CN108587228A - A kind of production method of 149 dyestuff of solvent red - Google Patents
A kind of production method of 149 dyestuff of solvent red Download PDFInfo
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- CN108587228A CN108587228A CN201810440139.6A CN201810440139A CN108587228A CN 108587228 A CN108587228 A CN 108587228A CN 201810440139 A CN201810440139 A CN 201810440139A CN 108587228 A CN108587228 A CN 108587228A
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- solvent
- dyestuff
- solvent red
- production method
- filter cake
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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
- 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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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of 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；（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；Cool down again and filter obtaining filter cake and filtrate；（c）The bubble filter cake is washed with isolation solvent, collection is washed bubble liquid and filtrate, is distilled to recover；Filter cake described in reusable heat water washing is dry to neutrality.The 149 dyestuff △ E of solvent red of acquisition<0.5, △ C is approximate partially gorgeous, pressure value<0.2, product quality disclosure satisfy that the application demand of high-end customer.
Description
Technical field
The present invention relates to a kind of preparation methods of dyestuff, and in particular to a kind of production method of 149 dyestuff of solvent red.
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；Contained methanol, chlorobenzene solvent and excessive cyclohexylamine recovered must cover to reduce production cost in mother liquor, and reduce to ring
The pollution risk in border, but three kinds of mixed solvent recycling of this in actual production process are more difficult, exist and intersect miscible phenomenon, Jin Erying
Ring the accurate metering of charge ratio and solvent.
Invention content
A kind of production method of 149 dyestuff of solvent red is provided the invention aims to overcome the deficiencies in the prior art.
In order to solve the above technical problems, a kind of technical solution that the present invention takes is：A kind of production of 149 dyestuff of solvent red
Method, 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 one or more compositions in oxalic acid, sulfuric acid, pyrovinic acid and p-methyl benzenesulfonic acid
The weight ratio of mixture, the cyclohexylamine and bromo- N- methyl -9, the 10- Anthrapyridones of the 4- is 1 ~ 3：1, the auxiliary agent matter
Amount 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；Then drop
Temperature is added isolation solvent and is isolated to 50 ~ 70 DEG C；Cool down again and filter obtaining filter cake and filtrate；
（c）The bubble filter cake is washed with isolation solvent, collection is washed bubble liquid and filtrate, is distilled to recover；Described in reusable heat water washing
Filter cake is dry to neutrality.
Optimally, step（b）In, it is cooled to 30 ~ 45 DEG C and is filtered.
Optimally, step（c）In, the temperature of the hot water is 80 ~ 90 DEG C.
Optimally, step（c）In, the solvent of distillation recovery is applied to next batch.
Further, step（a）In, when applying mechanically the solvent of distillation recovery, first it is warming up to 100 ~ 110 DEG C and is taken off
Water adds bromo- N- methyl -9, the 10- Anthrapyridones of the 4- and auxiliary agent.
Optimally, step（a）In, the weight ratio of the cyclohexylamine and bromo- N- methyl -9, the 10- Anthrapyridones of the 4-
It is 1.8 ~ 2：1.
Optimally, step（b）In, the isolation solvent is methanol, ethyl alcohol, isopropanol, DMF, ethylene glycol monomethyl ether or diethyl
Glycol monomethyl ether.
The advantageous effect that the present invention is brought is：The production method of 149 dyestuff of solvent red of the present invention directly uses excessive ring
Hexylamine is reacted as reactant simultaneously as solvent, can overcome organic salt in product to avoid acid binding agent is used in this way
It is difficult to separation problem；And using cyclohexylamine as solvent, it can make their separation when isolating solvent when using methanol etc.
Simply, through commonly distilling；In addition addition auxiliary agent makes byproduct of reaction reduce, and a small amount of by-product of generation is dissolved in hexamethylene entirely
Amine makes not dissolving in cyclohexylamine under product low temperature by isolation, to improve product purity；Yield improves about compared with current technology
10%, up to 95% or more, economic benefit is apparent and pollutant discharge amount is reduced；Importantly, 149 dyestuff of solvent red obtained
△E <0.5, △ C is approximate partially gorgeous, pressure value<0.2, product quality disclosure satisfy that the application demand of high-end customer.
