CN101845234B - Monoazo disperse blue dye and bi-component disperse blue dye as well as preparation method thereof - Google Patents
Monoazo disperse blue dye and bi-component disperse blue dye as well as preparation method thereof Download PDFInfo
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- CN101845234B CN101845234B CN 200910048417 CN200910048417A CN101845234B CN 101845234 B CN101845234 B CN 101845234B CN 200910048417 CN200910048417 CN 200910048417 CN 200910048417 A CN200910048417 A CN 200910048417A CN 101845234 B CN101845234 B CN 101845234B
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Abstract
The invention discloses a monoazo disperse blue dye and a bi-component disperse blue dye as well as a preparation method thereof. The monoazo disperse blue dye is a compound having a structural formula (I) shown in the specification. Through verification, the bi-component disperse blue dye can be applied to staining of hydrophobic fiber and blend fabric thereof such as terylene, nylon, polyurethane fiber and the like, has bright-coloured luster and is equalled to disperse blue 2BLN. Through changing the proportion of coupling components A and B in reaction raw materials, the functions of regulating the colored light of the dye and realizing synergia can be achieved so as to satisfy the requirement on different application conditions. In addition, the dye has high lifting property, favorable color fastness for washing, solarization, sublimation and the like, and has more excellent comprehensive performance than the disperse blue 2BLN. The invention has the advantages of low production cost and wide application prospect.
Description
Technical field
The invention belongs to the dyestuff chemistry field, particularly a kind of monoazo dispersed blue dye and a kind of two-pack dispersed blue dye and preparation method thereof.
Background technology
Azo dispersion dyes is the important synthetic dyestuff of a class, and its chromatogram is complete, various in style, excellent property, and reaction is simple in the synthetic preparation process, structure is changeable, with low cost, is the dye of widespread use in the dyeing.Wherein, again with blue kind consumption maximum, but because it lacks the blueness of excellent performance, so can't replace the more expensive anthraquinone class dispersed blue dye 2BLN of price always; Therefore in the dyeing utilization ratio of color, dyestuff and the requirement of economic benefit are improved constantly in addition, develop a kind of excellent performance, enhancing is good, coloured light is adjustable, inexpensive blue disperse dye is the dye industry urgent problem.
Summary of the invention
Therefore, the technical problem to be solved in the present invention is exactly that dark, the gorgeous degree of color and luster that exists at existing azo dispersed blue dye is low, the deficiency of poor-performing, provides a kind of azo dispersed blue dye, this azo dispersed blue dye lovely luster, coloured light is adjustable, has excellent enhancing and colour fastness.
The present invention solves the problems of the technologies described above one of technical scheme of being adopted, a kind of monoazo dispersed blue dye, and it is a structural formula suc as formula the compound shown in (I):
The present invention solves the problems of the technologies described above two of the technical scheme that adopted, a kind of two-pack dispersed blue dye, and it is by forming suc as formula the compound shown in (I) with suc as formula the compound shown in (II):
Wherein, described suc as formula the compound shown in (I) with and be 1: 99～50: 50 suc as formula the mol ratio of the compound shown in (II), better is 5: 95～30: 70.
Two-pack dispersed blue dye of the present invention is by forming suc as formula the compound shown in (I) with suc as formula two kinds of components of the compound shown in (II).The two-pack dispersed blue dye can be to prepare respectively suc as formula the compound shown in (I) with suc as formula the compound shown in (II), they is mixed obtaining then.More preferably following method prepares simultaneously suc as formula the compound shown in (I) with suc as formula the compound shown in (II), and preparation is two-pack dispersed blue dye of the present invention when finishing.
Therefore, to solve the problems of the technologies described above three of the technical scheme that adopted be that a kind of preparation method of two-pack dispersed blue dye as described may further comprise the steps in the present invention:
In water, in under the strong acidic condition of pH value 1～2, with as the formula (1) diazonium salt with carry out coupled reaction suc as formula the compound shown in (A) with suc as formula the mixture of the compound shown in (B), adding alkali adjusting pH value after reaction is finished is 3～5, filter washing, obtain with suc as formula the compound shown in (A) and corresponding suc as formula Compound I shown in (I) and the two-pack dispersed blue dye that forms suc as formula the compound shown in (II) suc as formula the compound shown in (B)
Wherein, be the N-ethyl-N hydroxyethyl meta-aminotoluene suc as formula the compound shown in (A), be N-ethyl-N-cyanogen ethoxyethyl group meta-aminotoluene suc as formula the compound shown in (B), all commercial getting.
