CN102702469B - Ultraviolet-curable aqueous polyurethane dispersion and preparation method thereof - Google Patents
Ultraviolet-curable aqueous polyurethane dispersion and preparation method thereof Download PDFInfo
- Publication number
- CN102702469B CN102702469B CN 201210206961 CN201210206961A CN102702469B CN 102702469 B CN102702469 B CN 102702469B CN 201210206961 CN201210206961 CN 201210206961 CN 201210206961 A CN201210206961 A CN 201210206961A CN 102702469 B CN102702469 B CN 102702469B
- Authority
- CN
- China
- Prior art keywords
- aqueous polyurethane
- product
- polyurethane dispersion
- weight part
- add
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920003009 polyurethane dispersion Polymers 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 18
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920005862 polyol Polymers 0.000 claims abstract description 13
- 150000003077 polyols Chemical class 0.000 claims abstract description 13
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 9
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 44
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 33
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 14
- 238000000605 extraction Methods 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 11
- -1 hydroxyl vinyl Chemical group 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-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
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 7
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 239000003863 metallic catalyst Substances 0.000 claims description 6
- 125000002524 organometallic group Chemical group 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 150000003512 tertiary amines Chemical group 0.000 claims description 5
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- 239000003643 water by type Substances 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 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 2
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 claims description 2
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 2
- JTUOCQAUKNBEGY-UHFFFAOYSA-N 2-ethoxy-2-hydroxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(O)(OCC)C(=O)C1=CC=CC=C1 JTUOCQAUKNBEGY-UHFFFAOYSA-N 0.000 claims description 2
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 2
- TUOBEAZXHLTYLF-UHFFFAOYSA-N [2-(hydroxymethyl)-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(CC)COC(=O)C=C TUOBEAZXHLTYLF-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- SSOONFBDIYMPEU-UHFFFAOYSA-N [3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COCC(CO)(CO)COC(=O)C=C SSOONFBDIYMPEU-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 2
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229940059574 pentaerithrityl Drugs 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 2
- 150000003754 zirconium Chemical class 0.000 claims description 2
- XLZMWNWNBXSZKF-UHFFFAOYSA-N 4-propan-2-ylmorpholine Chemical compound CC(C)N1CCOCC1 XLZMWNWNBXSZKF-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 23
- 238000010438 heat treatment Methods 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 8
- 238000003860 storage Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000004359 castor oil Substances 0.000 abstract 2
- 235000019438 castor oil Nutrition 0.000 abstract 2
- 238000001816 cooling Methods 0.000 abstract 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 abstract 2
- 125000001302 tertiary amino group Chemical group 0.000 abstract 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract 1
- 229920002554 vinyl polymer Polymers 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- 239000004814 polyurethane Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 229920002635 polyurethane Polymers 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 229910052797 bismuth Inorganic materials 0.000 description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 7
- 238000009775 high-speed stirring Methods 0.000 description 7
- 238000002329 infrared spectrum Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000003848 UV Light-Curing Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229920002396 Polyurea Polymers 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000011527 polyurethane coating Substances 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 241000276489 Merlangius merlangus Species 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229940117969 neopentyl glycol Drugs 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 210000000697 sensory organ Anatomy 0.000 description 1
- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses an ultraviolet-curable aqueous polyurethane dispersion, also provides a preparation method of the ultraviolet-curable aqueous polyurethane dispersion and aims to provide an ultraviolet-curable aqueous polyurethane dispersion with a highly-branched structure, high double bond content and storage stability. The technical solution is that the dispersion is prepared by the following steps: 1), adding castor oil into a reactor, heating and dewatering the castor oil, cooling, adding polyisocyanate, heating till reaction begins, and thus obtaining a product A; 2), cooling theproduct A, adding a solvent A, dripping low molecular polyol with tertiary amino groups, and reacting to obtain a product B; 3), adding a vinyl monomer with hydroxyl and an organic metal catalyst into the product B, and reacting to obtain a product C; 4), uniformly mixing 30-100 parts of acid by weight and 1000-2000 parts of water by weight, dripping the mixture into the product C, removing the solvent, and thus obtaining a product D; and 5), adding a photoinitiator and methyl pyrrolidone into the product D to obtain the ultraviolet-curable aqueous polyurethane dispersion. The preparation method of the ultraviolet-curable aqueous polyurethane dispersion belongs to the technical field of preparation of chemical dispersion.
Description
Technical field
The present invention relates to a kind of dispersion system, specifically, is a kind of photocurable aqueous polyurethane dispersion, the invention still further relates to the preparation method of this dispersion system, belongs to chemical industry dispersion system preparing technical field.
Background technology
UV-curing technology has been widely used in the polymer cure, is characterized in that resin at room temperature can become solid-state from flowable state through UV-irradiation.Traditional ultraviolet light polymerization system generally is made up of light trigger, the oligopolymer that contains unsaturated double-bond and reactive reactive thinner.The main effect of thinner is the viscosity of reduction system, but it has strong smell, simultaneously sense organ and skin is had stronger stimulation.Pay attention to day by day along with to changing commanders with safety should gradually reduce or forbid the application of this thinner.In this case, the aqueous photo-curing system is arisen at the historic moment; This system is dispersion agent with water, has both reduced the pollution to environment, has reduced the inflammableness of system simultaneously again.
