CN107254251B - A kind of aqueous UV urethane acrylate dispersoid and preparation method thereof with self-initiating function - Google Patents
A kind of aqueous UV urethane acrylate dispersoid and preparation method thereof with self-initiating function Download PDFInfo
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- CN107254251B CN107254251B CN201710565042.3A CN201710565042A CN107254251B CN 107254251 B CN107254251 B CN 107254251B CN 201710565042 A CN201710565042 A CN 201710565042A CN 107254251 B CN107254251 B CN 107254251B
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- Prior art keywords
- aqueous
- self
- urethane acrylate
- reaction
- polyol
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- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 46
- 150000003077 polyols Chemical class 0.000 claims abstract description 30
- 229920005862 polyol Polymers 0.000 claims abstract description 29
- 229920000570 polyether Polymers 0.000 claims abstract description 19
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 18
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- VSNHCAURESNICA-UHFFFAOYSA-N Hydroxyurea Chemical compound NC(=O)NO VSNHCAURESNICA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- 239000003112 inhibitor Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 229960001330 hydroxycarbamide Drugs 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 68
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000009413 insulation Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- 229920000728 polyester Polymers 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 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 5
- SVLIBCWCEABYRF-UHFFFAOYSA-N 1-ethenyl-1-(2-hydroxyethyl)urea Chemical compound NC(=O)N(C=C)CCO SVLIBCWCEABYRF-UHFFFAOYSA-N 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- 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 4
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 claims description 3
- 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
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-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
- NNTWKXKLHMTGBU-UHFFFAOYSA-N 4,5-dihydroxyimidazolidin-2-one Chemical compound OC1NC(=O)NC1O NNTWKXKLHMTGBU-UHFFFAOYSA-N 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 3
- 229960002887 deanol Drugs 0.000 claims description 3
- 239000012972 dimethylethanolamine Substances 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
- 239000000203 mixture Substances 0.000 claims description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 3
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 239000004632 polycaprolactone Substances 0.000 claims description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 claims description 2
- QRIMLDXJAPZHJE-UHFFFAOYSA-N 2,3-dihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CO QRIMLDXJAPZHJE-UHFFFAOYSA-N 0.000 claims description 2
- HOYRZHJJAHRMLL-UHFFFAOYSA-N 2,6-dinitro-p-cresol Chemical group CC1=CC([N+]([O-])=O)=C(O)C([N+]([O-])=O)=C1 HOYRZHJJAHRMLL-UHFFFAOYSA-N 0.000 claims description 2
- DUMPKRLSSRTFMY-UHFFFAOYSA-N 2-butan-2-yl-3,4-dinitrophenol Chemical group CCC(C)C1=C(O)C=CC([N+]([O-])=O)=C1[N+]([O-])=O DUMPKRLSSRTFMY-UHFFFAOYSA-N 0.000 claims description 2
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 claims description 2
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical group CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-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
- YKXAYLPDMSGWEV-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCO YKXAYLPDMSGWEV-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical group CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- 235000015511 Liquidambar orientalis Nutrition 0.000 claims description 2
- 239000004870 Styrax Substances 0.000 claims description 2
- 244000028419 Styrax benzoin Species 0.000 claims description 2
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 2
- AFSQFGXTYWXFPP-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methyl 2-methylprop-2-enoate Chemical class CC(=C)C(=O)OCC1(CO)CCCCC1 AFSQFGXTYWXFPP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- 210000000056 organ Anatomy 0.000 claims description 2
- HXDOZKJGKXYMEW-UHFFFAOYSA-N para-ethyl phenol Natural products CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229960003742 phenol Drugs 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 3
- SEPPVOUBHWNCAW-FNORWQNLSA-N (E)-4-oxonon-2-enal Chemical compound CCCCCC(=O)\C=C\C=O SEPPVOUBHWNCAW-FNORWQNLSA-N 0.000 claims 1
- ZFMFIBDSZCASNS-UHFFFAOYSA-N 2-pentylbenzene-1,4-diol Chemical group CCCCCC1=CC(O)=CC=C1O ZFMFIBDSZCASNS-UHFFFAOYSA-N 0.000 claims 1
- LLBZPESJRQGYMB-UHFFFAOYSA-N 4-one Natural products O1C(C(=O)CC)CC(C)C11C2(C)CCC(C3(C)C(C(C)(CO)C(OC4C(C(O)C(O)C(COC5C(C(O)C(O)CO5)OC5C(C(OC6C(C(O)C(O)C(CO)O6)O)C(O)C(CO)O5)OC5C(C(O)C(O)C(C)O5)O)O4)O)CC3)CC3)=C3C2(C)CC1 LLBZPESJRQGYMB-UHFFFAOYSA-N 0.000 claims 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims 1
