CN106431872B - The method for preparing 9 intermediate 4BR of Vat Orange 2 RT and vat black - Google Patents
The method for preparing 9 intermediate 4BR of Vat Orange 2 RT and vat black Download PDFInfo
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- CN106431872B CN106431872B CN201610822503.6A CN201610822503A CN106431872B CN 106431872 B CN106431872 B CN 106431872B CN 201610822503 A CN201610822503 A CN 201610822503A CN 106431872 B CN106431872 B CN 106431872B
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Abstract
The present invention relates to a kind of methods for preparing 9 intermediate 4BR of Vat Orange 2 RT and vat black, mainly solve the problems, such as that spent acid discharge amount is larger in the prior art.The present invention is by using a kind of method for preparing 9 intermediate 4BR of Vat Orange 2 RT and vat black, using gold orange as raw material, bromine is bromide reagent, oleum concentrated sulfuric acid mixed liquor is reaction dissolvent, and iodine or sulphur are catalyst, and reactant is after 5~70 DEG C of 3~10h of reaction, add water isolation, filtering, the technical solution for obtaining 9 intermediate 4BR of Vat Orange 2 RT or vat black preferably solve the above problem, can be used for preparing in 9 intermediate 4BR of Vat Orange 2 RT and vat black.
Description
Technical field
The present invention relates to a kind of methods for preparing 9 intermediate 4BR of Vat Orange 2 RT and vat black.
Background technique
Vat Orange 2 RT is a kind of important pyrene anthrone class reducing dye, can be used for the fabrics such as cotton, silk, wool, polyamide fibre
Dyeing and stamp, molecular formula C30H12Br2O2, molecular weight 564.22, general structure are as follows:
Patent US876810 with gold orange (Vat Orange9, C.I.59700) for raw material, using nitrobenzene as solvent, in sulfonic acid chloride or
Vat Orange 2 RT is synthesized in the presence of person's chlorine.For patent US2013790 using gold orange as raw material, the concentrated sulfuric acid is solvent, under chlorine atmosphere
Reaction under high pressure synthesizes Vat Orange 2 RT for 24 hours.Above-mentioned patent technique uses hypertoxic harmful influence chlorine or sulfonic acid chloride, high temperature and pressure, reaction
Time is long, and is not suitable for industrialized production.
Vat black 9 is a kind of important black vat dye, and structural formula is as follows:
Dyeing and stamp, level-dyeing property and the affinity performance that can be used for cotton fiber, cotton, dye viscose fiber, silk etc. are excellent
More, it is uniform to obtain color.Its key intermediate 4BR, molecular formula C30H10Br4O2, molecular weight 722.02, structural formula is as follows:
Used vat black 9 intermediate 4BR and Vat Orange 2 RT is by gold orange (vat orange on domestic and international market at present
9, C.I.59700) bromination is made under normal pressure in chlorosulfonic acid, and the technological reaction formula is as follows:
There are two big disadvantages for the traditional handicraft: 1, using country to keep under strict control harmful influence chlorosulfonic acid as reaction dissolvent, transport is given birth to
It is big to produce security risk；2, reaction terminates that diluting concentrated sulfuric acid need to be added, and spent acid discharge amount is huge.
The present invention is based on this technical backgrounds, are changed to the preparation process of 9 intermediate 4BR of Vat Orange 2 RT and vat black
Into.
Summary of the invention
The technical problem to be solved by the present invention is to the problem that spent acid discharge amount in the prior art is larger, provide a kind of new
The method for preparing 9 intermediate 4BR of Vat Orange 2 RT and vat black.This method has the advantages that spent acid discharge amount is lesser.
To solve the above problems, The technical solution adopted by the invention is as follows: a kind of prepare in Vat Orange 2 RT and vat black 9
The method of mesosome 4BR puts into gold orange, iodine or sulfur catalyst, oleum and the concentrated sulfuric acid in the reaction kettle with reflux unit
Mixed liquor puts into bromine after gold orange dissolution, in 5~70 DEG C temperature-programmed reaction 3~10 hours, will after the completion of bromination reaction
Reaction solution is put into the dilution kettle for having installed water additional, stirring isolate, be filtered, washed, drying among Vat Orange 2 RT or vat black 9
Body 4BR.
In above-mentioned technical proposal, it is preferable that the mass ratio of oleum and the concentrated sulfuric acid is 0.2~15:1.
In above-mentioned technical proposal, it is preferable that catalyst is iodine or sulphur.
