CN110499039A - A kind of synthetic method of solvent blue 19 22 - Google Patents
A kind of synthetic method of solvent blue 19 22 Download PDFInfo
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- CN110499039A CN110499039A CN201910782073.3A CN201910782073A CN110499039A CN 110499039 A CN110499039 A CN 110499039A CN 201910782073 A CN201910782073 A CN 201910782073A CN 110499039 A CN110499039 A CN 110499039A
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- solvent blue
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- 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
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
- C09B1/51—N-substituted amino-hydroxy anthraquinone
- C09B1/514—N-aryl derivatives
- C09B1/5145—N-aryl derivatives only amino and hydroxy groups
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The present invention relates to a kind of synthetic method of solvent blue 19 22, includes the following steps: that water, hydrochloric acid, para aminoacet anilide are added into reaction vessel by a, stir evenly, obtain the first mixed solution；Isosorbide-5-Nitrae-dihydroxy anthraquinone, Isosorbide-5-Nitrae-dihydroxy anthraquinone leuco compound, water, catalyst CJ are added into another reaction vessel by b, obtain the second mixed solution, and catalyst CJ is catalyst of the palladium as active constituent using one or more of aluminium oxide as carrier；First mixed solution is slowly dropped to progress condensation reaction in the second mixed solution and obtains solvent blue 19 22 by c.The present invention is added dropwise by being made into the solution of equalization stable with hydrochloric acid and para aminoacet anilide and enters material, reaction rate and solute effect is enable to be controlled better；Solvent is made with water, improves operating environment, simplifies reaction time, improves production capacity, has saved cost；Novel catalyst CJ, greatly reduces the pollution in sewage to water body, improves the conversion ratio of product, reduces the temperature and pressure of reaction.
Description
Technical field
The present invention relates to a kind of synthetic methods of dyestuff, and in particular to a kind of synthetic method of solvent blue 19 22.
Background technique
Solvent blue 19 22 is a kind of important solvent dye, and also known as transparent blue R, transparent blue 2RA, its chemical name is N- [4-
[(4- hydroxy-anthraquione -1- base) amino] phenyl] acetamide, English name is Solvent Blue 122, and molecular formula is
C22H16N2O4, molecular weight 372.37, No. CAS is 67905-17-3.This product appearance is atropurpureus powder, not soluble in water, solvable
It is in dirty-green in the concentrated sulfuric acid in organic solvents such as benzene, chlorobenzene, dimethylbenzene, DMF, it is heavy to feux rouges blue that olive is generated after dilution
It forms sediment.Solvent blue 19 22 can be used for the coloring of various resin and plastics, such as polyacrylic resin, ABS resin, polystyrene, organic glass
Glass, polyester resin, polycarbonate etc. obtain feux rouges blue；There are excellent heat resistance, light resistance and resistance to migration, tinting strength, tinting power is good, thoroughly
Lightness is high, applied widely.
The prior art of chemical synthesis solvent blue 19 22 is to make catalyst with boric acid in butanol, Isosorbide-5-Nitrae-dihydroxy anthraquinone,
1,4- dihydroxy anthraquinone leuco compound and para aminoacet anilide, which are condensed, is made solvent blue 19 22.The characteristics of technique is that raw material is easy to get,
But major defect is, for butanol as solvent, smell is heavier, and site environment is severe.The reaction of para aminoacet anilide simultaneously turns
Rate is lower, and reaction is held time longer, and production efficiency is low, also virtually increases cost.
It in China Patent Publication No. CN104341790A, describes in water, one or more of anionic surfactants
In the presence of, Isosorbide-5-Nitrae-dihydroxy anthraquinone, Isosorbide-5-Nitrae-dihydroxy anthraquinone leuco compound, para aminoacet anilide, in special autoclave pressure
In, 120 DEG C are reacted 22 hours.After discharging, then with DMF aqueous solution refine, crude yield 91.65%, total recovery exists after purification
81.74%.The technique during the reaction, due to raw material water solubility it is all poor, it is easy to just clump together, influence to react.Instead
It is long between seasonable, special device is needed, reacts more demanding, is not easy to industrial production operation.
