CN107541094A - Compound polyurethane-based high-molecular black dye and preparation method thereof - Google Patents
Compound polyurethane-based high-molecular black dye and preparation method thereof Download PDFInfo
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- CN107541094A CN107541094A CN201710827593.2A CN201710827593A CN107541094A CN 107541094 A CN107541094 A CN 107541094A CN 201710827593 A CN201710827593 A CN 201710827593A CN 107541094 A CN107541094 A CN 107541094A
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- polyurethane
- small molecule
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- compounding
- black dyes
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 19
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 150000001875 compounds Chemical class 0.000 title abstract description 4
- 239000000975 dye Substances 0.000 claims abstract description 63
- 238000013329 compounding Methods 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000001045 blue dye Substances 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 239000011347 resin Substances 0.000 claims abstract description 7
- 229920005989 resin Polymers 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 5
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 150000003384 small molecules Chemical class 0.000 claims description 21
- 229920002521 macromolecule Polymers 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- 241000625836 Ochrolechia Species 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 235000019248 orcein Nutrition 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- NZTGGRGGJFCKGG-UHFFFAOYSA-N 1,4-diamino-2,3-diphenoxyanthracene-9,10-dione Chemical compound C=1C=CC=CC=1OC1=C(N)C=2C(=O)C3=CC=CC=C3C(=O)C=2C(N)=C1OC1=CC=CC=C1 NZTGGRGGJFCKGG-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- -1 aromatic isocyanate Chemical class 0.000 claims description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 claims description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 claims description 2
- 101710130081 Aspergillopepsin-1 Proteins 0.000 claims description 2
- 102100031007 Cytosolic non-specific dipeptidase Human genes 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical class COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- JSFUMBWFPQSADC-UHFFFAOYSA-N Disperse Blue 1 Chemical compound O=C1C2=C(N)C=CC(N)=C2C(=O)C2=C1C(N)=CC=C2N JSFUMBWFPQSADC-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004218 Orcein Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- XREZMAAQVYVESP-UHFFFAOYSA-N acetyloxymethyl 2-[n-[2-(acetyloxymethoxy)-2-oxoethyl]-2-[2-[2-[bis[2-(acetyloxymethoxy)-2-oxoethyl]amino]-4-fluorophenoxy]ethoxy]-5-fluoroanilino]acetate Chemical compound CC(=O)OCOC(=O)CN(CC(=O)OCOC(C)=O)C1=CC(F)=CC=C1OCCOC1=CC=C(F)C=C1N(CC(=O)OCOC(C)=O)CC(=O)OCOC(C)=O XREZMAAQVYVESP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000004807 desolvation Methods 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002334 glycols Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000012974 tin catalyst Substances 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- QOSTVEDABRQTSU-UHFFFAOYSA-N 1,4-bis(methylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NC)=CC=C2NC QOSTVEDABRQTSU-UHFFFAOYSA-N 0.000 claims 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 8
- 238000004043 dyeing Methods 0.000 abstract description 5
- 239000001043 yellow dye Substances 0.000 abstract description 5
- 239000010985 leather Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000003086 colorant Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000001047 purple dye Substances 0.000 abstract 3
- 239000001044 red dye Substances 0.000 abstract 3
- 238000001816 cooling Methods 0.000 abstract 1
- 239000003973 paint Substances 0.000 abstract 1
- 229920005862 polyol Polymers 0.000 abstract 1
- 150000003077 polyols Chemical class 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 description 6
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000012544 Viola sororia Nutrition 0.000 description 3
- 241001106476 Violaceae Species 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- OALHHIHQOFIMEF-UHFFFAOYSA-N 3',6'-dihydroxy-2',4',5',7'-tetraiodo-3h-spiro[2-benzofuran-1,9'-xanthene]-3-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 OALHHIHQOFIMEF-UHFFFAOYSA-N 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 2
- 125000005474 octanoate group Chemical group 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- DMVOXQPQNTYEKQ-UHFFFAOYSA-N biphenyl-4-amine Chemical compound C1=CC(N)=CC=C1C1=CC=CC=C1 DMVOXQPQNTYEKQ-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a compound polyurethane-based high-molecular black dye and a preparation method thereof, wherein polymer polyol is heated to 90-110 ℃, and is dehydrated for 1-2 hours under the condition that the vacuum degree is less than or equal to 0.1MPa, and nitrogen is introduced for protection; cooling to 50-70 ℃, adding polyisocyanate, a solvent and a catalyst by weight, and reacting for 1-3 h at 60-90 ℃; dissolving micromolecular red, blue, purple and yellow dyes in a solvent, sequentially adding the micromolecular red, blue, purple and yellow dyes, and reacting for 6-12 hours at 50-90 ℃ to prepare a black polyurethane polymer dye solution; and (4) removing the solvent in vacuum to obtain the compound polyurethane-based high-molecular black dye resin. The invention utilizes the principle of three primary colors, and is prepared by connecting red, blue, purple and yellow dyes into a polyurethane chain through a compounding technology, thereby not only improving the blackness and utilization rate of the dyes, but also improving the dyeing performance and color fastness performance of the dyes. Can be directly dyed to prepare various coatings, leather and paint products, and the complicated dispersing and dyeing processes can be saved.