- OMRDSWJXRLDPBB-UHFFFAOYSA-N N=C=O.N=C=O.C1CCCCC1 Chemical compound N=C=O.N=C=O.C1CCCCC1 OMRDSWJXRLDPBB-UHFFFAOYSA-N 0.000 claims 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- RFXSFVVPCLGHAU-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1.OC1=CC=CC=C1 RFXSFVVPCLGHAU-UHFFFAOYSA-N 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- DMFQXOQJSOTYKY-UHFFFAOYSA-N prop-2-ene-1,1-diol;urea Chemical compound NC(N)=O.OC(O)C=C DMFQXOQJSOTYKY-UHFFFAOYSA-N 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 239000003292 glue Substances 0.000 abstract description 10
- 238000007711 solidification Methods 0.000 abstract description 8
- 230000008023 solidification Effects 0.000 abstract description 8
- 239000003999 initiator Substances 0.000 abstract description 6
- 238000007790 scraping Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 238000001723 curing Methods 0.000 description 8
- -1 diisocyanate Ester Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 229920006150 hyperbranched polyester Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- 238000003848 UV Light-Curing Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 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 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 230000007246 mechanism Effects 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
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- GXZLBUYKJFLNLF-UHFFFAOYSA-N prop-2-ene-1,1-diol Chemical group OC(O)C=C GXZLBUYKJFLNLF-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- 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
- C08G18/3271—Hydroxyamines
- C08G18/3293—Hydroxyamines containing heterocyclic groups
-
- 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
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- 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
- C08G18/44—Polycarbonates
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- 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
- C08G18/6705—Unsaturated polymers not provided for in the groups C08G18/671, C08G18/6795, C08G18/68 or C08G18/69
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
- C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
Abstract
The invention discloses a kind of aqueous UV urethane acrylate dispersoid and preparation method thereof with self-initiating function, which includes the constitutive material of following parts by weight: polyester polyol or 10~20 parts of polyether polyol；10~30 parts of diisocyanate；2~10 parts of multi-hydroxy carboxy acid；0.04~0.2 part of catalyst；5~15 parts of organic solvent；1~5 part of hydroxycarbamide；0.1~0.6 part of polymerization inhibitor；10~30 parts of monohydroxy acrylate monomer；15~35 parts of oligomer containing light-initiated group and terminal hydroxy group；1~5 part of organic amine；140~180 parts of deionized water.The aqueous UV urethane acrylate dispersoid has the function of self-initiating or causes altogether under micro initiator effect that resin solidification is high-efficient and can carry out deep cure, and the surface resistance to scraping of glue film is good, hardness is big, weatherability and chemical resistance are excellent.
Description
Technical field
The present invention relates to aqueous UV curing coating technical fields, and in particular to a kind of aqueous UV with self-initiating function is poly-
Urethane acrylate dispersion and preparation method thereof.
Background technique
For UV-curing technology because it is efficient, energy saving, low emission is quickly grown due to the advantages that, photoinitiator is that traditional light is solid
Important component in change system, photoinitiator used at present are largely aromatic compound, itself has certain toxicity,
After undergoing ultraviolet light irradiation, a large amount of undecomposed photoinitiator small molecules of remaining in cured film all can to environment and contact personnel
It has a adverse impact, limits photocuring technology in the application in the fields such as high request, high standard industry.
Self-initiation ultraviolet-curing system is not required to photoinitiator due to it or only needs a small amount of photoinitiator, it will be able to
It is generated free radicals under ultraviolet radiation and completes cross-linking and curing reaction, aroused great concern.And can self-initiating it is aqueous
UV curing system is nontoxic, has more wide application prospect on environmental-protecting performance.Earliest self-initiating solidification is low
Polymers is the new product of Ya Shilan company, U.S. research and development, it is that Michael occurs by multi-functional acrylate and 'beta '-ketoester
Made from addition reaction.Related researcher develops many self-initiating curing systems on this basis, still, existing to draw certainly
Material or solidification rate are sent out relatively slowly or there are certain mixing the dispersion, the quality of later product is adversely affected.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, provide one
Kind has the function of self-initiating or causes altogether under micro initiator effect that resin solidification is high-efficient and can carry out deep cure, glue
The aqueous UV urethane acrylate dispersoid that the surface resistance to scraping of film is good, hardness is big, weatherability and chemical resistance are excellent, and
Accordingly provide a kind of preparation method of aqueous UV urethane acrylate dispersoid.
