CN108586338A - A kind of low stain production method of 149 dyestuff of solvent red - Google Patents
A kind of low stain production method of 149 dyestuff of solvent red Download PDFInfo
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- CN108586338A CN108586338A CN201810440138.1A CN201810440138A CN108586338A CN 108586338 A CN108586338 A CN 108586338A CN 201810440138 A CN201810440138 A CN 201810440138A CN 108586338 A CN108586338 A CN 108586338A
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- solvent
- filter cake
- auxiliary agent
- washed
- dyestuff
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/04—Ortho- or peri-condensed ring systems
- C07D221/18—Ring systems of four or more rings
-
- 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
- C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
- C09B5/02—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings the heterocyclic ring being only condensed in peri position
- C09B5/14—Benz-azabenzanthrones (anthrapyridones)
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of low stain production methods of 149 dyestuff of solvent red, it includes the following steps：（a）Cyclohexylamine, 4 bromine N methyl, 9,10 Anthrapyridone and auxiliary agent, stirring and dissolving are sequentially added into reaction vessel obtains the first mixture；The auxiliary agent is 1 butyl sulfonic acid, 3 methylimidazolium hydrogen sulphate salt, and the weight ratio of the cyclohexylamine and 4 bromine N methyl, 9,10 Anthrapyridone is 1 ~ 3：1, the auxiliary agent quality is the 0.5 ~ 1% of the bromo Anthrapyridone quality；（b）First mixture is warming up to 80 ~ 150 DEG C to react, is detected using HPLC and determines reaction end；50 ~ 70 DEG C are then cooled to, isolation solvent is added and is isolated, then filters to obtain filter cake and filtrate；The isolation solvent is methanol, ethylene glycol monomethyl ether or diethylene glycol monomethyl ether；（c）The bubble filter cake is washed with isolation solvent, collection is washed bubble liquid and filtrate, is distilled to recover；The filter cake is washed to neutrality, drying with 80 ~ 90 DEG C of hot water again.To improve product purity, economic benefit is apparent and pollutant discharge amount is reduced.
Description
Technical field
The present invention relates to a kind of preparation methods of dyestuff, and in particular to a kind of low stain producer of 149 dyestuff of solvent red
Method.
Background technology
Solvent red 149 is also known as fluorescein HFG, and its chemical name is 6- (Cyclohexylamino) -3-N- methyl Anthrapyridones, English
Literary fame is known as Solvent Red 149, molecular formula C23H22N2O2, molecular weight 358.43, No. CAS is 71902-18-6.It is glimmering
The red HFG of light can be used for the coloring of various resin and plastics, such as polyacrylic resin, ABS resins, polystyrene, organic glass, wash
It is red to obtain gorgeous blue light for synthetic fibre resin, makrolon etc.；There are excellent heat resistance, light resistance and resistance to migration, tinting strength, tinting power is good, transparent
Degree is high, applied widely.
Currently, the common processes of production solvent red 149 are：It is 1 that weight ratio is first added in reaction kettle：1 solvent chlorobenzene,
Cyclohexylamine, opens stirring, and input bromo Anthrapyridone, sodium carbonate are thrown and finish capping, open condenser Inlet and outlet water, steamed into chuck
Vapour heats up, and is warming up to 120 ~ 130 DEG C within 1 hour or so, keeps the temperature 20 hours under reflux state, heat preservation terminates, and is cooled to 40 DEG C, opens
Open bottom valve blowing and enter suction filtration tank, vacuum drains mother liquor, with formic acid foam washing filter cake, filter cake again with 80 ~ 90 DEG C of hot water wash to
It is neutral；Filter cake enters oven drying, through crushing blending packaging to get 149 finished product of solvent red.Solvent red through this technique productions
149 product quality are bad, coloured light poor reproducibility, form and aspect △ E>0.5 account for total output about 30%, part single batch product need through
Solvent refining can be only achieved qualified quality, cause the wasting of resources, while also resulting in pollution to environment；Reaction yield is low, about
It is 85%, generated competitive elimination side reaction is not easy to control in reaction process, influences reaction selectivity and then influence product is received
Rate.