Among the present invention, described suc as formula the shared molecular fraction in of the compound shown in (A) suc as formula compound shown in (A) and total amount suc as formula the mixture of the compound shown in (B) preferable be 1.0%～50%, better is 5.0～30%.The mol ratio preferably 1: 1～1.08 of the mixture of described diazonium salt and compound shown in general formula (A) and the compound shown in general formula (B), better is 1: 1.05.Little excessive the carrying out that react of helping of diazonium salt.Carry out under the strong acidic condition of the pH of being reflected at value 1～2 of the present invention, can add strong acid and reach required strong acidic condition, the strong acid that is added is preferable is selected from the vitriol oil, hydrochloric acid, acetic acid, propionic acid and phosphoric acid, and purpose is that coupling component is dissolved.Among the present invention, what the temperature of reaction of described coupled reaction was preferable is 0～10 ℃.Reaction times is till detecting reactant runs out of, and preferable is 2～5 hours, gets final product in general 2～3 hours.In the described coupled reaction, preferable, also add thionamic acid or urea, best is thionamic acid.The purpose that adds thionamic acid or urea is a unreacted nitrosyl sulfuric acid when reacting away diazotization.In the described coupled reaction, preferable a little emulsifying agent of also adding is as paregal O, NP-10, S-60, AEO-7 and 1307 etc.
Among the present invention, after described coupled reaction is finished, add alkali in the reaction product and regulate pH value to 2～7.Described alkali is preferable is selected from sodium hydroxide, potassium hydroxide, yellow soda ash and ammoniacal liquor, filter washing then, the filter cake oven dry is promptly suc as formula the compound shown in (A) and corresponding suc as formula Compound I shown in (I) and the two-pack dispersed blue dye formed suc as formula the compound shown in (II) suc as formula the compound shown in (B).
Above-mentioned preparation method of the present invention is a preferred methods, is suitable for industrial production.Because in suitability for industrialized production, suc as formula the compound shown in (B) by making suc as formula compound and the acrylonitrile reactor shown in (A), synthetic is suc as formula all containing more reactant in the compound shown in (B) in various degree, promptly suc as formula the compound shown in (A), its content can be determined by HPLC.An amount of by adding suc as formula the compound shown in (A), just can in follow-up coupled reaction process, directly obtain two-pack dispersed blue dye of the present invention, the step that simplifies the operation reduces cost greatly.
Among the present invention, described diazonium salt can adopt prior art for preparing, preferable comprises the steps: in 93～98% (wt) vitriol oil, its consumption is preferable is 4～6 times of diazo component gross weight, 3-amino-5-nitro-[2,1]-benzisothiazole and diazo reagent nitrosyl sulfuric acid carry out diazotization reaction, form diazonium salt:
In this diazotization reaction, what temperature of reaction was preferable is 0～10 ℃.
Among the present invention, described two-pack dispersed blue dye can carry out post-treatment by the method for this area routine, and as adding auxiliary agents such as diffusant in proportion, sand milling obtains the dyestuff finished product.
Therefore, the present invention solves the problems of the technologies described above four of the technical scheme that adopted and is, a kind of two-pack disperse dye composition, and it contains described two-pack dispersed blue dye and colour additive.Wherein, described colour additive is an auxiliary agent conventional in the dye field, as Dispersant MF, CNF, NNO or sodium lignosulfonate etc.
Raw material that the present invention is used or reagent except that specifying, all commercially available getting.
Than prior art, beneficial effect of the present invention is as follows: the two-pack azo dispersed blue dye that the present invention relates to, empirical tests can be applicable to the dyeing of hydrophobic fibres such as terylene, nylon, spandex and BLENDED FABRIC thereof, have the stronger collaborative dark effect that increases; And, can reach dye shade and the synergic effect regulated by changing the ratio of coupling component A, B in the reaction raw materials, to satisfy demand to the different application condition.Simultaneously, dyestuff enhancing height of the present invention, every fastness such as washing, Exposure to Sunlight, distillation are good, and over-all properties is more excellent more than DISPERSE BLUE 2BLN.Low production cost has broad application prospects.
Embodiment
Further specify the present invention with embodiment below, but the present invention is not limited.Raw materials used and reagent city is purchased and can be got in the following example, the experimental technique of unreceipted actual conditions, and usually according to normal condition, or the condition of advising according to manufacturer.Component A described in the embodiment or A promptly are of the present invention suc as formula the compound shown in (A), and described B component or B promptly are of the present invention suc as formula the compound shown in (B).The molecular fraction that below relates to component A in the coupling component only gets 1%, 10%, 25%, 50%, actually is not limited only to this.