Summary of the invention
A kind of conjunction of environmentally friendly solvent blue 19 22 is provided the invention aims to overcome the deficiencies in the prior art
At method.
In order to achieve the above objectives, the technical solution adopted by the present invention is that: a kind of synthetic method of solvent blue 19 22, it includes
Following steps:
(a) water, hydrochloric acid, para aminoacet anilide are added into reaction vessel, is stirred evenly at 40~50 DEG C, obtains the
The molar ratio of one mixed solution, the para aminoacet anilide and the hydrochloric acid is 1.05~1.25:1；
(b) 1,4- dihydroxy anthraquinone, 1,4- dihydroxy anthraquinone leuco compound, water, catalyst are added into another reaction vessel
CJ obtains the second mixed solution, and the catalyst CJ is using one or more of aluminium oxide as carrier, and palladium is urged as active constituent
Agent；
(c) it by first mixed solution at 85~90 DEG C, is slowly dropped in second mixed solution and contracts
Reaction is closed, it is synthesis under normal pressure 10~14 hours, post-treated to obtain the solvent blue 19 22 after dripping.
Catalyst CJ of the invention be effective catalyst, can be improved the conversion ratio of reaction, make reaction 85~90 DEG C, often
It can be completed in the case of pressure, in step (c), the hydrochloric acid that condensation reaction generates can also help to be catalyzed, instead of boric acid, subtract significantly
Few pollution to water body.
Specifically, in step (a), the molar ratio of the para aminoacet anilide always to feed intake mole with the hydrochloric acid
For 1.05~1.25:1.
Specifically, in step (b), the Isosorbide-5-Nitrae-dihydroxy anthraquinone, the Isosorbide-5-Nitrae-dihydroxy anthraquinone leuco compound gross mass
Ratio with the quality of the catalyst CJ is 100:2~6.
Specifically, the post-processing of step (c) is to filter while hot, and reusable heat water washs into the solid being obtained by filtration
Property, then obtained solid is dried.
Specifically, step (c), the time being slowly added dropwise are 3~5h.
Specifically, in step (b), the manufacturing process of the catalyst CJ is as follows, and 1 part of aluminium oxide is added to 5 parts of quality
It is acidified in the boric acid solution that number is 2%, forms slurries, then drips ball forming and through drying, formed and carried after 350 DEG C of calcinings
Body is placed into the maceration extract containing palladium 0.1% that 100 parts prepare and is impregnated, then through drying, obtains catalyst in 500 DEG C of calcining and activatings
CJ finished product.
Reaction equation of the invention is as follows:
Due to the application of the above technical scheme, compared with the prior art, the invention has the following advantages: the present invention is a kind of molten
The synthetic method of agent indigo plant 122, by being made into the solution of equalization stable with hydrochloric acid and para aminoacet anilide, dropwise addition enters material,
So that reaction rate and arriving for solute effect is preferably controlled, solve too fast due to feeding intake during the reaction, material agglomeration,
Even buoyant phenomena such as, or excessively slow, material aoxidizes, the problem of influencing yield；Solvent is made with water, this greatly improves operation
Environment also solves later period solvent recovery, a series of problems, such as applying, enormously simplifies reaction time, improves production capacity, also saves
About cost；Using a kind of novel catalyst CJ, instead of catalyst such as boric acid before, boron is greatly reduced in sewage to water
The pollution of body, while the conversion ratio of product is improved, reduce the temperature and pressure of reaction；The solvent blue of this kind of synthetic method synthesis
122 yields can be improved 8% or so relative to conventional method, achieve preferable economic benefit and environmental benefit.
Detailed description of the invention
Fig. 1 is flow diagram of the invention.
