CN107400453A - A kind of preparation method of white fluorescent aqueous polyurethane coating - Google Patents
A kind of preparation method of white fluorescent aqueous polyurethane coating Download PDFInfo
- Publication number
- CN107400453A CN107400453A CN201710696679.6A CN201710696679A CN107400453A CN 107400453 A CN107400453 A CN 107400453A CN 201710696679 A CN201710696679 A CN 201710696679A CN 107400453 A CN107400453 A CN 107400453A
- Authority
- CN
- China
- Prior art keywords
- white fluorescent
- aqueous polyurethane
- dihydric alcohol
- fluorescence
- preparation
- 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.)
- Granted
Links
- 239000011527 polyurethane coating Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000004814 polyurethane Substances 0.000 claims abstract description 50
- 229920002635 polyurethane Polymers 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000839 emulsion Substances 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 28
- 239000004970 Chain extender Substances 0.000 claims abstract description 22
- 239000013530 defoamer Substances 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 13
- 150000004985 diamines Chemical class 0.000 claims abstract description 10
- 229920002521 macromolecule Polymers 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000006097 ultraviolet radiation absorber Substances 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
- 125000003827 glycol group Chemical group 0.000 claims abstract description 7
- 239000002562 thickening agent Substances 0.000 claims abstract description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 64
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 41
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 38
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 14
- 229940043237 diethanolamine Drugs 0.000 claims description 14
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 12
- 125000000129 anionic group Chemical group 0.000 claims description 11
- 239000012043 crude product Substances 0.000 claims description 11
- 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 10
- 125000002091 cationic group Chemical group 0.000 claims description 10
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 claims description 8
- 229940043267 rhodamine b Drugs 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- 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 7
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 125000004427 diamine group Chemical group 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- KKAJSJJFBSOMGS-UHFFFAOYSA-N 3,6-diamino-10-methylacridinium chloride Chemical compound [Cl-].C1=C(N)C=C2[N+](C)=C(C=C(N)C=C3)C3=CC2=C1 KKAJSJJFBSOMGS-UHFFFAOYSA-N 0.000 claims description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 5
- 229940023020 acriflavine Drugs 0.000 claims description 5
- 229920001610 polycaprolactone Polymers 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003480 eluent Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- -1 small molecule diol Chemical class 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 239000000126 substance Substances 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 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 101100412856 Mus musculus Rhod gene Proteins 0.000 claims description 2
- 235000003140 Panax quinquefolius Nutrition 0.000 claims description 2
- 240000005373 Panax quinquefolius Species 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- BGLGAKMTYHWWKW-UHFFFAOYSA-N acridine yellow Chemical compound [H+].[Cl-].CC1=C(N)C=C2N=C(C=C(C(C)=C3)N)C3=CC2=C1 BGLGAKMTYHWWKW-UHFFFAOYSA-N 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical class OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 239000004567 concrete Substances 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- 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 2
- 238000000926 separation method Methods 0.000 claims description 2
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 125000003916 ethylene diamine group Chemical group 0.000 claims 1
- 238000011017 operating method Methods 0.000 claims 1
- 230000005855 radiation Effects 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- 230000002688 persistence Effects 0.000 abstract description 2
- 235000019441 ethanol Nutrition 0.000 description 29
- 238000001291 vacuum drying Methods 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 239000000243 solution Substances 0.000 description 7
- 150000003384 small molecules Chemical class 0.000 description 6
- 239000003973 paint Substances 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 5
- 229960002668 sodium chloride Drugs 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 208000005156 Dehydration Diseases 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- ARSRBNBHOADGJU-UHFFFAOYSA-N 7,12-dimethyltetraphene Chemical compound C1=CC2=CC=CC=C2C2=C1C(C)=C(C=CC=C1)C1=C2C ARSRBNBHOADGJU-UHFFFAOYSA-N 0.000 description 3
- VFZRZRDOXPRTSC-UHFFFAOYSA-N DMBA Natural products COC1=CC(OC)=CC(C=O)=C1 VFZRZRDOXPRTSC-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 230000003098 cholesteric effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229920001109 fluorescent polymer Polymers 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 125000003944 tolyl group Chemical group 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
- C09D175/08—Polyurethanes from polyethers
-
- 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
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—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
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/22—Luminous paints
Abstract
The invention discloses a kind of preparation method of white fluorescent aqueous polyurethane coating, is characterized in first preparing red fluorescence dihydric alcohol and blue-fluorescence dihydric alcohol, then they are mixed to get into white fluorescent powder with green fluorescence diamine；It is combined using the fluorescent material with dihydric alcohol, partly or entirely substitute the glycol chain extender used in aqueous polyurethane building-up process, by being reacted with diisocyanate, macromolecule dihydric alcohol and hydrophilic chain extender, white fluorescent aqueous polyurethane emulsion is prepared；Then defoamer, levelling agent, thickener, ultra-violet absorber and deionized water are sequentially added in the emulsion, is compounded in scuffing of cylinder bore, white fluorescent aqueous polyurethane coating is made.Using the inventive method, by the design and combination to red-green-blue fluorescent chromophore, obtained white fluorescent aqueous polyurethane coating can be made to launch white fluorescent, and chromophore is not easy to migrate, and fluorescence persistence is good, and color fastness is high.
Description
Technical field
The invention belongs to feature water-base polyurethane material preparing technical field, and in particular to white fluorescent aqueous polyurethane
Coating and preparation method thereof.
