CN117343578B - Polyurethane color paste with high permeability and high dispersibility and preparation method thereof - Google Patents
Polyurethane color paste with high permeability and high dispersibility and preparation method thereof Download PDFInfo
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- CN117343578B CN117343578B CN202311656914.9A CN202311656914A CN117343578B CN 117343578 B CN117343578 B CN 117343578B CN 202311656914 A CN202311656914 A CN 202311656914A CN 117343578 B CN117343578 B CN 117343578B
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- color paste
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 65
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 230000035699 permeability Effects 0.000 title claims abstract description 9
- 239000000049 pigment Substances 0.000 claims abstract description 33
- 239000000945 filler Substances 0.000 claims abstract description 27
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 17
- 239000000839 emulsion Substances 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 64
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 64
- 238000003756 stirring Methods 0.000 claims description 44
- 239000000377 silicon dioxide Substances 0.000 claims description 32
- 239000004408 titanium dioxide Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 235000010288 sodium nitrite Nutrition 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- -1 alkyl orthosilicate Chemical compound 0.000 claims description 8
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 8
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 7
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 7
- 229920001690 polydopamine Polymers 0.000 claims description 7
- REJHVSOVQBJEBF-OWOJBTEDSA-N 5-azaniumyl-2-[(e)-2-(4-azaniumyl-2-sulfonatophenyl)ethenyl]benzenesulfonate Chemical compound OS(=O)(=O)C1=CC(N)=CC=C1\C=C\C1=CC=C(N)C=C1S(O)(=O)=O REJHVSOVQBJEBF-OWOJBTEDSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003995 emulsifying agent Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical group Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 230000001804 emulsifying effect Effects 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- 229920000428 triblock copolymer Polymers 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 4
- 239000004088 foaming agent Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 3
- 239000004970 Chain extender Substances 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 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 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 229940113116 polyethylene glycol 1000 Drugs 0.000 claims description 3
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 3
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 3
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 3
- 229920000053 polysorbate 80 Polymers 0.000 claims description 3
- KBAFDSIZQYCDPK-UHFFFAOYSA-M sodium;octadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCS([O-])(=O)=O KBAFDSIZQYCDPK-UHFFFAOYSA-M 0.000 claims description 3
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- MXXDSLLVYZMTFA-UHFFFAOYSA-N octadecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 MXXDSLLVYZMTFA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- HEBRGEBJCIKEKX-UHFFFAOYSA-M sodium;2-hexadecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HEBRGEBJCIKEKX-UHFFFAOYSA-M 0.000 claims description 2
- AYFACLKQYVTXNS-UHFFFAOYSA-M sodium;tetradecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCS([O-])(=O)=O AYFACLKQYVTXNS-UHFFFAOYSA-M 0.000 claims description 2
- ORLPWCUCEDVJNN-UHFFFAOYSA-N sodium;tetradecyl benzenesulfonate Chemical compound [Na].CCCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 ORLPWCUCEDVJNN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 239000012071 phase Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- 230000006872 improvement Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006757 chemical reactions by type Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- PNGBYKXZVCIZRN-UHFFFAOYSA-M sodium;hexadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCS([O-])(=O)=O PNGBYKXZVCIZRN-UHFFFAOYSA-M 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
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- 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
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/003—Pigment pastes, e.g. for mixing in paints containing an organic pigment
-
- 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
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- 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
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/10—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group
- C09B29/12—Monoazo dyes prepared by diazotising and coupling from coupling components containing hydroxy as the only directing group of the benzene series
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0079—Azoic dyestuff preparations
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0083—Solutions of dyes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0084—Dispersions of dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0097—Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3669—Treatment with low-molecular organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3676—Treatment with macro-molecular organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3692—Combinations of treatments provided for in groups C09C1/3615 - C09C1/3684
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
Abstract
The invention provides a polyurethane color paste with high permeability and high dispersibility and a preparation method thereof, and belongs to the technical field of polyurethane color paste. The adhesive is prepared from the following components in parts by weight: 100-120 parts of aqueous polyurethane emulsion, 2-4 parts of composite silane coupling agent, 10-15 parts of pigment and filler and 1-3 parts of dispersing agent. The high-permeability high-dispersibility polyurethane color paste prepared by the invention has the advantages of excellent color uniformity, good stability, good color fastness, good transparency, low color shading, environment friendliness and wide application range, and can improve the transparency of colored transparent polyurethane products.
Description
Technical Field
The invention relates to the technical field of polyurethane color paste, in particular to high-permeability and high-dispersibility polyurethane color paste and a preparation method thereof.
