CN101089050A - Acid anthraquinone dye and its prepn and application - Google Patents
Acid anthraquinone dye and its prepn and application Download PDFInfo
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Abstract
The present invention belongs to the field of dye technology, and is especially one kind of acid anthraquinone dye and its preparation process and application. The acid anthraquinone dye in the structure as shown is prepared through extracting 2-ethyl-6-sec-butylamine or 2-methyl-6-sec-butylamine from waste industrial oil, condensation reaction with 1, 4-dihydroxy anthraquinone, and sulfonating in a solvent process. The acid anthraquinone dye is applied in dyeing wool and wool fabric to obtain glow blue or bright purple, and has fastness performance similar to available acid anthraquinone dye.
Description
Technical field
The invention belongs to technical field of dye, relate to a class acid anthraquinone dye and preparation thereof and application particularly.
Background technology
Acid anthraquinone dye is one of structure type main in the matching stain, is mainly used in the dyeing and the stamp of wool and wool fabric.For example, all with 1, the 4-dihydroxyanthraquinone is a starting raw material at acid anthraquinone dyes such as the acid violet 43 of Chinese mass production and application, acid blues 80, through with condensation of arylamine list or double condensation reaction after, sulfonation reaction makes again.Because raw material arylamine price is higher, causes costing an arm and a leg of such dyestuff, its application quantity has been subjected to certain limitation.With acid blue 80 is example, and the consuming cost of raw material 2,4,6-trimethylaniline accounts for the 40%-50% of the total raw materials cost of dyestuff.Therefore,, prepare the matching stain that a kind of color and every application performance index can satisfy application requiring, then can reduce cost of dye, enhance one's market competitiveness if can replace 2,4,6-trimethylaniline with a kind of arylamine of cheapness.
Summary of the invention
The objective of the invention is to develop similarly approaching, the acid anthraquinone dye that satisfies wool or wool fabric dyeing requirement of commercialization matching stain of a kind of novel structure, with low cost, color and every application performance index and existing structure.
Have now found that, with 1, the 4-dihydroxyanthraquinone is a raw material, with 2-ethyl-6-sec-butyl aniline or 2-methyl-6-sec-butyl aniline through with condensation of arylamine list or double condensation reaction after, carry out sulfonation reaction again, can obtain similarly approaching, the acid anthraquinone dye that satisfies wool or wool fabric dyeing requirement of commercialization matching stain of color and every application performance index and existing structure.
In order to realize purpose of the present invention, it is a kind of from producing 2 that the present invention provides simultaneously, reclaim the method for 2-ethyl-6-sec-butyl aniline or 2-methyl-6-sec-butyl aniline in the industrial waste oil that 6-Diethyl Aniline (vehicle economy A) and/or 2-methyl-6-ethylaniline (being called for short MEA) are produced, solve the cheap raw material source, thereby satisfied the requirement that reduces cost of dye.
Technical scheme of the present invention is as follows:
The invention provides a kind of acid anthraquinone dye, the compound shown in general formula (I):
In the formula:
R
1Be selected from hydroxyl or
R
2Be selected from methyl or ethyl.
The present invention provides the method preparation of the acid anthraquinone dye shown in a kind of general formula (I) simultaneously:
(1) from the industrial by-product waste oil of DEA or MEA, adopt rectification under vacuum technology to extract 2-ethyl-6-sec-butyl aniline or 2-methyl-6-sec-butyl aniline;
(2) in the presence of catalyzer, 2-ethyl-6-sec-butyl aniline or 2-methyl-6-sec-butyl aniline and 1,4-dihydroxyanthraquinone and leuco compound generation condensation reaction thereof after atmospheric oxidation, make the middle dyestuff shown in general formula (II);
(3) the middle dyestuff shown in the general formula (II) is carried out sulfonation reaction, sulfonic group is introduced in the imino-contraposition on the aniline ring, makes the acid anthraquinone dye shown in the general formula (I).
Reaction formula is as follows:
In the formula:
R
1Be selected from hydroxyl or
R
2Be selected from methyl or ethyl.