CN200810039199.3 has disclosed a kind of ultraviolet light solidfication water polyurethane coating, at first be respectively the method for terminal hydroxy group by chemical bond with polyvalent alcohol and alkene and be incorporated in polyurethane polyol or the isocyanate-terminated base polyurethane prepolymer for use as, contain the water-borne PU dispersion coatings of multi-thiol and polynary alkene again by the self-emulsifying preparation; Be prepared into aqueous polyurethane coating with above-mentioned two kinds of polyurethane aqueous dispersions coating as the basis then, its solid content is 15～55%; The CN101613449A disclosure of the Invention a kind of waterborne polyurethane resin of ultraviolet light polymerization, the waterborne polyurethane resin of this kind ultraviolet light polymerization is introduced polyether glycol in the polyurethane backbone, and can introduce more two key in the such polyurethane chain of monomer end-blocking with the monohydroxy esters of acrylic acid and carry out crosslinking polymerization, improved the crosslinked and relative molecular weight of filming, effectively improve the chemical resistance of UV curable water-borne system, can take into account hardness and snappiness two sides performance simultaneously.
But there is the defective that double bond content is low, cross-linking density is low in the above-mentioned patent, after causing solidifying, defective such as water tolerance, solvent resistance and mechanical property are not good enough, and hardness is on the low side.Because molecular weight is little, problems such as breakdown of emulsion, layering appear in poor storage stability easily in storage process simultaneously.
Summary of the invention
At above-mentioned deficiency, the present invention discloses photocurable aqueous polyurethane dispersion of a kind of height cladodification structure, double bond content height, stable storing and preparation method thereof.
Last technical scheme of the present invention is such: a kind of aqueous polyurethane dispersion of uV curable,, this dispersion system prepares by following step:
1) taking by weighing 300～600 weight part Viscotrol C is added in the reactor of belt stirrer, be heated to 100～130 ℃ of vacuum hydro-extraction 30～120min, when being cooled to 50～60 ℃, 200～600 weight part polyisocyanates of Jia Ruing while stirring, after being warming up to 60～100 ℃ of reaction 60～240min, obtain product A;
When 2) product A being cooled to 55～65 ℃, add 100～400 parts by weight solvent, 40～50 ℃ of low molecular weight polyols that drip 60～200 weight part band tertiary amine groups while stirring, after 1～3 hour, obtain product B 40～60 ℃ of reactions;
3) add hydroxyl vinyl monomer and 0.001～0.1 weight part organo-metallic catalyst of 20～120 weight parts to product B, 40～80 ℃ of reactions 1～3 hour, obtain product C;
4) 30～100 weight parts acid and 1000～2000 weight parts waters are mixed after, drop in the product C, continuously stirring product C in the dropping process, drip finish to continue to stir 30～60min after, solvent is deviate from underpressure distillation again, obtains product D;
5) add 0.1～2% light trigger and 1～10 weight part methyl-2-pyrrolidone in the product D, stir, namely obtain the aqueous polyurethane dispersion of this uV curable.
The aqueous polyurethane dispersion of above-mentioned a kind of uV curable, it is characterized in that, step 1) takes by weighing 300～600 weight part Viscotrol C and is added in the reactor of belt stirrer, after being heated to 100～130 ℃ of vacuum hydro-extraction 30～120min, add 1～100 weight part low molecular weight polyols, when being cooled to 50～60 ℃, 200～600 weight part polyisocyanates of Jia Ruing while stirring, after being warming up to 60～100 ℃ of reaction 60～240min, obtain product A;
The aqueous polyurethane dispersion of above-mentioned a kind of uV curable, it is characterized in that, step 5) adds the polyfunctionality UV reactive thinner of 0.1～100 weight part to product D, light trigger and 1～10 weight part methyl-2-pyrrolidone of adding 0.1～2% after stirring, stir, namely obtain the aqueous polyurethane dispersion of this uV curable.
Back of the present invention one technical scheme is such: the preparation method of the aqueous polyurethane dispersion of this uV curable comprises following preparation process successively:
1) takes by weighing the there-necked flask that 300～600 weight part Viscotrol C are added to belt stirrer, be heated to 100～130 ℃ of vacuum hydro-extraction 30～120min, add low molecular weight polyols 0～100 weight part while stirring; When being cooled to 50～60 ℃, polyisocyanates 200～600 weight parts of Jia Ruing are warming up to 60～100 ℃ of reaction 60～240min while stirring, obtain product A;
2) when product A is cooled to 55～65 ℃, add 100～400 parts by weight solvent, drip the low molecular weight polyols that contains 60～200 weight part tertiary amine groups while stirring at 40～50 ℃, 40～60 ℃ of reactions 1～3 hour, obtain product B;
3) add hydroxyl vinyl monomer and 0.001～0.1 weight part organo-metallic catalyst of 20～120 weight parts to product B, 40～80 ℃ of reactions 1～3 hour, obtain product C;
4) 30～100 weight parts acid and 1000～2000 weight parts waters are mixed after, drop in the product C, continuously stirring product C in the dropping process, drip finish to continue stirring 30～60min after, solvent is deviate from underpressure distillation, obtains product D;
5) add the polyfunctionality UV reactive thinner of 0～100 weight part in the product D, stir, add light trigger and 1～10 weight part methyl-2-pyrrolidone solution of 0.1～2 weight part, stir, namely obtain the aqueous polyurethane dispersion of this uV curable.
