CN110294694A - A kind of improved preparation method of intermediate DAS of paratonere 177 - Google Patents
A kind of improved preparation method of intermediate DAS of paratonere 177 Download PDFInfo
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- CN110294694A CN110294694A CN201910690480.1A CN201910690480A CN110294694A CN 110294694 A CN110294694 A CN 110294694A CN 201910690480 A CN201910690480 A CN 201910690480A CN 110294694 A CN110294694 A CN 110294694A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
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Abstract
It the present invention relates to a kind of improved preparation method of intermediate DAS of paratonere 177, reacts and copper powder is first added when starting, the mass ratio of copper powder quality and bromamine acid is (1~2): 5, after reaction system reacts 3-4h, add copper powder；The mass ratio of copper powder quality and bromamine acid is (2~1): 5, then react 1-1.5h；Add citric acid, the mass ratio range of citric acid quality and bromamine acid is (1~10): 5.The technology of the present invention method, by the way that copper powder is added portionwise, makes the former reaction time 7-8h of bromamine acid ullmann reaction, shortens reaction time 2-3h, keep reaction more complete, production efficiency is higher using the amount of identical catalyst；Intermediate DAS is solved the problems, such as since for purity less than 90%, raising purity to 98% or more, mantoquita content is lower than 0.001% caused by adulterating mantoquita.
Description
Technical field
The invention belongs to organic pigment preparation field, what is involved is in a kind of improved paratonere 177 for specific summary of the invention
The preparation method of mesosome DAS, i.e., about the side for containing a small amount of metallic copper in the adding manner of catalyst and removal intermediate DAS
Method.
Background technique
C.I. paratonere 177 (hereinafter PR177) is a kind of organic pigment of top grade, has a variety of excellent performances, packet
Include weather-proof, heat-resisting, solvent resistant, chemical resistance, tinting strength, tinting power height etc..It is widely used in paint, ink, plastics, synthetic resin, synthesis
Fiber, coating, liquid crystal etc..4,4 '-diaminostilbenes, 1 '-bi-anthraquinone -3,3 '-disulfonic acid (abbreviation DAS) are synthesis PR177
Intermediate, be the key that synthesis PR177.
Under green, environmental protection, the requirement of recyclable principle, using copper powder as catalyst, raw material bromamine acid is in DMF (abbreviation
DMF Liv Ullmann coupling reaction) and in METHANOL MEDIUM is carried out, DAS can be synthesized, without discharge of wastewater.Reaction equation is as follows:
DAS further progress desulfonation reaction in ion liquid medium or sulfuric acid obtains C.I. paratonere 177.DAS
It is the key intermediate of PR177 pigment.
Synthetic intermediate DAS is mainly prepared by sodium bromaminate Liv Ullmann coupling reaction.
The synthesis of intermediate DAS can carry out in organic media, and main preparation process is as follows: be usually first by catalyst
Copper powder is pre-processed in sulfuric acid and ethyl alcohol, coupling reaction is then carried out in the organic media of DMF and methanol, wait react
Entirely, copper powder is filtered out, filtrate is distilled, it is to be distilled to arrive certain volume, after cooling, a certain amount of methylene chloride is added and carries out
Stirring is precipitated.Filter cake is obtained by filtration.
Raw material bromamine acid carries out Liv Ullmann coupling reaction under conditions of copper powder is as catalyst, and copper powder would generally be disposable
It is added, this just causes part copper powder to inactivate during the reaction；Bromide ion can be taken off by raw material bromamine acid synthetic intermediate DAS,
And bromide ion can and copper powder combine and generate inorganic salts copper bromide, lead to that mantoquita can be contained in DAS product, and then lead to that DAS's is pure
Degree is less than 90%.DAS containing higher copper salt can make PR177 second-rate after deviating from sulfonic group.
From the aspect of environmental protection, health, product quality and energy consumption, there are following distinct disadvantages for above-mentioned production process:
(1) being added at one time for catalyst copper powder causes part copper powder catalytic property to inactivate, both increases copper powder
Dosage, and extend the reaction time.The mass ratio of copper powder and sodium bromaminate is 3:5 in technology before the present invention, when reaction
Between need 7-8 hours.
(2) during synthetic intermediate DAS, the bromide ion of raw material bromamine acid, bromide ion meeting and catalyst copper powder can be taken off
In conjunction with remaining in filtrate, cause to contain mantoquita in last DAS product, and then cause the purity of DAS less than 90%.The present invention
In technology before, for the content of mantoquita between 1.25%-2.5%, mantoquita content is too high in DAS product.
(3) can have an adverse effect to the quality of PR177 in DAS containing the mantoquita of high level.
It is above-mentioned therefore, it is desirable to be improved, be solved the problems, such as by better technology of preparing.