Embodiment 1
Diazotization: in 100 milliliters of there-necked flasks, add 57 milliliters of 93% (wt) vitriol oils, begin to stir, add 3-amino-5-nitro-[2 of 99% (wt), 1]-benzisothiazole 19.6 grams, this moment, temperature was increased to 35～45 ℃, and insulated and stirred 4 hours is dissolved diazo component fully.Be cooled to 0 ℃ with ice-water bath, slowly drip 40% (wt) nitrosyl sulfuric acid, 34 grams, control reaction temperature is at 10 ℃ then, and stirring reaction gets brown diazonium saline solution after 4 hours standby.
The preparation of coupling component and coupling (it is 1% that A accounts for the overall molecular fraction of coupling component):
In 3000 ml beakers, add 300 milliliters in water, stir and add 2 milliliters of 93% (wt) vitriol oils (this moment, pH was about 2), component A 0.19 gram (0.00105 mole), B component 24.15 grams (0.10395 mole), paregal O 0.3 gram, thionamic acid 0.7 gram down, after being stirred well to each raw material and dissolving fully, add trash ice and be cooled to 7 ℃, beginning slowly drips 3 hours (adding diazonium salt 0.1mol altogether) of above-mentioned diazonium saline solution, and ice and frozen water will constantly be added in the centre.Continue insulated and stirred and react after 2 hours, about 185 milliliters of adding 30% (wt) caustic lye of soda transfers pH to be about 3, is heated to 65～70 ℃ of insulations after 2 hours, filters, washes, and filter cake is dried to such an extent that former dyestuff 40.6 restrains molecular-weight average 438, yield 93% (wt); Efficient liquid phase chromatographic analysis dyestuff mol ratio is I: II=1.1: 98.9.
Embodiment 2
Diazotization: in 100 milliliters of there-necked flasks, add 57 milliliters of 98% (wt) vitriol oils, begin to stir, add 3-amino-5-nitro-[2 of 99% (wt), 1]-benzisothiazole 19.6 grams, this moment, temperature was increased to 35～45 ℃, and insulated and stirred 4 hours is dissolved diazo component fully.Be cooled to 0 ℃ with ice-water bath, slowly drip 40% (wt) nitrosyl sulfuric acid, 34 grams, control reaction temperature is at 10 ℃ then, and stirring reaction gets brown diazonium saline solution after 4 hours standby.
The preparation of coupling component and coupling (it is 10% that A accounts for the overall molecular fraction of coupling component):
In 3000 ml beakers, add 300 milliliters in water, add 10 milliliters of 98% (wt) vitriol oils (this moment, pH was about 1), component A 1.88 grams (0.0105 mole), B component 21.96 grams (0.0945 mole), paregal O 0.3 gram, thionamic acid 0.7 gram under stirring, after being stirred well to each raw material and dissolving fully, add trash ice and be cooled to 0 ℃, beginning slowly drips 3 hours (adding diazonium salt 0.1mol altogether) of above-mentioned diazonium saline solution, and ice and frozen water will constantly be added in the centre.Continue insulated and stirred and react after 4 hours, about 200 milliliters of adding 30% (wt) caustic lye of soda transfers pH to be about 4, is heated to 65～70 ℃ of insulations after 2 hours, filters, washes, and filter cake is dried to such an extent that former dyestuff 40.1 restrains molecular-weight average 435, yield 92% (wt); Efficient liquid phase chromatographic analysis dyestuff mol ratio is I: II=8.5: 91.5.
Embodiment 3
Diazotization: in 100 milliliters of there-necked flasks, add 57 milliliters of 95% (wt) vitriol oils, begin to stir, add 3-amino-5-nitro-[2 of 99% (wt), 1]-benzisothiazole 19.6 grams, this moment, temperature was increased to 35～45 ℃, and insulated and stirred 4 hours is dissolved diazo component fully.Be cooled to 0 ℃ with ice-water bath, slowly drip 40% (wt) nitrosyl sulfuric acid, 34 grams, control reaction temperature is at 10 ℃ then, and stirring reaction gets brown diazonium saline solution after 4 hours standby.
