CN1107489A - 靛蓝的提纯 - Google Patents
靛蓝的提纯 Download PDFInfo
- Publication number
- CN1107489A CN1107489A CN94112827A CN94112827A CN1107489A CN 1107489 A CN1107489 A CN 1107489A CN 94112827 A CN94112827 A CN 94112827A CN 94112827 A CN94112827 A CN 94112827A CN 1107489 A CN1107489 A CN 1107489A
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- Prior art keywords
- indigo
- procrypsis
- solvent
- alkali metal
- metal salt
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Links
- 235000000177 Indigofera tinctoria Nutrition 0.000 title claims abstract description 40
- 229940097275 indigo Drugs 0.000 title claims abstract description 40
- 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 40
- 238000000746 purification Methods 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 21
- -1 leuco indigo alkali metal Chemical class 0.000 claims abstract description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 239000012442 inert solvent Substances 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 7
- 239000000284 extract Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000007796 conventional method Methods 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims 1
- 230000008929 regeneration Effects 0.000 claims 1
- 238000011069 regeneration method Methods 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 239000012266 salt solution Substances 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 230000001172 regenerating effect Effects 0.000 abstract 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 10
- 239000012535 impurity Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 3
- PCKPVGOLPKLUHR-UHFFFAOYSA-N indoxyl Chemical compound C1=CC=C2C(O)=CNC2=C1 PCKPVGOLPKLUHR-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- YACLCMMBHTUQON-UHFFFAOYSA-N 1-chloro-1-fluoroethane Chemical compound CC(F)Cl YACLCMMBHTUQON-UHFFFAOYSA-N 0.000 description 1
- ZYVYEJXMYBUCMN-UHFFFAOYSA-N 1-methoxy-2-methylpropane Chemical compound COCC(C)C ZYVYEJXMYBUCMN-UHFFFAOYSA-N 0.000 description 1
- RMGHERXMTMUMMV-UHFFFAOYSA-N 2-methoxypropane Chemical compound COC(C)C RMGHERXMTMUMMV-UHFFFAOYSA-N 0.000 description 1
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 description 1
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 description 1
- 229920004449 Halon® Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004440 Isodecyl alcohol Substances 0.000 description 1
- 239000004439 Isononyl alcohol Substances 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004904 shortening 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
- 238000005406 washing Methods 0.000 description 1
- 239000003799 water insoluble solvent Substances 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
- C09B7/00—Indigoid dyes
- C09B7/02—Bis-indole indigos