In order to solve the above technical problems, technical solution proposed by the present invention are as follows:
A kind of aqueous UV urethane acrylate dispersoid with self-initiating function, the composition including following parts by weight are former
Material: polyester polyol or 10~20 parts of polyether polyol, 10~30 parts of diisocyanate, 2~10 parts of multi-hydroxy carboxy acid, catalyst
0.04~0.2 part, 5~15 parts of organic solvent, 1~5 part of hydroxycarbamide, 0.1~0.6 part of polymerization inhibitor, monohydroxy acrylate monomer
10~30 parts, containing light-initiated group and 1~5 part of 15~35 parts of oligomer, the organic amine of terminal hydroxy group, deionized water 140~180
Part.
The above-mentioned aqueous UV urethane acrylate dispersoid with self-initiating function, it is preferred that described containing light-initiated
The oligomer of group and terminal hydroxy group includes the constitutive material of following parts by weight: 30~50 parts of hydroxyl photoinitiator mixed solution,
10~20 parts of diisocyanate, 30~60 parts of polyol polyester acrylate, wherein the hydroxyl photoinitiator mixed solution
By the hydroxyl photoinitiator of 30~70 parts by weight, the catalyst of the organic solvent of 20~60 parts by weight and 0.1~0.5 parts by weight
Composition.
The above-mentioned aqueous UV urethane acrylate dispersoid with self-initiating function, it is preferred that the hydroxyl light
Initiator in Darocur 1173, Irgacure 184, Irgacure 2959, Irgacure 1000, styrax one
Kind is several；The organic solvent is acetone or butanone；The catalyst is organic tin catalyst, is selected from two fourth of tin dilaurate
One or more of Ji Xi, stannous octoate, dibutyl tin dichloride.
The above-mentioned aqueous UV urethane acrylate dispersoid with self-initiating function, it is preferred that the diisocyanate
Ester is the compound at least one isocyanate-reactive group, is selected from isophorone diisocyanate, dicyclohexyl first
Alkane diisocyanate, toluene di-isocyanate(TDI), hexamethylene diisocyanate, methyl diphenylene diisocyanate, hexamethylene two
One or more of isocyanates, tetramethylene diisocyanate.
The above-mentioned aqueous UV urethane acrylate dispersoid with self-initiating function, it is preferred that the polyhydroxy polycarboxylic
Ester acrylate be selected from six degrees of functionality, twelve interior organs can spend, one of the hyperbranched polyester acrylic ester of 18 degrees of functionality or more
Kind, the mass ratio of polyol polyester acrylate and the hydroxyl photoinitiator is (1.5~10.0): 1.
The above-mentioned aqueous UV urethane acrylate dispersoid with self-initiating function, it is preferred that the polyester polyols
Alcohol is one or more of polycaprolactone polyol, polycarbonate polyol, polyadipate dihydric alcohol, point of polyester polyol
Son amount is 500~2000；The polyether polyol is graft type polyether polyol, polytetrahydrofuran polyol, heterocyclic modified poly-
One or more of ethoxylated polyhydric alcohol, the molecular weight of polyether polyol are 400~1000.
The above-mentioned aqueous UV urethane acrylate dispersoid with self-initiating function, it is preferred that the polyhydroxy carboxylic
Acid is one or both of dihydromethyl propionic acid and dimethylolpropionic acid, multi-hydroxy carboxy acid and the polyester polyol or polyethers
The mass ratio of polyalcohol is (0.2~0.8): 1；The hydroxycarbamide is selected from hydroxycarbamide, hydroxyethyl vinyl urea, dihydroxymethyl ethylene
The matter of one or more of urea, hydroxymethyl-2 dihydroxy-ethylene urea, hydroxycarbamide and the polyester polyol or polyether polyol
Amount is than being 1: (0.1~0.6).
