CN100577740C - A kind of anthraquinone type solvent dye and preparation thereof and application - Google Patents
A kind of anthraquinone type solvent dye and preparation thereof and application Download PDFInfo
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- CN100577740C CN100577740C CN200610046424A CN200610046424A CN100577740C CN 100577740 C CN100577740 C CN 100577740C CN 200610046424 A CN200610046424 A CN 200610046424A CN 200610046424 A CN200610046424 A CN 200610046424A CN 100577740 C CN100577740 C CN 100577740C
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- methyl
- ethyl
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Abstract
The invention belongs to technical field of dye.A kind of anthraquinone type solvent dye and preparation thereof and application are specifically disclosed.Compound of the present invention is shown in general formula (I): in the formula: R
1Be selected from hydroxyl or (seeing right formula); R
2Be selected from methyl or ethyl.The present invention adopts rectification under vacuum technology to extract 2-ethyl-6-sec-butyl aniline or 2-methyl-6-sec-butyl aniline from industrial waste oil; with 1,4-dihydroxyanthraquinone generation condensation reaction prepares general formula (I) compound again; thereby reduced the production cost of dyestuff, be beneficial to environment protection simultaneously more.Anthraquinone type solvent dye of the present invention is applied in oil product, hard plastic cement and the coloring resin, obtains the blue and gorgeous purple of bright-coloured ruddiness respectively, and every fastness ability can reach or the approaching dyes of anthraquinone of commercial similar now.
Description
Technical field
The invention belongs to technical field of dye, relate to a kind of anthraquinone type solvent dye and preparation thereof and application particularly.
Background technology
Germany Bayer company researches and develops success and commercial high-grade solvent dye C.I. solvent blue 19 04[116-75-6 in one's early years] and C.I. solvent blue 97[61969-44-6] a bright-coloured transparent blue had, good heat-resistant stability and light fastness are applicable to that thermoplastics (duroplasts) is painted.Such dyestuff is by 2,2,4,6-triethyl aniline (or 2, the 6-diethyl-p-tlouidine) respectively with 1, the 4-dihydroxyanthraquinone carries out two condensation reactions and obtains.But because its raw material 2,2,4,6-triethyl aniline (or 2,6-diethyl-p-tlouidine) price is higher, causes costing an arm and a leg of such dyestuff, and its application quantity has been subjected to certain limitation.
On the other hand, we find to contain in some industrial waste oil that acts as a fuel many substituted alkyl arylamine and are not fully utilized.For example, in preparation 2, in the production process of 6-Diethyl Aniline (vehicle economy A) and 2-methyl-6-ethylaniline (being called for short MEA), residue accounts for the dark oil by product (abbreviation industrial waste oil) of the about 13-17% of product population during the finished product distillation.Contain a large amount of organic arylamine in these waste oil, the analysis showed that wherein 2-ethyl-6-sec-butyl aniline or 2-methyl-6-sec-butyl aniline account for 60-65%.These industrial waste oils are burnt in fuel oil mainly as fuel blending all the time.DEA and MEA all are important two intermediates that become more meticulous, and are widely used in to make agricultural chemicals, medicine and spices etc., and output is very big.The industrial waste oil of by-product only acts as a fuel and burns not only etching apparatus, harm environment thereupon, and the waste resource.
Summary of the invention
The objective of the invention is to recycle 2-ethyl-6-sec-butyl aniline or the 2-methyl-6-sec-butyl aniline that exists in the industrial waste oil, the anthraquinone type solvent dye of developing a kind of novel structure, and not only cost is low to make such dyestuff, and color and every application performance and existing structure similarly the commercialization solvent dye is approaching.
In order to realize purpose of the present invention, the present invention simultaneously a kind of method that reclaims 2-ethyl-6-sec-butyl aniline or 2-methyl-6-sec-butyl aniline from industrial waste oil is provided, to satisfy with the lower requirement of this raw material synthetic anthraquinone type solvent dye cost.
Technical scheme of the present invention is as follows:
The invention provides a kind of anthraquinone type solvent dye, the compound shown in general formula (I):
In the formula:
R
1Be selected from hydroxyl or
R
2Be selected from methyl or ethyl.
Work as R
1When being selected from hydroxyl, resulting compound is the red-purple dyestuff with bright-colored and higher coloring intensity, has good solubility in polarity or non-polar organic solvent, and light fastness 6-7 level has good heat-resistant stability and resistance to migration.
Work as R
1When being selected from 2-ethyl-6-sec-butylbenzene amido or 2-methyl-6-sec-butylbenzene amido, resulting compound is the blue dyes with bright-colored and higher coloring intensity, in polarity or non-polar organic solvent, has good solubility, light fastness reaches 7 grades, has good heat-resistant stability and resistance to migration.
Above-mentioned anthraquinone type solvent dye is applied to oil product, hard plastic cement and coloring resin, and every fastness ability can reach or the approaching dyes of anthraquinone of commercial similar now.
The present invention provides the preparation method of the compound shown in the general formula (I) simultaneously, may further comprise the steps:
(1) from producing 2, adopt rectification under vacuum technology to extract 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) or 2-methyl-6-ethylaniline (being called for short MEA) are produced.
