CN116589377A - 4,4' -azo-bis-benzoic acid ethylenediamine dye eutectic and preparation method thereof - Google Patents

4,4' -azo-bis-benzoic acid ethylenediamine dye eutectic and preparation method thereof Download PDF

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Publication number
CN116589377A
CN116589377A CN202310319745.3A CN202310319745A CN116589377A CN 116589377 A CN116589377 A CN 116589377A CN 202310319745 A CN202310319745 A CN 202310319745A CN 116589377 A CN116589377 A CN 116589377A
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dye
ethylenediamine
acid
crystal
azobisbenzoic
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罗亚楠
白羽
陶然
白红旭
宋佳慕
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Jilin Medical College
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Jilin Medical College
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
    • C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
    • C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
    • C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
    • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C211/09—Diamines
    • C07C211/10—Diaminoethanes
    • 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
    • C09B43/00—Preparation of azo dyes from other azo compounds
    • C09B43/32—Preparation of azo dyes from other azo compounds by reacting carboxylic or sulfonic groups, or derivatives thereof, with amines; by reacting keto-groups with amines
    • 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
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0079—Azoic dyestuff preparations
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs
    • 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
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

The invention discloses a 4,4' -azo-bis-benzoic acid ethylenediamine dye eutectic with a molecular formula of C 30 H 24 N 6 O 8 The structural formula isThe preparation method specifically comprises the following steps: (1) 4,4' -azobisbenzoic acid, ethylenediamine and solvent are put into a reaction vessel together under the airtight conditionPlacing the mixture on a stirrer for stirring and fully reacting; (2) Sealing the mouth of the reaction vessel with tinfoil, punching a plurality of small holes on the tinfoil with a needle, standing for volatilization, and obtaining the red transparent blocky crystal after the red transparent blocky crystal begins to be separated out from the reaction vessel. Compared with the dye, the dye eutectic of the invention has obviously improved thermal stability, and the fluorescence intensity of the dye eutectic of the invention is improved by 5 times compared with the dye, thus greatly solving the problems of the original dye in stability and fluorescence intensity.

Description

4,4' -azo-bis-benzoic acid ethylenediamine dye eutectic and preparation method thereof
Technical Field
The invention relates to the technical field of solid dye eutectic, in particular to 4,4' -azo-bis-benzoic acid ethylenediamine dye eutectic and a preparation method thereof.
Background
In 1894, germany e.fischer proposed a "lock-key" model based on the idea of "intermolecular selectivity", i.e. a prototype of the modern supermolecular science theory. In 1937, K.L.Wolf et al, germany, created the term "supramolecule" to describe highly ordered entities formed by molecular association. In a general sense, any collection of molecules has interactions, so one often refers to the structural hierarchy of the material in an aggregated state as a "supermolecule". Until 1978, professor j.m.lehn in france eventually proposed the complete concept of "supermolecular chemistry" based on traditional guest-host system studies rooted in organic chemistry.
Supermolecular chemistry is the science of studying molecular aggregates that are complex and ordered and have specific structures and functions formed by the association of intermolecular interactions, which is "chemistry beyond the molecular domain", and such molecular aggregates are abbreviated as "supermolecules". Therefore, the basis of supermolecule chemistry is the science of intermolecular noncovalent interactions, which is a functional system formed by studying the noncovalent interactions between a plurality of different species of molecules.
Supermolecular chemistry has the following significant features: a. the strong binding force of the supermolecular compound is the result of superposition and synergy of weak interaction forces among different molecules, and is the comprehensive expression of various forces; b. supermolecular compounds self-assembled from different molecules exhibit novel functions that are completely different from those of the original self-assembled molecules. Molecular recognition and supramolecular self-assembly by synergism of weak intermolecular interactions are the core part of supramolecular chemistry studies.
The crystal engineering applies the principle and method of supermolecular chemistry to the design and growth of crystals, and obtains new crystals with adjustable structure and specific physicochemical properties through the combined action of molecular recognition and self-assembly processes. It is feasible to design dye eutectic routes by using crystal engineering theory, and the organic dye component and other eutectic precursors are connected through hydrogen bonds to form new crystals by using the crystal engineering theory. Organic dye components in crystalline form have traditionally been limited to their weak fluorescence intensity and poor thermal stability. The organic dye component itself has high application value in terms of intellectual property, wherein the structure and the constituent components are the most important constituent components. The Cambridge Structure Database (CSD) in the united kingdom is a major source of microscopic information about the structure of matter for molecular and material design.