The preparation of coupling component and coupling (it is 25% that A accounts for the overall molecular fraction of coupling component):
In 3000 ml beakers, add 300 milliliters in water, stir 95% (wt) vitriol oil 10 milliliters of (this moment, pH was about 1), component A 4.71 grams (0.02625 mole), B component 18.30 grams (0.07875 mole), paregal O 0.3 gram, thionamic acid 0.7 gram down, after being stirred well to each raw material and dissolving fully, add trash ice and be cooled to 10 ℃, beginning slowly drips 3 hours (adding diazonium salt 0.1mol altogether) of above-mentioned diazonium saline solution, and ice and frozen water will constantly be added in the centre.Continue insulated and stirred and react after 5 hours, about 190 milliliters of adding 30% (wt) caustic lye of soda transfers pH to be about 5, is heated to 65～70 ℃ of insulations after 2 hours, filters, washes, and filter cake is dried to such an extent that former dyestuff 39.8 restrains molecular-weight average 430, yield 93% (wt); Efficient liquid phase chromatographic analysis dyestuff mol ratio is I: II=23.4: 76.6.
Embodiment 4
Diazotization: in 100 milliliters of there-necked flasks, add 57 milliliters of 98% (wt) vitriol oils, begin to stir, add 3-amino-5-nitro-[2 of 99% (wt), 1]-benzisothiazole 19.6 grams, this moment, temperature was increased to 35～45 ℃, and insulated and stirred 4 hours is dissolved diazo component fully.Be cooled to 0 ℃ with ice-water bath, slowly drip 40% (wt) nitrosyl sulfuric acid, 34 grams, control reaction temperature is at 10 ℃ then, and stirring reaction gets brown diazonium saline solution after 4 hours standby.
The preparation of coupling component and coupling (it is 50% that A accounts for the overall molecular fraction of coupling component):
In 3000 ml beakers, add 300 milliliters in water, stir 98% (wt) vitriol oil 10 milliliters of (this moment, pH was about 1), component A 9.41 grams (0.0525 mole), B component 12.20 grams (0.0525 mole), paregal O 0.3 gram, thionamic acid 0.7 gram down, after being stirred well to each raw material and dissolving fully, add trash ice and be cooled to 4 ℃, beginning slowly drips 3 hours (adding diazonium salt 0.1mol altogether) of above-mentioned diazonium saline solution, and ice and frozen water will constantly be added in the centre.Continue insulated and stirred and react after 3 hours, about 200 milliliters of adding 30% (wt) caustic lye of soda transfers pH to be about 4, is heated to 65～70 ℃ of insulations after 5 hours, filters, washes, and filter cake is dried to such an extent that former dyestuff 38.5 restrains molecular-weight average 421, yield 91% (wt); Efficient liquid phase chromatographic analysis dyestuff mol ratio is I: II=49.2: 51.8.
Embodiment 5
The dyestuff finished product that the former dyestuff of embodiment 1～4 is obtained through aforesaid method dyes to terylene according to 2.0% dye level, carry out according to following processing step: respectively get the even aqueous dispersions that above-mentioned finished product dyestuff is made into 5g/L, transfer pipet pipettes in 20mL to the 80mL water, it is 5 that damping fluid is regulated the pH value, be warming up to 70 ℃ and put into the pure woven dacron of 5g, speed with 2 ℃/min is warming up to 130 ℃, insulation 50min; Cold water is cooled to 80 ℃ with the fabric taking-up, through caustic soda, vat powder reduction clearing (80 ℃ * 20min), dry are finalized the design (180 ℃ * 30s), obtain the cloth specimen that dyes.
Through the test of computer color measurement instrument, to compare with DISPERSE BLUE 2BLN, the dyestuff that the present invention relates to has enhancing preferably, and two kinds of components are collaborative, have good synergism.Coloured light can match in excellence or beauty with 2BLN, Exposure to Sunlight simultaneously.Every application performances such as washing, distillation are also preferable, and test result sees in the table 1.
The performance of table 1. dyestuff
Annotate: 1. coloured light is standard with blue 2BLN, obtains through the computer color measurement instrument; 2. " zero " expression is suitable fully, and " ◎ " expression is general.
In addition, dyestuff and the assembly of other dyestuffs that the present invention relates to mixed, can have the excellent compatibility energy.The dyestuff finished product that obtains according to embodiment 1～4 dye cloth specimen increasing along with the shared molecular fraction of A in the coupling component, its coloured light shifts to the green glow direction, thereby the dyestuff that the present invention relates to is become adapt to printing and dyeing industry production requirement, a series of dispersed dye that coloured light is adjustable.