Summary of the invention
Object of the present invention is to a kind of improved preparation method of intermediate DAS of paratonere 177, it is to provide a kind of solution and urges
Agent copper powder is added at one time the problem of leading to copper powder partial inactivation, allows copper powder to give full play to the effect of catalyst, in equal amount
Catalyst under, the former reaction time be 7-8h, improve technique after, 2-3h will be shortened in the reaction time.For containing in intermediate DAS
There is mantoquita to lead to the case where purity is less than 90%, the mantoquita for dissolving in organic solvent is made to be converted to the object that cannot be dissolved in organic solvent
Matter, filtering removal.The technology of the present invention can make mantoquita content in DAS be reduced to 0.001% hereinafter, DAS purity is higher than 98%.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows:
A kind of improved preparation method of intermediate DAS of paratonere 177, it is characterized in that catalyst copper powder is added portionwise, so
Addition citric acid removes mantoquita afterwards.
The mode that catalyst copper powder is added portionwise is that copper powder, copper powder quality and bromine ammonia is first added in reaction when starting
The mass ratio of acid is (1~2): 5, after reaction system reacts 3-4h, add copper powder；The mass ratio of copper powder quality and bromamine acid
For (2~1): 5, then react 1-1.5h；Add citric acid, the mass ratio range of citric acid quality and bromamine acid be (1~
10):5。
A kind of improved preparation method of intermediate DAS of paratonere 177, solution catalyst copper powder, which is added at one time, leads to portion
The method for dividing copper powder inactivation, is added portionwise catalyst copper powder, catalyst copper powder is made to give full play to catalytic action.It is a kind of
Solution catalyst mantoquita, which enters intermediate DAS, causes purity less than 90%, and the higher method of copper content, into reaction system
Citric acid is added, after so that the part mantoquita for dissolving in solvent is converted to the mantoquita insoluble in dicyandiamide solution, filtering removal is insoluble
Property mantoquita, not only improved the purity of DAS, but also reduce the content of mantoquita in DAS.
Basic process of the invention are as follows:
The proportional region for weighing copper powder quality and bromamine acid quality is (1~2): sulfuric acid and ethyl alcohol is added in temperature in 5 copper powder
Degree is 42 DEG C of stirring half an hour, is then allowed to stand, and supernatant liquor is poured out, and retains copper powder；
Raw material bromamine acid, solvent DMF and methanol are added into above-mentioned copper powder, reacts 3- under conditions of temperature is 55 DEG C
4h, then adding into the proportional region of copper powder quality and bromamine acid quality is (2~1): 5 copper powder；
After addition second batch copper powder reacts 1-1.5h again, the mass ratio range that citric acid quality and bromamine acid is added is (1
~10): 5 citric acid, be added citric acid after react 0.5-1h again after, reaction terminates, and filters out copper powder.
Advantages of the present invention:
The technology of the present invention method, by the way that copper powder is added portionwise, makes bromine ammonia using the amount of identical catalyst
The former reaction time of sour ullmann reaction is 7-8h, shortens reaction time 2-3h, keeps reaction more complete, production efficiency is higher；
Solve the problems, such as intermediate DAS due to caused by doping mantoquita purity improve purity to 98% or more less than 90%, mantoquita
Content is lower than 0.001%.
Specific embodiment
Combined with specific embodiments below, technical solution of the present invention is further elaborated.
Embodiment 1
Copper powder is added portionwise.Copper powder quality is first added and sodium bromaminate mass ratio is 2:5, it is rear that copper powder quality and bromine is added
Propylhomoserin sodium mass ratio is 1:5.
The mass ratio of citric acid quality and sodium bromaminate is 1:10.
2g copper powder is weighed, is added in four-hole boiling flask, 3g ethyl alcohol and 3g sulfuric acid is added, flask is placed in water-bath,
42 DEG C of stirring 0.5h of temperature pour out supernatant liquor after standing the 0.5h time.Addition 5g sodium bromaminate, 55g DMF, 110g methanol,
Reaction system is heated to 55 DEG C of progress ullmann reaction 4h, adds 1g copper powder.0.5g citric acid is added when reacting 5h in system,
After system reacts 5.5h, stop stirring, filtering.PH value=1-2 of filtrate, the remaining suitable filter of distillation are adjusted before distillation filtrate
Liquid is cooled to room temperature, and 20mL methylene chloride is added, and stirs 2h, filtering.It obtains drying 8h at filter cake is 75 DEG C in temperature.It is whole
Reaction time is 5.5h, and DAS color is kermesinus.Detect intermediate DAS tenor < 0.001%.The purity of DAS is
98.6%.
Embodiment 2
Copper powder is added portionwise.Copper powder is first added and sodium bromaminate mass ratio is 1:5, it is rear that copper powder quality and bromamine acid is added
Sodium mass ratio is 2:5.
The mass ratio of citric acid and sodium bromaminate is 1:8.
