentylmethacrylate, hexyl methacrylate, isooctyl methacrylate and methyl-prop
The mixture that one or more of olefin(e) acid ethylene oxidic ester arbitrarily matches.
The mixture of methyl methacrylate and butyl acrylate in embodiment 1 can also be methyl acrylate, propylene
Acid butyl ester, styrene, n-octyl, Hexyl 2-propenoate, methyl methacrylate, butyl methacrylate, metering system
The mixture that one or more of sour n-octyl, hexyl methacrylate arbitrarily match；
Polycaprolactone diols in embodiment 1 can also for polyadipate of the molecular weight between 1000~2000 oneself
One of diol ester, poly adipate succinic acid ester, polycaprolactone glycol, polycarbonate glycol, polytetrahydrofuran diol or two
The mixture of any proportion of kind.
Isophorone diisocyanate in embodiment 1 can also be different for hexamethylene diisocyanate, isophorone two
The mixture that one or both of cyanate, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate arbitrarily match.
Dimethylolpropionic acid in embodiment 1 can also be one or two kinds of in dihydromethyl propionic acid, dimethylolpropionic acid
It is any with one or more of dihydroxy propanesulfonate, 2- aminoethylamino ethanesulfonic acid sodium and diamino benzene sulfonic acid sodium
The mixture of proportion.
Hydroxy-ethyl acrylate in embodiment 1 can also be hydroxy-ethyl acrylate, hydroxypropyl acrylate, acrylamide, first
The mixture that one or both of base hydroxy-ethyl acrylate, hydroxy propyl methacrylate, hydroxymethyl acrylamide arbitrarily match.
The product that the embodiment of the present invention is made is tested below:
It is characterized by the laser Raman spectroscopy of Fig. 1 polymerizable macromolecule emulsifier of the present invention, it can be seen that 1640cm-1The peak at place
Represent the double bond of emulsifier end, it was demonstrated that the double bond of polymerisable emulsifier retains.
By the grain size distribution of Fig. 2 polyurethane/acrylate hybridisation emulsion of the present invention, lotion average grain diameter is 88.2nm.
In short, preparation method of the invention uses chain tra nsfer catalysis method, first using water as continuous phase, vinyl-based hydrophilic list
Body is reaction object, and divalent cobalt is catalyst, prepares the water-wet side point that unsaturated double-bond is contained in end by solution polymerization process
Subchain, being subject to vinyl oleophylic monomer later, the reaction was continued, and the amphipathic copolymer of block that end retains double bond is made.Then plus
Enter in the ethenyl blocking polyurethane macromolecular performed polymer that inertia vinyl monomer is continuous phase, it is polymerizable that initiator initiation is added
Molecules surfactant, acrylic ester monomer and the mixing of polyurethane (PU) macromolecular are copolymerized, and in reaction process, can be gathered
Co-emulsifier is coated and fixed by double bond on emulsion colloidal surface, and such lotion avoids this kind of emulsifier in the drying process
To the migration on surface, it ensure that this kind of lotion has good waterproof performance.Therefore, a kind of polyurethane/propylene of the present invention
Acid esters hybridisation emulsion can be used for the surface coverings such as woodenware, paper, metal.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
A specific embodiment of the invention is only limitted to this, for those of ordinary skill in the art to which the present invention belongs, not every
Under the premise of from present inventive concept, several simple deduction or replace can also be made, the present invention is all shall be regarded as belonging to and is mentioned
Claims of friendship determine scope of patent protection.