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 DYE PRODUCTION method of solvent red of the present invention.
Specific implementation mode
The production method of 149 dyestuff of solvent red of the present invention, it includes the following steps：（a）It is sequentially added into reaction vessel
Bromo- N- methyl -9, the 10- Anthrapyridone of cyclohexylamine, 4- and auxiliary agent, stirring and dissolving obtain the first mixture；The auxiliary agent be selected from
The mixture of one or more compositions in oxalic acid, sulfuric acid, pyrovinic acid and p-methyl benzenesulfonic acid, the cyclohexylamine and the 4-
The weight ratio of bromo- N- methyl -9,10- Anthrapyridones is 1 ~ 3：1, the auxiliary agent quality is the bromo Anthrapyridone quality
0.5 ~ 1%；（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；Cool down again and filter obtaining filter cake and filtrate；（c）It is molten with isolating
The bubble filter cake is washed in agent, and collection is washed bubble liquid and filtrate, is distilled to recover；Filter cake described in reusable heat water washing is dry to neutrality
.It can overcome organic salt in product to avoid acid binding agent is used and be difficult to separation problem in this way；And use cyclohexylamine conduct
Solvent, when using methanol etc. their separation can be made simple when isolating solvent, through commonly distilling；In addition auxiliary agent is added
Byproduct of reaction is set to reduce, a small amount of by-product of generation is dissolved in cyclohexylamine entirely, makes not dissolving in hexamethylene under product low temperature by isolation
Amine, to improve product purity；Yield improves about 10% compared with current technology, and up to 95% or more, economic benefit is apparent and pollutes
Object discharge capacity is reduced；Importantly, the 149 dyestuff △ E of solvent red obtained<0.5, △ C is approximate partially gorgeous, pressure value<
0.2, product quality disclosure satisfy that the application demand of high-end customer.
Step（b）In, it is cooled to 30 ~ 45 DEG C and is filtered, so that by-product does not dissolve in cyclohexylamine, and then improve production
Quality.Step（c）In, the temperature of the hot water is 80 ~ 90 DEG C so that by-product is substantially soluble in hot water, and then improves production
Quality.Step（c）In, the solvent of distillation recovery is applied to next batch；It is preferred that when applying mechanically the solvent of distillation recovery, first will
It is warming up to 100 ~ 110 DEG C and is dehydrated, and adds bromo- N- methyl -9, the 10- Anthrapyridones of the 4- and auxiliary agent；Such energy
It enough reduces the production cost of enterprise and keeps the quality of product.Step（a）In, the cyclohexylamine and bromo- methyl -9 N- the 4-,
The weight ratio of 10- Anthrapyridones is preferably 1.8 ~ 2：1.Step（b）In, the isolation solvent is preferably methanol, ethyl alcohol, isopropyl
Alcohol, DMF, ethylene glycol monomethyl ether or diethylene glycol monomethyl ether.
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 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 pyrovinic acid, throws and finishes 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 502 kilograms of 149 finished product of solvent red；Yield
It is 95.5%, content 99.2%；△ E 0.106, △ C-0.053 approximations, pressure value 0.19.
Embodiment 2
The present embodiment provides a kind of production method of 149 dyestuff of solvent red, it with it is almost the same in embodiment 1, unlike：
Step（a）The amount that middle ring amine is added is 1250 kilograms；Finally through drying, crushing, pack to obtain 505 kilograms of 149 finished product of solvent red；
Yield is 96%, content 99.4%；△ E 0.337, △ C 0.29 be partially gorgeous, pressure value 0.14.
Embodiment 3
The present embodiment provides a kind of production method of 149 dyestuff of solvent red, it with it is almost the same in embodiment 1, unlike：
Step（a）Middle 2.5 kilograms of addition oxalic acid, step（b）In be warming up to 120 ~ 130 DEG C；Finally through drying, crushing, pack to obtain solvent
500 kilograms of red 149 finished product；Yield is 95.1%, content 99.2%；△ E 0.192, △ C -0.093 are approximate, pressure value 0.18.
