CN117551117A - Recycling method of 4-hydroxy-1, 5-naphthyridine europium complex preparation mother solution - Google Patents

Recycling method of 4-hydroxy-1, 5-naphthyridine europium complex preparation mother solution Download PDF

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CN117551117A
CN117551117A CN202311558796.8A CN202311558796A CN117551117A CN 117551117 A CN117551117 A CN 117551117A CN 202311558796 A CN202311558796 A CN 202311558796A CN 117551117 A CN117551117 A CN 117551117A
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mother liquor
naphthyridine
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europium
complex
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魏晨
卫慧波
缪倩倩
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Suzhou Ruiersi Technology Co ltd
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    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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Abstract

The invention discloses a method for recycling 4-hydroxy-1, 5-naphthyridine europium complex mother liquor, which is characterized in that the complex mother liquor is dehydrated by a dehydrating agent, and then the dehydrating agent is separated or distilled to obtain an anhydrous alcohol solvent, and the anhydrous alcohol solvent is recycled for preparing 4-hydroxy-1, 5-naphthyridine europium complex, so that the complex mother liquor is recycled. Because the water generated in the preparation process of the 4-hydroxy-1, 5-naphthyridine europium complex can not be directly used as the mother liquor, the mother liquor can only be used as hazardous waste treatment, not only is the alcohol solvent wasted, but also the cost is increased, and the water in the complex mother liquor can be removed by adding the dehydrating agent such as calcium oxide, molecular sieve and the like, so that the alcohol solvent in the mother liquor is used, the cost can be reduced, and the hazardous waste is reduced.

Description

Recycling method of 4-hydroxy-1, 5-naphthyridine europium complex preparation mother solution
Technical Field
The invention belongs to the field of preparation of rare earth complex luminescent materials, and particularly relates to a recycling method of a mother solution for preparing 4-hydroxy-1, 5-naphthyridine europium complex.
Background
The rare earth complex luminescent material has the characteristics of narrow-band emission and large Stokes displacement, and can be used in the fields of fluorescence anti-counterfeiting, light conversion agricultural films, illumination, display and the like. However, the complex based on the traditional beta-diketone ligand has low luminous efficiency and poor light stability, can be rapidly degraded under ultraviolet light irradiation, and has the phenomenon of photo-bleaching, thereby limiting the practical application of the material.
In the past research, the research and development team developed a 4-hydroxy-1, 5-naphthyridine (referred to as naphthyridine, ND) rare earth luminescent material with high luminous efficiency and excellent light stability. The material has a rigid molecular structure, so that the resistance to photodegradation is greatly improved (Chinese patent 20110139842.1; adv. Function. Mater.2016,26, 2085). Subsequently, the research and development team opens up a production process route of the 4-hydroxy-1, 5-naphthyridine europium complex (Chinese patent 202210338200.2), and sequentially completes the small-scale, pilot-scale and industrial production of the material.
In large-scale production, the application of the solvent is significant for saving cost and reducing emission. The disclosed production process of the 4-hydroxy-1, 5-naphthyridine rare earth complex luminescent material does not relate to the technical scheme of solvent recovery and reuse. The 4-hydroxy-1, 5-naphthyridine rare earth complex is prepared by reacting naphthyridine ligand, alkali, rare earth salt and other neutral ligand in alcohol solvent. The mother liquor for preparing the naphthyridine rare earth complex consists of alcohol solvents (methanol, ethanol and the like), salts, a small amount of naphthyridine complex and impurities. In actual production, the team finds that the recycling of alcohol mother liquor of naphthyridine rare earth complex is very difficult, and the recovery and the application of solvent can not be realized by direct application or simple distillation means. If alcohol solvent is obtained by direct application or simple distillation and is used continuously, the purity of the prepared rare earth complex product is reduced, and the luminous efficiency is reduced.
Therefore, the mother liquor recycling of naphthyridine rare earth complex still has technical problems. Solves the difficult problem of recycling the mother liquor of the naphthyridine rare earth complex, and has important significance for saving the cost of solvents and reducing the emission of organic waste liquid in the industrial production process of the materials.
Disclosure of Invention
The invention aims to solve the technical problem that complex preparation mother liquor in the process of preparing naphthyridine rare earth complex is difficult to directly reuse, and provides a recycling method of 4-hydroxy-1, 5-naphthyridine europium complex preparation mother liquor, which can greatly reduce the use amount of alcohol organic solvents and the discharge amount of organic waste liquid, thereby reducing the production cost and environmental pollution.