Background
The aqueous polyurethane takes water as a dispersion medium, avoids the defects of environmental pollution, harm to human bodies and the like of the traditional organic solvent, and is a novel polyurethane material with environmental protection, safety and reliability. The water-based polyurethane material is widely applied to the industries of light spinning, color paste, printing and dyeing, leather processing, coating, adhesive, papermaking and the like. Safety is a major trend in the future, and there is an increasing demand for green products in various industries. With the progress of technology, there is an increasing demand for aqueous polyurethane materials having special functions.
The color paste, as the name implies, is a colored paste which is prepared by using different pigments through strict processing technology such as pigment surface treatment, surface wrapping and the like. The color paste is cooperated in the nature to dress up the whole world, is small enough to wear the dress up, daily use, toys and the like, is large enough to bridge, house building and the like, and does not show the colorful color.
For the use of color paste, the traditional color paste dye is usually prepared by directly mixing polyurethane with small molecular pigment or dye, and the method is simple, but the emulsion and the functionality of the product lack stability and durability due to poor compatibility between the pigment or dye and the polymer, and sedimentation, gelation and the like occur. In addition, in the film forming process, pigment or dye has migration phenomenon, when the product is unevenly dispersed, the color floats on the surface of a paint film, so that the surface of the paint film floats to be colored, and the pigment or dye migrated to the surface also has great harm to human bodies and the environment.
In addition, the traditional polyurethane color paste is added into polyurethane, so that the problems of poor dispersibility and the like often exist, and organic pigment color paste is prepared by matching with other types of dispersing agents, so that the transparency of the polyurethane is also reduced.
Disclosure of Invention
The invention aims to provide the polyurethane color paste with high transparency and high dispersibility and the preparation method thereof, which have the advantages of excellent color uniformity, good stability and good color fastness, meanwhile, the transparency is good, the transparency of the colored transparent polyurethane product can be improved, the color is low, the environment is protected, and the application range of the product is greatly widened.
The technical scheme of the invention is realized as follows:
the invention provides a high-permeability high-dispersibility polyurethane color paste which is prepared from the following components in parts by weight: 100-120 parts of aqueous polyurethane emulsion, 2-4 parts of composite silane coupling agent, 10-15 parts of pigment and filler and 1-3 parts of dispersing agent;
the preparation method of the pigment and filler comprises the following steps:
s1, preparing mesoporous silica/titanium dioxide spheres: dissolving alkyl orthosilicate and tetrabutyl titanate in an organic solvent to obtain an oil phase; adding a mesoporous pore-forming agent and an emulsifying agent into water to obtain a water phase; adding the oil phase into the water phase, emulsifying, dropwise adding ammonia water, stirring for reaction, centrifuging, washing, drying, and calcining to obtain mesoporous silica/titanium dioxide spheres;
s2, modifying polydopamine: adding the mesoporous silica/titanium dioxide spheres prepared in the step S1 into water, adding dopamine hydrochloride and a catalyst, heating and stirring for reaction, centrifuging, washing and drying to prepare modified mesoporous silica/titanium dioxide spheres;
s3, loading of dye: adding dye into ethanol water solution, stirring and mixing uniformly, adding the modified mesoporous silica/titanium dioxide balls prepared in the step S2, stirring and reacting, centrifuging, washing and drying to obtain pigment and filler;
the structural formula of the dye is shown in formula I:a formula I;
wherein n=1-3.
As a further improvement of the invention, the composite silane coupling agent is a mixture of KH550 and KH602, and the mass ratio is 2-4:5-7; the dispersing agent is at least one selected from sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium tetradecyl benzene sulfonate, sodium tetradecyl sulfonate, sodium hexadecyl benzene sulfonate, sodium octadecyl benzene sulfonate and sodium octadecyl sulfonate.
As a further improvement of the invention, the preparation method of the aqueous polyurethane emulsion comprises the following steps: mixing and heating 20-30 parts by weight of isophorone diisocyanate, 90-140 parts by weight of polyethylene glycol 1000 and 0.01-0.02 part by weight of catalyst dibutyltin dilaurate to 70-75 ℃ for reaction for 1-2 hours, then adding 1-1.5 parts by weight of chain extender 2, 2-dimethylolpropionic acid and 0.5-1 part by weight of 1, 4-butanediol, and 20 parts by weight of acetone, heating to 75-80 ℃ for reaction for 2-3 hours, then cooling to 40-45 ℃, adding 2-3 parts by weight of triethylamine, stirring for reaction for 20-30 minutes, adding 500-700 parts by weight of water, and stirring and mixing uniformly to obtain the aqueous polyurethane emulsion.
