CN112142759A - Plastic colorant fluorescein 3G and preparation method thereof - Google Patents
Plastic colorant fluorescein 3G and preparation method thereof Download PDFInfo
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- CN112142759A CN112142759A CN202010956029.2A CN202010956029A CN112142759A CN 112142759 A CN112142759 A CN 112142759A CN 202010956029 A CN202010956029 A CN 202010956029A CN 112142759 A CN112142759 A CN 112142759A
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- fluorescein
- benzothiazole
- solvent
- plastic colorant
- dicarboxylic anhydride
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/06—Peri-condensed systems
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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
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/14—Benzoxanthene dyes; Benzothioxanthene dyes
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
Abstract
The invention belongs to the technical field of plastic colorants, and particularly relates to a plastic colorant fluorescein 3G and a preparation method thereof. The plastic colorant is prepared from 3G benzothiazole dicarboxylic anhydride and cyclohexylamine, wherein the molar ratio of the benzothiazole dicarboxylic anhydride to the cyclohexylamine is 0.8-1.2: 1. the preparation method of the plastic colorant fluorescein 3G comprises the following steps: 1) condensation: adding benzothiazole dicarboxylic anhydride and cyclohexylamine into a condensation kettle according to a ratio, and carrying out reflux reaction for 11-13 hours at the temperature of 115-125 ℃; 2) washing and drying: after the reaction is finished, cooling to 45-70 ℃, adding a first solvent for washing to obtain a filter cake, and distilling a washing liquid to recover the first solvent; and washing the filter cake with a second solvent until the pH value is neutral, and then placing the filter cake in a drying device for drying to obtain the plastic colorant fluorescein 3G. The cyclohexylamine is used as a raw material and is colorless liquid, and the operations such as dissolution and the like are not needed during production, so that the process steps are simplified, and the reaction conditions are mild.
Description
Technical Field
The invention belongs to the technical field of plastic colorants, and particularly relates to a plastic colorant fluorescein 3G and a preparation method thereof.
Background
Fluorescein 3G, also known as solvent yellow 98. Conventional fluorescein 3G (CAS number: 12671-74-8) is prepared from 4-nitro-1, 8-naphthalic anhydride, o-aminothiophenol and octadecylamine. Firstly, 4-nitro-1, 8-naphthalic anhydride is condensed with o-amino thiophenol to prepare thioether compounds, then the thioether compounds are condensed with octadecylamine to prepare naphthalimide intermediates, and finally free amino in molecules is diazotized, closed-loop and treated by liquid alkali to obtain the product. Filtering, drying and crushing to obtain the finished product.
The octadecylamine in the above production method is a white wax-like crystal, and the reaction operation is complicated and requires operations such as melting and stirring. And the octadecylamine is a long-chain compound, and the reaction efficiency of the long-chain compound is low, so the requirements on reaction conditions are harsh, the process is complex, and the production cost is high.
Disclosure of Invention
The invention aims to provide a plastic colorant fluorescein 3G and a preparation method thereof, and aims to solve the technical problems of complex process and high production cost of the preparation method of the fluorescein 3G in the prior art.
In order to achieve the above object, an embodiment of the present invention provides a plastic colorant fluorescein 3G, which has a structure represented by formula (1):
optionally, the plastic colorant fluorescein 3G comprises the following raw materials: benzothiazole dicarboxylic anhydride and cyclohexylamine, wherein the molar ratio of the benzothiazole dicarboxylic anhydride to the cyclohexylamine is 0.8-1.2: 1.
alternatively, the molar ratio of the benzothiazole dicarboxylic anhydride to the cyclohexylamine is 1: 1.
alternatively, the benzothiazole dicarboxylic anhydride comprises the following starting materials: 4- (2-amino diazonium salt benzenesulfydryl) -1, 8-naphthalic anhydride and copper catalase.
Optionally, the copper catalase is copper sulfate.
One or more technical schemes in the plastic colorant fluorescein 3G provided by the embodiment of the invention have at least one of the following technical effects: the plastic colorant fluorescein 3G replaces an octadecane agent with cyclohexane, the cyclohexane and a heterocycle can easily form a stable structure, and the plastic colorant fluorescein 3G has beautiful fluorescence and higher light fastness and heat-resisting temperature.