General formula shown in the present (I) compound comprises four dyestuffs altogether:
Dyestuff a (R
1=2-ethyl-6-sec-butyl-4-sulfonic benzo amido, R
2=ethyl), dyestuff b (R
1=2-methyl-6-sec-butyl-4-sulfonic benzo amido, R
2=methyl), dyestuff c (R
1=OH, R
2=ethyl) and dyestuff d (R
1=OH, R
2=methyl).
Sulfonation reaction involved in the present invention can realize in the vitriol oil.An amount of oleum that adds, can make reaction at a lower temperature (60-70 ℃) finish.After reaction is finished, sulfonation reaction liquid poured into dyestuff is separated out, filter and obtain product.But adopt this synthetic method will produce the acid waste water relatively large, that color is darker, the about 8-10% of sulfur acid.Therefore the present invention preferably adopts solvent sulfonated method, promptly in non-aqueous inert solvent, adds middle dyestuff shown in the general formula (II) and an amount of sulfuric acid and carries out sulfonation reaction.Preparation dyestuff a or dyestuff b, the mol ratio of sulfuric acid and middle dyestuff is 2.0-4.0, preferred 2.2-2.8; Preparation dyestuff c or dyestuff d, the mol ratio of sulfuric acid and middle dyestuff is 1.0-2.0, preferred 1.1-1.5.Under reflux state,, reaction is accomplished by constantly dehydration.Sulfonated product is insoluble to solvent, and promptly separable by simple filtration, solvent recuperation is used again; Filter cake and water making beating, the backflow desolventizing, the solvent that removes can be applied mechanically.Compare with common sulfuric acid process sulfonation, solvent method process for sulfonation wastewater flow rate is very little, and the concentration of acid is very low in the waste water, and by adding in the small amounts calcium and adsorption treatment, waste water substantially can qualified discharge.By contrast, the solvent method sulfonation is more conducive to environment protection.Two kinds of dyestuff uniform qualities that method of sulfonating obtains, yield is basic identical.
General formula shown in the present (I) compound has dyeing behavior and fastness ability preferably, belongs to high-grade weak acid dye.Wherein: dyestuff a and dyestuff b are bright blue; Dyestuff c and dyestuff d are the ruddiness purple.The light fastness 4-5 level of dyestuff, moisture resistant fastness 4-5 level, dye uptake is more than 85%, and has level-dyeing property preferably.Above-mentioned dyestuff all is applicable to the dyeing of wool and wool fabric.
General formula provided by the invention (I) compound not only has the practical value of high-grade weak acid dye as matching stain, and because its raw material arylamine derives from the waste oil recovery, both reduced cost of dye, is beneficial to the environmental protection and the utilization of resources again.The commercial dye close with existing coloured light compared, and the raw materials cost of dyestuff provided by the invention reduces about 20-35%, so product has more the market competitiveness.
Embodiment
Below the present invention will be further described by specific embodiment, but the present invention is not limited thereto.
Example 1: separate purification 2-ethyl-6-sec-butyl aniline
Rectifying: in the 1000ml there-necked flask, add 600g production industrial waste oil that DEA produced, and add zeolite, feed nitrogen by bottom insert canal.The rectifying condition: rectifying tower diameter 30mm, stainless steel triangle filler, packed height 1100mm, vacuum tightness is 10mmHg, reflux ratio 5: 1.When liquidus temperature reaches 137 ℃, produce and reflux, collect 141～144 ℃ fraction, obtain the main distillate fraction of 300g, be 2-ethyl-6-sec-butyl aniline, content 95%.Analytical data is as follows:
1H NMR (DCCl
3, 300MHz) δ 0.89-0.94 (m, 3H, CH
3), 1.22-1.29 (m, 6H, CH
3), 1.54-1.71 (m, 2H, CH
2), 2.49-2.57 (m, 2H, CH
2), 2.65-2.68 (m, 1H, CH); 6.73-6.7 (m, 1H, Ar), 6.94-7.01 (m, 2H, Ar), 3.64 (s, 2H, NH
2); M/z:177.