The preparation method of the aqueous polyurethane dispersion of above-mentioned uV curable, step 1) and step 2) described in low molecular weight polyols be that make up arbitrarily one of them or they of ethylene glycol, propylene glycol, butyleneglycol, glycol ether, Diethylene Glycol, pentanediol, neopentyl glycol, trishydroxymethyl propyl alcohol, glycerol, tetramethylolmethane.
Further, the preparation method of the aqueous polyurethane dispersion of above-mentioned uV curable, the described polyisocyanates of step 1) is 1, the 6-hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, 2,2,4-trimethylammonium-hexamethylene diisocyanate, 2,4,4-trimethylammonium-1, hexamethylene-diisocyanate, 4,4 ‵-isocyanic ester cyclohexyl methylmethane, isocyanatomethyl-1,8-octane vulcabond, 1,4-hexamethylene and isocyanic ester, 1, the 4-phenylene diisocyanate, 2,4 toluene diisocyanate, the arbitrary combination of 2,6-tolylene diisocyanate one of them or they.
Further, the preparation method of the aqueous polyurethane dispersion of above-mentioned uV curable, the hydroxyl vinyl monomer described in the step 3) is one of them of Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, pentaerythritol triacrylate or trimethylolpropane diacrylate or their arbitrary combination.
Further, the preparation method of the aqueous polyurethane dispersion of above-mentioned uV curable, step 2) described solvent is acetone or butanone.
Further, the preparation method of the aqueous polyurethane dispersion of above-mentioned uV curable, the described organo-metallic catalyst of step 3) is one of them of organic tin catalyzer, metal carboxylate catalyzer, titanate ester catalyzer, organic zirconium class catalyzer, organo-bismuth class catalyzer.
Further, the preparation method of the aqueous polyurethane dispersion of above-mentioned uV curable, the described acid of step 4) be acetic acid or formic acid or hydrochloric acid or oxalic acid one of.
Further, the preparation method of the aqueous polyurethane dispersion of above-mentioned uV curable, the described UV reactive thinner of step 5) is 1, in in 6-hexanediyl ester, dipropylene glycol two (methyl) acrylate, 1,4 butanediol diacrylate, neopentylglycol diacrylate, TriMethylolPropane(TMP) (methyl) acrylate, oxyethyl group Viscoat 295, tetramethylol methane tetraacrylate, Dipentaerythritol five acrylate, the dipentaerythritol acrylate one or their arbitrary combination.
Further; the preparation method of the aqueous polyurethane dispersion of above-mentioned uV curable, the described light trigger of step 5) be benzophenone or benzoin methyl ether or Alpha-hydroxy Benzoin ethyl ether or Alpha-hydroxy isopropyl benzene ketone or 4 '-(2-hydroxy ethoxy)-2-hydroxy-2-methyl Propiophenone, Alpha-hydroxy phenylcyclohexane ketone, isopropyl thioxanthone, 2-(4-methylthio phenyl formyl radical)-2-morpholinyl propane or one of them of oligomeric-hydroxyketone or their arbitrary combination.
Compared with prior art, the present invention's advantage specific as follows:
1. overcome surfaces of tacky after the preliminarily dried that prior art medium ultraviolet photocuring aqueous polyurethane causes for a short time because of molecular weight, defective that intensity is low.
2. owing to improved the content of two keys in the resin when introducing a large amount of cladodification structures, have very high cross-linking density behind ultraviolet light polymerization, cured article has very excellent hardness, water tolerance and solvent resistance.
3. the method provided by the present invention photocurable aqueous polyurethane stability in storage of producing is very excellent, at room temperature can deposit 2 years systems and not have considerable change.
4. the photocurable aqueous polyurethane produced of method provided by the present invention can be used for the top coat of base materials such as woodenware, paper, plastics, leather, textiles.
Embodiment
The present invention determines to build on the basis of a large amount of simultaneous tests and screening about the design of photocurable aqueous polyurethane and each component and usage quantity thereof, specific embodiments more given below are part preferred version of the present invention, further describe the present invention, but do not limit the invention to the scope of following embodiment.The preparation method who adopts among the embodiment and use together can be with reference to the art laboratory ordinary method, concrete preparation process is exemplified below:
Embodiment 1
The 2000Ml there-necked flask is furnished with thermometer, stirring, heating and whipping appts.Add refined caster oil 500g in the there-necked flask, be heated with stirring to 120 ± 5 ℃.Vacuum hydro-extraction 60min, be cooled to 70 ℃ and add IPDI (isophorone diisocyanate) 370.6 grams, keep 80 ± 5 ℃ of reactions 3 hours, be cooled to 60 ℃, add anhydrous propanone 300g, temperature is down to 45 ± 5 ℃ of addings, drip the 93g methyldiethanolamine, dropping time 30min dripped the back and adds organic bismuth catalyst 0.5g, in 50 ± 2 ℃ of insulations 3 hours.Add the hydroxyethyl methylacrylate 56g through processed, 60 ± 2 ℃ are reacted 2 hours to react completely (it is zero that the absorption peak that detects the NCO functionality of 2260～2280cm-1 by infrared spectra disappears).Be cooled to 30 ± 2 ℃, performed polymer is transferred in the 5L emulsion tank, add the mixing solutions of 46g acetic acid and 1200g deionized water under the high-speed stirring, get water dispersion, acetone is deviate from 45 ± 5 ℃ of underpressure distillation, translucent aqueous polyurethane dispersion, viscosity 130mpa.s, solid content are 41%; Take by weighing 0.5g Darocur 1173(Ciba company again, 2-hydroxy-2-methyl-1-phenyl-1-acetone) and N, N-Methyl pyrrolidone 2g dissolving evenly joins in the above-mentioned aqueous polyurethane dispersion of 100g, makes the aqueous polyurethane dispersion of uV curable.