In order to achieve the above object, an embodiment of the present invention further provides a method for preparing the plastic colorant fluorescein 3G, including the following steps:
1) condensation: adding benzothiazole dicarboxylic anhydride and cyclohexylamine into a condensation kettle according to a ratio, and carrying out reflux reaction for 11-13 hours at the temperature of 115-125 ℃;
2) washing and drying: after the reaction is finished, cooling to 45-70 ℃, adding a first solvent for washing to obtain a filter cake, and distilling a washing liquid to recover the first solvent; and washing the filter cake with a second solvent until the pH value is neutral, and then placing the filter cake in a drying device for drying to obtain the plastic colorant fluorescein 3G.
Optionally, the preparation method of the plastic colorant fluorescein 3G further comprises the following steps:
3) preparation of the benzothiazole dicarboxylic anhydride: adding 4- (2-amino diazo salt benzene mercapto) -1, 8-naphthalic anhydride and copper catalase into a closed-loop kettle, heating to 115-125 ℃, carrying out closed-loop reaction for 0.8-1.2 hours, pumping into a filter press for filter pressing after the reaction is finished, washing a filter cake with a third solvent, and drying to obtain the benzothiazole dicarboxylic anhydride.
Optionally, the first solvent is ethanol.
Optionally, the second solvent is hot water with the temperature of 40-90 ℃.
Optionally, the third solvent is water.
One or more technical schemes in the preparation method of the plastic colorant fluorescein 3G provided by the embodiment of the invention have at least one of the following technical effects: the preparation method of the plastic colorant fluorescein 3G takes cyclohexylamine as a raw material, the cyclohexylamine is colorless liquid, and operations such as dissolution and the like are not needed during production, so that the process steps are simplified, the reaction conditions are mild, the requirements on equipment are low, and the production cost is reduced; the cyclohexylamine is easier to condense with benzothiazole dicarboxylic anhydride, the reaction yield is high, and the conversion rate is high.
Detailed Description
The present invention will be further described with reference to the following examples, but the embodiments of the present invention are not limited thereto.
The plastic colorant of the invention, namely the fluorescent yellow 3G, has a structure shown as a formula (1):
the plastic colorant fluorescein 3G replaces an octadecane agent in the traditional fluorescein 3G with cyclohexane, the cyclohexane and a heterocycle can easily form a stable structure, and the plastic colorant fluorescein 3G has beautiful fluorescence and higher light fastness and heat-resisting temperature. Tests show that the light resistance is 7-8 grade, and the heat resistance in PS can reach 300 ℃.
In the invention, the plastic colorant fluorescein 3G comprises the following raw materials: benzothiazole dicarboxylic anhydride and cyclohexylamine, wherein the molar ratio of the benzothiazole dicarboxylic anhydride to the cyclohexylamine is 0.8-1.2: 1. in some embodiments of the invention, the molar ratio of the benzothiazole dicarboxylic anhydride to the cyclohexylamine may be 0.8: 1. 0.9: 1 or 1.2: 1, more preferably 1: 1.
in the present invention, the benzothiazole dicarboxylic anhydride comprises the following starting materials: 4- (2-amino diazonium salt benzenesulfydryl) -1, 8-naphthalic anhydride and copper catalase.
In the present invention, the copper catalase is copper sulfate. The copper sulfate is easy to obtain, the cost is low, the catalytic effect is high, and the environmental pollution is small.
The preparation method of the plastic colorant fluorescein 3G comprises the following steps:
1) condensation: adding benzothiazole dicarboxylic anhydride and cyclohexylamine into a condensation kettle according to a ratio, and carrying out reflux reaction for 11-13 hours at the temperature of 115-125 ℃;
2) washing and drying: after the reaction is finished, cooling to 45-70 ℃, adding a first solvent for washing to obtain a filter cake, and distilling a washing liquid to recover the first solvent; and washing the filter cake with a second solvent until the pH value is neutral, and then placing the filter cake in a drying device for drying to obtain the plastic colorant fluorescein 3G.
The chemical reaction formula of the preparation method of the plastic colorant fluorescein 3G is as follows:
the preparation method of the plastic colorant fluorescein 3G takes cyclohexylamine as a raw material, the cyclohexylamine is colorless liquid, and operations such as dissolution and the like are not needed during production, so that the process steps are simplified, the reaction conditions are mild, the requirements on equipment are low, and the production cost is reduced; the cyclohexylamine is easier to condense with benzothiazole dicarboxylic anhydride, the reaction yield is high, and the conversion rate is high.