In above-mentioned technical proposal, it is preferable that the mixed liquor and the mass ratio of gold orange are 5~10:1, catalyst iodine or sulphur
It is 0.03~0.1:1 with the mass ratio of gold orange, the mass ratio of bromine and gold orange is 0.4~1.5:1.
In above-mentioned technical proposal, it is preferable that the reaction temperature of bromination reaction is 5~70 DEG C, synthesis under normal pressure, and heating rate is
2~5 DEG C/h, the reaction time is 3~10h.
In above-mentioned technical proposal, it is preferable that the mass ratio of reaction solution and water is 0.2~1:1 in dilution kettle.
Traditional handicraft institute is substituted using relatively mild solvent oleum concentrated sulfuric acid mixed liquor as reaction dissolvent in this method
The hypertoxic dangerous solvents chlorosulfonic acid used, avoids the technical process of traditional handicraft enriching sulfuric acid acid out, reduces the dosage of acid,
Significantly reduce technique spent acid discharge amount.Compared to traditional handicraft, this method is easy to operate, and reaction condition is mild, the reaction time
Shorter, without using hypertoxic dangerous solvents chlorosulfonic acid, spent acid discharge amount reduces 30%, is more suitable among Vat Orange 2 RT and vat black 9
The industrialized production of body 4BR achieves preferable technical effect.
The present invention will be further described below by way of examples, but is not limited only to the present embodiment.
Specific embodiment
The Vat Orange 2 RT and vat black 9 prepared in embodiment for the standard specimen of staining versus for enterprise with chlorosulfonic acid technique
Exported product standard specimen.
Comparative example 1
Belt stirrer, reflux condenser, thermometer 250ml reaction kettle in be added 8g gold orange, 0.4g iodine, 64g
Chlorosulfonic acid, stirring and dissolving are cooled to 20 DEG C, are added 4.7g bromine, and under normal pressure, temperature-programmed reaction, 5 DEG C/h of heating rate is risen
Temperature to 50 DEG C of reactions terminate.After 32g diluting concentrated sulfuric acid is added, reaction solution is put into the dilution kettle equipped with 180g water, stirring analysis
Crystalline substance, filtering, Washing of Filter Cake to neutrality, drying obtain Vat Orange 2 RT 10.9g, and sample two-dimension spectrum curve, coloration and standard specimen are kissed
It closes.The entire raw spent acid 276g of technical process common property.
Embodiment 1
Belt stirrer, reflux condenser, thermometer 250ml reaction kettle in be added 8g gold orange, 0.4g iodine, 48g
Oleum (concentration 20%), the 16g concentrated sulfuric acid, stirring and dissolving are cooled to 10 DEG C, are added 3.8g bromine, under normal pressure, temperature programming
Reaction, 5 DEG C/h of heating rate, being warming up to 50 DEG C of reactions terminates.Reaction solution is put into the dilution kettle equipped with 120g water, stirring analysis
Crystalline substance, filtering, Washing of Filter Cake to neutrality, drying obtain Vat Orange 2 RT 10.8g, and sample two-dimension spectrum curve and standard specimen coincide, coloured light
It meets the requirements, dyes more bright-coloured.The entire raw spent acid 184g of technical process common property.
Comparative example 2
Belt stirrer, reflux condenser, thermometer 250ml reaction kettle in be added 8g gold orange, 0.4g iodine, 64g
Oleum (concentration 20%), stirring and dissolving are cooled to 5 DEG C, are added 3.8g bromine, under normal pressure, temperature-programmed reaction, and heating speed
5 DEG C/h of rate, being warming up to 40 DEG C of reactions terminates.Reaction solution is put into the dilution kettle equipped with 120g water, stirring and crystallizing, is filtered, filter
Cake is washed to neutrality, drying, obtains Vat Orange 2 RT 11.3g, sample two-dimension spectrum curve is the same as standard specimen coincide, coloration is compared with standard specimen
It is partially red, partially dark.
Comparative example 3
Belt stirrer, reflux condenser, thermometer 250ml reaction kettle in be added 8g gold orange, 0.4g iodine, 64g
The concentrated sulfuric acid, stirring and dissolving are cooled to 20 DEG C, are added 9.5g bromine, and under normal pressure, temperature-programmed reaction, 5 DEG C/h of heating rate is risen
Temperature to 120 DEG C of reactions terminate.Reaction solution is put into the dilution kettle equipped with 120g water, stirring and crystallizing, is filtered, Washing of Filter Cake is into
Property, it dries, obtains Vat Orange 2 RT 11.1g, sample two-dimension spectrum curve is the same as standard specimen coincide, coloration is partially yellow compared with standard specimen, partially dark.