As a further improvement of the invention, the mass ratio of the alkyl orthosilicate to the tetrabutyl titanate in the step S1 is 10-12:3-5; the mass ratio of the mesoporous pore-foaming agent to the emulsifier is 2-3:1-2, and the mesoporous pore-foaming agent is at least one of PEO20-PPO70-PEO20 and PEO106-PPO70-PEO106 which are ethylene oxide-propylene oxide triblock copolymers; the emulsifier is at least one selected from Tween-20, tween-40, tween-60 and Tween-80, and the calcination temperature is 350-450 ℃ and the calcination time is 2-4h.
As a further improvement of the invention, in the step S2, the mass ratio of the mesoporous silica/titanium dioxide spheres to the dopamine hydrochloride to the catalyst is 10-12:7-10:0.5-1, the catalyst is Tris-HCl solution with pH=8.5-9, the temperature of the heating and stirring reaction is 45-50 ℃, and the time is 1-3h.
As a further improvement of the invention, the mass ratio of the dye to the modified mesoporous silica/titanium dioxide spheres in the step S3 is 7-10:12-15, and the stirring reaction time is 1-3h.
As a further improvement of the present invention, the method for synthesizing the dye is as follows:
t1, the diaminostilbenedisulfonic acid and sodium nitrite react under the condition of hydrochloric acid to prepare an intermediate A, and the structure is as follows:；
t2 reacting the glycol ether with benzyl bromide under alkali condition to obtain an intermediate B with the following structure:wherein n=1-3;
and T3, reacting the intermediate A with the intermediate B to obtain the product.
As a further improvement of the invention, the sodium nitrite in the step T1 is 15-20wt% of sodium nitrite solution, the mass ratio of the diaminostilbenedisulfonic acid to the sodium nitrite solution is 1-2:50-100, and the reaction temperature is 0-5 ℃; the molar ratio of the glycol ether, the benzyl bromide and the alkali in the step T2 is 1-1.1:1:3-5; the molar ratio of the intermediate A to the intermediate B in the step T3 is 1:2-2.05.
As a further improvement of the present invention, the glycol ether is at least one selected from the group consisting of ethylene glycol, ethylene glycol monoformal and ethylene glycol diglycide; the alkali is at least one selected from NaOH, KOH, sodium carbonate, sodium bicarbonate and potassium carbonate.
The invention further provides a preparation method of the high-permeability high-dispersibility polyurethane color paste, which comprises the following steps:
(1) Adding pigment and filler and a composite silane coupling agent into ethanol, heating to 40-45 ℃, stirring and reacting for 1-2h, centrifuging, washing and drying to obtain a modified material;
(2) And (3) adding the modified material and the dispersing agent prepared in the step (1) into the aqueous polyurethane emulsion, and uniformly stirring and mixing to prepare the polyurethane color paste with high permeability and high dispersibility.
The invention has the following beneficial effects:
the azo reaction type dye molecule is synthesized, on one hand, the molecular structure of the azo reaction type dye molecule is provided with a large pi bond, so that the dye molecule has good and vivid color and has certain fluorescence, meanwhile, the azo reaction type dye molecule is provided with a double hydroxyl group, can be combined with a water-based polyurethane polymer skeleton through covalent bonds, has almost no toxicity after being polymerized by high polymers, and has the characteristics of high-transparency and high-dispersibility polyurethane color paste, such as high heat resistance, easy film forming property, solvent resistance, light intensity absorption, color colorfulness and the like of the prepared high-transparency and high-dispersibility polyurethane color paste.
In general, dye molecules are easily aggregated even at a very low concentration, and the aggregated dye molecules are easily released by thermal relaxation due to excitation energy, so that the optical activity is not reflected, and the coloring performance is greatly affected.
According to the invention, the prepared dye molecules are fixed on the modified mesoporous silica/titanium dioxide spheres to prepare the pigment and filler, on one hand, the mesoporous silica/titanium dioxide spheres have regular and ordered pore structures, so that the dye molecules can be effectively dispersed to avoid aggregation, and in addition, the mesoporous silica/titanium dioxide spheres modified by polydopamine can better stabilize the dye molecules through hydrogen bonds, so that the dye molecules show good optical activity in the pore channels of mesoporous materials, such as photoluminescence, fluorescence relaxation and the like, meanwhile, the benzene ring structure and the amino structure of polydopamine can also form pi electron system with the dye molecules to change, and the stronger interaction between hosts and customers causes great Stocks displacement to increase energy levels between ground states and excitation states, so that the prepared pigment and filler compound greatly widens absorption and emission wavelength. In addition, the dye molecules lose rotational freedom due to the formation of complexes, thereby reducing dimer formation.