Embodiment 2
The 2000Ml there-necked flask is furnished with thermometer, stirring, heating and whipping appts.Add refined caster oil 400g in the there-necked flask, be heated with stirring to 120 ± 5 ℃, vacuum hydro-extraction 60min, adding is cooled to 70 ℃ through the pentanediol 18g of processed, adds HMDI (dicyclohexyl methane diisocyanate, purity 〉=99.5%) 324.3 grams are kept 82 ± 2 ℃ of reactions 3 hours.Be cooled to 60 ℃, add anhydrous butanone 250g, temperature is down to 45 ± 5 ℃, drips the 99.8g methyldiethanolamine, drips time 30min, after dripping, in 50 ± 2 ℃ of insulations 3 hours.Add the Propylene glycol monoacrylate 100g through processed, organic bismuth catalyst 0.5g, 60 ± 2 ℃ are reacted 2 hours to react completely (it is zero that the absorption peak that detects the NCO functionality of 2260～2280cm-1 by infrared spectra disappears).Be cooled to 30 ± 2 ℃, performed polymer is transferred in the 5L emulsion tank, add the mixing solutions of 49.2g acetic acid and 1600g deionized water under the high-speed stirring, get water dispersion, acetone is deviate from 45 ± 5 ℃ of underpressure distillation, translucent aqueous polyurethane dispersion, viscosity 180mpa.s, solid content are 40.2%.
Take by weighing 0.5g Alpha-hydroxy phenylcyclohexane ketone and N again, N-Methyl pyrrolidone 2g dissolving evenly joins in the 100g above-mentioned steps gained aqueous polyurethane dispersion, makes the aqueous polyurethane dispersion of uV curable.
Embodiment 3
The 2000Ml there-necked flask is furnished with thermometer, stirring, heating and whipping appts.Add refined caster oil 600g in the there-necked flask, be heated with stirring to 120 ± 5 ℃, vacuum hydro-extraction 60min, be cooled to 70 ℃, add through 1 of processed 4-butyleneglycol 20g, add IPDI (isophorone diisocyanate) 419.3 grams, keep 82 ± 2 ℃ of reactions 3 hours.Be cooled to 60 ℃, add anhydrous propanone 250g, temperature is down to 45 ± 5 ℃, drips the 99.8g methyldiethanolamine, drips time 30min, after dripping, in 50 ± 2 ℃ of insulations 3 hours.Add the Propylene glycol monoacrylate 100g through processed, organic bismuth catalyst 0.5g, 60 ± 2 ℃ are reacted 2 hours to react completely (it is zero that the absorption peak that detects the NCO functionality of 2260～2280cm-1 by infrared spectra disappears).Be cooled to 30 ± 2 ℃, performed polymer is transferred in the 5L emulsion tank, add the mixing solutions of 49.2g acetic acid and 1600g deionized water under the high-speed stirring, get water dispersion, acetone is deviate from 45 ± 5 ℃ of underpressure distillation, translucent aqueous polyurethane dispersion, viscosity 300mpa.s, solid content are 39.2%.
Take by weighing 0.5g Alpha-hydroxy phenylcyclohexane ketone and N again, N-Methyl pyrrolidone 3g dissolving evenly joins in the 100g above-mentioned steps gained aqueous polyurethane dispersion, makes the aqueous polyurethane dispersion of uV curable.
Embodiment 4
The 2000Ml there-necked flask is furnished with thermometer, stirring, heating and whipping appts.Add refined caster oil 275.0g in the there-necked flask, be heated with stirring to 120 ± 5 ℃, vacuum hydro-extraction 60min, be cooled to 70 ℃, add through 1 of processed 4-butyleneglycol 50g, add TDI (tolylene diisocyanate) 398 grams when being cooled to 50 ℃ and mix, keep 70 ± 5 ℃ of reactions 3 hours.Be cooled to 60 ℃, add anhydrous butanone 300g, temperature is down to 45 ± 5 ℃ of addings, drips the 128g methyldiethanolamine, drips time 30min, after dripping, in 50 ± 2 ℃ of insulations 3 hours, to NCO content 1.0%.Add TriMethylolPropane(TMP) (methyl) the triacrylate ester 80g through processed, organic bismuth catalyst 0.5g, 60 ± 2 ℃ are reacted 2 hours to react completely (it is zero that the absorption peak that detects the NCO functionality of 2260～2280cm-1 by infrared spectra disappears).Be cooled to 30 ± 2 ℃, performed polymer is transferred in the 5L emulsion tank, add the mixing solutions of 64g acetic acid and 1400g deionized water under the high-speed stirring, get water dispersion, butanone is deviate from 55 ± 5 ℃ of underpressure distillation, translucent aqueous polyurethane dispersion, viscosity 500mpa.s, solid content are 38.5%.