Fluorescence is an important property of substances, playing a vital role in many technical fields, such as fluorescent tumor markers, OLEDs, etc. In some dyes, due to the structural characteristics and the characteristics of the functional groups, the dyes have certain fluorescent properties, and further have more applications. However, in the case of solid-state dyes, in the case of close packing, exciton coupling occurs between dye molecules to generate new exciton states, resulting in quenching of the fluorescent properties of the dye.
Therefore, how to maintain or enhance the fluorescence properties of solid-state dyes is a problem that needs to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the present invention aims to provide a 4,4' -azobisbenzoic acid ethylenediamine dye eutectic and a preparation method thereof, so as to solve the defects in the prior art.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
4,4' -azo-bis-benzoic acid ethylenediamine dye eutectic with molecular formula of C 30 H 24 N 6 O 8 The structural formula is
Further, the 4,4 '-azo dibenzoic acid ethylenediamine dye eutectic is prepared by taking 4,4' -azo dibenzoic acid dye as an organic dye component and ethylenediamine as a precursor through reaction;
wherein the molecular formula of the 4,4' -azo dibenzoic acid is C 14 H 10 N 2 O 4 The structural formula is shown as a, is
The molecular formula of the ethylenediamine is C 2 H 8 N 2 The structural formula is shown as b, is
The technical scheme has the beneficial effects that the azo compound 4,4' -azobisbenzoic acid and ethylenediamine molecules form eutectic, so that the thermal stability is obviously improved compared with the dye. And the co-crystal is formed with ethylenediamine molecules, so that the transfer of electrons among dye molecules is enhanced, the fluorescence intensity of the co-crystal is improved by about 5 times relative to that of the dye, and the problems of poor thermal stability and weak fluorescence intensity of the original dye are greatly solved.
Further, the crystal structure of the 4,4' -azobisbenzoic acid ethylenediamine dye eutectic is: one ethylenediamine molecule and two 4,4' -azobisbenzoic acid molecules are combined together through hydrogen bonds to form a basic structural unit.
Further, in the above-mentioned co-crystal of ethylenediamine 4,4 '-azobisbenzoate dye, one N atom (N1) on the amino group in one ethylenediamine molecule is used as a hydrogen bond donor, and O atoms (O2 and O2) on the carboxylic acid in two 4,4' -azobisbenzoate molecules i ) Two hydrogen bonds are formed as hydrogen bond acceptors.
Further, the space group of the 4,4' -azo-bis-benzoic acid ethylenediamine dye eutectic is monoclinic system, and the unit cell parameters are as follows: the axial length a= 26.894-27.294, b= 4.495-4.895 and c= 11.836-12.236; the shaft angle α=90.00, β= 92.904 to 93.304, γ=90.00.
Further, XRD spectrum characteristic peaks of the 4,4' -azo ethylenediamine dibenzoate dye eutectic appear at 5.96-6.36 degrees, 9.54-9.94 degrees, 10.34-10.74 degrees, 13.68-14.08 degrees, 15.85-16.25 degrees, 18.76-19.16 degrees, 22.37-22.77 degrees, 26.39-26.79 degrees and 28.52-28.92 degrees. More specifically 6.16 °, 9.74 °, 10.54 °, 13.88 °, 16.05 °, 18.96 °, 22.57 °, 26.59 °, 28.72 °.
Further, the thermal weight curve of the 4,4' -azobisbenzoic acid ethylenediamine dye eutectic under the air atmosphere test condition is as follows: the weight loss is 18 to 19 percent at the temperature of 152 to 248 ℃, and then the mixture is completely decomposed at the temperature of 385 to 542 ℃.
The preparation method of the 4,4' -azo-bis-benzoic acid ethylenediamine dye eutectic (solvent room temperature volatilization method) specifically comprises the following steps:
(1) Placing 4,4' -azobisbenzoic acid, ethylenediamine and a solvent into a reaction vessel, placing the reaction vessel on a stirrer under a closed condition, stirring, and fully reacting to obtain a red clear liquid;
(2) Sealing the mouth of the reaction container with tinfoil, punching a plurality of small holes on the tinfoil with a needle, standing for volatilization, and obtaining the 4,4' -azo-bis-benzoic acid ethylenediamine dye eutectic when red transparent block crystals begin to be separated out from the reaction container.