The composite silane coupling agent used in the invention is a mixture of KH550 and KH602, and can promote the dispersibility and the binding capacity between the prepared pigment filler and the aqueous polyurethane on the one hand and promote the reaction of dye molecules on the pigment filler and the polyurethane on the other hand, thereby being beneficial to preparing polyurethane color paste with high uniformity, high dispersibility and low color shading, and the addition of the pigment filler and the aqueous polyurethane has a synergistic effect.
The high-permeability high-dispersibility polyurethane color paste prepared by the invention has the advantages of excellent color uniformity, good stability, good color fastness, good transparency, low color shading, environment friendliness and wide application range, and can improve the transparency of colored transparent polyurethane products.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Preparation example 1 preparation of aqueous polyurethane emulsion
The method comprises the following steps:
25 parts by weight of isophorone diisocyanate, 115 parts by weight of polyethylene glycol 1000 and 0.015 part by weight of catalyst dibutyltin dilaurate are mixed and heated to 75 ℃, stirred and reacted for 1.5 hours, then 1.2 parts by weight of chain extender 2, 2-dimethylolpropionic acid and 0.7 part by weight of 1, 4-butanediol and 20 parts by weight of acetone are added, heated to 80 ℃, stirred and reacted for 2.5 hours, then cooled to 45 ℃, 2.5 parts by weight of triethylamine is added, stirred and reacted for 25 minutes, added into 600 parts by weight of water, stirred and mixed for 20 minutes at 1000r/min, and the aqueous polyurethane emulsion is prepared.
Synthesis of dye of preparation example 2
The synthetic route is as follows;；
；
the method comprises the following steps:
t1, dissolving 1g of diaminostilbenedisulfonic acid in 30mL of concentrated hydrochloric acid, adding 50g of 20wt% sodium nitrite solution, stirring and reacting for 2h at 0 ℃, dissolving 20g of urea in 200mL of water, adding the system, stirring and mixing for 2h to remove excessive sodium nitrite, filtering, washing and drying to obtain an intermediate A; ESI-MS calculated: c14h12n4o6s2 (m+h) + 464.94, found: 464.9, the yield was 82.1%.
Nuclear magnetic results: 1H NMR (300 MHz, CDCl 3) delta 7.92 (s, 2H), 7.65 (d, J=5.6 Hz, 2H), 7.22 (d, J=5.6 Hz, 2H), 7.12 (d, 2H), 2.0 (br, 2H).
T2. dissolving 0.1mol of ethylene glycol and 0.1mol of benzyl bromide in 200mL of dichloromethane, adding 0.3mol of NaOH, heating to 60 ℃, and stirring for 4h to obtain an intermediate B; ESI-MS calculated: c11h17o3 (m+h) +197.11, found: 197.1, the yield was 90.7%.
Nuclear magnetic results: 1H NMR (300 MHz, CDCl 3) delta 7.16 (m, 5H), 4.62 (s, 2H), 3.68 (t, 2H), 3.53-3.57 (m, 6H), 2.2 (br, 1H).
T3. 0.1mol of intermediate A and 0.2mol of intermediate B are added into 200mL of ethanol, stirred and reacted for 1h at 4 ℃, filtered, washed and recrystallized from ethanol to obtain the product. ESI-MS calculated: c36H41N4O12S2 (m+h) + 785.21, found: 785.2, yield was 78.9%.
Nuclear magnetic results: 1H NMR (300 MHz, CDCl 3) delta 8.64 (s, 2H), 7.89-7.91 (m, 4H), 7.87 (d, J=7.0 Hz, 4H), 7.36 (d, J=7.1 Hz, 4H), 7.10 (d, 2H), 4.64 (s, 4H), 3.67 (t, 4H), 3.52-3.59 (t, 12H), 2.0-2.3 (br, 4H).
Synthesis of dye of preparation example 3
The method comprises the following steps:
t1, dissolving 2g of diaminostilbenedisulfonic acid in 30mL of concentrated hydrochloric acid, adding 100g of 15wt% sodium nitrite solution, stirring and reacting for 2h at 5 ℃, dissolving 25g of urea in 200mL of water, adding the system, stirring and mixing for 2h to remove excessive sodium nitrite, filtering, washing and drying to obtain an intermediate A; the yield thereof was found to be 83.3%.
T2. dissolving 0.11mol of ethylene glycol and 0.1mol of benzyl bromide in 200mL of dichloromethane, adding 0.5mol of KOH, heating to 60 ℃, and stirring for 4h to obtain an intermediate B; ESI-MS calculated: c9h13o2 (m+h) +153.08, found: 153.1, yield 92.5%.
Nuclear magnetic results: 1H NMR (300 MHz, CDCl 3) delta 7.24 (m, 5H), 4.62 (s, 2H), 3.75 (t, 2H), 3.52 (t, 2H), 2.0 (br, 1H).
