CN1043654C - 靛蓝的纯化 - Google Patents
靛蓝的纯化 Download PDFInfo
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- CN1043654C CN1043654C CN93107883A CN93107883A CN1043654C CN 1043654 C CN1043654 C CN 1043654C CN 93107883 A CN93107883 A CN 93107883A CN 93107883 A CN93107883 A CN 93107883A CN 1043654 C CN1043654 C CN 1043654C
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- indigo
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- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 235000000177 Indigofera tinctoria Nutrition 0.000 title claims abstract description 35
- 229940097275 indigo Drugs 0.000 title claims abstract description 35
- 238000000746 purification Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 14
- 229940095102 methyl benzoate Drugs 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 14
- 239000000975 dye Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 7
- 238000004821 distillation Methods 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- COHYTHOBJLSHDF-BUHFOSPRSA-N indigo dye Chemical compound N\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-BUHFOSPRSA-N 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JYVLIDXNZAXMDK-UHFFFAOYSA-N methyl propyl carbinol Natural products CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000004758 synthetic textile Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0096—Purification; Precipitation; Filtration
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0014—Influencing the physical properties by treatment with a liquid, e.g. solvents
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Pyrrole Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Detergent Compositions (AREA)
- Coloring (AREA)
Abstract
本发明涉及靛蓝的纯化方法，其特征在于：将靛蓝在惰性有机溶剂中于150°-250℃、最好于180°-220℃加热。
Description
靛蓝是最广泛生产的合成织物染料，尽管利用很先进的生产工艺，但仍然含有杂质，例如含苯胺达0.6重量％、N-甲基苯胺达0.4重量％。此外，还存在少量需要去除的其它化合物。
因此本发明的目的是提供靛蓝的高效和经济的纯化方法，用该方法能生产出不含或基本不含芳香胺类用其它杂质的染料。
人们试图用常规的纯化方法如和稀酸洗涤或搅拌、用蒸汽蒸馏或用有机溶剂萃取除去含在靛蓝中的芳香胺类，但到目前为止还尚未获得成功，甚至连对于磨得极细的染料也未获得成功。
现在我们发现将染料合成后用有机溶剂于高温进行处理能获得基本纯的靛蓝。
纯化靛蓝新方法的效率是惊人的和令人难以预料的，因为在先有技术的实验中，用有机溶剂如甲醇、正丁醇和甲苯处理，即使在回流的条件下也没达到过这样的纯化效果。
用有机溶剂处理可以在含水靛蓝糊中进行，也可以在干染料中进行。
纯化溶剂的用量约为染料重量的3-12倍。
靛蓝在所有的有机溶剂中均极难溶解，因此，即使在所述的固体与溶剂的比率下该染料也是悬浮在溶剂中，即基本上未溶。
本发明方法具体按下述方法实施较为有利：将1份靛蓝粉或4份含水靛蓝糊(固体含量：25％)置于3-12份、最好为5-9份有机溶剂中，于150°-250℃最好为180°-220℃搅拌处理2-12小时，4-8小时为佳，如果是含水靛蓝糊则随后通过蒸馏除去任何存在的水份。
经以收率大于99％的反应混合物(纯度≥98％，经光密度检测)的纯化后得到的纯靛蓝仅含0-0.08％苯胺和0-0.04％N-甲基苯胺。
实施该方法可用或不用压力可连续进行或分批进行。合适的溶剂的例子是在该工艺条件下惰性的溶剂例如烃类、卤代烃类、醚类、酮类、酰胺类、腈类和醇类以及酯或它们的混合物。
具体来讲，优选的溶剂是苯甲酸甲酯、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮和邻二氯苯。
用于纯化靛蓝的溶剂可反复使用而不必进行中间的再蒸馏。
本发明用以下实施例说明如下，其中份数和百分数均按重量计。
实施例1
将350份苯甲酸甲酯置于容量为1L的带搅拌的反应器中。在50份靛蓝粉(纯度96.5％，苯胺含量为0.6％,N-甲基苯胺含量为0.35％)中搅拌后，将反应混合物于198℃回流搅拌6小时。将反应混合物冷却至室温后过滤。将滤过的物料置于300份水中并用蒸汽蒸馏除去附着的苯甲酸甲酯。随后于100℃真空干燥，得48.5份纯度为98.6％的靛蓝(经光密度测定)。