Claims (9)
1. a kind of polyurethane/acrylate hybridisation emulsion, it is characterised in that: the raw material including following parts by weight:
0.5~2 part of polymerizable macromolecule emulsifier, 5~20 parts of acrylic ester monomers, 10~18 parts of aqueous polyurethane micro emulsions
Liquid, 0.1~0.3 part of water soluble starter are dissolved in manufactured initiator solution in 5~10 parts of water；
The polymerizable macromolecule emulsifier the preparation method comprises the following steps:
To equipped with blender reactor in be added 50~120 parts of water, 0.01~0.1 part of divalent cobalt and 0.1~0.5 part it is aqueous
Initiator after being sufficiently stirred, with freeze-thaw pump circulation method to system deoxygenation, fills protection gas to carrying out vacuumizing in flask later
Body；Then it keeps the temperature at 65-85 DEG C, vinyl hydrophilic monomer is at the uniform velocity added dropwise in reactor, the reaction was continued 0.5 after being added dropwise
~1.5 hours, then 100~150 parts of vinyl oleophylic monomers are disposably put into flask, sustained response to termination, Zhi Houli
I.e. cooling stops reaction, and product drying for standby under room temperature in vacuum conditions obtains polymerizable macromolecule emulsifier；
The Polyurethane Microemulsion the preparation method comprises the following steps:
Into dry reactor be added 15~30 parts of inertia vinyl monomers, 7~18 parts of polymer polyatomic alcohols, 5~15 part two it is different
Cyanate esters, 2~8 parts of anion mixing hydrophilic chain extenders and 0.10~0.35 part of catalyst, constant reaction temperature is 75
~85 DEG C, the reaction time is 2~4 hours；The hydrophilic vinylic monomer that 2~9 parts of hydroxyls or amino are added is blocked, and is protected
Temperature reaction 0.5~1 hour adds 2.3~9.6 parts of bases salt forming agents and carries out neutralization reaction, is eventually adding deionized water, sufficiently
It is dispersed with stirring to get Polyurethane Microemulsion；
Polyurethane/acrylate hybridisation emulsion the preparation method comprises the following steps:
Temperature be 75~85 DEG C under conditions of, into drying receptacle be added 10~18 parts of Polyurethane Microemulsions, 0.5~2 part can
Polymerize macromole emulsifying agent, then by 0.1~0.3 part of initiator be dissolved in 5~10 parts of water manufactured initiator solution and 5~
20 parts of acrylic ester monomers are uniformly added dropwise in reactor in 1~3 hour, after being added dropwise, continue insulation reaction to eventually
Only, it takes out and is cooled to room temperature, adjusting pH is alkalinity to get polyurethane/acrylate hybridisation emulsion.
2. polyurethane/acrylate hybridisation emulsion according to claim 1, it is characterised in that:
The divalent cobalt class catalyst is that cobalt II oxime is fluorinated boron complex；
The water soluble starter is one or more of ammonium persulfate, potassium peroxydisulfate and sodium peroxydisulfate；
The catalyst is dibutyl tin dilaurate, stannous octoate or di-n-butylacetic acid tin.
3. polyurethane/acrylate hybridisation emulsion according to claim 1, it is characterised in that:
The vinyl hydrophilic monomer be acrylic acid, methacrylic acid, 2- acrylamide-2-methyl propane sulfonic, sodium methanesulfonate,
The mixture that one or more of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride arbitrarily matches；
The vinyl oleophylic monomer is methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid penta
Ester, Hexyl 2-propenoate, Isooctyl acrylate monomer, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methyl
One of butyl acrylate, pentylmethacrylate, hexyl methacrylate, isooctyl methacrylate and styrene or two
The mixture of kind any of the above proportion.
4. polyurethane/acrylate hybridisation emulsion according to claim 1, it is characterised in that:
The acrylic ester monomer is methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid penta
Ester, Hexyl 2-propenoate, Isooctyl acrylate monomer, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methyl
Butyl acrylate, pentylmethacrylate, hexyl methacrylate, isooctyl methacrylate and methyl propenoic acid glycidyl
The mixture that one or more of ester arbitrarily matches.
5. polyurethane/acrylate hybridisation emulsion according to claim 1, it is characterised in that:
The inertia vinyl monomer be (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate,
(methyl) Hexyl 2-propenoate, (methyl) n-octyl, (methyl) 2-EHA, styrene, Alpha-Methyl benzene second
One of alkene, two or more mixture arbitrarily matched.