Take by weighing 0.6g Darocur 1173(Ciba company again, 2-hydroxy-2-methyl-1-phenyl-1-acetone) and N, N-Methyl pyrrolidone 3g dissolving evenly joins in the 100g above-mentioned steps gained aqueous polyurethane dispersion, makes the aqueous polyurethane dispersion of uV curable.
Embodiment 5
The 2000Ml there-necked flask is furnished with thermometer, stirring, heating and whipping appts.Add refined caster oil 300g in the there-necked flask, be heated with stirring to 120 ± 5 ℃, vacuum hydro-extraction 60min adds HDI (1,6-hexamethylene diisocyanate) 200g and mixes when being cooled to 70 ℃, keep 90 ± 5 ℃ of reactions 3 hours.Be cooled to 60 ℃, add anhydrous butanone 200g, temperature is down to 45 ± 5 ℃ of addings, drips the 37.5g methyldiethanolamine, drips time 30min, after dripping, in 50 ± 2 ℃ of insulations 3 hours.Add the hydroxyethyl methylacrylate 37g through processed, organic bismuth catalyst 0.5g, 60 ± 2 ℃ are reacted 2 hours to react completely (it is zero that the absorption peak that detects the NCO functionality of 2260～2280cm-1 by infrared spectra disappears).Be cooled to 30 ± 2 ℃, performed polymer is transferred in the 5L emulsion tank, add the mixing solutions of 38g acetic acid and 1000g deionized water under the high-speed stirring, get water dispersion, butanone is deviate from 55 ± 5 ℃ of underpressure distillation, translucent aqueous polyurethane dispersion, viscosity 700mpa.s, solid content are 39.2%.
Take by weighing 0.6g Darocur 1173(Ciba company again, 2-hydroxy-2-methyl-1-phenyl-1-acetone) and N, N-Methyl pyrrolidone 3g dissolving evenly joins in the 100g above-mentioned steps gained aqueous polyurethane dispersion, makes the aqueous polyurethane dispersion of uV curable.
Comparative Examples 1:
The 2000Ml there-necked flask is furnished with thermometer, stirring, heating and whipping appts.Add refined caster oil 500g in the there-necked flask, be heated with stirring to 120 ± 5 ℃.Vacuum hydro-extraction 60min, be cooled to 70 ℃ and add IPDI (isophorone diisocyanate) 370.6 grams, keep 80 ± 5 ℃ of reactions 3 hours, be cooled to 60 ℃, add anhydrous propanone 300g, temperature is down to 45 ± 5 ℃ of addings, drip the 93g methyldiethanolamine, dropping time 30min dripped the back and adds organic bismuth catalyst 0.5g, in 50 ± 2 ℃ of insulations 3 hours.Add the hydroxyethyl methylacrylate 56g through processed, 60 ± 2 ℃ are reacted 2 hours to react completely (it is zero that the absorption peak that detects the NCO functionality of 2260～2280cm-1 by infrared spectra disappears).Be cooled to 30 ± 2 ℃, performed polymer is transferred in the 5L emulsion tank, add the mixing solutions of 46g acetic acid and 1200g deionized water under the high-speed stirring, get water dispersion, acetone is deviate from 45 ± 5 ℃ of underpressure distillation, translucent aqueous polyurethane dispersion, viscosity 130mpa.s, solid content are 41%; Take by weighing 0.5g Darocur 1173(Ciba company again, 2-hydroxy-2-methyl-1-phenyl-1-acetone) and N, N-Methyl pyrrolidone 2g dissolving evenly joins in the above-mentioned aqueous polyurethane dispersion of 100g, makes the aqueous polyurethane dispersion of uV curable.
Comparative Examples 2:
The 1000Ml there-necked flask is furnished with thermometer, stirring, heating and whipping appts.Add two functionality polyether glycol 300g(GE210 in the there-necked flask, the Shanghai Gaoqiao petrochemical industry), be heated with stirring to 120 ± 5 ℃, vacuum hydro-extraction 60min, adding IPDI186.3g and 0.5g organic bismuth catalyst mix when being cooled to 70 ℃, keep 85 ± 5 ℃ of reactions 3 hours, be cooled to 60 ℃, add DMPA (dimethylol propionic acid) 40g and 80g NMP (N, N-Methyl pyrrolidone) mixing solutions, 65 ± 2 ℃ are incubated 3 hours, add the Hydroxyethyl acrylate 55g through processed, react 2 hours to react completely (it is zero that the absorption peak that detects the NCO functionality of 2260～2280cm-1 by infrared spectra disappears).Be cooled to 50 ± 2 ℃, anhydrous propanone 150g, triethylamine 30.1g is cooled to 30 ± 2 ℃.Adding is transferred to performed polymer in the 3L emulsion tank, adds the mixing solutions of 900g deionized water under the high-speed stirring, gets water dispersion, and acetone is deviate from 45 ± 5 ℃ of underpressure distillation, gets translucent aqueous polyurethane dispersion, and viscosity 550mpa.s, solid content are 41%.