(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, prepare general formula (I) compound.
The key of above-mentioned synthetic method is that low cost obtains 2-ethyl-6-sec-butyl aniline or 2-methyl-6-sec-butyl aniline, thereby reduces the production cost of the anthraquinone type solvent dye shown in general formula (I) compound.
The industrial waste oil recoverying and utilizing method that the present invention relates to is as follows:
To produce 2, the by-product waste oil in 6-Diethyl Aniline or 2-methyl-6-ethylaniline process extracts 2-ethyl-6-sec-butyl aniline or 2-methyl-6-sec-butyl aniline through rectification under vacuum.For example, adopt distilling filled tower, the stainless steel triangle filler of theoretical plate number more than 20.Operational condition is: vacuum tightness is 10mmHg, reflux ratio 5～7: 1.
Collect 141～144 ℃ fraction during rectifying DEA waste oil, through gas chromatographic analysis, purity can reach more than 95%.By
1HNMR and MS instrumental analysis confirm that structure is 2-ethyl-6-sec-butyl aniline.
1H NMR data are as follows:
1HNMR (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).
Mass spectral molecular ion peak is m/z:177, and is consistent with the molecular weight of 2-ethyl-6-sec-butyl aniline.
Collect 130～132 ℃ fraction during rectifying MEA waste oil, through gas chromatographic analysis, purity is more than 93%.By
1HNMR and MS instrumental analysis confirm that structure is 2-methyl-6-sec-butyl aniline.
1H NMR data are 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).
Mass spectral molecular ion peak is m/z:163, and is consistent with the molecular weight of 2-methyl-6-sec-butyl aniline.
Condensation reaction prepares the currently known methods that general formula (I) compound can be used for reference the similar structures compound.Also can prepare in accordance with the following methods.
Synthesizing of blue dyes: the reaction formula of two replacement synthesizing blue dyestuffs is as follows:
Compound I (R
2=C
2H
5); Compound I I (R
2=CH
3).
In the presence of catalyzer, with 2-ethyl (or methyl)-6-sec-butyl aniline and 1 that rectifying obtains, 4-dihydroxyanthraquinone and leuco compound condensation thereof, usually with boric acid as catalyzer.Usually can be with excessive substituted aniline as reaction solvent, substituted aniline and 1 for example, the mol ratio of 4-dihydroxyanthraquinone (comprising leuco compound) is 5～6: 1, guarantees that reaction carries out smoothly.Temperature of reaction is 140～200 ℃, and suitable temperature is 150-170 ℃.Owing to use part 1,4-dihydroxyanthraquinone leuco compound is participated in reaction, after condensation reaction is finished, adds sodium hydroxide or potassium hydroxide, and 75～95 ℃ of bubbling air oxidations.Adopt conventional separation method can obtain Compound I or Compound I I, be the blue solvent dye of bright red light.
Synthesizing of purple dye: the synthetic purple dye reaction formula of single replacement is as follows:
Compound III (R
2=C
2H
5); Compound IV (R
2=CH
3).
In polar organic solvent, with boric acid catalyst, 2-ethyl-6-sec-butyl aniline or 2-methyl-6-sec-butyl aniline and 1,4-dihydroxyanthraquinone and the condensation of leuco compound list thereof that rectifying is obtained.Wherein: 2-ethyl-6-sec-butyl aniline or 2-methyl-6-sec-butyl aniline and 1, the mol ratio of 4-dihydroxyanthraquinone (comprising leuco compound) is 1-2: 1, better suited ratio is 1.2: 1; Temperature of reaction is 70-100 ℃, and better suited temperature is 80～90 ℃.After reaction is finished, obtain compound III or compound IV, be gorgeous purple solvent dye.
Waste oil separation purification provided by the present invention and dyestuff synthesis technique are simple, easy to operate, are easy to the industrialization operation.
Because the raw material arylamine derives from waste oil, cost is low, and can make blueness and purple solvent dye that color, fastness ability can both reach the requirement of application, therefore, general formula provided by the invention (I) compound not only has practical value as solvent dye, and will have the stronger market competitiveness.
In addition, the technology of Separation and Recovery substituted aromatic amines from waste oil has not only turned waste into wealth, has promoted the practical value of waste oil, has favorable economic benefit; And reduced and burned the atmospheric pollution that brought, be beneficial to environment protection more, therefore have better social benefit.
Embodiment
Below the present invention is further elaborated and explanation by concrete operational instances, but the present invention is not limited to these operational instances.
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%.
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%.
Example 3: Compound I synthetic
In the 100ml four-hole bottle, add 7.0g 1 successively, the 4-dihydroxyanthraquinone, 3.0g 1,4-dihydroxyanthraquinone leuco compound, 1.2g boric acid, 32g 2-ethyl 6-sec-butyl aniline stirs and 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 5g, and the bubbling air oxidation, treat that purple all disappears, be the oxidation terminal point, reaction solution is slowly analysed to the 100ml hot ethanol, through cooling, filtration, washing, obtain the 16.1g Compound I, yield 69.4% then.