Description
Technical field
The present invention relates to a kind of high molecular dye, more particularly to a kind of compounding polyurethane-base macromolecule black dyes and
Its preparation method.
Background technology
Small molecule dyes adhesion is not strong, dye utilization rate is low, and the aspect of performance such as resistance to migration, heat-resisting and solvent resistant
Shortcoming, and pollution on the environment is serious in use, limits the application in various fields.
Traditional small molecule dyes producing high-molecular can effectively be solved the above problems.High molecular dye is by certain change
Learn reaction and chromophoric group is introduced to a kind of new coloured macromolecule polymer formed on high molecular main chain or side chain, that is, have
High molecular high intensity, easy film forming, solvent resistance, resistance to migration, heat resistance and machinability, but organic dyestuff is to the strong of light
Absorbability and colorful property, show the features such as bright-colored, good color fastness, dye utilization rate are high, nontoxic and easy to use.
In the market, black dyes dosage accounts for the 65% of dyestuff total amount, and black dyes is in weaving, printing and dyeing, leather, painting
There is very important status in the fields such as dress, ink.The early stage black dyes mainly azo dyes as derived from benzidine, has
The advantages of pitch black degree is good, dye-uptake and degree of fixation are high.But producing with carcinogenic intermediate biphenyl amine can be discharged in use, seriously
Environment is polluted, if these dyestuffs are absorbed by the body, can be detrimental to health again and cause serious consequence.Therefore, 70 years last century
Generation black dyes of all kinds as derived from benzidine is in succession disabled.
At present, most of black dyes is that pitch black degree existing for the dispersed black dye of the small molecule of one-component is low, lifted
The subject matters such as power deficiency, fastness are poor and environmental pollution is serious.
Compounded technology is the focus of current dyestuff research, obtains certain progress.Black dyes is obtained by compounded technology.No
But dyestuff pitch black degree and utilization rate can be improved, the dyeability and fastness ability of dyestuff can also be improved.
《Dyestuff and dyeing》(the 4th 10-14 pages of phases of volume 52 in 2015) report the compounding skill of environment-friendly black disperse dyes
Art.It is that raw material is compounded with C.I. disperse violets 93, C.I. disperse blues 291: 1, C.I. disperse oranges 73 and C.I. disperse oranges 44,
Obtain the more superior Compound disperse black dyestuff of dyeability.
《Tianjin textile technology》(the 204th 22-25 pages of phase in 2015) reports compounded technology and dispersed black dye is matched somebody with somebody
Side's design.By compounded formula design gained scattered black ECTT dyestuffs there is good dyeability, compared with the market using compared with
More Disperse Black EX-SFs 300% increase on depth and dyefastness.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of compounding polyurethane-base macromolecule black dye
Material and preparation method thereof, by compounded technology, red, blue, purple, yellow dye is accessed into polyurethane chain.