Comparative Examples 3:
0.5g Darocur 1173(Ciba company, 2-hydroxy-2-methyl-1-phenyl-1-acetone) and N, N-Methyl pyrrolidone 2g dissolving evenly joins in the 100g Comparative Examples 1 gained aqueous polyurethane dispersion, makes the aqueous polyurethane dispersion of uV curable.
The performance test of aqueous polyurethane-polyurea dispersions
Get above-mentioned aqueous polyurethane-polyurea dispersions 50 grams, room temperature was placed 24 hours on the tetrafluoroethylene plate of 20cm*20cm, surface drying, and then under 60 ℃, drying is 4 hours in blast drier, puts into UV curing machine at last, level places under the 500W medium pressure mercury lamp shone 1 minute, finished curing.Comparative Examples 1 and Comparative Examples 2 are without the UV curing schedule.
Water-fast test: cured film is cut into the 5cm*5cm size, is placed in the beaker that deionized water is housed, the surface covers with culture dish, places moisture evaporation.Be placed in the baking oven, oven temperature is set at 40 ℃, the variation of the outward appearance of observation film after 24 hours.Not whitening fully is 1 grade, and what serious whiting was dissolved is 5 ranks.
The solvent resistance test: cured film is cut into the 5cm*5cm size, is placed in the beaker that toluene and alcohol are housed respectively, the surface covers with culture dish, and ambient stable is set at 25 ℃, and swelling ratio is calculated in the variation of test membrane area after 72 hours.
The test of hardness: carry out according to " GB/T 6739-2006 paint and varnish pencil method is measured hardness of paint film ".
Test result sees the following form
| Dispersion | Water tolerance | The toluene swell rate | The alcohol swelling ratio | Hardness |
| Embodiment 1 | 1 | 32% | 45% | 2H |
| Embodiment 2 | 1 | 30% | 41% | 2H |
| Embodiment 3 | 1 | 28% | 35% | 3H |
| Embodiment 4 | 1 | 10% | 21% | 3H |
| Embodiment 5 | 1 | 40% | 60% | H |
| Comparative Examples 1 | 2 | 210% | Dissolving | B |
| Comparative Examples 2 | Dissolving | Dissolving | Dissolving | --(annotating 1) |
| Comparative Examples 3 | 2 | 190% | Dissolving | HB |
Annotate 1: hardness is too low, and pencil hardness method can't be measured.
Show from test result, adopt the photocurable washing leather polyurethane dispersions of the present invention's preparation, even after drying, solidify without UV, had excellent water tolerance, solvent resistance and physical and mechanical properties, after the UV aftertreatment, can increase substantially water tolerance, solvent resistance and hardness, performance index reach solvent-borne type or the requirement of no-solvent type UV system.
Claims (13)
1. the aqueous polyurethane dispersion of a uV curable is characterized in that, this dispersion system prepares by following step:
1) taking by weighing 300～600 weight part Viscotrol C is added in the reactor of belt stirrer, be heated to 100～130 ℃ of vacuum hydro-extraction 30～120min, when being cooled to 50～60 ℃, add 200～600 weight part polyisocyanates while stirring, after being warming up to 60～100 ℃ of reaction 60～240min, obtain product A;
When 2) product A being cooled to 55～65 ℃, add 100～400 parts by weight solvent, 40～50 ℃ of low molecular weight polyols that drip 60～200 weight part band tertiary amine groups while stirring, after 1～3 hour, obtain product B 40～60 ℃ of reactions;
3) add hydroxyl vinyl monomer and 0.001～0.1 weight part organo-metallic catalyst of 20～120 weight parts to product B, 40～80 ℃ of reactions 1～3 hour, obtain product C;
4) 30～100 weight parts acid and 1000～2000 weight parts waters are mixed after, drop in the product C, continuously stirring product C in the dropping process, drip finish to continue to stir 30～60min after, solvent is deviate from underpressure distillation again, obtains product D;
5) add light trigger and 1～10 weight part methyl-2-pyrrolidone of 0.1～2 weight part in the product D, stir, namely obtain the aqueous polyurethane dispersion of this uV curable.
2. the aqueous polyurethane dispersion of a kind of uV curable according to claim 1, it is characterized in that, step 1) takes by weighing 300～600 weight part Viscotrol C and is added in the reactor of belt stirrer, after being heated to 100～130 ℃ of vacuum hydro-extraction 30～120min, add 1～100 weight part low molecular weight polyols, when being cooled to 50～60 ℃, add 200～600 weight part polyisocyanates while stirring, after being warming up to 60～100 ℃ of reaction 60～240min, obtain product A.