Background technology
The high polymer material of white fluorescent can be launched at present mainly two kinds of preparation methods, one kind be by macromolecule with it is organic
Small molecule is blended, and obtains organic molecule luminescent dye/polymer composite system, participates in the small molecule of blending and can fluoresce
Or can phosphorescent small-molecule substance.Chinese patent 201410680487.2 discloses a kind of LED light white light two times transfer with glimmering
Optical plastic agglomerate preparation method, Chinese patent 201610301213.7 disclose a kind of white fluorescent cholesteric based on chiral ion
Phase liquid crystal device and its preparation technology, prepared by the white light phosphor of the two is entered with small molecule to high molecular doped forms more
OK, resulting materials Shortcomings in terms of stability, processability, cost of manufacture, while these small molecule fluorescent dyestuffs are in high score
The generation that aggregation causes to be separated can occur in sub- body, cause fluorescence colourity uneven；Another kind is by " blue light and orange light two are former
The colorimetry principle of color synthesis white light " or " red-green-blue synthesis white light " is applied to the MOLECULE DESIGN of white light high polymer material
In chemical synthesis, the single Polymer Systems with 2 (two-color white lights) or 3 (three color white lights) centres of luminescence are built into.
A kind of three primary colours block copolymerization type white emitting fluorescent powder and preparation method thereof as disclosed in Chinese patent 201310711203.7, and
A kind of white fluorescent polymeric compounds and preparation method thereof disclosed in Chinese patent 200810243778.X.This kind of method is mostly free radical
Polymerization, severe reaction conditions and be difficult to control, and need to add a large amount of DMFs etc. in course of reaction organic molten
Agent, it is unfavorable for scale industrial production；And a large amount of introducings of organic solvent can bring potential safety hazard, environmental hazard and cost increase
The problems such as.
Aqueous polyurethane using water as medium, have it is non-ignitable, not quick-fried, nontoxic, tasteless, it is free from environmental pollution, can reduce and be produced into
The advantage such as this, is widely used to the industries such as coating, leather, adhesive, papermaking, building.Chinese patent 201310092827.5
Disclose a kind of preparation method based on the fluorescent type aqueous polyurethane emulsion of chromophore in diisocyanate, Chinese patent
201310222308.6 disclose a kind of fluorescent type aqueous polyurethane based on chromophore in dihydric alcohol and preparation method thereof, but this
A little methods are all the systems using single-shot light center, and chromophore chromatogram is not complete, and the water-based poly- ammonia that can send out white fluorescent can not be made
Ester material.
The content of the invention
It is an object of the invention to provide a kind of preparation method of white fluorescent aqueous polyurethane coating, to overcome prior art
Drawbacks described above.
The preparation method of white fluorescent aqueous polyurethane coating of the present invention, it is characterised in that：First prepare respectively red glimmering
Light dihydric alcohol and blue-fluorescence dihydric alcohol, they and green fluorescence diamine compounding are then obtained into white fluorescent powder, reused
The white fluorescent powder partly or entirely substitutes glycol chain extender, by with diisocyanate, macromolecule dihydric alcohol and hydrophilic expansion
Chain agent is reacted, and white fluorescent aqueous polyurethane emulsion is made；
The red fluorescence dihydric alcohol is prepared as follows：
Rhodamine B addition dichloromethane is completely dissolved to it, is 1.2-2 by with rhodamine B mol ratio：1-2：1-2：1
Diethanol amine, triethylamine and O- BTAs-tetramethylurea hexafluorophosphoric acid ester (HBTU) are added, reacts at room temperature 10 under agitation
After~24 hours, add and be diluted by the dichloromethane of 1.5-3 times of reaction solution volume, and with 0.3-0.6 times of reaction solution volume
1M sodium-chloride water solutions clean 2-5 times；After organic phase is dried with anhydrous magnesium sulfate, dichloromethane is sloughed under vacuum condition；Slightly
Dried after product ethyl alcohol recrystallization to constant weight, that is, obtain red fluorescence dihydric alcohol (RDB-OH), its structural formula is
The blue-fluorescence dihydric alcohol is prepared as follows：
It is 1 in molar ratio：5-10：4- fluorine benzophenone, diethanol amine and potassium hydroxide are warming up to by 1.5-3 under agitation
Room temperature is cooled to after 90~110 DEG C of reaction 12-24 hours, the water by 10-25 times of diethanol amine volume is added, stirs to thick
Precipitation separates out completely；The water on upper strata is removed, crude product is dried extremely after being purified using ethyl acetate as eluant, eluent using column chromatography for separation
Constant weight, that is, obtain blue-fluorescence dihydric alcohol (NBP), and its structural formula is
The green fluorescence diamine is selected from acriflavine (AF) or α acridine yellow G (AFG)；
The preparation of white fluorescent powder：Red fluorescence dihydric alcohol, blue-fluorescence dihydric alcohol and green fluorescence diamine are pressed into matter
Measure ratio 1：2.5-4：0.3-0.6 grindings are dried to constant weight after being uniformly mixed, that is, obtain white fluorescent powder；
Then the preparation of white fluorescent aqueous polyurethane emulsion is carried out：
According to used hydrophilic radical type when preparing aqueous polyurethane emulsion, by the white fluorescent aqueous polyurethane
It is divided into cationic white fluorescent aqueous polyurethane emulsion and anionic white fluorescent aqueous polyurethane emulsion two types；
When using cationic hydrophilic chain extender N methyldiethanol amine (MDEA) and diisocyanate, macromolecular binary