Further, in the step (1), the molar volume ratio of the 4,4' -azobisbenzoic acid, the ethylenediamine and the solvent is (0.12-0.14) mmol (0.16-0.18) mmol (8-10) mL; the solvent is prepared by mixing ethanol, methanol and water in a volume ratio of 7:2:1; stirring time is 1-3 h.
The adoption of the further technical scheme has the beneficial effects that the boiling point of the solvent selected by the invention is relatively low, so that crystals are separated out in the process of volatilizing the solvent.
Further, in the step (2), the time of standing and volatilizing is 7 to 10 days.
Compared with the prior art, the invention has the following beneficial effects:
the solid quinoline azo fluorescent dye eutectic with the novel structure has obviously improved thermal stability compared with the dye, and the fluorescence intensity of the eutectic is improved by 5 times compared with the dye, so that the problems of the original dye in stability and fluorescence intensity are solved greatly.
Drawings
FIG. 1 is a schematic diagram of the structural unit of the co-crystal of ethylenediamine 4,4' -azobisbenzoate dye prepared in example 1;
FIG. 2 is an XRD spectrum of the co-crystal of ethylenediamine 4,4' -azobisbenzoate dye prepared in example 1 and an XRD spectrum obtained by simulation;
FIG. 3 is a thermogram of the co-crystal of ethylenediamine 4,4' -azobisbenzoate dye prepared in example 1.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the examples below, the reaction vessel was a transparent glass vial, imported from a foreign country, and had a capacity of 20mL, and had a strong seal and maintained good tightness at temperatures below 120 ℃.
Example 1
The preparation method of the 4,4' -azo dibenzoic acid ethylenediamine dye eutectic specifically comprises the following steps:
(1) Firstly, respectively measuring 7mL of ethanol, 2mL of methanol and 1mL of water in a 20mL transparent glass vial by using a 10mL pipette, and mixing to obtain a solvent; then 0.13mmol (35.00 mg) of 4,4' -azobisbenzoic acid and 0.17mmol (10.20 mg) of ethylenediamine which are accurately weighed by an analytical balance are added, and the mixture is placed on a stirrer under a closed condition to be stirred for 2 hours, and fully reacted to obtain red clarified liquid;
(2) Taking out the stirrer, sealing the opening of the reaction vessel with tinfoil, punching a plurality of small holes on the tinfoil with a needle, standing and volatilizing for 9 days, and obtaining the 4,4' -azobisbenzoic acid ethylenediamine dye eutectic after the red transparent blocky crystal begins to be separated out from the reaction vessel.
Example 2
The preparation method of the 4,4' -azo dibenzoic acid ethylenediamine dye eutectic specifically comprises the following steps:
(1) Firstly, respectively measuring 7mL of ethanol, 2mL of methanol and 1mL of water in a 20mL transparent glass vial by using a 10mL pipette, and mixing to obtain a solvent; then 0.12mmol (32.00 mg) of 4,4' -azobisbenzoic acid and 0.16mmol (9.60 mg) of ethylenediamine which are accurately weighed by an analytical balance are added, and the mixture is placed on a stirrer under a closed condition to be stirred for 1 hour, and fully reacted to obtain red clarified liquid;
(2) Taking out the stirrer, sealing the opening of the reaction vessel with tinfoil, punching a plurality of small holes on the tinfoil with a needle, standing and volatilizing for 7 days, and obtaining the 4,4' -azobisbenzoic acid ethylenediamine dye eutectic after the red transparent blocky crystal begins to be separated out from the reaction vessel.