The present invention is achieved by the following technical solutions：A kind of compounding polyurethane-base macromolecule black dyes of the present invention
Preparation method, comprise the following steps：
(1) 20~60 parts of polymer polyatomic alcohols are warming up to 90~110 DEG C, under the conditions of vacuum≤0.1MPa, at dehydration
1~2h is managed, is passed through nitrogen protection；
(2) 50~70 DEG C are cooled to, by weight, add 10~35 parts of polyisocyanates, 30~50 parts of solvents and 0.1~
0.3 part of catalyst reacts 1~3h at 60~90 DEG C；
(3) by 3~7 parts of small molecule orchils, 3~7 parts of small molecule blue dyes, 3~7 parts of small molecule cudbears, 3
~7 parts of small molecule welds are dissolved in solvent, are sequentially added, and 6~12h is reacted at 50~90 DEG C, and it is high that black polyurethane is made
Molecular dye solution；
(4) vacuum desolvation agent, obtain compounding polyurethane-base macromolecule black dyes resin.
One of preferred embodiment as the present invention, the polyisocyanates is selected from aromatic isocyanate and aliphatic isocyanide
At least one of acid esters.
One of preferred embodiment as the present invention, the polymer polyatomic alcohol is in polyether Glycols and PEPA
At least one.
One of preferred embodiment as the present invention, the solvent are selected from acetone, butanone, dioxane, N, N- dimethyl acyls
Amine, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), ethyl acetate, acetic acid -2-ethoxy-ethyl ester, 1,2- dimethoxy-ethanes, second two
At least one of alcohol methyl ether, 2-Butoxyethyl acetate, the tertiary butyl ether of ethylene glycol list, ethylene glycol monobutyl ether.
One of preferred embodiment as the present invention, the catalyst is organic tin catalyst, selected from stannous octoate and two
At least one of dibutyl tin laurate.
One of preferred embodiment as the present invention, the small molecule orchil are selected from Red-1 200 7, dispersion red 11
At least one of (C.I.62015).
One of preferred embodiment as the present invention, the small molecule blue dyes are selected from disperse blue 60 (C.I.61104), divided
Dissipate at least one of 14 (C.I.61500) of indigo plant, disperse blue 1 (C.I.64500).
As one of preferred embodiment of the present invention, the small molecule cudbear be selected from disperse violet 4BN (C.I.62030),
At least one of solvent violet 59 (C.I.62025).
One of preferred embodiment as the present invention, the small molecule weld is scattered fluorescent yellow (CAS-RN:58232-
21-6)。
Dyestuff made from one kind compounding polyurethane-base macromolecule black dyes preparation method, the dyestuff is with total reactant
On the basis of quality, in polyurethane chain, the mass content containing small molecule dyes is 12~28%；In polyurethane backbone, contain
It is 40~70% to have the mass content of polyethers and/or polyester segment.
The present invention has advantages below compared with prior art：The polyurethane-base macromolecule black dyes that present invention compounding obtains
Resin, there is excellent rub resistance, resistance to migration, weather-proof, resistance to migration and safe feature.Polyurethane-base prepared by the present invention is black
Color high molecular dye, using the principle of three primary colours, by compounded technology, it will be made in red, blue, purple, yellow dye access polyurethane chain,
Dyestuff pitch black degree and utilization rate are not only improved, also improves the dyeability and fastness properties of dyestuff.It can be prepared with direct staining
Various coating, leather, painting, and also complicated scattered and dyeing course can also save.
Embodiment
Embodiments of the invention are elaborated below, the present embodiment is carried out lower premised on technical solution of the present invention
Implement, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
In N2Under protection, by equipped with agitator, condenser pipe, thermometer four-hole bottle in add 100g, the poly- tetrahydrochysenes of 0.1mol
Furans glycol, 110 DEG C, under the conditions of 0.1MPa, dewater treatment 2h.
Be cooled to 80 DEG C, be added dropwise 44.5g, 0.2mol IPDIs, 40ml 1-METHYLPYRROLIDONEs and
0.02g dibutyl tin laurates, 3h is reacted at 90 DEG C.
0.023mol 7.9g C.I. Red-1 200s 7,0.023mol 8.7g disperse blue 60s, 0.023mol 6.5g are disperseed
Purple 4BN, 0.023mol6.7g fluorescein is dissolved in 20ml acetone respectively.