Embodiment 2
Belt stirrer, reflux condenser, thermometer 250ml reaction kettle in be added 8g gold orange, 0.8g elemental sulfur, 48g
Oleum (concentration 20%), the 16g concentrated sulfuric acid, stirring and dissolving are cooled to 10 DEG C, are added 4.7g bromine, under normal pressure, temperature programming
Reaction, 5 DEG C/h of heating rate, being warming up to 50 DEG C of reactions terminates.Reaction solution is put into the dilution kettle equipped with 120g water, stirring analysis
Crystalline substance, filtering, Washing of Filter Cake to neutrality, drying obtain Vat Orange 2 RT 11g, and sample two-dimension spectrum curve and standard specimen coincide, coloration accords with
It closes and requires, dye more bright-coloured.
Embodiment 3
Belt stirrer, reflux condenser, thermometer 250ml reaction kettle in be added 8g gold orange, 0.4g iodine, 43g
Oleum (concentration 20%), the 21g concentrated sulfuric acid, stirring and dissolving are cooled to 10 DEG C, are added 3.8g bromine, under normal pressure, temperature programming
Reaction, 3 DEG C/h of heating rate, being warming up to 50 DEG C of reactions terminates.Reaction solution is put into the dilution kettle equipped with 120g water, stirring analysis
Crystalline substance, filtering, Washing of Filter Cake to neutrality, drying obtain Vat Orange 2 RT 10.9g, and sample two-dimension spectrum curve and standard specimen coincide, coloration
With the colorations such as standard specimen.
Embodiment 4
Belt stirrer, reflux condenser, thermometer 250ml reaction kettle in be added 8g gold orange, 0.8g elemental sulfur, 60g
Oleum (concentration 20%), the 20g concentrated sulfuric acid, stirring and dissolving are cooled to 10 DEG C, are added 3.8g bromine, under normal pressure, temperature programming
Reaction, 5 DEG C/h of heating rate, being warming up to 50 DEG C of reactions terminates.Reaction solution is put into the dilution kettle equipped with 120g water, stirring analysis
Crystalline substance, filtering, Washing of Filter Cake to neutrality, drying obtain Vat Orange 2 RT 10.9g, and sample two-dimension spectrum curve and standard specimen coincide, coloured light
It meets the requirements.
Embodiment 5
Belt stirrer, reflux condenser, thermometer 250ml reaction kettle in be added 8g gold orange, 0.4g elemental sulfur, 48g
Oleum (concentration 20%), the 16g concentrated sulfuric acid, stirring and dissolving are cooled to 10 DEG C, are added 4.7g bromine, under normal pressure, temperature programming
Reaction, 3 DEG C/h of heating rate, being warming up to 50 DEG C of reactions terminates.Reaction solution is put into the dilution kettle equipped with 120g water, stirring analysis
Crystalline substance, filtering, Washing of Filter Cake to neutrality, drying obtain Vat Orange 2 RT 10.8g, and sample two-dimension spectrum curve and standard specimen coincide, coloured light
It meets the requirements.
Comparative example 4
Belt stirrer, reflux condenser, thermometer 250ml reaction kettle in be added 8g gold orange, 0.4g iodine, 64g
Chlorosulfonic acid, stirring and dissolving are cooled to 20 DEG C, are added 9.5g bromine, and under normal pressure, temperature-programmed reaction, 5 DEG C/h of heating rate is risen
Temperature to 70 DEG C of reactions terminate.After 32g diluting concentrated sulfuric acid is added, reaction solution is put into the dilution kettle equipped with 180g water, stirring analysis
Crystalline substance, filtering, Washing of Filter Cake to neutrality, drying obtain 9 intermediate 4BR 14.0g of vat black.The entire raw spent acid of technical process common property
276g.9 sample two-dimension spectrum curve of vat black obtained, color are condensed with the intermediate and 1- amino anthraquinones and amino violanthrone
Degree coincide with standard specimen.
Embodiment 6
Belt stirrer, reflux condenser, thermometer 250ml reaction kettle in be added 8g gold orange, 0.4g iodine, 55g
Oleum (concentration 20%), the 9g concentrated sulfuric acid, stirring and dissolving are cooled to 20 DEG C, are added 8.2g bromine, under normal pressure, temperature programming
Reaction, 5 DEG C/h of heating rate, being warming up to 60 DEG C of reactions terminates.Reaction solution is put into the dilution kettle equipped with 120g water, stirring analysis
Crystalline substance, filtering, Washing of Filter Cake to neutrality, drying obtain 9 intermediate 4BR 14.2g of vat black.Technical process common property gives birth to spent acid 184g.