Example 2: separate purification 2-methyl-6-sec-butyl aniline
Rectifying: in the 1000ml there-necked flask, add 600g production industrial waste oil that MEA produced, and add zeolite, feed nitrogen by bottom insert canal.The rectifying condition: rectifying tower diameter 30mm, stainless steel triangle filler, packed height 1100mm, vacuum tightness is 10mmHg, reflux ratio 5: 1.When liquidus temperature reaches 127 ℃, produce and reflux, collect 130～133 ℃ fraction, obtain the main distillate fraction of 268g, be 2-methyl-6-sec-butyl aniline, content 93.5%.Analytical data is as follows:
1H NMR (DCCl
3, 300MHz) δ 0.88-0.92 (m, 3H, CH
3), 1.21-1.26 (m, 3H, CH
3), 1.54-1.71 (m, 2H, CH
2), 2.39-2.47 (m, 3H, CH
3), 2.65-2.68 (m, 1H, CH); 6.73-6.77 (m, 1H, Ar), 6.92-6.98 (m, 2H, Ar), 3.64 (s, 2H, NH
2); M/z:163.
Example 3: dyestuff a's is synthetic:
In the 100ml four-hole bottle, add 8.7g (0.0362mol) 1 successively, 4-dihydroxyanthraquinone, 3.7g (0.0152mol) 1,4-dihydroxyanthraquinone leuco compound, 1.5g boric acid, 40g 2-ethyl-6-sec-butyl aniline, stirring is warmed up to 150 ℃, removes the water that generation was brought and reacted to raw material into simultaneously.Adopt the method control reaction of thin-layer chromatography: when yellow and orange raw material spot disappears substantially, think that promptly reaction reaches terminal point, stopped reaction is cooled to 90 ℃, add potassium hydroxide 6g, and the bubbling air oxidation, treat that purple all disappears, be the oxidation terminal point, reaction solution is slowly analysed to the 120ml hot ethanol, through cooling, filtration, washing, obtain blue middle dyestuff 1,4-two (2-ethyl-6-sec-butylbenzene amido) anthraquinone 20.0g then.Analytical data is as follows:
1H NMR (DCCl
3, 300MHz) δ 0.77-0.83 (m, 3H, CH
3), 1.01-1.17 (m, 6H, CH
3), 1.48-1.1.54 (m, 2H, CH
2), 2.44-2.59 (m, 2H, CH
2), 2.82-2.87 (m, 1H, CH), 6.51-6.54 (s, 1H, anthraquinone), 7.13-7.17 (m, 2H, Ar), 7.24-7.30 (m, 1H, Ar), 7.75-7.79 (m, 1H, anthraquinone), 8.43-8.47 (m, 1H, anthraquinone), 11.90 (s, 1H, NH); M/z=558.
In the 250ml four-hole bottle, add the 20ml chlorobenzene, and add go up the step synthetic in the middle of dyestuff 20.0g (0.0358mol) slowly be warming up to backflow then, and drip 10.0g (0.100mol) 98% sulfuric acid with this understanding, and separate the moisture that generates simultaneously, dropwise, kept 1 hour under this temperature, reaction mass is reduced to room temperature, filters, solvent recuperation, filter cake adds in the 200ml water, and heat temperature raising refluxes, and isolates remaining solvent, material solution adds 10g sodium-chlor, and product can be separated out.Filter drying.
Obtain dyestuff a 22.8g, yield 61.6% (with 1,4-dihydroxyanthraquinone and leuco compound thereof are benchmark).
The mass spectrum m/z=716 of dyestuff a meets 1,4-two (2-ethyl-6-sec-butyl-4-sulfonic benzo amido) anthraquinone relative molecular weight.
The ultraviolet-visible absorption curve of dyestuff in water is near equivalent biabsorption peak: λ
Max1=628.0nm;
λ
max2＝582.0nm。
Example 4: dyestuff b's is synthetic:
Synthetic method is with example 3, but substitutes 2-ethyl-6-sec-butyl aniline with equivalent 2-methyl-6-sec-butyl aniline.Obtain blue middle dyestuff 1,4-two (2-methyl-6-sec-butylbenzene amido) anthraquinone 19.4g; The sulfuric acid add-on changes 9.5g (0.095mol) into.