Embodiment 4
The present embodiment provides a kind of production method of 149 dyestuff of solvent red, it with it is almost the same in embodiment 1, unlike：
Step（a）Middle 5 kilograms of addition pyrovinic acid；Finally through drying, crushing, pack to obtain 504 kilograms of 149 finished product of solvent red；Yield is
95.8%, content 99.5%；△ E 0.463, △ C 0.383 are partially gorgeous, pressure value 0.09.
Embodiment 5
The present embodiment provides a kind of production method of 149 dyestuff of solvent red, it with it is almost the same in embodiment 1, unlike：
Step（a）Middle addition ring amine（Upper batch applies mechanically）1000 kilograms, it is first warming up to 100 ~ 110 DEG C and is dehydrated, and then cools down
To room temperature；Add 2.5 kilograms of 500 kilograms of the bromo- N- methyl -9,10- Anthrapyridones of 4- and pyrovinic acid；Finally through drying,
It crushes, pack to obtain 502 kilograms of 149 finished product of solvent red；Yield is 95.5%, content 99.1%；△ E 0.122, △ C 0.072 is close
Seemingly, pressure value 0.19.
Embodiment 6
The present embodiment provides a kind of production method of 149 dyestuff of solvent red, it with it is almost the same in embodiment 1, unlike：
Step（b）It is warming up to 80 ~ 90 DEG C；Finally through drying, crushing, pack to obtain 486 kilograms of 149 finished product of solvent red；Yield is 92.5%,
Content 99.0%；△ E 0.367, △ C -0.114 are partially dark, pressure value 0.18.
Embodiment 7
The present embodiment provides a kind of production method of 149 dyestuff of solvent red, it with it is almost the same in embodiment 1, unlike：
Step（b）It is warming up to 140 ~ 150 DEG C；Finally through drying, crushing, pack to obtain 498 kilograms of 149 finished product of solvent red；Yield is
94.7%, content 99.1%；△ E 0.423, △ C 0.355 are partially gorgeous, pressure value 0.16.
Embodiment 8
The present embodiment provides a kind of production method of 149 dyestuff of solvent red, it with it is almost the same in embodiment 1, unlike：
Step（b）The middle isolation solvent used is ethylene glycol monomethyl ether；Finally through drying, crushing, pack that obtain 149 finished product of solvent red 504 public
Jin；Yield is 95.8%, content 99.1%；△ E 0.367, △ C 0.183 are partially gorgeous, pressure value 0.12.
Embodiment 9
The present embodiment provides a kind of production method of 149 dyestuff of solvent red, it with it is almost the same in embodiment 1, unlike：
Step（b）The middle isolation solvent used is diethylene glycol monomethyl ether；Finally through drying, crushing, pack to obtain 149 finished product of solvent red
503 kilograms；Yield is 95.7%, content 99.4%；△ E 0.467, △ C 0.415 are partially gorgeous, pressure value 0.13.
Embodiment 10
The present embodiment provides a kind of production method of 149 dyestuff of solvent red, it with it is almost the same in embodiment 1, unlike：
Step（b）The middle isolation solvent used is DMF；Finally through drying, crushing, pack to obtain 466 kilograms of 149 finished product of solvent red；Yield
It is 88.5%, content 99.0%；△ E 0.736, △ C 0.512 are partially gorgeous, pressure value 0.08.
Comparative example 1
The present embodiment provides a kind of production method of 149 dyestuff of solvent red, it with it is almost the same in embodiment 1, unlike：
Step（a）In pyrovinic acid is not added；Finally through drying, crushing, pack to obtain 472 kilograms of 149 finished product of solvent red；Yield is
89.8%, content 96.4%.