When alcohol, white fluorescent powder and small molecule diol reaction, then cationic white fluorescent aqueous polyurethane emulsion is obtained, specific behaviour
It is as follows to make step：
On the basis of non-aqueous in the aqueous polyurethane and quality of non-solvent component, by by Reference mass 35-75%'s
Macromolecule dihydric alcohol is dehydrated 15-60 minutes at 100-115 DEG C, adds the diisocyanate by Reference mass 20-55%, in
75-95 DEG C of reaction 1.5-3 hour, then sequentially add white fluorescent powder by Reference mass 0.5-12%, 0-10% binary
Alcohol chain extender, 0.01-0.05% dibutyl tin laurate (DBTDL) and 10-60% acetone or butanone, at 65-85 DEG C
2.5-5 hours are reacted, 30-40 DEG C is then cooled to, the N methyldiethanol amine by Reference mass 6-12% is dissolved in 10-40%
Acetone or butanone in after instill reaction system in, after dripping off 50-60 DEG C react 2-3 hours；Then 30-40 DEG C is cooled to,
Reference mass 3.2-6.5% acetic acid is added, after reacting 1-5 minutes, benchmark is added under 2000-4000 revs/min of rotating speed cutting
Quality 200-300% water and 0-5% diamine chain extenders, after stirring 5-25 minutes, emulsion Rotary Evaporators will be reacted
Acetone or butanone are sloughed under 40-50 DEG C of vacuum condition, that is, obtains cationic white fluorescent aqueous polyurethane emulsion；
When different using anionic hydrophilic chain extender dihydromethyl propionic acid (DMPA) or dimethylolpropionic acid (DMBA) and two
When cyanate, macromolecule dihydric alcohol, white fluorescent powder and small molecule diol reaction, then it is water-based to obtain anionic white fluorescent
Polyaminoester emulsion, concrete operation step are as follows：
On the basis of non-aqueous in the aqueous polyurethane and quality of non-solvent component, by by Reference mass 35-75%'s
Macromolecule dihydric alcohol is dehydrated 15-60 minutes at 100-115 DEG C, adds the diisocyanate by Reference mass 20-55%, in
75-95 DEG C of reaction 1.5-3 hour, then sequentially add anionic hydrophilic chain extender, the 0.5-12% by Reference mass 4-8%
White fluorescent powder, 0-10% glycol chain extender, 0.01-0.05% dibutyl tin laurate (DBTDL) and 20-
100% acetone or butanone, 3-7 hours are reacted at 65-85 DEG C, be then cooled to 30-40 DEG C, Reference mass 3-6% is pressed in addition
Triethylamine, after reacting 1-5 minutes, added under 2000-4000 revs/min of rotating speed cutting Reference mass 200-300% water and
0-5% diamine chain extenders, after stirring 5-25 minutes, by reaction emulsion Rotary Evaporators under 40-50 DEG C of vacuum condition
Acetone or butanone are sloughed, that is, obtains anionic white fluorescent aqueous polyurethane emulsion；
Finally press mass parts 100：(0.1-0.5)：(0.2-2)：(0.2-3)：(1-5)：(5-15) is water-based by white fluorescent
Polyaminoester emulsion, defoamer, levelling agent, thickener, ultra-violet absorber and deionized water, which are sequentially added in scuffing of cylinder bore, to be compounded,
30-90 minutes are stirred under 250-500 revs/min of mixing speed, white fluorescent aqueous polyurethane coating is made.
The macromolecule dihydric alcohol is selected from polyadipate -1,4- butyl glycol ester diols (PBA), polycaprolactone diols
(PCL), PCDL (PCDL), PTMG dihydric alcohol (PTMG) or polypropylene glycol (PPG)；
The diisocyanate is selected from toluene di-isocyanate(TDI) (TDI) or IPDI (IPDI)；
The glycol chain extender is selected from ethylene glycol (EG), 1,4- butanediols (BDO) or diglycol (DEG)；
The diamine chain extenders are selected from ethylenediamine (EDA) or IPD (IPDA).
The defoamer is selected from BYK 022, BYK 024, BYK 025, BYK 028, the BYK 093 of German Bi Ke chemistry,
Or Japanese Sheng Nuopuke SN Defoamer 327, SN Defoamer 328, SN Defoamer 399, SN-Defoamer
1310th, SN-Defoamer 1311, SN-Defoamer 1313, or the EFKA 2526 of EFKA auxiliary agent company, EFKA 2550,
EFKA 2580, or TEGO foamex 800, the TEGO foamex 805 that German enlightening is high, or U.S.'s aerochemistry
One or more in SURFYNOL DF 58, SURFYNOL DF 110D, SURFYNOL DF61, SURFYNOL MD 20.
The levelling agent is selected from BYK 331, BYK 346, BYK 348, the BYK 354 of German Bi Ke chemistry, or German enlightening
One or more in high TEGO 440, TEGO 450, TEGO 482.
The thickener is selected from the ACRYSOL of Rhom and HassTM RM 8W、ACRYSOLTM 12W、ACRYSOLTM
5000、ACRYSOLTMOne or several kinds in RM 2020NPR, or the Viscalex HV30 of BASF.
The ultra-violet absorber is selected from Yongguang Chemical Industry Co., Ltd., Taiwan Eversorb AQ1, Eversorb
One or more in AQ4, Eversorb AQ5, Eversorb AQ6.
Compared with prior art, preparation method of the present invention has advantages below：
1. prepare white fluorescent aqueous polyurethane coating using the inventive method, by small point of red-green-blue fluorescence
The design and combination of son, can launch good white fluorescent.
2. the white fluorescent aqueous polyurethane coating prepared using the inventive method, because fluorescent chromophore is to pass through chemistry
The mode of key entry is entered in the strand of polyurethane, and chromophore is not easy to migrate, and fluorescence persistence is good, and color fastness is high.
3. white fluorescent aqueous polyurethane coating is prepared using the inventive method, because white fluorescent powder is as chain extender
Use, can partly or entirely substitute other small molecule chain extenders, it is easy to which control chromophore is in polyurethane molecular as needed
Content in chain；In addition the solid content distribution of emulsion is wide and adjustable, so the chromophore content of white fluorescent aqueous polyurethane can
Controlled in wider scope, so as to obtain the white fluorescent aqueous polyurethane coating of various different colourities.
Brief description of the drawings
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the RDB-OH prepared by the embodiment of the present invention 1.
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the NBP prepared by the embodiment of the present invention 1.