Nuclear magnetic resonance data:
1H?NMR(DCCl
3，300MHz)δ0.77-0.83(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)。
Nuclear magnetic data meets 1, the chemical structure of 4-two (2-ethyl-6-sec-butylbenzene amido) anthraquinone.
Ultraviolet-visible absorption data: λ
Max1(nm)=630.0,0.620; λ
Max2(nm) 585.0,0.538.
Example 4: Compound I I's is synthetic
Synthetic method is with example 3, with etc. weight 2-methyl-6-sec-butyl aniline substitute 2-ethyl-6-sec-butyl aniline.Obtain 15.6g Compound I I, yield 71.0%.
Nuclear magnetic resonance data:
1H?NMR(DCCl
3，300MHz)δ0.76-0.81(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)。
Nuclear magnetic data meets 1, the chemical structure of 4-two (2-methyl-6-sec-butylbenzene amido) anthraquinone.
Ultraviolet-visible absorption data: λ
Max1(nm)=630.0,0.596; λ
Max2(nm) 585.0,0.513
Example 5: compound III synthetic
In the 100ml four-hole bottle, add 7.0g 1 successively, the 4-dihydroxyanthraquinone, 3.0g 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 adds potassium hydroxide 5g, and the bubbling air oxidation, treats that purple all disappears, and is the oxidation terminal point, and reaction solution is slowly analysed to the 100ml hot ethanol, through cooling, filtration, washing, obtains the 11.8g compound III, yield 71.2% then.
Nuclear magnetic resonance data:
1HNMR(DCCl
3，300MHz)：δ0.67-0.84(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)。
Nuclear magnetic data meets the chemical structure of 1-hydroxyl-4-(2-ethyl-6-sec-butylbenzene amido) anthraquinone.
Ultraviolet-visible absorption data: λ
Max1(nm)=585.0,0.514; λ
Max2(nm) 540.0,0.533
Example 6: compound IV synthetic
Synthetic method is with example 5, with etc. weight 2-methyl-6-sec-butyl aniline substitute 2-ethyl-6-sec-butyl aniline.Obtain the 11.5g compound IV, yield is 72.0%.
Nuclear magnetic resonance data:
1HNMR(DCCl
3，300MHz)：δ0.67-0.79(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)。
Nuclear magnetic data conforms to the chemical structure of 1-hydroxyl-4-(2-methyl-6-sec-butylbenzene amido) anthraquinone.
Ultraviolet-visible absorption data: λ
Max1(nm)=585.0,0.507; λ
Max2(nm) 540.0,0.526.
Example 7: effect test
Adopt injection moulding machine to prepare the plastics color chips, method is as follows:
1, transparent color chips (concentration 0.1%): the 0.400g dye sample, evenly spread in the 400g polystyrene (PG-383), on injection moulding machine, form transparent color chips in 185-190 ℃.
2, opaque color chips (concentration 0.05%): the 0.200g dye sample, 1.000g titanium dioxide (R-902) evenly spreads in the 400g polystyrene (PG-383), forms opaque color chips in 185-190 ℃ on injection moulding machine.
With the plastics color chips of making, carry out the color characteristics contrast and the test of dyestuff.The synthetic compound I of institute, II are bright red light blueness, compare with existing similar structures commercial dye (C.I. solvent blue 19 04 and C.I. solvent blue 97), and color and luster is close, vividness is good slightly, light fastness reaches 7 grades, has good heat-resistant stability and resistance to migration, the application performance basically identical; The synthetic compound III of institute, IV are gorgeous purple, compare with existing similar structures commercial dye (C.I. solvent violet 13), and light fastness 6-7 level has good heat-resistant stability and resistance to migration, its application performance and solvent violet 13 basically identicals.
Claims (1)
1. the preparation method of structure anthraquinone type solvent dye shown in general formula (I) is characterized in that, 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, the compound shown in the preparation general formula (I):
In the formula:
R
1Be selected from hydroxyl or
R
2Be selected from methyl or ethyl.
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|---|---|---|---|
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|---|---|---|---|
| CN200610046424A CN100577740C (en) | 2006-04-26 | 2006-04-26 | A kind of anthraquinone type solvent dye and preparation thereof and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105237417B (en) * | 2015-09-17 | 2017-05-17 | 江苏道博化工有限公司 | Synthetic method for solvent violet 13 |
| CN107936606A (en) * | 2017-10-25 | 2018-04-20 | 安徽凯奇化工科技股份有限公司 | A kind of synthetic method of blue dyes |
| CN112176738A (en) * | 2020-11-04 | 2021-01-05 | 季德虎 | Plastic colorant 2N blue and preparation method thereof |
| CN115010606B (en) * | 2022-06-09 | 2024-01-23 | 中国农业大学 | Synthesis method and application of 2-sec-butyl-6-ethylaniline |
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Non-Patent Citations (3)
| Title |
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| 国内外溶剂染料的进展（二）. 杨薇等.上海染料，第30卷第1期. 2002 |
| 国内外溶剂染料的进展(二). 杨薇等.上海染料，第30卷第1期. 2002 * |
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