T3. 0.1mol of intermediate A and 0.205mol of intermediate B are added into 200mL of ethanol, stirred and reacted for 1h at 4 ℃, filtered, washed and recrystallized from ethanol to obtain the product. ESI-MS calculated: c32H33N4O10S2 (m+h) + 697.16, found: 697.2, the yield was 80.8%.
Nuclear magnetic results: 1H NMR (300 MHz, CDCl 3) δ8.62 (s, 2H), 7.89-7.92 (m, 4H), 7.85 (d, J=7.2 Hz, 4H), 7.37 (d, J=7.1 Hz, 4H), 7.11 (d, 2H), 4.62 (s, 4H), 3.67 (t, 4H), 3.54 (t, 4H), 2.0-2.2 (br, 4H).
Preparation example 4 preparation of pigment filler
The method comprises the following steps:
s1, preparing mesoporous silica/titanium dioxide spheres: 10 parts by weight of methyl orthosilicate and 3 parts by weight of tetrabutyl titanate are dissolved in 200 parts by weight of dichloromethane to obtain an oil phase; adding 2 parts by weight of PEO106-PPO70-PEO106 and 1 part by weight of Tween-20 into 200 parts by weight of water to obtain a water phase; adding 100 parts by weight of oil phase into 200 parts by weight of water phase, emulsifying for 15min at 10000r/min, dropwise adding ammonia water to adjust the pH value of the solution to 9, stirring for reacting for 2h, centrifuging, washing, drying, and calcining at 350 ℃ for 2h to obtain mesoporous silica/titanium dioxide spheres;
s2, modifying polydopamine: adding 10 parts by weight of the mesoporous silica/titanium dioxide spheres prepared in the step S1 into 200 parts by weight of water, adding 7 parts by weight of dopamine hydrochloride and 0.5 part by weight of catalyst, heating to 45 ℃, stirring and reacting for 1h, centrifuging, washing and drying to prepare modified mesoporous silica/titanium dioxide spheres;
the catalyst is Tris-HCl solution with pH=8.5;
s3, loading of dye: adding 7 parts by weight of the dye prepared in the preparation example 2 into 200 parts by weight of 50wt% ethanol water solution, stirring and mixing uniformly, adding 12 parts by weight of the modified mesoporous silica/titanium dioxide spheres prepared in the step S2, stirring and reacting for 1h, centrifuging, washing and drying to obtain the pigment and filler.
Preparation example 5 preparation of pigment filler
The method comprises the following steps:
s1, preparing mesoporous silica/titanium dioxide spheres: 12 parts by weight of ethyl orthosilicate and 5 parts by weight of tetrabutyl titanate are dissolved in 200 parts by weight of dichloromethane to obtain an oil phase; adding 3 parts by weight of ethylene oxide-propylene oxide triblock copolymer PEO20-PPO70-PEO20 and 2 parts by weight of Tween-40 into 200 parts by weight of water to obtain a water phase; adding 100 parts by weight of oil phase into 200 parts by weight of water phase, emulsifying for 15min at 10000r/min, dropwise adding ammonia water to adjust the pH value of the solution to 9, stirring for reacting for 2h, centrifuging, washing, drying, and calcining at 450 ℃ for 4h to obtain mesoporous silica/titanium dioxide spheres;
s2, modifying polydopamine: adding 12 parts by weight of the mesoporous silica/titanium dioxide spheres prepared in the step S1 into 200 parts by weight of water, adding 10 parts by weight of dopamine hydrochloride and 1 part by weight of catalyst, heating to 50 ℃, stirring and reacting for 3 hours, centrifuging, washing and drying to prepare modified mesoporous silica/titanium dioxide spheres;
the catalyst is Tris-HCl solution with pH=9;
s3, loading of dye: adding 10 parts by weight of the dye prepared in preparation example 3 into 200 parts by weight of 50wt% ethanol aqueous solution, stirring and mixing uniformly, adding 15 parts by weight of the modified mesoporous silica/titanium dioxide spheres prepared in step S2, stirring and reacting for 3 hours, centrifuging, washing and drying to obtain the pigment and filler.