Invention content
A kind of low stain production of 149 dyestuff of solvent red is provided the invention aims to overcome the deficiencies in the prior art
Method.
In order to solve the above technical problems, a kind of technical solution that the present invention takes is：A kind of low dirt of 149 dyestuff of solvent red
Production method is contaminated, it includes the following steps：
（a）Bromo- N- methyl -9, the 10- Anthrapyridone of cyclohexylamine, 4- and auxiliary agent, stirring and dissolving are sequentially added into reaction vessel
Obtain the first mixture；The auxiliary agent is 1- butyl sulfonic acid -3- methylimidazolium hydrogen sulphate salt, the cyclohexylamine and the bromo- N- of the 4-
The weight ratio of methyl -9,10- Anthrapyridones is 1 ~ 3：1, the auxiliary agent quality is the 0.5 of the bromo Anthrapyridone quality
~1%；
（b）First mixture is warming up to 80 ~ 150 DEG C to react, is detected using HPLC and determines reaction end；Then drop
Temperature is added isolation solvent and is isolated, then filter to obtain filter cake and filtrate to 50 ~ 70 DEG C；The isolation solvent is methanol, ethylene glycol
Methyl ether or diethylene glycol monomethyl ether；
（c）The bubble filter cake is washed with isolation solvent, collection is washed bubble liquid and filtrate, is distilled to recover；Again with 80 ~ 90 DEG C of hot water
The filter cake is washed to neutrality, drying.
Optimally, step（b）In, it is cooled to 30 ~ 45 DEG C and is filtered.
The advantageous effect that the present invention is brought is：The low stain production method of 149 dyestuff of solvent red of the present invention, use are excessive
Cyclohexylamine is reacted as reactant simultaneously as solvent, can be overcome organic in product to avoid acid binding agent is used in this way
Salt is difficult to separation problem；And using cyclohexylamine as solvent, when point for using methanol etc. that can make them when isolating solvent
From simple, through commonly distilling；In addition addition auxiliary agent 1- butyl sulfonic acid -3- methylimidazolium hydrogen sulphates salt can be catalyzed reaction
It carries out and byproduct of reaction is made to reduce, to improve product purity, economic benefit is apparent and pollutant discharge amount is reduced.
Description of the drawings
Fig. 1 is the reaction equation of 149 dyestuff of solvent red of the present invention；
Fig. 2 is the process flow chart of 149 dyestuff low stain production method of solvent red of the present invention.
Specific implementation mode
The low stain production method of 149 dyestuff of solvent red of the present invention, it includes the following steps：（a）Into reaction vessel according to
Secondary addition cyclohexylamine, bromo- N- methyl -9, the 10- Anthrapyridones of 4- and auxiliary agent, stirring and dissolving obtain the first mixture；The auxiliary agent
For 1- butyl sulfonic acid -3- methylimidazolium hydrogen sulphate salt, the cyclohexylamine and bromo- N- methyl -9, the 10- Anthrapyridones of the 4-
Weight ratio is 1 ~ 3：1, the auxiliary agent quality is the 0.5 ~ 1% of the bromo Anthrapyridone quality；（b）Described first is mixed
Object is warming up to 80 ~ 150 DEG C and is reacted, and is detected using HPLC and determines reaction end；50 ~ 70 DEG C are then cooled to, isolation is added
Solvent is isolated, then filters to obtain filter cake and filtrate；The isolation solvent is methanol, ethylene glycol monomethyl ether or diethylene glycol list first
Ether；（c）The bubble filter cake is washed with isolation solvent, collection is washed bubble liquid and filtrate, is distilled to recover；Again with 80 ~ 90 DEG C of hot water
The filter cake is washed to neutrality, drying.It is reacted simultaneously as reactant as solvent using excessive cyclohexylamine, this
Sample can overcome organic salt in product and be difficult to separation problem to avoid acid binding agent is used；And using cyclohexylamine as solvent, when
Their separation can be made simple when methanol etc. being used to isolate solvent, through commonly distilling；In addition auxiliary agent 1- butyl is added
Sulfonic acid -3- methylimidazolium hydrogen sulphates salt can be catalyzed the progress of reaction and byproduct of reaction is made to reduce, pure to improve product
Degree, economic benefit is apparent and pollutant discharge amount is reduced.Above-mentioned steps（b）In, it is preferably cooled to 30 ~ 45 DEG C and is filtered.