Example 3
The preparation method of the 4,4' -azo dibenzoic acid ethylenediamine dye eutectic specifically comprises the following steps:
(1) Firstly, respectively measuring 7mL of ethanol, 2mL of methanol and 1mL of water in a 20mL transparent glass vial by using a 10mL pipette, and mixing to obtain a solvent; then 0.14mmol (38.00 mg) of 4,4' -azobisbenzoic acid and 0.18mmol (10.80 mg) of ethylenediamine which are accurately weighed by an analytical balance are added, and the mixture is placed on a stirrer under a closed condition to be stirred for 3 hours, and fully reacted to obtain red clear liquid;
(2) Taking out the stirrer, sealing the opening of the reaction vessel with tinfoil, punching a plurality of small holes on the tinfoil with a needle, standing and volatilizing for 10 days, and obtaining the 4,4' -azobisbenzoic acid ethylenediamine dye eutectic after red transparent block crystals begin to be separated out from the reaction vessel.
Performance testing
1. The structural units of the ethylenediamine 4,4' -azobisbenzoate dye co-crystal obtained in example 1 were measured by using a Bruker Apex II CCD X-ray single crystal diffractometer (Bruker SMART-APEX CCD Diffractometer). The results are shown in FIG. 1.
As can be seen from FIG. 1, one ethylenediamine molecule and two 4,4' -azobisbenzoic acid molecules are bonded together by hydrogen bonds to constitute a basic structural unit. Wherein one N atom (N1) on the amino group in one ethylenediamine molecule is used as a hydrogen bond donor, and the O atoms (O2 and O2) on the carboxylic acid in two 4,4' -azobisbenzoic acid molecules i ) Two hydrogen bonds are formed as hydrogen bond acceptors.
The space group of the eutectic is monoclinic system, and the unit cell parameters are as follows: the axial length a= 26.894-27.294, b= 4.495-4.895 and c= 11.836-12.236; the shaft angle α=90.00, β= 92.904 to 93.304, γ=90.00.
2. The co-crystal of ethylenediamine 4,4' -azobisbenzoate dye obtained in example 1 was used with X-Ray DIFFRACTOMETER (model XRD-6000, manufactured by Shimadzu corporation), cu-K.alpha. The XRD spectrum was measured at a tube voltage of 40kV, a tube current of 30mA, and a scanning speed of 8 DEG/min. And its XRD spectrum was simulated by Materials Studio software according to the crystal structure data. The results are shown in FIG. 2.
As can be seen from fig. 2, from the X-ray diffraction spectrum peaks (curve a) of the co-crystal, a series of characteristic peaks, more specifically, 6.16 °, 9.74 °, 10.54 °, 13.88 °, 16.05 °, 18.96 °, 22.57 °, 26.59 °, 28.72 °, are present at 5.96 ° to 6.36 °,9.54 ° to 9.94 °,10.34 ° to 10.74 °,13.68 ° to 14.08 °,15.85 ° to 16.25 °,18.76 ° to 19.16 °,22.37 ° to 22.77 °,26.39 ° to 26.79 °, 28.52 ° to 28.92 °. Further, it was found by comparison that these characteristic peaks were coincident with the simulated X-ray diffraction spectrum peaks (curve b).
3. The thermal thermogram of the ethylenediamine 4,4' -azobisbenzoate dye co-crystal obtained in example 1 was measured using a thermal weight loss (TGA) and a Differential Thermal Analyzer (DTA) of SIMULTANNEOUS DTA-TGAPPARATUS (model DTG-60, manufactured by Shimadzu corporation) using an air atmosphere at a heating rate of 10℃per minute. The results are shown in FIG. 3.
As can be seen from fig. 3, the thermogravimetric curve of the eutectic under the air atmosphere test conditions is: the weight loss is 18 to 19 percent at the temperature of 152 to 248 ℃, and then the mixture is completely decomposed at the temperature of 385 to 542 ℃.
4. The fluorescence intensities of the 4,4 '-azobisbenzoic acid and the prepared ethylenediamine 4,4' -azobisbenzoate dye co-crystals in example 1 were measured.