Preparation example 6 preparation of pigment filler
The method comprises the following steps:
s1, preparing mesoporous silica/titanium dioxide spheres: dissolving 11 parts by weight of ethyl orthosilicate and 4 parts by weight of tetrabutyl titanate in 200 parts by weight of dichloromethane to obtain an oil phase; adding 2.5 parts by weight of an ethylene oxide-propylene oxide triblock copolymer PEO20-PPO70-PEO20 and 1.5 parts by weight of Tween-80 to 200 parts by weight of water to obtain an aqueous phase; adding 100 parts by weight of oil phase into 200 parts by weight of water phase, emulsifying for 15min at 10000r/min, dropwise adding ammonia water to adjust the pH value of the solution to 9, stirring for reacting for 2h, centrifuging, washing, drying, and calcining at 400 ℃ for 3h to obtain mesoporous silica/titanium dioxide spheres;
s2, modifying polydopamine: adding 11 parts by weight of the mesoporous silica/titanium dioxide spheres prepared in the step S1 into 200 parts by weight of water, adding 8.5 parts by weight of dopamine hydrochloride and 0.7 part by weight of catalyst, heating to 47 ℃, stirring and reacting for 2 hours, centrifuging, washing and drying to prepare modified mesoporous silica/titanium dioxide spheres;
the catalyst is Tris-HCl solution with pH=8.8;
s3, loading of dye: adding 8.5 parts by weight of the dye prepared in the preparation example 3 into 200 parts by weight of 50wt% ethanol water solution, stirring and mixing uniformly, adding 13.5 parts by weight of the modified mesoporous silica/titanium dioxide spheres prepared in the step S2, stirring and reacting for 2 hours, centrifuging, washing and drying to obtain the pigment and filler.
Comparative preparation example 1
In comparison with preparation example 6, the difference is that tetrabutyl titanate was not added in step S1.
Comparative preparation example 2
The difference compared with preparation example 6 is that no mesoporous Kong Jiyang ethylene-oxypropylene triblock copolymer PEO20-PPO70-PEO20 was added in step S1.
Comparative preparation example 3
In comparison with preparation example 6, the difference is that step S2 is not performed.
Example 1
The embodiment provides a preparation method of high-permeability high-dispersibility polyurethane color paste, which comprises the following steps:
(1) Adding 10 parts by weight of the pigment and filler prepared in preparation example 4 and 2 parts by weight of the composite silane coupling agent into 200 parts by weight of ethanol, heating to 40 ℃, stirring and reacting for 1h, centrifuging, washing and drying to obtain a modified material;
the composite silane coupling agent is a mixture of KH550 and KH602, and the mass ratio is 2:5;
(2) And (3) adding the modified material prepared in the step (1) and 1 part by weight of sodium stearyl sulfonate into 100 parts by weight of the aqueous polyurethane emulsion prepared in the preparation example 1, and stirring and mixing for 20 minutes to prepare the polyurethane color paste with high permeability and high dispersibility.
Example 2
The embodiment provides a preparation method of high-permeability high-dispersibility polyurethane color paste, which comprises the following steps:
(1) Adding 15 parts by weight of the pigment and filler prepared in preparation example 5 and 4 parts by weight of a composite silane coupling agent into 200 parts by weight of ethanol, heating to 45 ℃, stirring and reacting for 2 hours, centrifuging, washing and drying to obtain a modified material;
the composite silane coupling agent is a mixture of KH550 and KH602, and the mass ratio is 4:7;
(2) And (3) adding the modified material prepared in the step (1) and 3 parts by weight of sodium dodecyl sulfate into 120 parts by weight of the aqueous polyurethane emulsion prepared in the preparation example 1, and stirring and mixing for 20 minutes to prepare the polyurethane color paste with high permeability and high dispersibility.
Example 3
The embodiment provides a preparation method of high-permeability high-dispersibility polyurethane color paste, which comprises the following steps:
(1) Adding 12 parts by weight of the pigment and filler prepared in preparation example 6 and 3 parts by weight of a composite silane coupling agent into 200 parts by weight of ethanol, heating to 42 ℃, stirring and reacting for 1.5 hours, centrifuging, washing and drying to obtain a modified material;
the composite silane coupling agent is a mixture of KH550 and KH602, and the mass ratio is 3:6;
(2) And (3) adding the modified material prepared in the step (1) and 2 parts by weight of sodium hexadecyl sulfonate into 110 parts by weight of the aqueous polyurethane emulsion prepared in the preparation example 1, and stirring and mixing for 20 minutes to prepare the polyurethane color paste with high permeability and high dispersibility.
Example 4
The difference compared to example 3 is that the complex silane coupling agent is a single KH550.
Example 5
The difference compared to example 3 is that the complex silane coupling agent is a single KH602.
Comparative example 1
The difference compared to example 3 is that no complex silane coupling agent is added.
Comparative examples 2 to 4
The difference compared to example 3 is that the pigment and filler are prepared from comparative preparation examples 1-3, respectively.
Comparative example 5
The difference compared to example 3 is that the pigment filler is replaced by the dye prepared in preparation 3.