6. polyurethane/acrylate hybridisation emulsion according to claim 1, it is characterised in that:
The polymer polyatomic alcohol is polyadipate hexylene glycol ester of the molecular weight between 1000~2000, polyadipate fourth two
The mixture that one or both of alcohol ester, polycaprolactone glycol, polycarbonate glycol, polytetrahydrofuran diol arbitrarily match；
The diisocyanate cpd is hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocynate
The mixture that one or both of ester, methyl diphenylene diisocyanate arbitrarily match.
7. polyurethane/acrylate hybridisation emulsion according to claim 1, it is characterised in that:
The anion mixing hydrophilic chain extender is dihydromethyl propionic acid, one or two kinds of with dihydroxy third in dimethylolpropionic acid
The mixing that one or more of sodium sulfonate, 2- aminoethylamino ethanesulfonic acid sodium and diamino benzene sulfonic acid sodium arbitrarily match
Object.
8. polyurethane/acrylate hybridisation emulsion according to claim 1, it is characterised in that:
The hydrophilic vinylic monomer of the hydroxyl or amino is hydroxy-ethyl acrylate, hydroxypropyl acrylate, acrylamide, first
The mixture that one or both of base hydroxy-ethyl acrylate, hydroxy propyl methacrylate, hydroxymethyl acrylamide arbitrarily match；
The bases salt forming agent is ammonium hydroxide or triethylamine.
9. a kind of preparation method of the polyurethane/acrylate hybridisation emulsion as described in claim 1 to 8 any one, special
Sign is: the following steps are included:
Step 1) prepares polymerizable macromolecule emulsifier:
To equipped with blender reactor in be added 50~120 parts of water, 0.01~0.1 part of divalent cobalt and 0.1~0.5 part it is aqueous
Initiator after being sufficiently stirred, with freeze-thaw pump circulation method to system deoxygenation, fills protection gas to carrying out vacuumizing in flask later
Body；Then it keeps the temperature at 65-85 DEG C, vinyl hydrophilic monomer is at the uniform velocity added dropwise in reactor, the reaction was continued 0.5 after being added dropwise
~1.5 hours, then 100~150 parts of vinyl oleophylic monomers are disposably put into flask, sustained response to termination, Zhi Houli
I.e. cooling stops reaction, and product drying for standby under room temperature in vacuum conditions obtains polymerizable macromolecule emulsifier；
Step 2) prepares Polyurethane Microemulsion:
Into dry reactor be added 15~30 parts of inertia vinyl monomers, 7~18 parts of polymer polyatomic alcohols, 5~15 part two it is different
Cyanate esters, 2~8 parts of anion mixing hydrophilic chain extenders and 0.10~0.35 part of catalyst, constant reaction temperature is 75
~85 DEG C, the reaction time is 2~4 hours；The hydrophilic vinylic monomer that 2~9 parts of hydroxyls or amino are added is blocked, and is protected
Temperature reaction 0.5~1 hour adds 2.3~9.6 parts of bases salt forming agents and carries out neutralization reaction, is eventually adding deionized water, sufficiently
It is dispersed with stirring to get Polyurethane Microemulsion；
Step 3) prepares hybridisation emulsion:
Temperature be 75~85 DEG C under conditions of, into drying receptacle be added 10~18 parts of Polyurethane Microemulsions, 0.5~2 part can
Polymerize macromole emulsifying agent, then by 0.1~0.3 part of initiator be dissolved in 5~10 parts of water manufactured initiator solution and 5~
20 parts of acrylic ester monomers are uniformly added dropwise in reactor in 1~3 hour, after being added dropwise, continue insulation reaction to eventually
Only, it takes out and is cooled to room temperature, adjusting pH is alkalinity to get polyurethane/acrylate hybridisation emulsion.
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