Abstract
一种提纯靛蓝的方法，它包括在隔绝氧的条件
下，用惰性溶剂萃取含水的隐色靛蓝碱金属盐溶液，
按常规方法用氧化反应再生靛蓝。
Description
作为在世界上大量使用的最大的合成纺织染料靛蓝，尽管用高级的生产方法，在初制备成的产品中仍有杂质存在，包括例如高达0.6%重量的苯胺和0.4%重量的N-甲基苯胺。即使存在少量其它化合物，也要将其理想的除去。
专利文献已公开了一些提纯靛蓝的方法。
例如：EP-A-509275涉及制备纯化的靛蓝的方法，通过在隔绝氧的条件下，在氧化成靛蓝前，用惰性的不溶于水溶剂萃取合成的含水的3-吲哚氧基化物的碱溶液。
EP-A-509274涉及提纯靛蓝的方法，通过用硫酸把靛蓝转化成靛蓝硫酸盐，将其分离出来，然后，水解，将其重新生成靛蓝，然后用稀释的过氧化氢溶液处理。
EP-A-523532公开了提纯靛蓝的方法，其中，该已合成的含水碱性3-吲哚氧基化物溶液，在其氧化成靛蓝之前，使其在隔绝氧的条件下，通过蒸馏或引入蒸汽或惰性气体的方法去掉其杂质，并接着将此已去掉杂质的3-吲哚氧基化物溶液通过用稀的过氧化氢溶液处理而进行的氧化作用而得到靛蓝。
最后，EP申请93 109841.2公开了通过在惰性溶剂中，从150-250℃，优选180-220℃下的加热靛蓝的提纯靛蓝的方法。我们已经发现具有良好收率的基本上纯的靛蓝是这样得到的，即，按照已知方式，通过将合成的染料以其稳色化合物的碱金属盐形式的还原作用而首先将其溶解在水中，然后将所得到的水溶液在隔绝氧的条件下，用水不溶解的惰性有机溶剂进行萃取，相分离之后，将此稳色靛蓝的萃取液按已知的方法氧化成靛蓝。
为确保从隐色靛蓝盐溶液中去掉可萃取的杂质的量，重要的是，在严格的隔绝氧的条件下，用有机溶剂进行萃取，它通过在氮气条件下进行，可便利地完成。
因为，即使很少量的氧与溶解的隐色靛蓝盐反应形成靛蓝，则就会接着不可逆地再吸收苯胺和N-甲基苯胺以及其它不希望的杂质。
在稳色的靛蓝盐溶液中，可以保证最大量地将杂质除去，例如，由5至25%重量的靛蓝以其稳色化合物盐的形式存在的溶液的情况下，使用隐色靛蓝盐：有机溶剂的重量比（相比例）是由1∶0.1至1∶10，优选1∶0.5至1∶5。
在本发明的方法的优越的实施方案中，是将含由5至25%重量的靛蓝进行还原作用所得到的含水碱性隐色靛蓝溶液，在氮气下，在由25至100℃，优选由40至70℃，以与惰性有机溶剂的相比为1∶1至1∶3来进行萃取，时间为10至30分钟，相分离之后，将该经萃取的隐色靛蓝盐溶液用通常方法用空气进行氧化，以得到具有由98至＞99.5%的非常高纯度的靛蓝（用光度法测定）。
染料通常无苯胺和N-甲基苯胺;其它杂质也同样通过萃取定量地去掉。
用于萃取的溶剂，它含有萃取杂质，可将其再蒸馏，然后再作为萃取剂用。
可断续地或连续地完成该方法。
适合的溶剂的例子包括在反应条件下是惰性的所有基本上不溶于水的溶剂，如烃，卤化烃，醚或醇类或它们的混合物。
适合溶剂的特殊例子是氯仿，二氯乙烷，全氯乙烷，二氯氟乙烷，氯苯，甲基异丙基醚，甲基异丁基醚，二-正丁基醚，二异戊基醚，正-已醇，正-辛醇，2-乙基-己醇，正-壬醇，正-癸醇，异壬醇（同分异构体混合物），异癸醇（同分异构体混合物），己烷，环己烷，辛烷，癸烷，适当沸点范围的石油醚，甲苯，二甲苯，二乙基酮，甲基异丁基酮，二-正丁基酮或环己酮和它们的混合物。
优选的溶剂特别是二甲苯，甲苯和2-乙基己醇。
用于萃取的含有水的隐色靛蓝盐溶液，是由常规方法制备的，通过使用还原剂如氢气/阮内镍，连二亚硫酸钠（Na2S2O4）或羟基丙酮还原靛蓝而成。
实施例1
用常规方法制备200份隐色靛蓝钠盐溶液，它通过催化加氢的40份靛蓝和600份甲苯，在2升充氮气的烧瓶中加热搅拌至65℃，在保持氮气氛下，在65℃用力搅拌15分钟，搅拌速度500rpm而制得的。分离掉甲苯相，用常规的方法在65～85℃，通过向溶液中通入空气将无色靛蓝钠盐的萃取液转化成靛蓝。过滤出染料，然后洗涤至中性并干燥。
获得的靛蓝纯度98～99%（光度法测定），无苯胺，N-甲基苯胺和其它不希望的杂质。
实施例2
按实施例1的方法制备600份隐色靛蓝钠盐溶液，它接通常方法用连二亚硫酸钠（Na2S2O4）将40g靛蓝进行还原作用，再用600份甲苯在2升烧瓶中进行搅拌。
获得的靛蓝纯度＞99.5%（用光度法测定），并无苯胺，N-甲基苯胺和其它不希望的杂质。
Claims (4)
1、一种提纯靛蓝的方法，它包括在隔绝氧的条件下，用惰性溶剂萃取含水的隐色靛蓝碱金属盐溶液，并按常规方法用氧化反应再生成靛蓝。
2、一种根据权利要求1所说的方法，其中，萃取无色靛蓝碱金属盐溶液是在25～100℃，优选在40～70℃进行。
3、一种根据权利要求1所说的方法，其中，进行萃取所用的隐色靛蓝碱金属盐溶液：溶剂的重量比为由1∶0.1至1∶10，优选从1∶0.5至1∶5。
4、一种根据权利要求1所说的方法，其中，所用的溶剂为甲苯。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4336032A DE4336032A1 (de) | 1993-10-22 | 1993-10-22 | Verfahren zur Reinigung von Indigo |
| DEP4336032.7 | 1993-10-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1107489A true CN1107489A (zh) | 1995-08-30 |
| CN1061069C CN1061069C (zh) | 2001-01-24 |
Family
ID=6500739
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94112827A Expired - Fee Related CN1061069C (zh) | 1993-10-22 | 1994-10-22 | 靛蓝的提纯 |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5536842A (zh) |
| JP (1) | JPH07157684A (zh) |
| CN (1) | CN1061069C (zh) |
| BR (1) | BR9404156A (zh) |
| DE (1) | DE4336032A1 (zh) |