In the invention, the preparation method of the plastic colorant fluorescein 3G also comprises the following steps:
3) preparation of the benzothiazole dicarboxylic anhydride: adding 4- (2-amino diazo salt benzene mercapto) -1, 8-naphthalic anhydride and copper catalase into a closed-loop kettle, heating to 115-125 ℃, carrying out closed-loop reaction for 0.8-1.2 hours, pumping into a filter press for filter pressing after the reaction is finished, washing a filter cake with a third solvent, and drying to obtain the benzothiazole dicarboxylic anhydride.
The chemical reaction formula of the preparation method of the benzothiazole dicarboxylic anhydride is as follows:
in the present invention, the first solvent is ethanol. The ethanol has the advantages of easy obtaining, low cost, less pollution, easy recovery and the like. The first solvent may be an organic solvent such as xylene, toluene, or diethyl ether.
In the invention, the second solvent is hot water with the temperature of 40-90 ℃. In some embodiments of the invention, the temperature of the hot water may be 40 ℃, 50 ℃, 60 ℃, 80 ℃ and 90 ℃.
In the present invention, the third solvent is water.
For further understanding of the present invention, the following examples are provided to illustrate the preparation method of the silica gel film of the present invention, and the scope of the present invention is not limited by the following examples. In the following examples, the starting materials used are all commercially available products. In the following examples, the molar ratio of the benzothiazole dicarboxylic anhydride and the cyclohexylamine is 1: 1. the first solvent is ethanol. The second solvent is hot water with the temperature of 60 ℃. The third solvent is water.
Example 1
The preparation method of the plastic colorant fluorescein 3G provided by the embodiment comprises the following steps:
1) preparation of the benzothiazole dicarboxylic anhydride: adding 4- (2-amino diazonium salt benzenethiol) -1, 8-naphthalic anhydride and copper catalase into a closed-loop kettle, heating to 115 ℃, carrying out closed-loop reaction for 1.2 hours, pumping into a filter press for filter pressing after the reaction is finished, washing a filter cake with a third solvent, and drying to obtain the benzothiazole dicarboxylic anhydride.
2) Condensation: adding benzothiazole dicarboxylic anhydride and cyclohexylamine into a condensation kettle according to the proportion, and carrying out reflux reaction for 13 hours at the temperature of 115 ℃.
3) Washing and drying: after the reaction is finished, cooling to 45 ℃, adding a first solvent for washing to obtain a filter cake, and distilling a washing liquid to recover the first solvent; and washing the filter cake with a second solvent until the pH value is neutral, and then placing the filter cake in a drying device for drying to obtain the plastic colorant fluorescein 3G.
Example 2
The preparation method of the plastic colorant fluorescein 3G provided by the embodiment comprises the following steps:
1) preparation of the benzothiazole dicarboxylic anhydride: adding 4- (2-amino diazonium salt benzenethiol) -1, 8-naphthalic anhydride and copper catalase into a closed-loop kettle, heating to 120 ℃, carrying out closed-loop reaction for 1 hour, pumping into a filter press for filter pressing after the reaction is finished, washing a filter cake with a third solvent, and drying to obtain the benzothiazole dicarboxylic anhydride.
2) Condensation: adding benzothiazole dicarboxylic anhydride and cyclohexylamine into a condensation kettle according to a ratio, and carrying out reflux reaction for 12 hours at the temperature of 120 ℃.
3) Washing and drying: after the reaction is finished, cooling to 60 ℃, adding a first solvent for washing to obtain a filter cake, and distilling a washing liquid to recover the first solvent; and washing the filter cake with a second solvent until the pH value is neutral, and then placing the filter cake in a drying device for drying to obtain the plastic colorant fluorescein 3G.
Example 3
The preparation method of the plastic colorant fluorescein 3G provided by the embodiment comprises the following steps:
1) preparation of the benzothiazole dicarboxylic anhydride: adding 4- (2-amino diazo salt benzene mercapto) -1, 8-naphthalic anhydride and copper catalase into a closed-loop kettle, heating to 125 ℃, carrying out closed-loop reaction for 0.8 hour, pumping into a filter press for filter pressing after the reaction is finished, washing a filter cake with a third solvent, and drying to obtain the benzothiazole dicarboxylic anhydride.