As a result, it was found that 4,4' -azobisbenzoic acid was found to be at lambda EX/EM PeakA at 280/322nm [ fluorescence intensity 56 (a.u.)]After forming the eutectic of the 4,4' -azo-bis-benzoic acid ethylenediamine dye with ethylenediamine molecules, the mixture is formed at lambda EX/EM PeakA at 312/334nm [ fluorescence intensity of 286 (a.u.)]。
The experiment shows that the solid quinoline azo fluorescent dye eutectic with the novel structure has obviously improved thermal stability compared with the dye, and the fluorescence intensity of the solid quinoline azo fluorescent dye eutectic is improved by 5 times compared with the dye, so that the problems of the original dye in stability and fluorescence intensity are solved greatly.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A4, 4' -azo dibenzoic acid ethylenediamine dye eutectic is characterized in that the molecular formula is C 30 H 24 N 6 O 8 The structural formula is
2. The co-crystal of 4,4 '-azobisbenzoic acid ethylenediamine dye according to claim 1, wherein the dye 4,4' -azobisbenzoic acid is used as an organic dye component, ethylenediamine is used as a precursor, and the co-crystal is prepared by reaction;
the molecular formula of the 4,4' -azo dibenzoic acid is C 14 H 10 N 2 O 4 The structural formula is
The molecular formula of the ethylenediamine is C 2 H 8 N 2 The structural formula is
3. The co-crystal of 4,4' -azobisbenzoic acid ethylenediamine dye according to claim 2, wherein the crystal structure is: one ethylenediamine molecule and two 4,4' -azobisbenzoic acid molecules are combined together through hydrogen bonds to form a basic structural unit.
4. The co-crystal of 4,4 '-azobisbenzoic acid ethylenediamine dye according to claim 3, wherein one N atom on an amino group in one ethylenediamine molecule is used as a hydrogen bond donor, and an O atom on a carboxylic acid in two 4,4' -azobisbenzoic acid molecules is used as a hydrogen bond acceptor to form two hydrogen bonds.
5. The co-crystal of ethylenediamine 4,4' -azobisbenzoate dye according to claim 1 wherein the space group is monoclinic, the unit cell parameters are: the axial length a= 26.894-27.294, b= 4.495-4.895 and c= 11.836-12.236; the shaft angle α=90.00, β= 92.904 to 93.304, γ=90.00.
6. The co-crystal of 4,4' -azobisbenzoic acid ethylenediamine dye according to claim 1 wherein the XRD spectrum characteristic peaks appear at 5.96 ° to 6.36 °,9.54 ° to 9.94 °,10.34 ° to 10.74 °,13.68 ° to 14.08 °,15.85 ° to 16.25 °,18.76 ° to 19.16 °,22.37 ° to 22.77 °,26.39 ° to 26.79, 28.52 ° to 28.92 °.
7. The co-crystal of ethylenediamine 4,4' -azobisbenzoate dye according to claim 1 wherein the thermogravimetric curve under air atmosphere test conditions is: the weight loss is 18 to 19 percent at the temperature of 152 to 248 ℃, and then the mixture is completely decomposed at the temperature of 385 to 542 ℃.
8. A method for preparing the co-crystal of the 4,4' -azobisbenzoic acid ethylenediamine dye according to claim 1, comprising the following steps:
(1) Placing 4,4' -azobisbenzoic acid, ethylenediamine and a solvent into a reaction vessel, placing the reaction vessel on a stirrer under a closed condition, stirring, and fully reacting to obtain a red clear liquid;
(2) Sealing the mouth of the reaction container by using tinfoil, punching a plurality of small holes on the tinfoil by using a needle, standing for volatilization, and obtaining the 4,4' -azo-bis-benzoic acid ethylenediamine dye eutectic when red transparent blocky crystals begin to be separated out from the reaction container.
9. The method for preparing an ethylenediamine 4,4 '-azobisbenzoate dye co-crystal according to claim 8, wherein in the step (1), the molar volume ratio of the ethylenediamine to the 4,4' -azobisbenzoate dye is (0.12-0.14) mmol (0.16-0.18) mmol (8-10) mL; the solvent is prepared by mixing ethanol, methanol and water in a volume ratio of 7:2:1; the stirring time is 1-3 h.
10. The method for preparing an ethylenediamine 4,4' -azobisbenzoate dye co-crystal according to claim 8, wherein in the step (2), the standing volatilization time is 7-10 days.
CN202310319745.3A 2023-03-29 2023-03-29 4,4' -azo-bis-benzoic acid ethylenediamine dye eutectic and preparation method thereof Pending CN116589377A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118308893A (en) * 2024-04-23 2024-07-09 绍兴高温印染有限公司 Water-saving polyester cotton printing and dyeing process

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118308893A (en) * 2024-04-23 2024-07-09 绍兴高温印染有限公司 Water-saving polyester cotton printing and dyeing process

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