2h addition reactors are spaced successively and react 10h at 80 DEG C, and compounding black polyurethane high molecular dye solution is made.
Abjection solvent is finally evaporated under reduced pressure, compounding black polyurethane based black high molecular dye resin is made.
Gained dyestuff, 280~360 DEG C of first stage heat decomposition temperature, second stage heat decomposition temperature 360~550
DEG C, 65 DEG C of glass transition temperature.
Embodiment 2
In N2Under protection, by equipped with agitator, condenser pipe, thermometer four-hole bottle in add 100g, 0.1mol gathers in oneself
Esterdiol, 110 DEG C, under the conditions of 0.1MPa, dewater treatment 2h.
Be cooled to 70 DEG C, 50g, 0.2mol4,4- methyl diphenylene diisocyanates (MDI), 20ml dioxane and
0.02g stannous octoates, 3h is reacted at 80 DEG C.
By 0.023mol7.9g C.I. Red-1 200s 7,0.023mol6.1g disperse blues 14,0.023mol9.7g solvent violets
59th, 0.023mol6.7g fluoresceins are dissolved in 20ml acetone respectively.
2h is spaced successively and is added at 80 DEG C of reactor and reacts 10h, reacts 2h at 90 DEG C, and compounding black polyurethane high score is made
Sub- dye solution.Abjection solvent is finally evaporated under reduced pressure, compounding black polyurethane based black high molecular dye resin is made.
Gained dyestuff, 285~380 DEG C of first stage heat decomposition temperature, second stage heat decomposition temperature 380~550
DEG C, 68 DEG C of glass transition temperature.
Embodiment 3
Into equipped with thermometer, agitator, reflux condenser and dropping funel flask, 100g, 0.1mol polyoxies are added
Change propylene glycol, 110 DEG C, under the conditions of 0.1MPa, dewater treatment 1.5h.
It is cooled to 80 DEG C, is added dropwise 34.8g, 0.2mol toluene di-isocyanate(TDI)s, 20ml butanone and 0.02g stannous octoates, 90
3h is reacted at DEG C.
By 0.023mol 7.9g C.I. Red-1 200s 7,0.023mol6.2g disperse blues 1,0.023mol 9.7g solvent violets
59th, 0.023mol6.7g fluoresceins are dissolved in 20ml acetone respectively.
2h is spaced successively and is added at 80 DEG C of reactor and reacts 10h, reacts 2h at 90 DEG C, and compounding black polyurethane high score is made
Sub- dye solution.Abjection solvent is finally evaporated under reduced pressure, compounding black polyurethane based black high molecular dye resin is made.
Gained dyestuff, 227~350 DEG C of first stage heat decomposition temperature, second stage heat decomposition temperature 350~550
DEG C, 60 DEG C of glass transition temperature.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should be included in the scope of the protection.
Claims (10)
1. one kind compounding polyurethane-base macromolecule black dyes preparation method, it is characterised in that comprise the following steps：
(1) 20~60 parts of polymer polyatomic alcohols are warming up to 90~110 DEG C, under the conditions of vacuum≤0.1MPa, dewater treatment 1~
2h, it is passed through nitrogen protection；
(2) 50~70 DEG C are cooled to, by weight, adds 10~35 parts of polyisocyanates, 30~50 parts of solvents and 0.1~0.3
Part catalyst reacts 1~3h at 60~90 DEG C；
(3) by 3~7 parts of small molecule orchils, 3~7 parts of small molecule blue dyes, 3~7 parts of small molecule cudbears, 3~7
Part small molecule weld is dissolved in solvent, is sequentially added, and 6~12h is reacted at 50~90 DEG C, and black polyurethane macromolecule is made
Dye solution；
(4) vacuum desolvation agent, obtain compounding polyurethane-base macromolecule black dyes resin.
A kind of 2. compounding polyurethane-base macromolecule black dyes preparation method according to claim 1, it is characterised in that institute
State polyisocyanates and be selected from least one of aromatic isocyanate and aliphatic isocyanates.