2) Condensation: adding benzothiazole dicarboxylic anhydride and cyclohexylamine into a condensation kettle according to a ratio, and carrying out reflux reaction for 11 hours at the temperature of 125 ℃.
3) Washing and drying: after the reaction is finished, cooling to 70 ℃, adding a first solvent for washing to obtain a filter cake, and distilling a washing liquid to recover the first solvent; and washing the filter cake with a second solvent until the pH value is neutral, and then placing the filter cake in a drying device for drying to obtain the plastic colorant fluorescein 3G.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A plastic colorant, fluorescein 3G, having the structure shown in formula (1):
2. the plastic colorant fluorescein 3G as claimed in claim 1, comprising the following raw materials: benzothiazole dicarboxylic anhydride and cyclohexylamine, wherein the molar ratio of the benzothiazole dicarboxylic anhydride to the cyclohexylamine is 0.8-1.2: 1.
3. the plastic colorant fluorescein 3G, as claimed in claim 2, wherein the molar ratio of benzothiazole dicarboxylic anhydride to cyclohexylamine is from 1: 1.
4. the plastic colorant fluorescein 3G, as claimed in claim 2 or 3, wherein the benzothiazole dicarboxylic anhydride comprises the following starting materials: 4- (2-amino diazonium salt benzenesulfydryl) -1, 8-naphthalic anhydride and copper catalase.
5. The plastic colorant fluorescein, 3G, as claimed in claim 4, wherein the copper catalase is copper sulfate.
6. The method for preparing the plastic colorant fluorescein 3G as claimed in claim 4 or 5, which is characterized by comprising the following steps:
1) condensation: adding benzothiazole dicarboxylic anhydride and cyclohexylamine into a condensation kettle according to a ratio, and carrying out reflux reaction for 11-13 hours at the temperature of 115-125 ℃;
2) washing and drying: after the reaction is finished, cooling to 45-70 ℃, adding a first solvent for washing to obtain a filter cake, and distilling a washing liquid to recover the first solvent; and washing the filter cake with a second solvent until the pH value is neutral, and then placing the filter cake in a drying device for drying to obtain the plastic colorant fluorescein 3G.
7. The plastic colorant fluorescein, 3G, as claimed in claim 6, further comprising the steps of:
3) preparation of the benzothiazole dicarboxylic anhydride: adding 4- (2-amino diazo salt benzene mercapto) -1, 8-naphthalic anhydride and copper catalase into a closed-loop kettle, heating to 115-125 ℃, carrying out closed-loop reaction for 0.8-1.2 hours, pumping into a filter press for filter pressing after the reaction is finished, washing a filter cake with a third solvent, and drying to obtain the benzothiazole dicarboxylic anhydride.
8. The plastic colorant fluorescein 3G, as claimed in claim 6, wherein the first solvent is ethanol.
9. The plastic colorant fluorescein 3G as claimed in claim 6 or 8, wherein the second solvent is hot water at a temperature of 40-90 ℃.
10. The plastic colorant fluorescein, 3G, as claimed in claim 7, wherein the third solvent is water.
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| CN202010956029.2A CN112142759A (en) | 2020-09-11 | 2020-09-11 | Plastic colorant fluorescein 3G and preparation method thereof |
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| CN202010956029.2A CN112142759A (en) | 2020-09-11 | 2020-09-11 | Plastic colorant fluorescein 3G and preparation method thereof |
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| WO2004024801A1 (en) * | 2002-09-12 | 2004-03-25 | 3M Innovative Properties Company | Oligomeric dyes and use thereof |
| WO2004024830A1 (en) * | 2002-09-12 | 2004-03-25 | 3M Innovative Properties Co | Oligomeric dyes and preparation thereof |
| JP2008050463A (en) * | 2006-08-24 | 2008-03-06 | Kaneka Corp | Methacrylate polymer with reactive thioxanthene compound used therein, and its resin composition |
| CN102020872A (en) * | 2009-09-23 | 2011-04-20 | 国家纳米科学中心 | Composite fluorescent dye, base material containing same and preparation methods thereof |
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