In order to achieve the technical purpose, the technical scheme of the invention is as follows: the recycling method of the preparation mother liquor of the 4-hydroxy-1, 5-naphthyridine europium complex, wherein the 4-hydroxy-1, 5-naphthyridine europium complex is prepared according to the method of Chinese patent 202210338200.2 or 201510130379.2, and the preparation mother liquor of the complex is generated; the complex preparation mother solution consists of an aqueous alcohol solvent, salts, a small amount of residual 4-hydroxy-1, 5-naphthyridine europium complex and impurities;
the recycling method comprises the following steps:
1) Dehydrating: the complex preparation mother liquor and the dehydrating agent are mixed according to the mass ratio of 1: mixing in the proportion of 0.05-0.5, stirring at room temperature-reflux temperature for 10 min-24 h;
2) Separation and/or distillation: cooling the dehydrated preparation mother liquor obtained in the step 1) to room temperature, and then separating a dehydrating agent and other insoluble matters to obtain dehydrated mother liquor B which is used for preparing europium complexes in the next batch, thereby realizing the recycling of the preparation mother liquor of 4-hydroxy-1, 5-naphthyridine europium complexes; or directly distilling the dehydrated preparation mother liquor obtained in the step 1) to obtain an anhydrous alcohol solvent, and using the alcohol solvent for preparing europium complexes in the next batch to realize the recycling of the preparation mother liquor of 4-hydroxy-1, 5-naphthyridine europium complexes;
the structure of the 4-hydroxy-1, 5-naphthyridine europium complex is shown as formula I or II:
in the formulas I and II, R 1 、R 2 、R 3 、R 4 、R 5 Selected from hydrogen atom, halogen atom, cyano group, methyl group, ethyl groupAny one of a group, trifluoromethyl, pentafluoroethyl; l is a neutral ligand, x=1 to 3; m is any one of positive monovalent alkali metal ions and quaternary ammonium ions;
the neutral ligand is a nitrogen-containing aromatic heterocyclic ligand, a methyl or phenyl substituted nitrogen-containing aromatic heterocyclic ligand, a nitrogen-containing aromatic heterocyclic-N-oxide ligand, a methyl or phenyl substituted nitrogen-containing aromatic heterocyclic-N-oxide ligand, or a methyl or phenyl substituted phosphono ligand.
Wherein, the water content in the preparation mother liquor is less than 10 percent according to the mass ratio. More preferably, the water content in the preparation mother liquor is less than 5%.
Wherein the alcohol solvent in the mother liquor is any one or any combination of ethanol, methanol and n-butanol.
Wherein the impurities in the preparation mother liquor comprise ligand oxides contained in the 4-hydroxy-1, 5-naphthyridine ligands and complexes generated by combining iron ions with the ligands. The ligand oxide is dark color, and is derived from oxidation byproducts or conjugation-enlarged carbonization byproducts generated at high temperature in the preparation process of the 4-hydroxy-1, 5-naphthyridine ligand, the impurities of the byproducts are not completely removed in the ligand purification process, and a small amount of residues are brought into the complex mother liquor. The complex generated by combining iron ions and the ligand is reddish brown complex, and the source of the iron ions is stainless steel materials in a reaction kettle, a storage tank and a pipeline. These impurities adversely affect the mother liquor application and must be removed after a large accumulation.
Wherein, the structural general formula of salts in the preparation mother solution is MX, M is alkali metal ion or quaternary ammonium ion, X is chloride ion, acetate ion or nitrate ion; the salts are cations (M) in the base MOH during the preparation of the ligand + ) With trivalent europium salt EuX 3 y(H 2 Anions (X) in O) - ) Generated by combining; wherein y represents the amount of water of crystallization in the trivalent europium salt and y=1 to 6. The quaternary ammonium ion is selected from linear or branched alkyl, phenyl or benzyl substituted quaternary ammonium ion with C1-C18, more preferably tetramethyl ammonium ion, tetraethyl ammonium ion,Any one of tetrabutylammonium ion, phenyltrimethylammonium ion, benzyltrimethylammonium ion and hexadecyltrimethylammonium ion.
Wherein the dehydrating agent is calcium oxide or molecular sieve.
Preferably, the calcium oxide is an industrial grade or analytically pure anhydrous calcium oxide powder.