Fig. 3 is the white fluorescent aqueous polyurethane emulsion and white fluorescent aqueous polyurethane prepared by the embodiment of the present invention 1
Steady state emission spectrum figure of the paint film under 365nm ultraviolet excitations.
Embodiment
Embodiment 1：
1.48 grams of rhodamine Bs and 30 milliliters of dichloromethane are added in three-necked flask, stirs to rhodamine B and is completely dissolved
Afterwards, 0.42 gram of diethanol amine, 0.35 gram of triethylamine, 1.31 grams of HBTU are added；Room temperature reaction 15 is small under magnetic stirrer
Shi Hou, 70 milliliters of dchloromethanes are poured into, and cleaned 3 times with 50 milliliters of 1M sodium-chloride water solution；The anhydrous sulphur of organic phase
After sour magnesium is dried, dichloromethane is sloughed under vacuum condition；Crude product is dry to perseverance with being placed in after ethyl alcohol recrystallization in vacuum drying oven
Weight, obtains red fluorescence dihydric alcohol RDB-OH；
2.16 grams of 4- fluorine benzophenone, 7.1 grams of diethanol amine and 1.12 grams of potassium hydroxide are added in three-necked flask, used
Magnetic stirrer, 100 DEG C are warming up to, reaction terminates reaction after 18 hours；After being cooled to room temperature, 100 milliliters of distillations are added
Water, quick stirring to thick precipitation separate out completely；The water on upper strata is removed, crude product is using ethyl acetate as eluant, eluent column chromatography
It is placed in vacuum drying oven and is dried to constant weight after partition method separating-purifying, obtains blue-fluorescence dihydric alcohol NBP；
Then 1 gram of RDB-OH, 0.5 gram of green fluorescence diamine AF and 3.2 grams of NBP are placed in mortar, grinding stirring, mixed
It is placed in vacuum drying oven and is dried to constant weight after closing uniformly, obtains white fluorescent powder；
By 20 grams average molecular weight Mn50 DEG C are cooled to after 1 hour for PTMG110 DEG C of 2000 dehydration, add 15 grams
IPDI, the white fluorescent powder, 2.4 grams of DMPA, 3 grams of BDO, 0.01 of 0.5 gram of above-mentioned preparation are added after 2 hours in 80 DEG C of stirring reactions
Gram DBTDL and 20 gram of acetone, constant temperature are cooled to 30 DEG C after 6 hours in 70 DEG C of stirring reactions；Reaction product is transferred to high speed shear
Dispersion machine, adds 1.82 grams of TEA and 10 gram of acetone under the conditions of 3000 revs/min of rotating speed cutting, and reaction adds 95 grams after 3 minutes
Water, Rotary Evaporators are transferred to after being stirred for 5 minutes, slough acetone under 50 DEG C, 0.01MPa vacuum conditions, obtain anionic
White fluorescent aqueous polyurethane emulsion；
It is 100 by mass parts：0.5：1：2：5：15 by white fluorescent aqueous polyurethane emulsion, defoamer, levelling agent, thickening
Agent, ultra-violet absorber and deionized water, which are sequentially added in scuffing of cylinder bore, to be compounded, and is stirred under 500 revs/min of mixing speed
60 minutes, white fluorescent aqueous polyurethane coating is made；
White fluorescent aqueous polyurethane coating obtained above is subjected to spraying application, with spray gun spraying in the sample polished
On slab plate, the model steel plate after spraying is placed to film surface drying at room temperature, solidifies 30 minutes in 80 DEG C, obtains thickness
For 15 μm of white fluorescent waterborne polyurethane paint film.
Accompanying drawing 1 is the synthetically prepared RDB-OH of the present embodiment hydrogen nuclear magnetic resonance spectrogram, it is confirmed that RDB-OH success
Synthesis, its structural formula are：
Fig. 2 is the synthetically prepared NBP of the present embodiment hydrogen nuclear magnetic resonance spectrogram, it was demonstrated that NBP successful synthesis, its structural formula
For：
Fig. 3 is the white fluorescent aqueous polyurethane emulsion and white fluorescent waterborne polyurethane paint film prepared by the present embodiment 1
Steady state emission spectrum figure under 365nm ultraviolet excitations.Marked in figure WWPU (latex) for white fluorescent aqueous polyurethane
Fluorescence emission spectrum of the emulsion in the case where 365nm is excited；WWPU (film) white fluorescent waterborne polyurethane paint film is marked in 365nm
Fluorescence emission spectrum under exciting.
, can be by adjusting PTMG, TPDI, DMPA and white fluorescent powder quality in the case where keeping other conditions constant
Than obtaining white fluorescent powder water-based poly- ammonia of the different white fluorescent of content in non-aqueous non-solvent material in aqueous polyurethane
Ester paint.
If other conditions of the present embodiment are constant, and PTMG is substituted for into PCDL, the white fluorescent water that can be also stablized
Property polyurethane coating.
If other conditions of the present embodiment are constant, and DMPA is substituted for into DMBA, the white fluorescent water that can be also stablized
Property polyurethane coating.
If other conditions of the present embodiment are constant, and BDO is substituted for EG or DEG respectively, the white that can be also stablized
Fluorescence aqueous polyurethane coating.