The above-mentioned aqueous UV urethane acrylate dispersoid with self-initiating function, it is preferred that the polymerization inhibitor is
Phenolic inhibitor is selected from hydroquinone, p methoxy phenol, para hydroxybenzene ether, p-tert-Butylcatechol, two tertiary pentyls pair
Benzenediol, dinitro-p-cresol, dinitro sec-butyl phenol, p-tert-Butylcatechol, in di-t-butyl paraethyl phenol
It is one or more of；The monohydroxy acrylate monomer is selected from hydroxyethyl methacrylate, hydroxy-ethyl acrylate, pentaerythrite three
Acrylate, hydroxy propyl methacrylate, 2- hydroxy-n-butyl methacrylate, 3- hydroxy-n-butyl methacrylate,
4- hydroxy-n-butyl methacrylate, cyclohexanedimethanol monomethacrylates, one in glycerol monomethacrylate
Kind is several.
The above-mentioned aqueous UV urethane acrylate dispersoid with self-initiating function, it is preferred that described containing light-initiated
The oligomer of group and terminal hydroxy group and the mass ratio of the polyester polyol or polyether polyol are (0.5~3.0): 1；It is described to have
Machine amine is one or more of triethylamine, dimethylethanolamine, methyl diethanolamine, organic amine and the polyester polyol or
The mass ratio of polyether polyol is (0.15~0.4): 1.
As a general technical idea, another aspect of the present invention provides a kind of above-mentioned aqueous with self-initiating function
The preparation method of UV urethane acrylate dispersoid, comprising the following steps:
(1) preparation of the oligomer containing light-initiated group and terminal hydroxy group
Hydroxyl photoinitiator, organic solvent and catalyst are mixed according to the ratio, stirred at 50 DEG C~80 DEG C molten
Solution obtains hydroxyl photoinitiator mixed solution, set aside for use to transparency liquid；Diisocyanate is added in reaction vessel, is risen
Hydroxyl photoinitiator mixed solution is added dropwise to 60 DEG C~65 DEG C in temperature while stirring, and control rate of addition is 0.5 drop/sec~1.5
Drop/sec, until all dripping off, 70 DEG C~75 DEG C are warming up to, the reaction was continued 2.0h~4.0h；After NCO% reaches theoretical value, it is added
Polyol polyester acrylate, insulation reaction 2.0h~4.0h, when NCO% is lower than 0.1%, reaction terminates, and obtains drawing containing light
Send out the oligomer of group and terminal hydroxy group；
(2) preparation of aqueous UV urethane acrylate dispersoid
Diisocyanate, polyester polyol or polyether polyol, multi-hydroxy carboxy acid and catalyst are added according to the ratio anti-
It answers in container, is uniformly mixed, is filled with nitrogen, is reacted at 60 DEG C~70 DEG C, keep the temperature 2.0h~4.0h, add in reaction process
Enter organic solvent viscosity reduction, detect the NCO% content of reaction process, when NCO% content is close to theoretical value, be added it is dry after hydroxyl
Base urea carries out chain extending reaction, insulation reaction 2.0h~4.0h, then detects the NCO% content of reaction process, when NCO% content is close
When theoretical value, polymerization inhibitor and monohydroxy acrylate monomer is added, 0.5h~2.0h is reacted at 60 DEG C~65 DEG C, is then added
Carry out graft reaction containing the oligomer of light-initiated group and terminal hydroxy group obtained by step (1), reacted at 60 DEG C~65 DEG C 2.0h~
4.0h detects the NCO% content of reaction process, and reaction temperature is down to 45 DEG C~50 DEG C when NCO% content is lower than 0.1%,
Organic amine is added and carries out neutralization reaction, adds deionized water, under high velocity agitation dispersion and emulsion 0.5h~1.5h, then steams
Solvent is to get the aqueous UV urethane acrylate dispersoid with self-initiating function.
Compared with the prior art, the advantages of the present invention are as follows: the aqueous UV polyurethane with self-initiating function of the invention
Acrylate dispersoid using the structure containing urea bond small molecule carry out chain extending reaction, introduce with help cause function urea bond with
Tertiary amine structure, while also improving the mechanical property of glue film；It is anti-by the grafting with light-initiated group and the oligomer of terminal hydroxy group
It answers, light-initiated group has been also introduced into the end of performed polymer macromolecular, after dispersion and emulsion, has obtained the water with self-initiating characteristic
Property UV urethane acrylate dispersoid, the solid content of dispersion is between 25.0%~45.0%, lotion storage stability
Well, surface of the paint film resistance to scraping, hardness, chemical resistance are good.The dispersion has dual self-initiating mechanism, in ultraviolet radiation
Under the conditions of, it can be realized self-initiating or cause altogether under being acted under micro initiator, and curing rate is not less than by light-initiated
The cured aqueous UV urethane acrylate of agent.