Preferably, the molecular sieve is any one or any combination of any two of a dehydrated and activated 3A molecular sieve and a dehydrated and activated 4A molecular sieve, and the state of the molecular sieve is granular or powdery. The molecular sieve is further preferably a dehydrated activated molecular sieve raw powder in a powdery state. The dehydration and activation are to heat the molecular sieve to 200-500 ℃ under normal pressure, vacuum state or inert gas flow (such as nitrogen gas flow) to remove the adsorbed moisture. The molecular sieve can be activated and reused after absorbing water, thereby realizing repeated use.
Preferably, in the dehydration operation of step 1, the ratio of the complex preparation mother liquor to the dehydrating agent is 1 (0.1-0.3).
Preferably, after the mother solution B is repeatedly recycled for 0-5 times, the mother solution B which is repeatedly recycled can be dehydrated in the mode of the step 1), and then distilled to obtain the anhydrous alcohol solvent which is used for preparing europium complex in the next batch for further recycling. The mother liquor B is recycled repeatedly, namely, the recycling is completed according to the mode of separating the dehydrating agent in the step 2) instead of distilling.
The technical scheme of the invention can be generalized into two forms, namely, after the step 1) of mixing the complex preparation mother liquor with the dehydrating agent and removing the moisture in the complex preparation mother liquor, the step 2) has two modes, namely, the dehydrating agent can be separated out to obtain mother liquor B for preparing europium complexes in the next batch, and the dehydrated alcohol solvent can be directly distilled for preparing europium complexes in the next batch, so that the recycling of the 4-hydroxy-1, 5-naphthyridine europium complex preparation mother liquor can be completed. Both forms of technical solutions are within the scope of the invention. In step 2), compared with distillation, the method for separating the dehydrating agent to obtain the mother liquor B which is directly recycled to the preparation of the europium complex in the next batch is a low energy consumption mode. In addition, after the mother solution B is reused for many times in a mode of separating the dehydrating agent instead of distilling, more impurities are accumulated in the mother solution B, the dehydrating agent in the mother solution B can be removed, and then the anhydrous alcohol solvent is obtained by distilling, so that the anhydrous alcohol solvent is used for preparing the 4-hydroxy-1, 5-naphthyridine europium complex and is further reused. In the distillation process, salts and impurities can be left in the kettle and finally treated as waste liquid; the purity of the absolute alcohol solvent obtained by distillation is very high, and the absolute alcohol solvent has similar effect to the newly purchased analytical alcohol solvent when being reused.
The synthetic route of the 4-hydroxy-1, 5-naphthyridine europium complex is analyzed, and a specific reaction equation is as follows:
in the reaction equations a and b, the formula III is 4-hydroxy-1, 5-naphthyridine ligand; MOH represents a base, M is a positive monovalent alkali metal ion or a quaternary ammonium ion; euX (EuX) 3 y(H 2 O) is a hydrochloride, nitrate or acetate of trivalent europium, X is a negative monovalent chloride, nitrate or acetate ion, y represents the amount of water of crystallization in the trivalent europium salt and y=1 to 6; l represents neutral ligands, x represents the number of neutral ligands and x=1 to 3. In the equation a, the europium complex shown in the formula I is prepared by reacting 3 parts of 4-hydroxy-1, 5-naphthyridine ligand shown in the formula III, 3 parts of alkali (MOH), 1 part of trivalent europium salt (containing y parts of water molecules) and x parts of neutral ligand L. In the equation b, the complex shown in the formula II is obtained by reacting 4 parts of 4-hydroxy-1, 5-naphthyridine ligand shown in the formula III, 4 parts of Alkali (AOH) and 1 part of trivalent europium salt (containing y parts of water molecules).
The neutral ligand L is a nitrogen-containing aromatic heterocyclic ligand, a methyl or phenyl substituted nitrogen-containing aromatic heterocyclic ligand, a nitrogen-containing aromatic heterocyclic-N-oxide ligand, a methyl or phenyl substituted nitrogen-containing aromatic heterocyclic-N-oxide ligand, or a methyl or phenyl substituted phosphono ligand.
The nitrogen-containing aromatic heterocyclic ligand is selected from monodentate or polydentate ligands derived from pyridine, imidazole, pyrazole, thiazole, oxazole, oxadiazole and triazole, and more preferably is a bidentate or tridentate ligand formed by connecting the groups. When the nitrogen-containing aromatic heterocyclic ligand is selected from the structures, the heterocyclic nitrogen atoms in the compound have higher electron cloud density, so that the nitrogen-containing aromatic heterocyclic ligand has stronger coordination capability. The nitrogen-containing aromatic heterocyclic ligands are exemplified by 1, 10-phenanthroline, 2 '-bipyridine, 2':6', 2' -terpyridine, benzimidazole, benzoxazole, benzothiazole, quinoline, isoquinoline, 2- (1-methylimidazol-2-yl) pyridine, 2- (pyrazol-1-yl) pyridine, 2- (1, 2,3 triazol-1-yl) pyridine, 2- (pyridin-2-yl) oxazole, 2- (pyridin-2-yl) thiazole, 2- (pyridin-2-yl) -1,3, 4-oxadiazole.