Embodiment 2：
4.8 grams of rhodamine Bs and 50 milliliters of dichloromethane are added in three-necked flask, are stirred to rhodamine B after being completely dissolved,
Add 1.8 grams of diethanol amine, 1.3 grams of triethylamines, 4 grams of HBTU；After being reacted at room temperature 18 hours under magnetic stirrer, pour into
100 milliliters of dchloromethanes, and cleaned 4 times with 50 milliliters of 1M sodium-chloride water solution；Organic phase is dried with anhydrous magnesium sulfate
Afterwards, dichloromethane is sloughed under vacuum condition；Crude product is dry to constant weight with being placed in after ethyl alcohol recrystallization in vacuum drying oven, obtains red
Color fluorescence dihydric alcohol RDB-OH；
1.08 grams of 4- fluorine benzophenone, 4.0 grams of diethanol amine and 0.3 gram of potassium hydroxide are added in three-necked flask, used
Magnetic stirrer, 90 DEG C are warming up to, reaction terminates reaction after 24 hours；After being cooled to room temperature, 50 milliliters of distilled water are added,
Quick stirring to thick precipitation separates out completely；The water on upper strata is removed, crude product uses column chromatography method (using ethyl acetate to wash
De- agent) it is placed in vacuum drying oven after separating-purifying and dries to constant weight, obtain blue-fluorescence dihydric alcohol NBP；
Then 2 grams of RDB-OH, 1.2 grams of green fluorescence diamine AFG and 7 grams of NBP are placed in mortar, grinding stirring, mixed
It is placed in vacuum drying oven and is dried to constant weight after closing uniformly, obtains white fluorescent powder；
By 14 grams average molecular weight Mn50 DEG C are cooled to after 1 hour in 110 DEG C of dehydrations for 2000 PTMG, add 7 grams
IPDI, in 80 DEG C of stirring reactions add after 2 hours the white fluorescent powder of 0.48 gram of above-mentioned preparation, 1.5 grams of DMPA, 0.9 gram of BDO,
0.01 gram of DBTDL and 10 gram of butanone, constant temperature are cooled to 20 DEG C after 6 hours in 70 DEG C of stirring reactions；Reaction product is transferred at a high speed
Dispersion machine is sheared, 1.13 grams of TEA and 10 gram of acetone are added under the conditions of 3000 revs/min of rotating speed cutting, reaction adds after 3 minutes
55 grams of water；Be transferred to Rotary Evaporators after being stirred for 5 minutes, acetone sloughed under 50 DEG C, 0.01MPa vacuum conditions, obtain it is cloudy from
Subtype white fluorescent aqueous polyurethane emulsion；
It is 90 by mass parts：0.3：0.8：1：2：10 by white fluorescent aqueous polyurethane emulsion, defoamer, levelling agent, increasing
Thick dose, ultra-violet absorber and deionized water, which are sequentially added in scuffing of cylinder bore, to be compounded, and is stirred under 400 revs/min of mixing speed
Mix 50 minutes, white fluorescent aqueous polyurethane coating is made.
Embodiment 3：
1.6 grams of rhodamine Bs and 30 milliliters of dichloromethane are added in three-necked flask, are stirred to rhodamine B after being completely dissolved,
Add 0.4 gram of diethanol amine, 0.4 gram of triethylamine, 1.4 grams of HBTU；After being reacted at room temperature 10 hours under magnetic stirrer, fall
Enter 60 milliliters of dchloromethanes, and cleaned 5 times with 40 milliliters of 1M sodium-chloride water solution；Organic phase is dried with anhydrous magnesium sulfate
Afterwards, dichloromethane is sloughed under vacuum condition；Crude product is dry to constant weight with being placed in after ethyl alcohol recrystallization in vacuum drying oven, obtains red
Color fluorescence dihydric alcohol RDB-OH；
2.1 grams of 4- fluorine benzophenone, 9 grams of diethanol amine and 0.8 gram of potassium hydroxide are added in three-necked flask, use magnetic force
Agitator stirs, and is warming up to 110 DEG C, reaction terminates reaction after 15 hours；After being cooled to room temperature, 90 milliliters of distilled water are added, soon
Speed stirring to thick precipitation separates out completely；The water on upper strata is removed, crude product uses column chromatography method, and (ethyl acetate is elution
Agent) it is placed in after separating-purifying in vacuum drying oven and dries to constant weight, obtain blue-fluorescence dihydric alcohol NBP；
Then 1 gram of RDB-OH, 0.4 gram of green fluorescence diamine AF and 3 grams of NBPP are placed in mortar, grinding stirring, mixed
It is placed in vacuum drying oven and is dried to constant weight after closing uniformly, obtains white fluorescent powder；
By 20 grams average molecular weight Mn50 DEG C are cooled to after 1 hour in 110 DEG C of dehydrations for 2000 PCL, add 15 grams
IPDI, in 80 DEG C of stirring reactions add after 2 hours the white fluorescent powder of 1 gram of above-mentioned preparation, 1.2 grams of BDO, 0.01 gram of DBTDL and
10 grams of acetone, constant temperature are cooled to 55 DEG C after 5 hours in 70 DEG C of stirring reactions；Then 4 grams MDEA and 5 gram third was added dropwise in 2 hours
The mixed solution of ketone, 50 DEG C reaction 2 hours after be cooled to 20 DEG C；Reaction product is transferred to high speed shear dispersion machine, 3000 turns/
2.12 grams of acetic acid and 10 grams of acetone are added under conditions of point, reaction adds 95 grams of water after 2 minutes, rotation is transferred to after being stirred for 5 minutes
Turn evaporimeter, acetone is sloughed under 50 DEG C, 0.01MPa vacuum conditions, obtain cationic white fluorescent aqueous polyurethane emulsion；
It is 80 by mass parts：0.2：0.9：1.5：2：10 by white fluorescent aqueous polyurethane emulsion, defoamer, levelling agent,
Thickener, ultra-violet absorber and deionized water, which are sequentially added in scuffing of cylinder bore, to be compounded, under 300 revs/min of mixing speed
Stirring 60 minutes, white fluorescent aqueous polyurethane coating is made.
Such as keep other conditions constant, by adjusting PTMG, TPDI, DMPA and white fluorescent powder mass ratio, can obtain
The white fluorescent dyestuff white fluorescent aqueous polyurethane that content is different in non-aqueous non-solvent material in aqueous polyurethane applies
Material.
If other conditions of the present embodiment are constant, and PTMG is substituted for into PCDL, the white fluorescent water that can be also stablized
Property polyurethane coating.