Obtain dyestuff b 20.8g.Yield 58.50% (with 1,4-dihydroxyanthraquinone and leuco compound thereof are benchmark).
The analytical data of dyestuff in the middle of blue:
1H NMR (DCCl
3, 300MHz) δ 0.76-0.81 (m, 3H, CH
3), 1.01-1.14 (m, 3H, CH
3), 1.46-1.52 (m, 2H, CH
2), 2.41-2.49 (m, 3H, CH
3), 2.82-2.87 (m, 1H, CH), 6.51-6.54 (s, 1H, anthraquinone), 7.13-7.16 (m, 2H, Ar), 7.23-7.30 (m, 1H, Ar), 7.75-7.79 (m, 1H, anthraquinone), 8.42-8.45 (m, 1H, anthraquinone), 11.90 (s, 1H, NH); M/z=530.
The mass spectrum m/z=610 of dyestuff b meets 1,4-two (2-methyl-6-sec-butyl-4-sulfonic benzo amido) anthraquinone relative molecular weight.
The ultraviolet-visible absorption curve of dyestuff in water is near equivalent biabsorption peak: λ
Max1(nm)=628.0;
λ
max2(nm)585.0。
Example 5: dyestuff c's is synthetic:
In the 100ml four-hole bottle, add 7.0g (0.0292mol) 1 successively, 4-dihydroxyanthraquinone, 3.0g (0.0123mol) 1,4-dihydroxyanthraquinone leuco compound, 1.0g boric acid, 8.9g 2-ethyl 6-sec-butyl aniline, 30ml ethylene glycol monomethyl ether.Stirring is warming up to 90 ℃ of reactions.Adopt the method control reaction of thin-layer chromatography: when yellow and orange raw material spot disappears substantially, think that promptly reaction reaches terminal point.Stopped reaction, add potassium hydroxide 5g, and bubbling air oxidation, treat that purple all disappears, be the oxidation terminal point, reaction solution is slowly analysed to the 100ml hot ethanol, then through cooling, filtration, washing, drying obtains the middle dyestuff 1-(2-ethyl-6-sec-butylbenzene amido) of purple-4-hydroxyanthraquinone 11.8g.Analytical data:
1HNMR (DCCl
3, 300MHz): δ 0.67-0.84 (m, 3H, CH
3), 1.10-1.19 (m, 6H, CH
3), 1.51-1.1.58 (m, 2H, CH
2), 2.50-2.58 (m, 2H, CH
2), 2.83-2.87 (m, 1H, CH), 6.71-6.75 (s, 1H, Ar), 7.07-7.13 (m, 1H, anthraquinone) 7.19-7.25 (m, 2H, Ar), 7.30-7.35 (m, 1H, anthraquinone), 7.76-7.80 (m, 2H, anthraquinone), 8.33-8.41 (m, 2H, anthraquinone), 11.90 (s, 1H, NH), 13.71 (s, 1H, OH); M/z=399.
In the 100ml four-hole bottle, add the 50ml chlorobenzene, the middle dyestuff 11.8g (0.0296mol) that the step makes in the adding, slowly be warming up to backflow then, and drip 4.25g (0.0425mol) 98% sulfuric acid with this understanding, drip and separate the moisture that generates simultaneously, dropwise, kept 1 hour under this temperature, reaction mass is reduced to room temperature, filter, solvent recuperation, filter cake adds in the 200ml water, heat temperature raising refluxes, isolate remaining solvent, surplus solution adds 11g sodium-chlor, and product can be separated out.Filter, obtain dyestuff c 12.2g, yield 59.8% (with 1,4-dihydroxyanthraquinone and leuco compound thereof are benchmark).
The mass spectral m/z=479 of dyestuff c meets 1-hydroxyl-4-(2-ethyl-6-sec-butyl-4-sulfonic benzo amido) anthraquinone relative molecular weight.