Specific embodiment
To facilitate the understanding of the present invention, present invention work more comprehensively, is meticulously described below in conjunction with preferred embodiment,
But the protection scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1:
A kind of aqueous UV urethane acrylate dispersoid and preparation method thereof with self-initiating function of the invention.It should
The preparation method of aqueous UV urethane acrylate dispersoid the following steps are included:
(1) preparation of the oligomer containing light-initiated group and terminal hydroxy group:
173 photoinitiator of 24.6g Darocurl, 30g acetone, 0.08g dibutyl tin dilaurate are added to single port
In flask, stirring and dissolving obtains hydroxyl photoinitiator mixed solution, set aside for use to transparency liquid at 60 DEG C；By 25.2g
1, hexamethylene-diisocyanate is added in reaction vessel, is warming up to 65 DEG C, and it is molten that the mixing of hydroxyl photoinitiator is added dropwise while stirring
Liquid, control rate of addition are 1.0 drops/sec to all dripping off, and are warming up to 70 DEG C, the reaction was continued 4.0h；When NCO% (100g sample
The quality of contained isocyanates (- NCO) group) reach theoretical value after, be added 91.2g hyperbranched polyester acrylic ester, heat preservation
3.0h is reacted, when NCO% is lower than 0.1%, reaction terminates, and obtains the oligomer containing light-initiated group and terminal hydroxy group.
(2) preparation of aqueous UV urethane acrylate dispersoid:
By 25.2g isophorone diisocyanate, 16.7g polycaprolactone diols, 4.5g dihydromethyl propionic acid and
0.06g dibutyl tin dilaurate is added in reaction vessel, is uniformly mixed, is filled with nitrogen, is reacted at 60 DEG C, is kept the temperature
12g acetone viscosity reduction is added in reaction process, detects the NCO% content of reaction process by 4.0h；When NCO% is close to theoretical value, In
2.2g hydroxyethyl vinyl urea after drying is added at 65 DEG C carries out chain extending reaction, and insulation reaction 3.0h detects reaction process
NCO% content；When NCO% is close to theoretical value, 0.25g p methoxy phenol, 4.3g hydroxy-ethyl acrylate, 18.1g season is added
Penta tetrol triacrylate reacts 1.5h at 65 DEG C, be added 28.6g step (1) preparation containing light-initiated group and terminal hydroxy group
Oligomer and 0.05g dibutyl tin dilaurate carry out graft reaction, and insulation reaction 2.5h detects the NCO% of reaction process
Content；When NCO% content is lower than 0.1%, reaction temperature is down to 45 DEG C, 3.4g triethylamine is added and carries out neutralization reaction, then
146g deionized water is added, under high velocity agitation dispersion and emulsion 1.5h, then steams solvent using Rotary Evaporators to get tool is arrived
There is the aqueous UV urethane acrylate dispersoid of self-initiating function.
Aqueous UV urethane acrylate dispersoid with self-initiating function is formed a film alone solidification, tests glue film not
Curing rate, hardness, resistance to alcohol performance under the conditions of same curing mode and solidification energy, test method are as follows: according to GB/T
6739-2006 measures glue film hardness；Glue film is immersed at room temperature in ethanol solution and measures resistance to alcohol performance.Test result is such as
Shown in table 1, table 2.
Embodiment 2:
A kind of aqueous UV urethane acrylate dispersoid and preparation method thereof with self-initiating function of the invention.It should
The preparation method of aqueous UV urethane acrylate dispersoid the following steps are included:
(1) preparation of the oligomer containing light-initiated group and terminal hydroxy group:
36.2g Irgacure2959 photoinitiator, 35g butanone, 0.15g stannous octoate are added in single-necked flask, In
Stirring and dissolving obtains hydroxyl photoinitiator mixed solution, set aside for use to transparency liquid at 55 DEG C；By 36.5g isophorone two
Isocyanates is added in reaction vessel, is warming up to 65 DEG C, and hydroxyl photoinitiator mixed solution, control drop are added dropwise while stirring
Acceleration is 1.0 drops/sec to all dripping off, and is warming up to 75 DEG C, the reaction was continued 3.0h；After NCO% reaches theoretical value, it is added
97.3g hyperbranched polyester acrylic ester, insulation reaction 3.5h, when NCO% is lower than 0.1%, reaction terminates, and obtains containing light-initiated
The oligomer of group and terminal hydroxy group.