Comparative example 6
In comparison with example 3, the pigment filler was replaced by intermediate A prepared in preparation 3.
Comparative example 7
The difference compared to example 3 is that the pigment filler is replaced by acid red 87.
Test example 1
The high-permeability and high-dispersibility polyurethane color paste prepared by the embodiment and the comparative example is subjected to performance test.
Stability: the test samples were tested for storage stability by the method described in GB/T6753.3-1986, and were left to stand for 1 hour after centrifugation at 3000r/min for 15min, and if no significant sedimentation was observed, the test samples were generally considered to have storage stability for more than 6 months.
Solvent resistance: 1g of the color paste was placed in 20mL of hot water at 95℃and 5wt% hydrochloric acid and 5wt% NaOH solution, toluene, respectively, and subjected to shaking for 2 hours.
The results are shown in Table 1.
TABLE 1
As shown in the table above, the high-permeability and high-dispersibility polyurethane color paste prepared in the examples 1-3 has good stability and solvent resistance.
Test example 2
The high-permeability and high-dispersibility polyurethane color paste prepared by the embodiment and the comparative example is subjected to performance test.
Evaluation was performed by dry and wet rub test methods with reference to the method in GB/T3920-2008. The selected test cloth is fixed on the friction head, the friction times are 10 times, and the vertical pressure is 9N. In testing wet rubbing fastness, the water content of the test cloth should reach 7%. After the test is completed, the rating is made with reference to the gray sample card in GB/T250-2008.
Referring to the method in GB/T3921-2008, the wash fastness of the coated fabric formed from the color paste was tested and rated by a standard gray sample card.
The results are shown in Table 2.
TABLE 2
As can be seen from the above table, the high-permeability and high-dispersibility polyurethane color paste prepared in the examples 1-3 has good color fastness, washing fastness and high visible light transmittance.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. The polyurethane color paste with high permeability and high dispersibility is characterized by being prepared from the following components in parts by weight: 100-120 parts of aqueous polyurethane emulsion, 2-4 parts of composite silane coupling agent, 10-15 parts of pigment and filler and 1-3 parts of dispersing agent;
the preparation method of the pigment and filler comprises the following steps:
s1, preparing mesoporous silica/titanium dioxide spheres: dissolving alkyl orthosilicate and tetrabutyl titanate in an organic solvent to obtain an oil phase; adding a mesoporous pore-forming agent and an emulsifying agent into water to obtain a water phase; adding the oil phase into the water phase, emulsifying, dropwise adding ammonia water, stirring for reaction, centrifuging, washing, drying, and calcining to obtain mesoporous silica/titanium dioxide spheres;
s2, modifying polydopamine: adding the mesoporous silica/titanium dioxide spheres prepared in the step S1 into water, adding dopamine hydrochloride and a catalyst, heating and stirring for reaction, centrifuging, washing and drying to prepare modified mesoporous silica/titanium dioxide spheres;
s3, loading of dye: adding dye into ethanol water solution, stirring and mixing uniformly, adding the modified mesoporous silica/titanium dioxide balls prepared in the step S2, stirring and reacting, centrifuging, washing and drying to obtain pigment and filler;
the structural formula of the dye is shown in formula I:
a formula I;
wherein n=1-3.
2. The high-permeability and high-dispersibility polyurethane color paste according to claim 1, wherein the composite silane coupling agent is a mixture of KH550 and KH602, and the mass ratio is 2-4:5-7; the dispersing agent is at least one selected from sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium tetradecyl benzene sulfonate, sodium tetradecyl sulfonate, sodium hexadecyl benzene sulfonate, sodium octadecyl benzene sulfonate and sodium octadecyl sulfonate.
3. The high-permeability high-dispersibility polyurethane color paste according to claim 1, wherein the preparation method of the aqueous polyurethane emulsion is as follows: mixing and heating 20-30 parts by weight of isophorone diisocyanate, 90-140 parts by weight of polyethylene glycol 1000 and 0.01-0.02 part by weight of catalyst dibutyltin dilaurate to 70-75 ℃ for reaction for 1-2 hours, then adding 1-1.5 parts by weight of chain extender 2, 2-dimethylolpropionic acid and 0.5-1 part by weight of 1, 4-butanediol, and 20 parts by weight of acetone, heating to 75-80 ℃ for reaction for 2-3 hours, then cooling to 40-45 ℃, adding 2-3 parts by weight of triethylamine, stirring for reaction for 20-30 minutes, adding 500-700 parts by weight of water, and stirring and mixing uniformly to obtain the aqueous polyurethane emulsion.