| GB (1) | GB2283022A (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI760544B (zh) * | 2017-08-11 | 2022-04-11 | 瑞士商亞齊羅馬Ｉｐ公司 | 極低苯胺含量之靛白溶液及其製備方法及對應之製備靛藍的方法 |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5024295A (en) * | 1988-06-21 | 1991-06-18 | Otis Elevator Company | Relative system response elevator dispatcher system using artificial intelligence to vary bonuses and penalties |
| KR100388898B1 (ko) * | 2000-11-23 | 2003-06-25 | 임용진 | 건조 쪽으로부터 인디고의 추출방법 |
| US7520567B2 (en) * | 2004-09-23 | 2009-04-21 | Crown Equipment Corporation | Systems and methods for seat repositioning |
| US7121608B2 (en) * | 2004-09-23 | 2006-10-17 | Crown Equipment Corporation | Rotating and/or swiveling seat |
| US7059680B2 (en) * | 2004-09-23 | 2006-06-13 | Crown Equipment Corporation | Seat repositioning device with release on control handle |
| EP3441430B1 (en) | 2017-08-11 | 2020-11-25 | Archroma IP GmbH | Leucoindigo salt solution with very low content of aniline and method of making same |
| EP3441431B1 (en) | 2017-08-11 | 2021-07-14 | Archroma IP GmbH | Methods of making leucoindigo salt solutions with very low aniline content |
| ES2900511T3 (es) | 2018-05-18 | 2022-03-17 | Archroma Ip Gmbh | Método para preparar soluciones de sal de leucoíndigo sin anilina |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US5109137A (en) * | 1991-04-15 | 1992-04-28 | Basf Aktiengesellschaft | Purification of indigo |
| US5116996A (en) * | 1991-07-17 | 1992-05-26 | Basf Aktiengesellschaft | Purification of indigo |
| DE4220804A1 (de) * | 1992-06-25 | 1994-01-05 | Basf Ag | Verfahren zur Reinigung von Indigo |
-
1993
- 1993-10-22 DE DE4336032A patent/DE4336032A1/de not_active Withdrawn
-
1994
- 1994-10-18 JP JP6252237A patent/JPH07157684A/ja not_active Withdrawn
- 1994-10-19 BR BR9404156A patent/BR9404156A/pt not_active IP Right Cessation
- 1994-10-21 GB GB9421247A patent/GB2283022A/en not_active Withdrawn
- 1994-10-21 US US08/326,851 patent/US5536842A/en not_active Expired - Fee Related
- 1994-10-22 CN CN94112827A patent/CN1061069C/zh not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI760544B (zh) * | 2017-08-11 | 2022-04-11 | 瑞士商亞齊羅馬Ｉｐ公司 | 極低苯胺含量之靛白溶液及其製備方法及對應之製備靛藍的方法 |
| US11299633B2 (en) | 2017-08-11 | 2022-04-12 | Archroma Ip Gmbh | Leucoindigo salt solution with very low content of aniline and method of making same |
| US11384245B2 (en) | 2017-08-11 | 2022-07-12 | Archroma Ip Gmbh | Purified concentrated aqueous leucoindigo salt solutions |
Also Published As
| Publication number | Publication date |
|---|---|
| US5536842A (en) | 1996-07-16 |
| JPH07157684A (ja) | 1995-06-20 |
| GB9421247D0 (en) | 1994-12-07 |
| BR9404156A (pt) | 1995-06-20 |
| GB2283022A (en) | 1995-04-26 |
| DE4336032A1 (de) | 1995-04-27 |
| CN1061069C (zh) | 2001-01-24 |
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