CN107541094A - One kind compounding polyurethane-base macromolecule black dyes and preparation method thereof - Google Patents
One kind compounding polyurethane-base macromolecule black dyes 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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Abstract
The invention discloses one kind compounding polyurethane-base macromolecule black dyes and preparation method thereof, polymer polyatomic alcohol is warming up to 90~110 DEG C, under the conditions of vacuum≤0.1MPa, 1~2h of dewater treatment, is passed through nitrogen protection；50~70 DEG C are cooled to, by weight, polyisocyanates, solvent and catalyst is added and 1~3h is reacted at 60~90 DEG C；By small molecule is red, blue, purple, weld is dissolved in solvent, sequentially adds, 6~12h is reacted at 50~90 DEG C, black polyurethane high molecular dye solution is made；Vacuum desolvation agent, obtain compounding polyurethane-base macromolecule black dyes resin.The present invention utilizes the principle of three primary colours, by compounded technology, will be made in red, blue, purple, yellow dye access polyurethane chain, not only improves dyestuff pitch black degree and utilization rate, also improve the dyeability and fastness properties of dyestuff.Various coating, leather, painting can be prepared, and complicated scattered and dyeing course can also save with direct staining.
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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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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| 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 polymeric dye, preparing method and application |
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2017
- 2017-09-14 CN CN201710827593.2A patent/CN107541094A/en active Pending
Patent Citations (3)
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| 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 polymeric dye, preparing method and application |
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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 |
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Application publication date: 20180105 |