(2) preparation of aqueous UV urethane acrylate dispersoid:
By 16.7g polytetrahydrofuran dihydric alcohol, 29.7g dicyclohexyl methyl hydride diisocyanate, 5.0g dimethylolpropionic acid
And 0.08g stannous octoate is added in reaction vessel, is uniformly mixed, is filled with nitrogen, is reacted at 70 DEG C, is kept the temperature
15g acetone viscosity reduction is added in reaction process, detects the NCO% content of reaction process by 2.5h；When NCO% is close to theoretical value, In
2.7g hydroxymethyl-2 dihydroxy-ethylene urea after drying is added at 65 DEG C carries out chain extending reaction, insulation reaction 3.0h, detection reaction
The NCO% content of process；When NCO% is close to theoretical value, 0.25g hydroquinone, 4.3g hydroxy-ethyl acrylate, 5.2g first is added
Base hydroxypropyl acrylate reacts 1.0h at 65 DEG C, and the low containing light-initiated group and terminal hydroxy group of 30.3g step (1) preparation is added
Polymers and 0.05g stannous octoate carry out graft reaction, and insulation reaction 3.0h detects the NCO% content of reaction process；When
When NCO% content is lower than 0.1%, reaction temperature is down to 50 DEG C, 3.4g dimethylethanolamine is added and carries out neutralization reaction, then plus
Enter 146g deionized water, under high velocity agitation dispersion and emulsion 0.5h, then steams solvent using Rotary Evaporators to get to having
The aqueous UV urethane acrylate dispersoid of self-initiating function.
The properties of the aqueous UV urethane acrylate dispersoid with self-initiating function are tested, are tested
Method is with embodiment 1, and test result is as shown in table 1, table 2.
Embodiment 3:
A kind of aqueous UV urethane acrylate dispersoid and preparation method thereof with self-initiating function of the invention.It should
The preparation method of aqueous UV urethane acrylate dispersoid the following steps are included:
(1) preparation of the oligomer containing light-initiated group and terminal hydroxy group:
45.4g Irgacure184 photoinitiator, 45g acetone, 0.18g dibutyl tin dichloride are added to single-necked flask
In, stirring and dissolving obtains hydroxyl photoinitiator mixed solution, set aside for use to transparency liquid at 50 DEG C；By bis- hexamethylene of 31.4g
Dicyclohexylmethane diisocyanate is added in reaction vessel, is warming up to 60 DEG C, and it is molten that the mixing of hydroxyl photoinitiator is added dropwise while stirring
Liquid, control rate of addition are 1.0 drops/sec to all dripping off, and are warming up to 70 DEG C, the reaction was continued 2.0h；When NCO% reaches theoretical value
Afterwards, 72.9g hyperbranched polyester acrylic ester is added, insulation reaction 4.0h, when NCO% is lower than 0.1%, reaction terminates, and obtains
Oligomer containing light-initiated group and terminal hydroxy group.
(2) preparation of aqueous UV urethane acrylate dispersoid:
By 17.5g polycarbonate glycol, 26.5g isophorone diisocyanate, 4.7g dihydromethyl propionic acid and
0.08g dibutyl tin dichloride is added in reaction vessel, is uniformly mixed, is filled with nitrogen, is reacted at 65 DEG C, is kept the temperature
15g acetone viscosity reduction is added in reaction process, detects the NCO% content of reaction process by 2.0h；When NCO% is close to theoretical value, In
2.3g hydroxyethyl vinyl urea after drying is added at 70 DEG C carries out chain extending reaction, and insulation reaction 4.0h detects reaction process
NCO% content；When NCO% is close to theoretical value, be added 0.28g p-tert-Butylcatechol, 5.1g hydroxy propyl methacrylate,
20.6g pentaerythritol triacrylate reacts 2.0h at 60 DEG C, and 32.9g step (1) preparation is added contains light-initiated group and end
The oligomer and 0.06g dibutyl tin dichloride of hydroxyl carry out graft reaction, and insulation reaction 3.0h detects reaction process
NCO% content；When NCO% content is lower than 0.1%, reaction temperature is down to 45 DEG C, 3.6g triethylamine is added and neutralize instead
It answers, adds 146g deionized water, under high velocity agitation dispersion and emulsion 1.5h, then steam solvent using Rotary Evaporators, i.e.,
Obtain the aqueous UV urethane acrylate dispersoid with self-initiating function.