The ultraviolet-visible absorption curve of dyestuff in water is near equivalent biabsorption peak: λ
Max1(nm)=584.0;
λ
max2(nm)548.0。
Example 6: dyestuff d's is synthetic:
Synthetic method is with example 5, but substitutes 2-ethyl-6-sec-butyl aniline with equivalent 2-methyl-6-sec-butyl aniline.Obtain the middle dyestuff 11.5g of purple; The sulfonation sulfuric acid amount changes 4.0g (0.04mol) into, obtains dyestuff d 12.0g.Yield 60.6% (with 1,4-dihydroxyanthraquinone and leuco compound thereof are benchmark).
Dyestuff analytical data in the middle of the purple:
1HNMR (DCCl
3, 300MHz): δ 0.67-0.79 (m, 3H, CH
3), 1.07-1.14 (m, 3H, CH
3), 1.51-1.1.57 (m, 2H, CH
2), 2.48-2.55 (m, 3H, CH
3), 2.83-2.87 (m, 1H, CH), 6.71-6.75 (s, 1H, Ar), 7.04-7.11 (m, 1H, anthraquinone) 7.19-7.23 (m, 2H, Ar), 7.30-7.35 (m, 1H, anthraquinone), 7.76-7.80 (m, 2H, anthraquinone), 8.33-8.41 (m, 2H, anthraquinone), 11.90 (s, 1H, NH), 13.71 (s, 1H, OH); M/z=385.
The m/z=465 of dyestuff d meets 1-hydroxyl-4 (2-methyl-6-sec-butyl-4-sulfonic benzo amido) anthraquinone relative molecular weight.
The ultraviolet-visible absorption curve of dyestuff in water is near equivalent biabsorption peak: λ
Max1(nm)=584.0;
λ
max2(nm)548.0。
Comparative example 1: the sulfuric acid process of dyestuff a
In the 100ml there-necked flask, add the 30g vitriol oil, slowly add 10g 1 under the water bath condition, 4-two (2-ethyl-6-sec-butylbenzene amido) anthraquinone, the oleum 35g of dropping 103% under 70 ℃ of conditions, dropwise, kept 2 hours under this temperature, reaction finishes.Stir down reaction solution is injected in about 800g frozen water separate out, filter, saturated common salt water washing on a small quantity, oven dry.Obtain dyestuff a 12g.Obtain the acid waste water of having of about 900ml of denseer hepatic sulfur acid 6%-8% simultaneously.
Comparative example 2: the sulfuric acid process of dyestuff c
In the 100ml there-necked flask, add the 30g vitriol oil, slowly add 10g1-hydroxyl-4-(2-ethyl-6-sec-butylbenzene amido) anthraquinone under the water bath condition, the oleum 17.5g of dropping 103% under 70 ℃ of conditions, dropwising the back kept 2 hours under this temperature, reaction finishes, material is diluted in about 800g frozen water, and the dispersed with stirring after-filtration obtains 1-hydroxyl-4-aryl amine anthraquinone sulfonic acid compound.Obtain dyestuff c 10.9g.Obtain having of about 900ml of denseer purpureal acid waste water simultaneously, sulfuric acid concentration 6%-8%.
Example 7: effect test
Dyeing is as follows:
Dyestuff 1% to be measured (fiber is heavy relatively)
Crystallization Sodium sulfate anhydrous.min(99) 10% (fiber is heavy relatively)
Acetate (50%) 3% (fiber is heavy relatively)
Bath raio 50: 1
Wool fabric after the cleaning goes into to dye in 40 ℃, and (temperature rise rate is 1 ℃/1～1.5min), and dyeing is 45 minutes under this temperature, washing oven dry then to be warming up to 90 ℃ in 30 minutes.
With the wool painting cloth of making, carry out the color characteristics contrast and the test of dyestuff, the result is as follows:
The synthetic dyestuff a of institute, dyestuff b are bright red light blueness, compare with existing similar structures commercial dye (C.I. acid blue 80), coloured light is red partially, vividness is good slightly, light fastness reaches the 4-5 level, moisture resistant fastness 4-5 level, dye uptake be more than 85%, and have level-dyeing property preferably, the application performance basically identical.