If other conditions of the present embodiment are constant, and DMPA is substituted for into DMBA, the white fluorescent water that can be also stablized
Property polyurethane coating.
If other conditions of the present embodiment are constant, and BDO is substituted for EG or DEG respectively, the white that can be also stablized
Fluorescence aqueous polyurethane coating.
Embodiment 4：
4.8 grams of rhodamine Bs and 50 milliliters of dichloromethane are added in three-necked flask, are stirred to rhodamine B after being completely dissolved,
Add 1.8 grams of diethanol amine, 1.3 grams of triethylamines, 4 grams of HBTU；After being reacted at room temperature 22 hours under magnetic stirrer, pour into
90 milliliters of dchloromethanes, and cleaned 5 times with 60 milliliters of 1M sodium-chloride water solution；Organic phase is dried with anhydrous magnesium sulfate
Afterwards, dichloromethane is sloughed under vacuum condition；Crude product is dry to constant weight with being placed in after ethyl alcohol recrystallization in vacuum drying oven, obtains red
Color fluorescence dihydric alcohol RDB-OH；
1.08 grams of 4- fluorine benzophenone, 4.0 grams of diethanol amine and 0.3 gram of potassium hydroxide are added in three-necked flask, used
Magnetic stirrer, 95 DEG C are warming up to, reaction terminates reaction after 24 hours；After being cooled to room temperature, 50 milliliters of distilled water are added,
Quick stirring to thick precipitation separates out completely；The water on upper strata is removed, crude product uses column chromatography method, and (eluant, eluent is acetic acid second
Ester) it is placed in after separating-purifying in vacuum drying oven and dries to constant weight, obtain blue-fluorescence dihydric alcohol NBP；
Then 2 grams of RDB-OH, 1.2 grams of green fluorescence diamine AFG and 7 grams of NBP are placed in mortar, grinding stirring, mixed
It is placed in vacuum drying oven and is dried to constant weight after closing uniformly, obtains white fluorescent powder；
By 14 grams average molecular weight Mn50 DEG C are cooled to after 1 hour in 110 DEG C of dehydrations for 2000 PCL, add 7 grams
IPDI, white fluorescent powder, 0.4 gram of BDO, the 0.01 gram of DBTDL of 0.42 gram of above-mentioned preparation are added after 2 hours in 80 DEG C of stirring reactions
And 10 grams of butanone, constant temperature are cooled to 55 DEG C after 5 hours in 70 DEG C of stirring reactions；Then 1.9 grams of MDEA and 5 were added dropwise in 2 hours
The mixed solution of gram butanone, 50 DEG C of reactions are cooled to 20 DEG C after 2 hours；Reaction product is transferred to high speed shear dispersion machine,
1 gram of acetic acid and 5 grams of butanone are added under conditions of 3000 revs/min, reaction adds 55 grams of water after 2 minutes, is transferred to after being stirred for 5 minutes
Rotary Evaporators, acetone is sloughed under 50 DEG C, 0.01MPa vacuum conditions, obtain cationic white fluorescent aqueous polyurethane breast
Liquid；
It is 95 by mass parts：0.5：2：1.5：3：15 by white fluorescent aqueous polyurethane emulsion, defoamer, levelling agent, increasing
Thick dose, ultra-violet absorber and deionized water, which are sequentially added in scuffing of cylinder bore, to be compounded, and is stirred under 500 revs/min of mixing speed
Mix 30 minutes, white fluorescent aqueous polyurethane coating is made.
Claims (9)
- A kind of 1. preparation method of white fluorescent aqueous polyurethane coating, it is characterised in that：Red fluorescence two is first prepared respectively First alcohol and blue-fluorescence dihydric alcohol, they and green fluorescence diamine compounding are then obtained into white fluorescent powder, it is white to reuse this Color fluorescent material partly or entirely substitutes glycol chain extender, by with diisocyanate, macromolecule dihydric alcohol and hydrophilic chain extender Reacted, white fluorescent aqueous polyurethane emulsion is made；The red fluorescence dihydric alcohol is prepared as follows：Rhodamine B addition dichloromethane is completely dissolved to it, is 1.2-2 by with rhodamine B mol ratio：1-2：1-2：1 adds Diethanol amine, triethylamine and O- BTAs-tetramethylurea hexafluorophosphoric acid ester, react at room temperature 10~24 hours under agitation Afterwards, add and be diluted by the dichloromethane of 1.5-3 times of reaction solution volume, and with the 1M chlorinations of 0.3-0.6 times of reaction solution volume Sodium water solution cleans 2-5 times；After organic phase is dried with anhydrous magnesium sulfate, dichloromethane is sloughed under vacuum condition；Crude product second Dried after alcohol recrystallization to constant weight, that is, obtaining structural formula isRed fluorescence dihydric alcohol；The blue-fluorescence dihydric alcohol is prepared as follows：It is 1 in molar ratio：5-10：4- fluorine benzophenone, diethanol amine and potassium hydroxide is warming up to 90 by 1.5-3 under agitation~ Room temperature is cooled to after 110 DEG C of reaction 12-24 hours, the water by 10-25 times of diethanol amine volume is added, stirs to thick precipitation Separate out completely；The water on upper strata is removed, crude product is dried to constant weight after being purified using ethyl acetate as eluant, eluent using column chromatography for separation, Obtaining structural formula isBlue-fluorescence dihydric alcohol；By red fluorescence dihydric alcohol, blue-fluorescence dihydric alcohol and green fluorescence diamine acriflavine or α acridine yellow G in mass ratio 1：2.5-4：0.3-0.6 grindings are dried to constant weight after being uniformly mixed, and obtain white fluorescent