The preferred embodiment of the invention is described in detail below in conjunction with attached drawing：
Embodiment 1
The present embodiment provides a kind of low stain production methods of 149 dyestuff of solvent red, as shown in Fig. 2, it includes the following steps：
（a）900 kilograms of ring amine is added into the enamel reaction still of 3000L（Human metering）, put into the bromo- N- methyl -9,10- of 4-
500 kilograms of Anthrapyridone adds 2.5 kilograms of 1- butyl sulfonic acid -3- methylimidazolium hydrogen sulphates salt（CAS： 827320-59-
2）, throw and finish capping stirring；
（b）It opens the condenser Inlet and outlet water of reaction kettle and is heated up using jacket steam, be warming up to 100 ~ 110 DEG C within 1 hour or so（This
Temperature change in temperature range influences product quality little）, and maintain reaction 10 hours in this temperature（Reactional equation
Formula is as shown in Figure 1, HPLC detections at this time reach terminal）；60 DEG C are cooled to, 400 kilograms of methanol are added and are isolated, stirring is maintained
2 hours；It is cooled to 40 DEG C of unlatching bottom valves again to be discharged in filter pocket, drains mother liquor and obtains filter cake and filtrate；
（c）400 kilograms of methanol foam washings of filter cake collect filtrate and foam washing liquid, are distilled to recover solvent（Contain ring amine, methanol）；
Filter cake washs filter cake to neutrality with 80 ~ 90 DEG C of hot water again, through drying, crushing, packs to obtain 515 kilograms of 149 finished product of solvent red；Yield
It is 97.9%, content 99.5%.
Embodiment 2
The present embodiment provides a kind of low stain production method of 149 dyestuff of solvent red, it with it is almost the same in embodiment 1, no
Be：Step（a）The amount that middle ring amine is added is 1250 kilograms；Finally through drying, crushing, pack to obtain 149 finished product of solvent red
516 kilograms；Yield is 98.2%, content 99.4%.
Embodiment 3
The present embodiment provides a kind of low stain production method of 149 dyestuff of solvent red, it with it is almost the same in embodiment 1, no
Be：Step（a）Middle 5 kilograms of addition 1- butyl sulfonic acid -3- methylimidazolium hydrogen sulphates salt；Finally through drying, crushing, pack
518 kilograms of 149 finished product of solvent red；Yield is 98.5%, content 99.6%.
Embodiment 4
The present embodiment provides a kind of low stain production method of 149 dyestuff of solvent red, it with it is almost the same in embodiment 1, no
Be：Step（b）The middle isolation solvent used is ethylene glycol monomethyl ether；Through drying, crushing, pack to obtain 149 finished product of solvent red
515.5 kilogram；Yield is 98.0%, content 99.5%.
Embodiment 5
The present embodiment provides a kind of low stain production method of 149 dyestuff of solvent red, it with it is almost the same in embodiment 1, no
Be：Step（b）The middle isolation solvent used is diethylene glycol monomethyl ether；Through drying, crushing, pack solvent red 149 at
515.5 kilograms of product；Yield is 98.0%, content 99.5%.