Specific embodiment
A kind of synthetic method of solvent blue 19 22 of the invention includes the following steps:
(a) water, hydrochloric acid, para aminoacet anilide are added into reaction vessel, maintenance 25 is stirred evenly at 40~50 DEG C
~35min, obtains the first mixed solution, and the molar ratio of para aminoacet anilide and hydrochloric acid is 1.05~1.25:1；
(b) 1,4- dihydroxy anthraquinone, 1,4- dihydroxy anthraquinone leuco compound, water, catalyst are added into another reaction vessel
CJ, obtains the second mixed solution, and catalyst CJ is catalysis of the palladium as active constituent using one or more of aluminium oxide as carrier
Agent；1,4- dihydroxy anthraquinone, 1,4- dihydroxy anthraquinone leuco compound always feed intake mole and the molar ratio of hydrochloric acid be 1.05~
The ratio of the quality of 1.25:1, Isosorbide-5-Nitrae-dihydroxy anthraquinone, Isosorbide-5-Nitrae-dihydroxy anthraquinone leuco compound gross mass and catalyst CJ is
100:2~6；
(c) it by the first mixed solution at 85~90 DEG C, is slowly dropped in the second mixed solution and carries out condensation reaction, 3
~5h is added dropwise to complete, and synthesis under normal pressure 10~14 hours, is filtered while hot, reusable heat water to the solid being obtained by filtration washed to
Neutrality, then obtained solid is dried to obtain solvent blue 19 22.
Wherein, 1 part of aluminium oxide the manufacturing process of catalyst CJ: is added to the boric acid solution acid that 5 parts of mass fractions are 2%
After change, form slurries, then drips ball forming and through drying, form carrier after 350 DEG C of calcinings, place into 100 parts prepare containing palladium
It is impregnated in 0.1% maceration extract, then through drying, obtains catalyst CJ finished product in 500 DEG C of calcining and activatings.
The preparation of maceration extract containing palladium 0.1%: the presoma of palladium can select four ammino palladium of dichloro, palladium chloride etc. containing porpezite
Belong to compound, selects palladium chloride in the application.The solvent that the presoma of dissolution palladium is selected has deionized water, hydrochloric acid solution and alcohol
Class (methanol or ethyl alcohol), the solvent selected in the application are deionized water.
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention and not only limits
In this:
Embodiment 1
The present embodiment provides a kind of synthetic method of solvent blue 19 22, it the following steps are included:
(a) hot water 30ml, 30% hydrochloric acid 20g, para aminoacet anilide 30g are sequentially added in four-hole boiling flask, heating is stirred
It mixes, temperature dissolves para aminoacet anilide sufficiently, obtain the first mixed solution in 40 DEG C~50 DEG C maintenance 30min；
(b) in another four-hole boiling flask, water 80ml, Isosorbide-5-Nitrae-dihydroxy anthraquinone 28g, Isosorbide-5-Nitrae-dihydroxy anthraquinone leuco compound is added
8g, catalyst CJ 0.8g, obtains the second mixed solution；
(c) the first mixed solution is added dropwise to 85~90 DEG C in the heating stirring of the second mixed solution thereto, is dripped within 3~4 hours
It adds, maintains 12 hours, cooling, HPLC detects reaction end；It after terminal arrives, is filtered while hot, reusable heat water is to being obtained by filtration
Solid washed to neutrality, then obtained solid is dried into obtain 22 powder 53.6g of navy solvent blue 19, content
94.64%, yield 96.0%.
Embodiment 2
The present embodiment provides a kind of synthetic method of solvent blue 19 22, it with it is almost the same in embodiment 1, unlike,
25.92g para aminoacet anilide is added in step (b), eventually passes through filter, hot water is washed till neutrality, and filter cake dries to obtain solvent blue 19 22
Powder 53.1g, content 93.45%, yield 95.16%.