3. the aqueous polyurethane dispersion of a kind of uV curable according to claim 1, it is characterized in that, step 5) adds the polyfunctionality UV reactive thinner of 0.1～100 weight part to product D, the light trigger and 1～10 weight part methyl-2-pyrrolidone that add 0.1～2 weight part after stirring, stir, namely obtain the aqueous polyurethane dispersion of this uV curable.
4. the preparation method of the aqueous polyurethane dispersion of the described a kind of uV curable of claim 1 is characterized in that, comprises following preparation process successively:
1) takes by weighing the there-necked flask that 300～600 weight part Viscotrol C are added to belt stirrer, be heated to 100～130 ℃ of vacuum hydro-extraction 30～120min, add low molecular weight polyols 0～100 weight part while stirring; When being cooled to 50～60 ℃, add 200～600 weight part polyisocyanates while stirring, be warming up to 60～100 ℃ of reaction 60～240min, obtain product A;
2) when product A is cooled to 55～65 ℃, add 100～400 parts by weight solvent, drip the low molecular weight polyols that contains 60～200 weight part tertiary amine groups while stirring at 40～50 ℃, 40～60 ℃ of reactions 1～3 hour, obtain product B;
3) add hydroxyl vinyl monomer and 0.001～0.1 weight part organo-metallic catalyst of 20～120 weight parts to product B, 40～80 ℃ of reactions 1～3 hour, obtain product C;
4) 30～100 weight parts acid and 1000～2000 weight parts waters are mixed after, drop in the product C, continuously stirring product C in the dropping process, drip finish to continue stirring 30～60min after, solvent is deviate from underpressure distillation, obtains product D;
5) add the polyfunctionality UV reactive thinner of 0～100 weight part in the product D, stir, add light trigger and 1～10 weight part methyl-2-pyrrolidone of 0.1～2 weight part, stir, namely obtain the aqueous polyurethane dispersion of this uV curable.
5. the preparation method of the aqueous polyurethane dispersion of uV curable according to claim 4, it is characterized in that the described low molecular weight polyols of step 1) is that make up arbitrarily one of them or they of ethylene glycol, propylene glycol, butyleneglycol, glycol ether, Diethylene Glycol, pentanediol, trishydroxymethyl propyl alcohol, glycerol, tetramethylolmethane.
6. the preparation method of the aqueous polyurethane dispersion of uV curable according to claim 4, it is characterized in that, the described polyisocyanates of step 1) is 1, the 6-hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, 2,2,4-trimethylammonium-hexamethylene diisocyanate, 2,4,4-trimethylammonium-1, hexamethylene-diisocyanate, 4,4 ‵-isocyanic ester cyclohexyl methylmethane, isocyanatomethyl-1,8-octane vulcabond, 1,4-hexamethylene vulcabond, 1, the 4-phenylene diisocyanate, 2,4 toluene diisocyanate, the arbitrary combination of 2,6-tolylene diisocyanate one of them or they.
7. the preparation method of the aqueous polyurethane dispersion of uV curable according to claim 4 is characterized in that step 2) low molecular weight polyols of described tertiary amine groups is methyldiethanolamine.
8. the preparation method of the aqueous polyurethane dispersion of uV curable according to claim 4, it is characterized in that the hydroxyl vinyl monomer described in the step 3) is one of them of Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, pentaerythritol triacrylate or trimethylolpropane diacrylate or their arbitrary combination.
9. the preparation method of the aqueous polyurethane dispersion of uV curable according to claim 4 is characterized in that step 2) described solvent is acetone or butanone.
10. the preparation method of the aqueous polyurethane dispersion of uV curable according to claim 4, it is characterized in that the described organo-metallic catalyst of step 3) is one of them of organic tin catalyzer, titanate ester catalyzer, organic zirconium class catalyzer, organo-bismuth class catalyzer.
11. the preparation method of the aqueous polyurethane dispersion of uV curable according to claim 4 is characterized in that, the described acid of step 4) be acetic acid or formic acid or hydrochloric acid or oxalic acid one of.
12. the preparation method of the aqueous polyurethane dispersion of uV curable according to claim 4, it is characterized in that, the described polyfunctionality UV of step 5) reactive thinner is 1, the 6-hexanediyl ester, dipropylene glycol two (methyl) acrylate, 1,4 butanediol diacrylate, neopentylglycol diacrylate, TriMethylolPropane(TMP) (methyl) acrylate, the oxyethyl group Viscoat 295, tetramethylol methane tetraacrylate, Dipentaerythritol five acrylate, in in the dipentaerythritol acrylate one or their arbitrary combination.