A kind of 3. compounding polyurethane-base macromolecule black dyes preparation method according to claim 1, it is characterised in that institute
State polymer polyatomic alcohol and be selected from least one of polyether Glycols and PEPA.
A kind of 4. compounding polyurethane-base macromolecule black dyes preparation method according to claim 1, it is characterised in that institute
State solvent and be selected from acetone, butanone, dioxane, N, N- dimethylformamides, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), acetic acid second
Ester, acetic acid -2-ethoxy-ethyl ester, 1,2- dimethoxy-ethanes, ethylene glycol monomethyl ether, 2-Butoxyethyl acetate, ethylene glycol list uncle
At least one of butyl ether, ethylene glycol monobutyl ether.
A kind of 5. compounding polyurethane-base macromolecule black dyes preparation method according to claim 1, it is characterised in that institute
It is organic tin catalyst to state catalyst, selected from least one of stannous octoate and dibutyl tin laurate.
A kind of 6. compounding polyurethane-base macromolecule black dyes preparation method according to claim 1, it is characterised in that institute
State small molecule orchil and be selected from least one of Red-1 200 7, dispersion red 11.
A kind of 7. compounding polyurethane-base macromolecule black dyes preparation method according to claim 1, it is characterised in that institute
State small molecule blue dyes and be selected from least one of disperse blue 60, disperse blue 14, disperse blue 1.
A kind of 8. compounding polyurethane-base macromolecule black dyes preparation method according to claim 1, it is characterised in that institute
State small molecule cudbear and be selected from least one of disperse violet 4BN, solvent violet 59.
A kind of 9. compounding polyurethane-base macromolecule black dyes preparation method according to claim 1, it is characterised in that institute
It is scattered fluorescent yellow to state small molecule weld.
A kind of 10. compounding polyurethane-base macromolecule black dyes preparation method system using as described in any one of claim 1~9
The dyestuff obtained, it is characterised in that the dyestuff is on the basis of the quality of total reactant, in polyurethane chain, contains small molecule and contaminates
The mass content of material is 12~28%；In polyurethane backbone, the mass content containing polyethers and/or polyester segment be 40~
70%.
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| CN201710827593.2A CN107541094A (en) | 2017-09-14 | 2017-09-14 | Compound polyurethane-based high-molecular black dye and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113668261A (en) * | 2021-09-10 | 2021-11-19 | 拓烯科技(衢州)有限公司 | Dyeing liquid for optical resin and application method thereof |
| CN115073914A (en) * | 2022-06-24 | 2022-09-20 | 安徽大学 | Blue waterborne polyurethane color paste and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101024731A (en) * | 2007-02-09 | 2007-08-29 | 常州汉斯化学品有限公司 | Microcapsule disperse black, its preparing method and dyeing method for superfine synthesized fiber and fabric |
| CN104262570A (en) * | 2014-09-16 | 2015-01-07 | 中国科学技术大学 | Preparation method of black waterborne polyurethane dye |
| CN105949425A (en) * | 2016-06-07 | 2016-09-21 | 安徽建筑大学 | Polyurethane-based black high-molecular dye, preparation method and application |
-
2017
- 2017-09-14 CN CN201710827593.2A patent/CN107541094A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101024731A (en) * | 2007-02-09 | 2007-08-29 | 常州汉斯化学品有限公司 | Microcapsule disperse black, its preparing method and dyeing method for superfine synthesized fiber and fabric |
| CN104262570A (en) * | 2014-09-16 | 2015-01-07 | 中国科学技术大学 | Preparation method of black waterborne polyurethane dye |
| CN105949425A (en) * | 2016-06-07 | 2016-09-21 | 安徽建筑大学 | Polyurethane-based black high-molecular dye, preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 顾东雅 等: "环保性黑色分散染料的复配及表征", 《染料与染色》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113668261A (en) * | 2021-09-10 | 2021-11-19 | 拓烯科技(衢州)有限公司 | Dyeing liquid for optical resin and application method thereof |
| CN115073914A (en) * | 2022-06-24 | 2022-09-20 | 安徽大学 | Blue waterborne polyurethane color paste and preparation method thereof |
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