1g copper powder is weighed, is added in four-hole boiling flask, 3g ethyl alcohol and 3g sulfuric acid is added, flask is placed in water-bath,
42 DEG C of stirring 0.5h of temperature.After standing the 0.5h time, supernatant liquor is poured out.Addition 5g sodium bromaminate, 55g DMF, 110g methanol,
Reaction system is heated to 55 DEG C of progress ullmann reaction 3h.2g copper powder is added, 0.625g citric acid is added when reacting 4h in system,
After system reacts 5h, stop stirring, filtering.PH value=1-2 of filtrate, the remaining suitable filter of distillation are adjusted before distillation filtrate
Liquid is cooled to room temperature, and 20mL methylene chloride is added, and stirs 2h, filtering.It obtains drying 8h at filter cake is 75 DEG C in temperature.It is whole
Reaction time is 4.5h, and DAS color is kermesinus.Detect intermediate DAS tenor < 0.001%.The purity of DAS is
98.1%.
Embodiment 3
Copper powder is added portionwise.Copper powder is first added and sodium bromaminate mass ratio is 1.5:5, it is rear that copper powder quality and bromine ammonia is added
Sour sodium mass ratio is 1.5:5.
The mass ratio of citric acid quality and sodium bromaminate is 1:6.
1.5g copper powder is weighed, is added in four-hole boiling flask, 3g ethyl alcohol and 3g sulfuric acid is added, flask is placed in water-bath,
In 42 DEG C of stirring 0.5h of temperature.After standing the 0.5h time, supernatant liquor is poured out.5g sodium bromaminate, 55g DMF, 110g first is added
Reaction system is heated to 55 DEG C of progress ullmann reaction 3h by alcohol, and 1.5g copper powder is added, and 0.833g lemon is added when reacting 4h in system
Lemon acid after system reacts 4.5h, stops stirring, filtering.PH value=1-2 that filtrate is adjusted before distillation filtrate distills remaining suitable
The filtrate of amount, is cooled to room temperature, and 20mL methylene chloride is added, and stirs 2h, filtering.It obtains drying at filter cake is 75 DEG C in temperature
8h.The W-response time is 4.5h, and DAS color is kermesinus.Detect intermediate DAS tenor < 0.001%.The purity of DAS
It is 98.1%.
The invention is not limited to the technology described in embodiment, its description is illustrative, and unrestricted.
Permission of the invention is defined in the claims, and the side such as can change, recombinate according to the present invention based on those skilled in the art
The technology related to the present invention that method obtains, all within protection scope of the present invention.
Claims (5)
1. the improved preparation method of intermediate DAS of a kind of paratonere 177, it is characterized in that catalyst copper powder is added portionwise, then
It adds citric acid and removes mantoquita.
2. preparation method as described in claim 1, it is characterized in that the mode of catalyst copper powder, which is added portionwise, is, when reaction starts
Copper powder is first added, after reaction system reacts 3-4h, adds copper powder, then react 1-1.5h；Add citric acid.
3. preparation method as claimed in claim 2, it is characterized in that the mass ratio of addition copper powder quality and bromamine acid is for the first time
(1~2): 5.
4. preparation method as claimed in claim 2, it is characterized in that adding copper powder for the second time；The matter of copper powder quality and bromamine acid
Amount is than being (2~1): 5.
5. preparation method as claimed in claim 2, it is characterized in that citric acid quality and the mass ratio range of bromamine acid are (1
~10): 5.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115010630A (en) * | 2022-05-11 | 2022-09-06 | 宁夏彩妍科技有限公司 | Production method and production system of PR177 intermediate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3565923A (en) * | 1966-12-12 | 1971-02-23 | Ciba Ltd | Process for the manufacture of 4,4'-diamino-1,1'-dianthraquinonylenes |
| CN107459470A (en) * | 2017-08-25 | 2017-12-12 | 天津城建大学 | The method that heterogeneous system catalyzes and synthesizes bromamine acid condensation product |
-
2019
- 2019-07-29 CN CN201910690480.1A patent/CN110294694A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3565923A (en) * | 1966-12-12 | 1971-02-23 | Ciba Ltd | Process for the manufacture of 4,4'-diamino-1,1'-dianthraquinonylenes |
| CN107459470A (en) * | 2017-08-25 | 2017-12-12 | 天津城建大学 | The method that heterogeneous system catalyzes and synthesizes bromamine acid condensation product |
Non-Patent Citations (2)
| Title |
|---|
| 张天永等: "有机溶剂中合成4,4"-二氨基-1,1"-联蒽醌-3,3"-二磺酸", 《化工学报》 * |
| 韩广甸等: "《有机制备化学手册 中卷》", 31 May 1980, 化学工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115010630A (en) * | 2022-05-11 | 2022-09-06 | 宁夏彩妍科技有限公司 | Production method and production system of PR177 intermediate |
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