Embodiment 3
The present embodiment provides a kind of synthetic method of solvent blue 19 22, it with it is almost the same in embodiment 1, unlike,
30.86g para aminoacet anilide is added in step (b), eventually passes through filter, hot water is washed till neutrality, and filter cake dries to obtain solvent blue 19 22
Powder 54.2g, content 92.15%, yield 97.13%.
Embodiment 4
The present embodiment provides a kind of synthetic method of solvent blue 19 22, it with it is almost the same in embodiment 1, unlike,
Catalyst CJ 2g is added in step (b), eventually passes through filter, hot water is washed till neutrality, and filter cake dries to obtain 22 powder of solvent blue 19
53.2g, content 93.22%, yield 95.3%.
Embodiment 5
The present embodiment provides a kind of synthetic method of solvent blue 19 22, it with it is almost the same in embodiment 1, unlike,
Catalyst CJ 2.16g is added in step (b), eventually passes through filter, hot water is washed till neutrality, and filter cake dries to obtain 22 powder of solvent blue 19
53.4g, content 93.46%, yield 95.7%.
Embodiment 6
The present embodiment provides a kind of synthetic method of solvent blue 19 22, it with it is almost the same in embodiment 1, unlike,
Catalyst CJ 0.72g is added in step (b), eventually passes through filter, hot water is washed till neutrality, and filter cake dries to obtain 22 powder of solvent blue 19
51.9g, content 92.34%, yield 92.91%.
Comparative example 1
This comparative example provides a kind of synthetic method of solvent blue 19 22, it takes common processes, specifically: in four-hole boiling flask
In sequentially add butanol 120ml, water 30ml, Isosorbide-5-Nitrae-dihydroxy anthraquinone 30g, Isosorbide-5-Nitrae-dihydroxy anthraquinone leuco compound 6g, boric acid 6g is right
Amino acetanilide 30g, frame water segregator, heating dehydration, temperature start slowly to divide water after 98 DEG C of reflux, until 105 DEG C of temperature,
It maintaining for 24 hours, water-separating time is in 12h or so, and after the time arrives, HPLC detects reaction end, and after terminal arrives, water is added to steam butanol,
Heat filtering, hot water are washed till neutrality, drain, and filter cake are put into four-hole boiling flask, 120ml 80%DMF aqueous solution, 80 DEG C of mashing, often
Temperature filtering, filter cake dry to obtain finished product 48.2g, content 89.82%, yield 86.38%.
Comparative example 2
This comparative example provides a kind of synthetic method of solvent blue 19 22, it with it is almost the same in embodiment 1, unlike,
24.6g para aminoacet anilide is added in step (b), eventually passes through filter, hot water is washed till neutrality, and filter cake dries to obtain solvent blue 19 22
Powder 48.9g, content 83.25%, yield 87.54%.
Comparative example 3
This comparative example provides a kind of synthetic method of solvent blue 19 22, it with it is almost the same in embodiment 1, unlike,
It is added without catalyst CJ in step (b), changes catalyst boric acid into, eventually passes through filter, hot water is washed till neutrality, and filter cake dries to obtain solvent
122 powder 47.2g of indigo plant, content 80.45%, yield 84.49%.
The 22 material crystal form of solvent blue 19 of synthetic method synthesis of the present invention is obvious, and material particular diameter is evenly distributed, this guarantees
Good water permeability is washed, product per ton saves water 8 tons or so, while having ensured dry materials speed.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (6)
1. a kind of synthetic method of solvent blue 19 22, which is characterized in that it includes the following steps:
(a) water, hydrochloric acid, para aminoacet anilide are added into reaction vessel, is stirred evenly at 40~50 DEG C, it is mixed to obtain first
The molar ratio of conjunction solution, the para aminoacet anilide and the hydrochloric acid is 1.05~1.25:1；
(b) Isosorbide-5-Nitrae-dihydroxy anthraquinone, Isosorbide-5-Nitrae-dihydroxy anthraquinone leuco compound, water, catalyst CJ are added into another reaction vessel, obtains
To the second mixed solution；
(c) it by first mixed solution at 85~90 DEG C, is slowly dropped in second mixed solution and be condensed instead
It answers, it is synthesis under normal pressure 10~14 hours, post-treated to obtain the solvent blue 19 22 after dripping.