powder；The preparation of white fluorescent aqueous polyurethane emulsion：According to used hydrophilic radical type when preparing aqueous polyurethane emulsion, the white fluorescent aqueous polyurethane is divided into Cationic white fluorescent aqueous polyurethane emulsion and anionic white fluorescent aqueous polyurethane emulsion two types；When using cationic hydrophilic chain extender N methyldiethanol amine and diisocyanate, macromolecule dihydric alcohol, white fluorescent Powder and small molecule diol reaction, then obtain cationic white fluorescent aqueous polyurethane emulsion, and concrete operation step is as follows：On the basis of non-aqueous in the aqueous polyurethane and quality of non-solvent component, by by big point of Reference mass 35-75% Sub- dihydric alcohol is dehydrated 15-60 minutes at 100-115 DEG C, adds anti-in 75-95 DEG C by Reference mass 20-55% diisocyanate Answer 1.5-3 hours, then sequentially add the white fluorescent powder by Reference mass 0.5-12%, 0-10% glycol chain extender, 0.01-0.05% dibutyl tin laurate and 10-60% acetone or butanone, 2.5-5 hours are reacted at 65-85 DEG C, so After be cooled to 30-40 DEG C, after the N methyldiethanol amine by Reference mass 6-12% is dissolved in 10-40% acetone or butanone Instill in reaction system, react 2-3 hours at 50-60 DEG C after dripping off；Then 30-40 DEG C is cooled to, adds Reference mass 3.2- 6.5% acetic acid, after reacting 1-5 minutes, Reference mass 200-300% water is added under 2000-4000 revs/min of rotating speed cutting With 0-5% diamine chain extenders, after stirring 5-25 minutes, emulsion Rotary Evaporators will be reacted in 40-50 DEG C of vacuum condition Under slough acetone or butanone, that is, obtain cationic white fluorescent aqueous polyurethane emulsion；Divide when using anionic hydrophilic chain extender dihydromethyl propionic acid (DMPA) or dimethylolpropionic acid with diisocyanate, greatly Sub- dihydric alcohol, white fluorescent powder and small molecule diol reaction, then anionic white fluorescent aqueous polyurethane emulsion is obtained, had Body operating procedure is as follows：On the basis of non-aqueous in the aqueous polyurethane and quality of non-solvent component, by by big point of Reference mass 35-75% Sub- dihydric alcohol is dehydrated 15-60 minutes at 100-115 DEG C, adds anti-in 75-95 DEG C by Reference mass 20-55% diisocyanate Answer 1.5-3 hours, then sequentially add the anionic hydrophilic chain extender by Reference mass 4-8%, 0.5-12% it is white glimmering Light powder, 0-10% glycol chain extender, 0.01-0.05% dibutyl tin laurate and 20-100% acetone or fourth Ketone, 3-7 hours are reacted at 65-85 DEG C, are then cooled to 30-40 DEG C, add the triethylamine by Reference mass 3-6%, react 1-5 After minute, Reference mass 200-300% water and 0-5% diamine chain extension are added under 2000-4000 revs/min of rotating speed cutting Agent, after stirring 5-25 minutes, reaction emulsion is sloughed into acetone or butanone with Rotary Evaporators under 40-50 DEG C of vacuum condition, i.e., Obtain anionic white fluorescent aqueous polyurethane emulsion；Finally press mass parts 100：(0.1-0.5)：(0.2-2)：(0.2-3)：(1-5)：(5-15) is by the water-based poly- ammonia of white fluorescent Ester emulsion, defoamer, levelling agent, thickener, ultra-violet absorber and deionized water, which are sequentially added in scuffing of cylinder bore, to be compounded, 30-90 minutes are stirred under 250-500 revs/min of mixing speed, white fluorescent aqueous polyurethane coating is made.
- 2. the preparation method of white fluorescent aqueous polyurethane coating as claimed in claim 1, it is characterised by the macromolecular binary Alcohol is selected from polyadipate -1,4- butyl glycol ester diols, polycaprolactone diols, PCDL, PTMG two First alcohol or polypropylene glycol.
- 3. the preparation method of white fluorescent aqueous polyurethane coating as claimed in claim 1, is characterised by the diisocyanate Selected from toluene di-isocyanate(TDI) or IPDI.
- 4. the preparation method of white fluorescent aqueous polyurethane coating as claimed in claim 1, it is characterised by the dihydric alcohol chain extension Agent is selected from ethylene glycol, 1,4- butanediols or diglycol.
- 5. the preparation method of white fluorescent aqueous polyurethane coating as claimed in claim 1, it is characterised by the diamine chain extension Agent is selected from ethylenediamine or IPD.
- 6. the preparation method of white fluorescent aqueous polyurethane coating as claimed in claim 1, it is characterised by that the defoamer is selected from BYK 022, BYK 024, BYK 025, BYK 028, the BYK 093 of German Bi Ke chemistry, or Japanese Sheng Nuopuke SN Defoamer 327、SN Defoamer 328、SN Defoamer 399、SN-Defoamer 1310、SN-Defoamer 1311st, SN-Defoamer 1313, or the EFKA 2526 of EFKA auxiliary agent company, EFKA 2550, EFKA 2580, or Germany The high TEGO foamex 800 of enlightening, TEGO foamex 805, or SURFYNOL DF 58, the SURFYNOL of U.S.'s aerochemistry One or more in DF 110D, SURFYNOL DF61, SURFYNOL MD 20.
- 7. the preparation method of white fluorescent aqueous polyurethane coating as claimed in claim 1, it is characterised by that the levelling agent is selected from BYK 331, BYK 346, BYK 348, the BYK 354 of German Bi Ke chemistry, or the high TEGO 440 of German enlightening, TEGO 450, One or more in TEGO 482.
- 8. the preparation method of white fluorescent aqueous polyurethane coating as claimed in claim 1, it is characterised by that the thickener is selected from The ACRYSOL of Rhom and HassTM RM 8W、ACRYSOLTM 12W、ACRYSOLTM 5000、ACRYSOLTMRM 2020NPR, Or the one or several kinds in the Viscalex HV30 of BASF.