4. The high-transparency high-dispersibility polyurethane color paste according to claim 1, wherein the mass ratio of the alkyl orthosilicate to the tetrabutyl titanate in the step S1 is 10-12:3-5; the mass ratio of the mesoporous pore-foaming agent to the emulsifier is 2-3:1-2, and the mesoporous pore-foaming agent is at least one of an oxyethylene-oxypropylene triblock copolymer PEO20-PPO70-PEO20 and a PEO106-PPO70-PEO 106; the emulsifier is at least one selected from Tween-20, tween-40, tween-60 and Tween-80, and the calcination temperature is 350-450 ℃ and the calcination time is 2-4h.
5. The high-permeability and high-dispersibility polyurethane color paste according to claim 1, wherein in the step S2, the mass ratio of mesoporous silica/titanium dioxide spheres to dopamine hydrochloride to catalyst is 10-12:7-10:0.5-1, the catalyst is Tris-HCl solution with pH=8.5-9, the temperature of the heating and stirring reaction is 45-50 ℃, and the time is 1-3h.
6. The high-permeability and high-dispersibility polyurethane color paste according to claim 1, wherein the mass ratio of the dye to the modified mesoporous silica/titanium dioxide spheres in the step S3 is 7-10:12-15, and the stirring reaction time is 1-3h.
7. The high-permeability and high-dispersibility polyurethane color paste according to claim 6, wherein the synthesis method of the dye comprises the following steps:
t1, the diaminostilbenedisulfonic acid and sodium nitrite react under the condition of hydrochloric acid to prepare an intermediate A, and the structure is as follows: ；
t2 reacting the glycol ether with benzyl bromide under alkali condition to obtain an intermediate B with the following structure:wherein n=1-3;
and T3, reacting the intermediate A with the intermediate B to obtain the product.
8. The high-permeability and high-dispersibility polyurethane color paste according to claim 7, wherein in the step T1, the sodium nitrite is 15-20wt% of sodium nitrite solution, the mass ratio of the diaminostilbenedisulfonic acid to the sodium nitrite solution is 1-2:50-100, and the reaction temperature is 0-5 ℃; the molar ratio of the glycol ether, the benzyl bromide and the alkali in the step T2 is 1-1.1:1:3-5; the molar ratio of the intermediate A to the intermediate B in the step T3 is 1:2-2.05.
9. The high-transparency high-dispersibility polyurethane color paste according to claim 7, wherein the glycol ether is at least one selected from the group consisting of ethylene glycol monoformal and ethylene glycol diglycide; the alkali is at least one selected from NaOH, KOH, sodium carbonate, sodium bicarbonate and potassium carbonate.
10. A process for the preparation of a high-transparency high-dispersibility polyurethane paste according to any one of claims 1 to 9, comprising the steps of:
(1) Adding pigment and filler and a composite silane coupling agent into ethanol, heating to 40-45 ℃, stirring and reacting for 1-2h, centrifuging, washing and drying to obtain a modified material;
(2) And (3) adding the modified material and the dispersing agent prepared in the step (1) into the aqueous polyurethane emulsion, and uniformly stirring and mixing to prepare the polyurethane color paste with high permeability and high dispersibility.
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Citations (4)
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|---|---|---|---|---|
| US5603865A (en) * | 1992-11-27 | 1997-02-18 | Basf Corporation | Copolymer dispersant composition for inorganic pigments |
| JP2007254556A (en) * | 2006-03-22 | 2007-10-04 | Toyo Ink Mfg Co Ltd | Pigment composition and pigment dispersion |
| CN103803643A (en) * | 2014-03-03 | 2014-05-21 | 福州大学 | Monodisperse mesoporous hollow nano spherical titanium dioxide and preparation method thereof |
| CN111528229A (en) * | 2020-04-16 | 2020-08-14 | 江苏斯迪克新材料科技股份有限公司 | Long-acting antibacterial agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8242201B2 (en) * | 2005-12-22 | 2012-08-14 | Ricoh Company, Ltd. | Pigment dispersion, recording ink, ink cartridge, ink-jet recording method and ink-jet recording apparatus |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5603865A (en) * | 1992-11-27 | 1997-02-18 | Basf Corporation | Copolymer dispersant composition for inorganic pigments |
| JP2007254556A (en) * | 2006-03-22 | 2007-10-04 | Toyo Ink Mfg Co Ltd | Pigment composition and pigment dispersion |
| CN103803643A (en) * | 2014-03-03 | 2014-05-21 | 福州大学 | Monodisperse mesoporous hollow nano spherical titanium dioxide and preparation method thereof |
| CN111528229A (en) * | 2020-04-16 | 2020-08-14 | 江苏斯迪克新材料科技股份有限公司 | Long-acting antibacterial agent |
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