Claims (7)
1. a two-pack dispersed blue dye is characterized in that, it is by forming suc as formula the compound shown in (I) with suc as formula the compound shown in (II):
Described suc as formula the compound shown in (I) be 1: 99～50: 50 suc as formula the mol ratio of the compound shown in (II).
2. the preparation method of a two-pack dispersed blue dye as claimed in claim 1, it is characterized in that, may further comprise the steps: in water, under the strong acidic condition of pH value 1～2, with as the formula (1) diazonium salt with carry out coupled reaction suc as formula the compound shown in (A) with suc as formula the mixture of the compound shown in (B), adding alkali adjusting pH value after reaction is finished is 3～5, filter washing, obtain with suc as formula the compound shown in (A) and corresponding suc as formula compound shown in (I) and the two-pack dispersed blue dye that forms suc as formula the compound shown in (II) suc as formula the compound shown in (B)
Described is being 1.0%～50% suc as formula the compound shown in (A) suc as formula the compound shown in (A) with suc as formula shared molecular fraction in the mixture of the compound shown in (B) overall.
3. preparation method as claimed in claim 2 is characterized in that, described diazonium salt be 1: 1～1.08 suc as formula the compound shown in (A) with suc as formula the mol ratio of the mixture of the compound shown in (B).
4. preparation method as claimed in claim 2 is characterized in that, in the described coupled reaction, also adds thionamic acid.
5. preparation method as claimed in claim 2 is characterized in that, in the described coupled reaction, also adds emulsifying agent.
6. preparation method as claimed in claim 2 is characterized in that, the temperature of reaction of described coupled reaction is 0～10 ℃, and the reaction times is 2～5 hours.
7. a two-pack disperse dye composition is characterized in that, it contains two-pack dispersed blue dye as claimed in claim 1 and conventional colour additive.
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| CN 200910048417 CN101845234B (en) | 2009-03-27 | 2009-03-27 | Monoazo disperse blue dye and bi-component disperse blue dye as well as preparation method thereof |
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| CN 200910048417 CN101845234B (en) | 2009-03-27 | 2009-03-27 | Monoazo disperse blue dye and bi-component disperse blue dye as well as preparation method thereof |
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| CN101845234A CN101845234A (en) | 2010-09-29 |
| CN101845234B true CN101845234B (en) | 2013-07-31 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102226040B (en) * | 2011-04-29 | 2013-08-14 | 浙江闰土股份有限公司 | Disperse grey dye composition |
| CN103030601A (en) * | 2011-06-30 | 2013-04-10 | 上海安诺其纺织化工股份有限公司 | Preparation method of azoic compound |
| CN102504596A (en) * | 2011-11-15 | 2012-06-20 | 东营安诺其纺织材料有限公司 | Bi-component monoazo disperse blue dye composition |
| CN106928751A (en) * | 2015-12-29 | 2017-07-07 | 临沂市东裕新材料科技有限公司 | A kind of bi-component disperse dyes and processing technology |
| CN110698880B (en) * | 2019-10-29 | 2021-02-05 | 杭州维昂化工有限公司 | Disperse blue dye composition, disperse blue dye, preparation method of disperse blue dye and fabric |
| CN111304934A (en) * | 2020-04-03 | 2020-06-19 | 晋江市祺烽线带有限公司 | Dyeing method of polyester yarn |
| CN111995879B (en) * | 2020-08-27 | 2021-10-08 | 青岛大学 | Method for enhancing alkali resistance and oxidation resistance of benzisothiazole disperse dye |
| CN114773877B (en) * | 2022-05-20 | 2023-12-22 | 上海鸿源鑫创材料科技有限公司 | Disperse blue dye composition and product thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4464181A (en) * | 1982-02-12 | 1984-08-07 | Basf Aktiengesellschaft | Mixtures of benzisothiazole mono-azo dyes for cellulose acetate |
| CN1563204A (en) * | 2004-04-06 | 2005-01-12 | 蓬莱华茂精细化工有限公司 | Azo type disperse dyes in use for coloration in acid-alkalinity bath |
-
2009
- 2009-03-27 CN CN 200910048417 patent/CN101845234B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4464181A (en) * | 1982-02-12 | 1984-08-07 | Basf Aktiengesellschaft | Mixtures of benzisothiazole mono-azo dyes for cellulose acetate |
| CN1563204A (en) * | 2004-04-06 | 2005-01-12 | 蓬莱华茂精细化工有限公司 | Azo type disperse dyes in use for coloration in acid-alkalinity bath |
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