- 9. the preparation method of white fluorescent aqueous polyurethane coating as claimed in claim 1, is characterised by the ultraviolet radiation absorption Agent be selected from Yongguang Chemical Industry Co., Ltd., Taiwan Eversorb AQ1, Eversorb AQ4, Eversorb AQ5, One or more in Eversorb AQ6.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108559200A (en) * | 2018-04-13 | 2018-09-21 | 华东理工大学 | A kind of acrylic acid modified polyurethane and the preparation method and application thereof |
| CN108912305A (en) * | 2018-06-15 | 2018-11-30 | 山东师范大学 | A kind of cholesteric alcohols side-chain liquid crystal polyurethane-urea material and preparation method thereof |
| CN109568176A (en) * | 2018-11-21 | 2019-04-05 | 安徽清彩科技有限公司 | A kind of copolymerization color fluorescence aqueous polyurethane nail polish and preparation method thereof |
| CN110862507A (en) * | 2019-10-29 | 2020-03-06 | 温州大学 | Preparation method of self-recoverable mechanochromic fluorescent water-based polyurethane |
| CN110922551A (en) * | 2019-10-29 | 2020-03-27 | 温州大学 | Preparation method of rhodamine-polyurethane fluorescent probe for iron ion detection |
| CN111500172A (en) * | 2020-03-27 | 2020-08-07 | 江苏华彩化学科技有限公司 | Water-based environment-friendly anti-cracking interior wall coating for building and preparation method thereof |
| CN114075320A (en) * | 2021-06-18 | 2022-02-22 | 四川大学 | Fluorescent waterborne polyurethane with adjustable luminescent color and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002245820A (en) * | 2001-02-16 | 2002-08-30 | Oji Paper Co Ltd | Illumination light reflector paper |
| CN103172829A (en) * | 2013-03-21 | 2013-06-26 | 中国科学技术大学 | Preparation method of fluorescent waterborne polyurethane emulsion based on chromophore in diisocyanate |
| CN103254396A (en) * | 2013-06-05 | 2013-08-21 | 中国科学技术大学 | Fluorescent waterborne polyurethane based on chromophore in dihydric alcohol and preparation method thereof |
| CN105131806A (en) * | 2015-10-13 | 2015-12-09 | 厦门大学 | Waterborne fluorescent polyurethane coating and preparation method thereof through prepolymer mixing |
| CN105601567A (en) * | 2014-11-21 | 2016-05-25 | 江苏李文甲化工有限公司 | Fluorochrome monomer, copolymeric fluorescent polyurethane emulsion and fluorescent polyurethane-acrylic ester copolymer emulsion as well as preparation methods thereof |
-
2017
- 2017-08-15 CN CN201710696679.6A patent/CN107400453B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002245820A (en) * | 2001-02-16 | 2002-08-30 | Oji Paper Co Ltd | Illumination light reflector paper |
| CN103172829A (en) * | 2013-03-21 | 2013-06-26 | 中国科学技术大学 | Preparation method of fluorescent waterborne polyurethane emulsion based on chromophore in diisocyanate |
| CN103254396A (en) * | 2013-06-05 | 2013-08-21 | 中国科学技术大学 | Fluorescent waterborne polyurethane based on chromophore in dihydric alcohol and preparation method thereof |
| CN105601567A (en) * | 2014-11-21 | 2016-05-25 | 江苏李文甲化工有限公司 | Fluorochrome monomer, copolymeric fluorescent polyurethane emulsion and fluorescent polyurethane-acrylic ester copolymer emulsion as well as preparation methods thereof |
| CN105131806A (en) * | 2015-10-13 | 2015-12-09 | 厦门大学 | Waterborne fluorescent polyurethane coating and preparation method thereof through prepolymer mixing |
Non-Patent Citations (1)
| Title |
|---|
| 周静: ""基于BHORA和DIX荧光性水性聚氨酯的合成与荧光性能研究"", 《中国优秀硕士学位论文全文数据库》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108559200A (en) * | 2018-04-13 | 2018-09-21 | 华东理工大学 | A kind of acrylic acid modified polyurethane and the preparation method and application thereof |
| CN108912305A (en) * | 2018-06-15 | 2018-11-30 | 山东师范大学 | A kind of cholesteric alcohols side-chain liquid crystal polyurethane-urea material and preparation method thereof |
| CN108912305B (en) * | 2018-06-15 | 2020-09-29 | 山东师范大学 | Cholesterol side chain liquid crystal polyurethane urea material and preparation method thereof |
| CN109568176A (en) * | 2018-11-21 | 2019-04-05 | 安徽清彩科技有限公司 | A kind of copolymerization color fluorescence aqueous polyurethane nail polish and preparation method thereof |
| CN110862507A (en) * | 2019-10-29 | 2020-03-06 | 温州大学 | Preparation method of self-recoverable mechanochromic fluorescent water-based polyurethane |
| CN110922551A (en) * | 2019-10-29 | 2020-03-27 | 温州大学 | Preparation method of rhodamine-polyurethane fluorescent probe for iron ion detection |
| CN110922551B (en) * | 2019-10-29 | 2021-09-14 | 温州大学 | Preparation method of rhodamine-polyurethane fluorescent probe for iron ion detection |
| CN110862507B (en) * | 2019-10-29 | 2021-12-21 | 温州大学 | Preparation method of self-recoverable mechanochromic fluorescent water-based polyurethane |
| CN111500172A (en) * | 2020-03-27 | 2020-08-07 | 江苏华彩化学科技有限公司 | Water-based environment-friendly anti-cracking interior wall coating for building and preparation method thereof |
| CN114075320A (en) * | 2021-06-18 | 2022-02-22 | 四川大学 | Fluorescent waterborne polyurethane with adjustable luminescent color and preparation method thereof |
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