靛蓝的产量是47.82份(纯度按100％计算，收率为99.2％)。该靛蓝仍含0.014％苯胺和＜0.001％N-甲基苯胺。
滤液可不经再次蒸馏再用于纯化靛蓝一或两次。
实施例2
将700份苯甲酸甲酯置于容量为2L并配有蒸馏桥(distillationbridge)的带搅拌的反应器中。在370份含水靛蓝糊(固体含量：27.9％；干燥靛蓝的纯度：97.0％；苯胺含量：0.55％；N-甲基苯胺含量：0.35％)中搅拌后，将得到的悬浮液于约195℃加热并在2小时内蒸除所有水份。用回流冷凝器置换蒸馏桥并将反应混合物于198℃回流6小时。
然后将靛蓝悬浮液冷却并按实施例1中所述的方法来完成纯化，得100.8份纯度为98.2％的靛蓝(经光密度测定)。
靛蓝的产量是99.0份(按100％计算)，这等于用于纯化的靛蓝的99％。该染料仍含0.04％苯胺和0.02％N-甲基苯胺。
实施例3
将700份苯甲酸甲酯和370份与用在实施例2中的质量相同的含水靛蓝糊置于容量为2L搅拌的高压釜中。将高压釜密封后，搅拌下将反应混合物加热至200℃，将反应器中的压力升至1.5×106Pa。于200℃/1.5×106Pa搅拌5小时后，开启高压釜，随后将靛蓝悬浮液冷却至室温。
然后过滤，回收的靛蓝按实施例1中所述的方法来完成纯化，得99.6份纯度为99.7％(经光密度测定)的靛蓝。这相当于用于纯化的靛蓝的收率为99.3％。该染料含0.01苯胺和0.005％N-甲基苯胺。
Claims (7)
1．靛蓝的纯化方法，其特征在于：将靛蓝在选自苯甲酸甲酯，二甲基甲酰胺，二甲基乙酰胺，N-甲基吡咯烷酮及其混合物的惰性有机溶剂中于150°-250℃加热。
2．按照权利要求1的方法，其特征在于：将1份靛蓝悬浮于3-12份所述有机溶剂中。
3．按照权利要求1的方法，其中纯化处理进行2-12小时。
4．按照权利要求1的方法，其中所用的溶剂是苯甲酸甲酯。
5．按照权利要求1的方法，其中加热温度为180°-220℃。
6．按照权利要求2的方法，其中将1份靛蓝悬浮于5-9份所述有机溶剂中。
7．按照权利要求3的方法，其中纯化处理时间是6-10小时。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4220804A DE4220804A1 (de) | 1992-06-25 | 1992-06-25 | Verfahren zur Reinigung von Indigo |
| DEP4220804.1 | 1992-06-25 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1081191A CN1081191A (zh) | 1994-01-26 |
| CN1043654C true CN1043654C (zh) | 1999-06-16 |
Family
ID=6461784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93107883A Expired - Fee Related CN1043654C (zh) | 1992-06-25 | 1993-06-25 | 靛蓝的纯化 |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5424453A (zh) |
| EP (1) | EP0575925B1 (zh) |
| JP (1) | JPH0657165A (zh) |
| CN (1) | CN1043654C (zh) |
| BR (1) | BR9302417A (zh) |
| DE (2) | DE4220804A1 (zh) |
| ES (1) | ES2092187T3 (zh) |
| TW (1) | TW252142B (zh) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4336032A1 (de) * | 1993-10-22 | 1995-04-27 | Basf Ag | Verfahren zur Reinigung von Indigo |
| WO2009070637A1 (en) * | 2007-11-28 | 2009-06-04 | Mayan Pigments, Inc. | Higher purity hybrid pigments |
| CN101824231A (zh) * | 2010-04-01 | 2010-09-08 | 五邑大学 | 一种植物靛蓝的提纯方法 |
| CN103429249B (zh) * | 2011-03-14 | 2015-12-23 | 太阳星光齿磨公司 | 用于制造靛蓝植物叶提取物的方法 |
| CN105295435A (zh) * | 2015-11-24 | 2016-02-03 | 常州美胜生物材料有限公司 | 一种蓝靛草提取物的制备方法及应用 |
| WO2019030389A1 (en) | 2017-08-11 | 2019-02-14 | Archroma Ip Gmbh | AQUEOUS SOLUTIONS CONCENTRATED PURIFIED WITH SALT FROM LEUCOINDIGO |
| PT3441429T (pt) * | 2017-08-11 | 2021-06-28 | Archroma Ip Gmbh | Soluções de sal de leucoindigo aquoso purificado concentrado |
| CN111208103A (zh) * | 2020-01-16 | 2020-05-29 | 上海慧染生物科技有限公司 | 一种鉴别植物靛蓝染料和合成靛蓝染料的方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0036523A2 (de) * | 1980-03-13 | 1981-09-30 | BASF Aktiengesellschaft | Verfahren zur Formierung von feinteiligen organischen Rohpigmenten |