The properties of the aqueous UV urethane acrylate dispersoid with self-initiating function are tested, are tested
Method is with embodiment 1, and test result is as shown in table 1, table 2.
The standby initiation system the performance test results of aqueous UV urethane acrylate dispersoid in 1 Examples 1 to 3 of table
The total initiation system the performance test results of aqueous UV urethane acrylate dispersoid in 2 Examples 1 to 3 of table
Seen from table 1, prepared aqueous UV urethane acrylate dispersoid, can under the premise of without initiator is added outside
Photocuring is realized in initiation by itself photosensitive group, and cured glue film has preferable performance, and the power of solidification energy is right
The self-initiating efficiency of dispersion has certain influence, (the 600mJ/cm under strong energy radiation2), glue film performance is more excellent；Separately
The difference of outer dispersion structure, has an impact to curing efficiency, in embodiment 3, using polycarbonate glycol as main body knot
When structure, curing efficiency is better than other polyol structures.As can be seen from Table 2, under the premise of adding trace photoinitiator outside, low energy
Under (350mJ/cm2) glue film can obtain preferable hardness with it is resistance to alcohol repellency, then improve solidification energy (600mJ/cm2) glue film
Performance change is little, illustrates that prepared dispersion on the basis of adding micro initiator, can be achieved with efficiently solidifying, obtains good
Good film performance.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of aqueous UV urethane acrylate dispersoid with self-initiating function, which is characterized in that including following weight
The constitutive material of part:
The hydroxycarbamide be selected from one of hydroxyethyl vinyl urea, dihydroxymethyl ethylene urea, hydroxymethyl-2 dihydroxy-ethylene urea or
It is several；
The oligomer containing light-initiated group and terminal hydroxy group includes the constitutive material of following parts by weight:
30~50 parts of hydroxyl photoinitiator mixed solution；
10~20 parts of diisocyanate；
30~60 parts of polyol polyester acrylate；
Wherein, hydroxyl photoinitiator of the hydroxyl photoinitiator mixed solution by 30~70 parts by weight, 20~60 weight
The organic solvent of part and the catalyst composition of 0.1~0.5 parts by weight；
The polyol polyester acrylate is selected from six degrees of functionality, twelve interior organs can spend, the hyper-branched polyester propylene of 18 degrees of functionality
One of acid esters is a variety of.
2. the aqueous UV urethane acrylate dispersoid according to claim 1 with self-initiating function, feature exist
In the hydroxyl photoinitiator is selected from Darocur 1173, Irgacure 184, Irgacure 2959, Irgacure
1000, one or more of styrax；The organic solvent is acetone or butanone；The catalyst is organic tin catalysis
Agent is selected from one or more of dibutyl tin dilaurate, stannous octoate, dibutyl tin dichloride.
3. the aqueous UV urethane acrylate dispersoid according to claim 1 with self-initiating function, feature exist
In the diisocyanate is the compound at least one isocyanate-reactive group, is selected from two isocyanide of isophorone
Acid esters, dicyclohexyl methyl hydride diisocyanate, toluene di-isocyanate(TDI), hexamethylene diisocyanate, diphenyl methane two are different
One or more of cyanate, cyclohexane diisocyanate, tetramethylene diisocyanate.
4. the aqueous UV urethane acrylate dispersoid according to claim 1 with self-initiating function, feature exist
In the mass ratio of polyol polyester acrylate and the hydroxyl photoinitiator is (1.5~10.0): 1.
5. the aqueous UV urethane acrylate dispersoid according to claim 1 with self-initiating function, feature exist
In the polyester polyol is one of polycaprolactone polyol, polycarbonate polyol, polyadipate dihydric alcohol or several
Kind, the molecular weight of polyester polyol is 500~2000；The polyether polyol is graft type polyether polyol, polytetrahydrofuran
One or more of polyalcohol, heterocyclic modified polyether polyol, the molecular weight of polyether polyol are 400~1000.