2. the synthetic method of solvent blue 19 22 according to claim 1, it is characterised in that: in step (c), the Isosorbide-5-Nitrae-dihydroxy
Base anthraquinone, the 1,4- dihydroxy anthraquinone leuco compound always feed intake mole and the molar ratio of the hydrochloric acid be 1.05~
1.25:1。
3. the synthetic method of solvent blue 19 22 according to claim 1, it is characterised in that: in step (c), the Isosorbide-5-Nitrae-dihydroxy
The ratio of the quality of base anthraquinone, the gross mass of the 1,4- dihydroxy anthraquinone leuco compound and the catalyst CJ is 100:2~6.
4. the synthetic method of solvent blue 19 22 according to claim 1, it is characterised in that: the post-processing of step (d) is mistake while hot
Filter, reusable heat water wash to neutrality the solid being obtained by filtration, then obtained solid is dried.
5. the synthetic method of solvent blue 19 22 according to claim 1, it is characterised in that: step (d), the time being slowly added dropwise
For 3~5h.
6. the synthetic method of solvent blue 19 22 according to claim 1, it is characterised in that: in step (b), the catalyst CJ
Manufacturing process it is as follows, by 1 part of aluminium oxide be added to 5 parts of mass fractions be 2% boric acid solution in be acidified, formed slurry
Liquid, then drips ball forming and through drying, form carrier after 350 DEG C of calcinings, place into 100 parts of dippings containing palladium 0.1% prepared
It is impregnated in liquid, then through drying, obtains catalyst CJ finished product in 500 DEG C of calcining and activatings.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1931264A (en) * | 1931-01-12 | 1933-10-17 | Du Pont | Process for the manufacture of quinizarine green and related products |
| GB2013701A (en) * | 1978-02-03 | 1979-08-15 | Ici Ltd | An Improved Process for the Preparation of Arylamino Derivatives of Anthraquinone |
| CN101406837A (en) * | 2008-10-24 | 2009-04-15 | 傅骐 | Method for preparing palladium catalyst with alkali resistance for production of hydrogen peroxide and product |
| CN104341790A (en) * | 2014-09-25 | 2015-02-11 | 宁波龙欣精细化工有限公司 | Purified 1-hydroxy-4-arylamino-anthraquinone product and preparation method thereof |
-
2019
- 2019-08-23 CN CN201910782073.3A patent/CN110499039B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1931264A (en) * | 1931-01-12 | 1933-10-17 | Du Pont | Process for the manufacture of quinizarine green and related products |
| GB2013701A (en) * | 1978-02-03 | 1979-08-15 | Ici Ltd | An Improved Process for the Preparation of Arylamino Derivatives of Anthraquinone |
| CN101406837A (en) * | 2008-10-24 | 2009-04-15 | 傅骐 | Method for preparing palladium catalyst with alkali resistance for production of hydrogen peroxide and product |
| CN104341790A (en) * | 2014-09-25 | 2015-02-11 | 宁波龙欣精细化工有限公司 | Purified 1-hydroxy-4-arylamino-anthraquinone product and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 郑鑫: "贵金属Pd催化反应的应用", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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Denomination of invention: A synthetic method of solvent blue 122 Effective date of registration: 20220215 Granted publication date: 20210212 Pledgee: Hefei Science and Technology Rural Commercial Bank Co.,Ltd. Tongling sub branch Pledgor: ANHUI QINGKE RUIJIE NEW MATERIAL CO.,LTD. Registration number: Y2022980001535 |
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