Comparative example 2
The present embodiment provides a kind of production methods of 149 dyestuff of solvent red, it is carried out using common processes, specially：First anti-
It answers and solvent chlorobenzene is added in kettle（1500 kilograms）, 240 kilograms of cyclohexylamine, open stirring, put into 500 kilograms of bromo anthra pyridines
Ketone, 75 kilograms of sodium carbonate are thrown and finish capping, and condenser Inlet and outlet water is opened, and heat up into jacket steam, it is warming up within 1 hour or so 120 ~
130 DEG C, 20 hours are kept the temperature under reflux state, heat preservation terminates, and is cooled to 40 DEG C, opens bottom valve blowing and enters suction filtration tank, very
Sky drains mother liquor, and with formic acid foam washing filter cake, filter cake is washed with 80 ~ 90 DEG C of hot water to neutrality again；Filter cake enters oven drying, through powder
Spliced mixed packaging is to get 149 finished product of solvent red；450 kilograms of 149 finished product of solvent red through this technique productions, yield are
85.6%, content 95.4%.
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 (7)
1. a kind of 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 one or more compositions in oxalic acid, sulfuric acid, pyrovinic acid and p-methyl benzenesulfonic acid
The weight ratio of mixture, the cyclohexylamine and bromo- N- methyl -9, the 10- Anthrapyridones of the 4- is 1 ~ 3：1, the auxiliary agent matter
Amount 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；Then drop
Temperature is added isolation solvent and is isolated to 50 ~ 70 DEG C；Cool down again and filter obtaining filter cake and filtrate；
（c）The bubble filter cake is washed with isolation solvent, collection is washed bubble liquid and filtrate, is distilled to recover；Described in reusable heat water washing
Filter cake is dry to neutrality.
2. the production method of 149 dyestuff of solvent red according to claim 1, it is characterised in that：Step（b）In, it is cooled to
30 ~ 45 DEG C are filtered.
3. the production method of 149 dyestuff of solvent red according to claim 1, it is characterised in that：Step（c）In, the heat
The temperature of water is 80 ~ 90 DEG C.
4. the production method of 149 dyestuff of solvent red according to claim 1, it is characterised in that：Step（c）In, it distills back
The solvent of receipts is applied to next batch.
5. the production method of 149 dyestuff of solvent red according to claim 4, it is characterised in that：Step（a）In, when applying mechanically
It when the solvent of distillation recovery, is first warming up to 100 ~ 110 DEG C and is dehydrated, add bromo- N- methyl -9, the 10- anthracenes of the 4-
And pyridone and auxiliary agent.
6. the production method of 149 dyestuff of solvent red according to claim 1, it is characterised in that：Step（a）In, the ring
The weight ratio of hexylamine and the bromo- N- methyl -9,10- Anthrapyridones of the 4- is 1.8 ~ 2：1.
7. the production method of 149 dyestuff of solvent red according to claim 1, it is characterised in that：Step（b）In, it is described from
Analysis solvent is methanol, ethyl alcohol, isopropanol, DMF, ethylene glycol monomethyl ether or diethylene glycol monomethyl ether.
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| CN201810440139.6A CN108587228A (en) | 2018-05-10 | 2018-05-10 | A kind of production method of 149 dyestuff of solvent red |
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| CN201810440139.6A CN108587228A (en) | 2018-05-10 | 2018-05-10 | A kind of production method of 149 dyestuff of solvent red |
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| CN108587228A true CN108587228A (en) | 2018-09-28 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109705608A (en) * | 2019-02-20 | 2019-05-03 | 安徽清科瑞洁新材料有限公司 | A kind of environmental protection synthetic method of Anthrapyridone class dyestuff |
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| 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 |
| CN104725315A (en) * | 2013-12-21 | 2015-06-24 | 江苏道博化工有限公司 | Method used for preparing solvent red 149 |
-
2018
- 2018-05-10 CN CN201810440139.6A patent/CN108587228A/en active Pending
Patent Citations (4)
| 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 |
| CN104725315A (en) * | 2013-12-21 | 2015-06-24 | 江苏道博化工有限公司 | Method used for preparing solvent red 149 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109705608A (en) * | 2019-02-20 | 2019-05-03 | 安徽清科瑞洁新材料有限公司 | A kind of environmental protection synthetic method of Anthrapyridone class dyestuff |
| CN109705608B (en) * | 2019-02-20 | 2020-05-08 | 安徽清科瑞洁新材料有限公司 | Environment-friendly synthesis method of anthrapyridone dye |
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Application publication date: 20180928 |