With the intermediate and 1- amino anthraquinones and amino violanthrone be condensed 9 sample two-dimension spectrum curve of vat black obtained, coloration with
Standard specimen coincide.
Embodiment 7
Belt stirrer, reflux condenser, thermometer 250ml reaction kettle in be added 8g gold orange, 0.8g elemental sulfur, 60g
Oleum (concentration 20%), the 4g concentrated sulfuric acid, stirring and dissolving are cooled to 5 DEG C, are added 8.2g bromine, and under normal pressure, temperature programming is anti-
It answers, 5 DEG C/h of heating rate, being warming up to 70 DEG C of reactions terminates.Reaction solution is put into the dilution kettle equipped with 120g water, stirring analysis
Crystalline substance, filtering, Washing of Filter Cake to neutrality, drying obtain 9 intermediate 4BR 14.4g of vat black.Technical process common property gives birth to spent acid 184g.
With the intermediate and 1- amino anthraquinones and amino violanthrone be condensed 9 sample two-dimension spectrum curve of vat black obtained, coloration with
Standard specimen coincide.
It is noted that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting.Although referring to preferable
Embodiment describes the invention in detail, those skilled in the art should understand that, it can be to the technical side of invention
Case is modified or replaced equivalently, and without departing from the range of technical solution of the present invention, should all be covered in right of the invention
In claimed range.
Claims (1)
1. a kind of method for preparing 9 intermediate 4BR of Vat Orange 2 RT or vat black, in the reaction kettle with reflux unit, investment gold
The mixed liquor of orange, iodine or sulfur catalyst, oleum and the concentrated sulfuric acid puts into bromine, in 5~70 DEG C of programs after gold orange dissolution
Temperature reaction 3~10 hours, reaction solution is put into the dilution kettle for having installed water additional after the completion of bromination reaction, stirring isolation, filtering,
Washing, dry 9 intermediate 4BR of Vat Orange 2 RT or vat black；The mass ratio of oleum and the concentrated sulfuric acid is 0.2~15:1；It urges
Agent is iodine or sulphur；The mixed liquor and the mass ratio of gold orange are the mass ratio of 5~10:1, catalyst iodine or sulphur and gold orange
For 0.03~0.1:1, the mass ratio of bromine and gold orange is 0.4~1.5:1；The reaction temperature of bromination reaction is 5~70 DEG C, normal pressure
Reaction, heating rate are 2~5 DEG C/h, and the reaction time is 3~10h；Diluting the mass ratio of reaction solution and water in kettle is 0.2~1:
1。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2013790A (en) * | 1931-10-03 | 1935-09-10 | Du Pont | Bromination of pyranthrone |
| US4182882A (en) * | 1977-03-22 | 1980-01-08 | Ciba-Geigy Corporation | Process for the production of pyranthrones or flavanthrones |
| CN102086210A (en) * | 2010-12-11 | 2011-06-08 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for synthesizing 2, 3, 6, 7-tetrabromo-1, 4, 5, 8-naphthalene tetracarboxylic dianhydride at a low cost |
| JP2011128261A (en) * | 2009-12-16 | 2011-06-30 | Konica Minolta Business Technologies Inc | Organic photoreceptor, method of manufacturing organic photoreceptor, image forming apparatus and image forming method |
| JP2013109019A (en) * | 2011-11-17 | 2013-06-06 | Konica Minolta Business Technologies Inc | Organic photoreceptor and image formation device |
-
2016
- 2016-09-13 CN CN201610822503.6A patent/CN106431872B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2013790A (en) * | 1931-10-03 | 1935-09-10 | Du Pont | Bromination of pyranthrone |
| US4182882A (en) * | 1977-03-22 | 1980-01-08 | Ciba-Geigy Corporation | Process for the production of pyranthrones or flavanthrones |
| JP2011128261A (en) * | 2009-12-16 | 2011-06-30 | Konica Minolta Business Technologies Inc | Organic photoreceptor, method of manufacturing organic photoreceptor, image forming apparatus and image forming method |
| CN102086210A (en) * | 2010-12-11 | 2011-06-08 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for synthesizing 2, 3, 6, 7-tetrabromo-1, 4, 5, 8-naphthalene tetracarboxylic dianhydride at a low cost |
| JP2013109019A (en) * | 2011-11-17 | 2013-06-06 | Konica Minolta Business Technologies Inc | Organic photoreceptor and image formation device |
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