The synthetic dyestuff c of institute, dyestuff d are gorgeous purple, compare with existing similar structures commercial dye (C.I. acid violet 43), and coloured light is red partially, 4 grades of light fastnesses, moisture resistant fastness 4-5 level.
Claims (3)
1, a kind of acid anthraquinone dye, the compound shown in general formula (I):
In the formula:
R
1Be selected from hydroxyl or
R
2Be selected from methyl or ethyl.
2, a kind of preparation method of acid anthraquinone dye as claimed in claim 1 is characterized in that, reaction formula is as follows:
In the formula:
R
1Be selected from hydroxyl or
R
2Be selected from methyl or ethyl;
Reaction may further comprise the steps:
(1), adopt rectification under vacuum technology to extract 2-ethyl-6-sec-butyl aniline or 2-methyl-6-sec-butyl aniline in 6-Diethyl Aniline or the industrial waste oil that the 2-methyl-the 6-ethylaniline is produced from producing 2;
(2) in the presence of catalyzer, 2-ethyl-6-sec-butyl aniline or 2-methyl-6-sec-butyl aniline and 1,4-dihydroxyanthraquinone and leuco compound generation condensation reaction thereof make the middle dyestuff shown in general formula (II);
(3) the middle dyestuff shown in the general formula (II) is carried out sulfonation reaction, sulfonic group is introduced in the imino-contraposition on the aniline ring, makes the acid anthraquinone dye shown in the general formula (I).
3, acid anthraquinone dye as claimed in claim 1 is used for the purposes of wool and wool fabric dyeing thereof.
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|---|---|---|---|
| CNB2006100468943A CN100537670C (en) | 2006-06-14 | 2006-06-14 | Acid anthraquinone dye and its preparation and application |
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|---|---|---|---|
| CNB2006100468943A CN100537670C (en) | 2006-06-14 | 2006-06-14 | Acid anthraquinone dye and its preparation and application |
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| Publication Number | Publication Date |
|---|---|
| CN101089050A true CN101089050A (en) | 2007-12-19 |
| CN100537670C CN100537670C (en) | 2009-09-09 |
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ID=38942557
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277494A (en) * | 2014-09-27 | 2015-01-14 | 无锡市东北塘宏良染色厂 | Acid dye |
| CN111138884A (en) * | 2019-12-28 | 2020-05-12 | 江苏亚邦染料股份有限公司 | Method for synthesizing vat brown BR |
-
2006
- 2006-06-14 CN CNB2006100468943A patent/CN100537670C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277494A (en) * | 2014-09-27 | 2015-01-14 | 无锡市东北塘宏良染色厂 | Acid dye |
| CN111138884A (en) * | 2019-12-28 | 2020-05-12 | 江苏亚邦染料股份有限公司 | Method for synthesizing vat brown BR |
| CN111138884B (en) * | 2019-12-28 | 2021-11-02 | 江苏亚邦染料股份有限公司 | Method for synthesizing vat brown BR |
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Effective date of registration: 20100505 Address after: 110021 No. 8 Shen Liaodong Road, Tiexi District, Shenyang Co-patentee after: Anshan Hifichem Co., Ltd. Patentee after: Shenyang Research Institute of Chemical Industry Address before: 110021 Liaodong, Liaoning, Tiexi Shen road, No. 8, No. Co-patentee before: Anshan Huifeng Chemical Co., Ltd. Patentee before: Shenyang Institute of Chemical Engineering Effective date of registration: 20100505 Address after: 110021 No. 8 Shen Liaodong Road, Tiexi District, Shenyang Co-patentee after: Anshan Hifichem Co., Ltd. Patentee after: Shenyang Research Institute of Chemical Industry Address before: 110021 Liaodong, Liaoning, Tiexi Shen road, No. 8, No. Co-patentee before: Anshan Huifeng Chemical Co., Ltd. Patentee before: Shenyang Institute of Chemical Engineering |
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Granted publication date: 20090909 Termination date: 20190614 |
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| CF01 | Termination of patent right due to non-payment of annual fee |