6. the aqueous UV urethane acrylate dispersoid according to claim 1 with self-initiating function, feature exist
In, the multi-hydroxy carboxy acid be one or both of dihydromethyl propionic acid and dimethylolpropionic acid, multi-hydroxy carboxy acid with it is described
The mass ratio of polyester polyol or polyether polyol is (0.2~0.8): 1；Hydroxycarbamide and the polyester polyol or polyether polyols
The mass ratio of alcohol is 1:(0.1~0.6).
7. the aqueous UV urethane acrylate dispersoid according to claim 1 with self-initiating function, feature exist
In, the polymerization inhibitor be phenolic inhibitor, selected from hydroquinone, p methoxy phenol, para hydroxybenzene ether, to tert-butyl o benzene
Diphenol, two tertiary pentyl hydroquinones, dinitro-p-cresol, dinitro sec-butyl phenol, one in di-t-butyl paraethyl phenol
Kind is several；The monohydroxy acrylate monomer is selected from hydroxyethyl methacrylate, hydroxy-ethyl acrylate, pentaerythrite 3 third
Olefin(e) acid ester, hydroxy propyl methacrylate, 2- hydroxy-n-butyl methacrylate, 3- hydroxy-n-butyl methacrylate, 4-
One of hydroxy-n-butyl methacrylate, cyclohexanedimethanol monomethacrylates, glycerol monomethacrylate
Or it is several.
8. the aqueous UV urethane acrylate dispersoid according to claim 1 with self-initiating function, feature exist
In the oligomer containing light-initiated group and terminal hydroxy group is (0.5 with the mass ratio of the polyester polyol or polyether polyol
~3.0): 1；The organic amine be one or more of triethylamine, dimethylethanolamine, methyl diethanolamine, organic amine with
The mass ratio of the polyester polyol or polyether polyol is (0.15~0.4): 1.
9. a kind of such as the aqueous UV urethane acrylate according to any one of claims 1 to 8 with self-initiating function point
The preparation method of granular media, which comprises the following steps:
(1) preparation of the oligomer containing light-initiated group and terminal hydroxy group
Hydroxyl photoinitiator, organic solvent and catalyst are mixed according to the ratio, stirring and dissolving is extremely at 50 DEG C~80 DEG C
Transparency liquid obtains hydroxyl photoinitiator mixed solution, set aside for use；Diisocyanate is added in reaction vessel, is warming up to
60 DEG C~65 DEG C, while stirring be added dropwise hydroxyl photoinitiator mixed solution, control rate of addition be 0.5 drop/sec~1.5 drop/
Second, until all dripping off, 70 DEG C~75 DEG C are warming up to, the reaction was continued 2.0h~4.0h；After NCO% reaches theoretical value, it is added more
Hydroxyl polyester acrylate, insulation reaction 2.0h~4.0h, when NCO% is lower than 0.1%, reaction terminates, and obtains containing light-initiated
The oligomer of group and terminal hydroxy group；
(2) preparation of aqueous UV urethane acrylate dispersoid
Reaction is added in diisocyanate, polyester polyol or polyether polyol, multi-hydroxy carboxy acid and catalyst according to the ratio to hold
It in device, is uniformly mixed, is filled with nitrogen, is reacted at 60 DEG C~70 DEG C, keep the temperature 2.0h~4.0h, being added in reaction process has
Solvent viscosity reduction detects the NCO% content of reaction process, when NCO% content is close to theoretical value, be added it is dry after hydroxycarbamide
Chain extending reaction, insulation reaction 2.0h~4.0h are carried out, then detects the NCO% content of reaction process, when the close theory of NCO% content
When value, polymerization inhibitor and monohydroxy acrylate monomer is added, 0.5h~2.0h is reacted at 60 DEG C~65 DEG C, step is then added
(1) gained carries out graft reaction containing the oligomer of light-initiated group and terminal hydroxy group, and 2.0h~4.0h is reacted at 60 DEG C~65 DEG C,
Reaction temperature is down to 45 DEG C~50 DEG C when NCO% content is lower than 0.1% by the NCO% content for detecting reaction process, and addition has
Machine amine carries out neutralization reaction, adds deionized water, under high velocity agitation dispersion and emulsion 0.5h~1.5h, then steams solvent,
Up to the aqueous UV urethane acrylate dispersoid with self-initiating function.
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