| EP0206281A2 (de) * | 1985-06-25 | 1986-12-30 | BASF Aktiengesellschaft | Verfahren zum überführen von rohen Isoindolinpigmenten in eine Pigmentform |
| CN1036025A (zh) * | 1988-03-17 | 1989-10-04 | 三井东圧化学株式会社 | 靛蓝化合物的制备方法 |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3230125A1 (de) * | 1982-08-13 | 1984-02-16 | Hoechst Ag, 6230 Frankfurt | Verfahren zur herstellung eines organischen pigments auf basis 4,4',7,7'-tetrachlorthioindigo |
| EP0330419B1 (en) * | 1988-02-23 | 1994-10-26 | MITSUI TOATSU CHEMICALS, Inc. | Process for the preparation of indigo compound |
| EP0339887B1 (en) * | 1988-04-25 | 1996-07-10 | MITSUI TOATSU CHEMICALS, Inc. | Process for the preparation of indigo compounds |
| US5112987A (en) * | 1988-04-25 | 1992-05-12 | Mitsui Toatsu Chemicals, Inc. | Process for the preparation of indigo compounds |
| CA2055729C (en) * | 1990-11-22 | 1995-06-20 | Yoshihiro Yamamoto | Process for the preparation of indigo compounds |
| US5109137A (en) * | 1991-04-15 | 1992-04-28 | Basf Aktiengesellschaft | Purification of indigo |
| US5116997A (en) * | 1991-04-15 | 1992-05-26 | Basf Aktiengesellschaft | Purification of indigo |
| US5075458A (en) * | 1991-04-15 | 1991-12-24 | Basf Aktiengesellschaft | Purification of indigo |
| US5116996A (en) * | 1991-07-17 | 1992-05-26 | Basf Aktiengesellschaft | Purification of indigo |
-
1992
- 1992-06-25 DE DE4220804A patent/DE4220804A1/de not_active Withdrawn
-
1993
- 1993-05-26 TW TW082104156A patent/TW252142B/zh active
- 1993-06-14 US US08/075,881 patent/US5424453A/en not_active Expired - Lifetime
- 1993-06-21 BR BR9302417A patent/BR9302417A/pt not_active IP Right Cessation
- 1993-06-21 ES ES93109841T patent/ES2092187T3/es not_active Expired - Lifetime
- 1993-06-21 DE DE59304085T patent/DE59304085D1/de not_active Expired - Fee Related
- 1993-06-21 EP EP93109841A patent/EP0575925B1/de not_active Expired - Lifetime
- 1993-06-23 JP JP5152095A patent/JPH0657165A/ja not_active Withdrawn
- 1993-06-25 CN CN93107883A patent/CN1043654C/zh not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0036523A2 (de) * | 1980-03-13 | 1981-09-30 | BASF Aktiengesellschaft | Verfahren zur Formierung von feinteiligen organischen Rohpigmenten |
| EP0206281A2 (de) * | 1985-06-25 | 1986-12-30 | BASF Aktiengesellschaft | Verfahren zum überführen von rohen Isoindolinpigmenten in eine Pigmentform |
| CN1036025A (zh) * | 1988-03-17 | 1989-10-04 | 三井东圧化学株式会社 | 靛蓝化合物的制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0657165A (ja) | 1994-03-01 |
| BR9302417A (pt) | 1994-01-11 |
| TW252142B (zh) | 1995-07-21 |
| DE4220804A1 (de) | 1994-01-05 |
| EP0575925B1 (de) | 1996-10-09 |
| US5424453A (en) | 1995-06-13 |
| CN1081191A (zh) | 1994-01-26 |
| ES2092187T3 (es) | 1996-11-16 |
| EP0575925A1 (de) | 1993-12-29 |
| DE59304085D1 (de) | 1996-11-14 |
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