13. the preparation method of the aqueous polyurethane dispersion of uV curable according to claim 4; it is characterized in that, the described light trigger of step 5) be benzophenone or benzoin methyl ether or Alpha-hydroxy Benzoin ethyl ether or Alpha-hydroxy isopropyl benzene ketone or 4 '-(2-hydroxy ethoxy)-2-hydroxy-2-methyl Propiophenone, Alpha-hydroxy phenylcyclohexane ketone, isopropyl thioxanthone, 2-(4-methylthio phenyl formyl radical)-arbitrary combination of 2-morpholinyl propane one of them or they.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210206961 CN102702469B (en) | 2012-06-20 | 2012-06-20 | Ultraviolet-curable aqueous polyurethane dispersion and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210206961 CN102702469B (en) | 2012-06-20 | 2012-06-20 | Ultraviolet-curable aqueous polyurethane dispersion and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102702469A CN102702469A (en) | 2012-10-03 |
| CN102702469B true CN102702469B (en) | 2013-09-04 |
Family
ID=46895550
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210206961 Expired - Fee Related CN102702469B (en) | 2012-06-20 | 2012-06-20 | Ultraviolet-curable aqueous polyurethane dispersion and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102702469B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104031231A (en) * | 2014-06-19 | 2014-09-10 | 合肥工业大学 | Ultraviolet-curing waterborne epoxy-polyurethane-acrylate copolymer resin anticorrosive coating and preparation method thereof |
| CN105199076A (en) * | 2015-10-23 | 2015-12-30 | 青岛展辰新材料有限公司 | Preparation method of water-based ultraviolet light-cured biology-base polyurethane acrylate resin |
| JP7170538B2 (en) * | 2015-12-08 | 2022-11-14 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン | Functionalization-enhancing resins derived from renewable materials |
| CN106147587B (en) * | 2016-07-12 | 2018-04-24 | 叶有国 | A kind of antimicrobial UV coating containing castor oil-base and its preparation method and application |
| CN106189803B (en) * | 2016-07-12 | 2018-04-24 | 叶有国 | A kind of fingerprint recognition coating and its preparation method and application |
| CN106866929A (en) * | 2017-02-24 | 2017-06-20 | 中国林业科学研究院林产化学工业研究所 | A kind of polyfunctionality castor oil-base light-cured resin and its preparation method and application |
| CN106866915B (en) * | 2017-03-01 | 2020-01-10 | 宝鸡文理学院 | Bio-based water-based nano emulsion for canvas coating and preparation method thereof |
| JP2021147619A (en) * | 2020-03-17 | 2021-09-27 | 三菱ケミカル株式会社 | Method for producing urethane bond-containing compound |
| CN112375197B (en) * | 2020-10-26 | 2022-10-04 | 安徽大学 | Preparation method and application of ultraviolet-cured antibacterial aqueous polyurethane emulsion |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101418145B (en) * | 2008-12-11 | 2012-07-18 | 中国科学院长春应用化学研究所 | Cation waterborne ultraviolet curing resin coating and production method |
-
2012
- 2012-06-20 CN CN 201210206961 patent/CN102702469B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102702469A (en) | 2012-10-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102702469B (en) | Ultraviolet-curable aqueous polyurethane dispersion and preparation method thereof | |
| CN101235195B (en) | Cationic water-based polyurethane/acrylate composite emulsion and preparation method thereof | |
| CN108409955B (en) | auto parts and cars | |
| CN101875711B (en) | Preparation method of hydroxyl aqueous polyurethane-acrylate resin hybridized body | |
| CN107903373B (en) | UV-cured water-based hyperbranched polyurethane acrylate and preparation method thereof | |
| CN103467687B (en) | Preparation method of solvent-free waterborne polyurethane resin | |
| CN101759841B (en) | Core-shell type aqueous polyurethane-acrylic ester emulsion original position radiation polymerization method | |
| EP3328912B1 (en) | Polyurethane (meth)acrylate oligomers and curable compositions comprising said oligomers | |
| CN105482060A (en) | Hyperbranched waterborne polyurethane acrylate emulsion as well as preparation method and application thereof | |
| CN106750140A (en) | A kind of amine modified urethane acrylate light-cured resin and preparation method thereof | |
| CN104927024A (en) | Preparation method of fluorine modified light-cured polyurethane acrylate resin and application thereof as light-cured coating hydrophobic filling material | |
| CN103409058B (en) | Non-yellowing ultraviolet light curing abrasion resistant paint and preparation method thereof | |
| CN102863829A (en) | Humidity and ultraviolet dual-cured polyurethane woodware coating and preparation method thereof | |
| CN103554393B (en) | A kind of preparation method of natural polymer subbase light-cured resin | |
| CN106905504B (en) | Water-based ultraviolet-curing polyurethane resin and preparation method and application thereof | |
| CN114085353B (en) | Photo-thermal dual-curing resin and preparation method thereof | |
| CN110105578A (en) | A kind of highly-water-soluble UV-Curing Waterborne Resin and preparation method thereof with siliceous segment | |
| CN104017169A (en) | Preparation method of core-shell type waterborne polyurethane emulsion with crosslinked and hybrid structures | |
| CN106957406A (en) | A kind of calixarene type light-cured polyurethane resin and its coatings of preparation | |
| CN105801791A (en) | Castor oil-based UV-cured polyurethane acrylate and preparation method and application thereof | |
| CN115521437A (en) | A kind of preparation method of water-soluble ultraviolet light curing hyperbranched polyurethane acrylic resin | |
| CN105713168B (en) | A kind of base polyurethane prepolymer for use as and preparation method thereof | |
| CN114907763A (en) | A kind of preparation method of hyperbranched photocurable water-based polyurethane film | |
| CN115433482A (en) | A kind of preparation method of waterborne polyurethane water-resistant coating | |
| CN109824863A (en) | A kind of preparation method of polyurethane curing agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130904 Termination date: 20180620 |