Embodiment 6
The present embodiment provides a kind of low stain production method of 149 dyestuff of solvent red, it with it is almost the same in embodiment 1, no
Be：Step（b）In, it is cooled to 30 ~ 45 DEG C and is filtered again；Through drying, crushing, pack to obtain 149 finished product 515.5 of solvent red
Kilogram；Yield is 98.0%, content 99.5%.
Comparative example 1
The present embodiment provides a kind of dye production method of 149 dyestuff of solvent red, it with it is almost the same in embodiment 1, it is different
It is：Step（a）Middle addition is pyrovinic acid, and final packaging obtains 502 kilograms of 149 finished product of solvent red；Yield is 95.5%, content
99.2%。
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 (2)
1. a kind of low stain production method of 149 dyestuff of solvent red, which is characterized in that it includes the following steps：
（a）Bromo- N- methyl -9, the 10- Anthrapyridone of cyclohexylamine, 4- and auxiliary agent, stirring and dissolving are sequentially added into reaction vessel
Obtain the first mixture；The auxiliary agent is 1- butyl sulfonic acid -3- methylimidazolium hydrogen sulphate salt, the cyclohexylamine and the bromo- N- of the 4-
The weight ratio of methyl -9,10- Anthrapyridones is 1 ~ 3：1, the auxiliary agent quality is the 0.5 of the bromo Anthrapyridone quality
~1%；
（b）First mixture is warming up to 80 ~ 150 DEG C to react, is detected using HPLC and determines reaction end；Then drop
Temperature is added isolation solvent and is isolated, then filter to obtain filter cake and filtrate to 50 ~ 70 DEG C；The isolation solvent is methanol, ethylene glycol
Methyl ether or diethylene glycol monomethyl ether；
（c）The bubble filter cake is washed with isolation solvent, collection is washed bubble liquid and filtrate, is distilled to recover；Again with 80 ~ 90 DEG C of hot water
The filter cake is washed to neutrality, drying.
2. the low stain production method of 149 dyestuff of solvent red according to claim 1, it is characterised in that：Step（b）In,
30 ~ 45 DEG C are cooled to be filtered.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810440138.1A CN108586338A (en) | 2018-05-10 | 2018-05-10 | A kind of low stain production method of 149 dyestuff of solvent red |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810440138.1A CN108586338A (en) | 2018-05-10 | 2018-05-10 | A kind of low stain production method of 149 dyestuff of solvent red |
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| Publication Number | Publication Date |
|---|---|
| CN108586338A true CN108586338A (en) | 2018-09-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810440138.1A Pending CN108586338A (en) | 2018-05-10 | 2018-05-10 | A kind of low stain production method of 149 dyestuff of solvent red |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000191646A (en) * | 1999-01-01 | 2000-07-11 | Sumika Fine Chemicals Co Ltd | Production of anthrapyridone-based compound |
| CN1297000A (en) * | 1999-11-22 | 2001-05-30 | 江苏亚邦集团公司 | Cyclohexanamido anthrapyridone dye and production method thereof |
| CN1296999A (en) * | 1999-11-22 | 2001-05-30 | 江苏亚邦集团公司 | Anthrapyridone dye intermediate and production method thereof |
-
2018
- 2018-05-10 CN CN201810440138.1A patent/CN108586338A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000191646A (en) * | 1999-01-01 | 2000-07-11 | Sumika Fine Chemicals Co Ltd | Production of anthrapyridone-based compound |
| CN1297000A (en) * | 1999-11-22 | 2001-05-30 | 江苏亚邦集团公司 | Cyclohexanamido anthrapyridone dye and production method thereof |
| CN1296999A (en) * | 1999-11-22 | 2001-05-30 | 江苏亚邦集团公司 | Anthrapyridone dye intermediate and production method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 胡燚 等: "离子液体中缩合反应研究进展", 《化学试剂》 * |
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Application publication date: 20180928 |