The nitrogen-containing aromatic heterocycle-N-oxide ligand refers to N-oxide obtained by N-oxidation of nitrogen heteroatoms, wherein N-O bonds have large polarity, O atom electron cloud density is high, and the nitrogen-containing aromatic heterocycle-N-oxide ligand has strong coordination capacity. Examples of the nitrogen-containing aromatic heterocycle-N-oxide include pyridine-N-oxide, imidazole-N-oxide, pyrazole-N-oxide, 2' -bipyridine-N-oxide, and 1, 10-phenanthroline-N-oxide.
The methyl-or phenyl-substituted phosphono-type ligands are exemplified by triphenylphosphine oxide, 1, 3-bis-diphenylphosphinopropane.
Through analysis, the inventor groups found that in the preparation process of the complex, 3-4 parts of water molecules are generated by the neutralization reaction of the acidic 4-hydroxy-1, 5-naphthyridine ligand and alkali, and y parts of water molecules are generated after the rare earth salt containing crystal water is dissolved, so that the water content in the alcohol solvent is increased. Then moisture gradually builds up during repeated reuse of the solvent and eventually adversely affects.
Specifically, on one hand, the water molecules have strong coordination and can compete with other neutral ligands, so that the light emission of the rare earth complex is quenched by the high-frequency vibration of the water molecules; on the other hand, since 4-hydroxy-1, 5-naphthyridine type ligands are weak acids, contact with water molecules easily results in hydrolysis and dissociation of anionic ligands and results in coordination unsaturation and hydroxyl coordination bridging.
Therefore, the effective removal of water is important for the recycling of the 4-hydroxy-1, 5-naphthyridine europium complex mother solution.
For recovering the solvent, it is common practice in industry to separate the mixed solvent by distillation. However, water and alcohols form azeotropes and separation cannot be achieved by simple distillation or rectification.
Therefore, the invention provides a method for efficiently and simply removing the water in the complex alcohol mother liquor, so that the recycled solvent does not influence the purity and luminous efficiency of the complex product.
The present invention mixes the complex mother liquor with calcium oxide or molecular sieve to dewater. The calcium oxide reacts with water in the mother liquor to generate extremely fine calcium hydroxide particles, the molecular sieve is worn in the stirring process to generate a large amount of fine molecular sieve particles, if the solid-liquid separation is carried out in a decompression suction filtration mode, the treatment speed is very slow, and the solvent volatilization loss is very large; and a great amount of fine particles pass through the filter type centrifugal separation device to influence the application of mother liquor. In the technical scheme of the invention, the separation mode of the dehydrating agent particles is preferably sedimentation type centrifugation or static pressure filtration; the sedimentation type centrifugation is preferably cup type centrifugation and spiral centrifugation; the static filter pressing is preferably bag filter pressing and plate frame filter pressing. The molecular sieve can be activated and reused after absorbing water, thus realizing repeated use. The mother solution after the water removal can be repeatedly used, the alcohol solvent obtained by distillation in the mother solution preparation can be further used for preparing 4-hydroxy-1, 5-naphthyridine europium complex, the luminous efficiency of the product is not obviously changed, and the requirement of industrial production is met.
The invention has the beneficial effects that: the invention discovers and discloses that the accumulation of moisture is an important adverse factor in the recycling of 4-hydroxy-1, 5-naphthyridine europium complex mother liquor. The invention adopts calcium oxide or molecular sieve to adsorb and remove water in the 4-hydroxy-1, 5-naphthyridine complex mother liquor, can be directly used and recycled after filtration or centrifugation, and is used for preparing the next batch of complex products, or the alcohol solvent is recovered by distillation, and is used for preparing the next batch of complex products, thereby realizing the recycling of the 4-hydroxy-1, 5-naphthyridine complex mother liquor.
The technical scheme of the invention is simple and easy to operate, the water removal effect is good, the purity and luminous efficiency of the complex prepared by applying the water removal mother solution are consistent with those of the complex product prepared by using the fresh solvent, the production cost can be reduced, and the waste liquid discharge can be reduced.
Drawings
FIG. 1 is a graph of the luminescence intensity (excitation wavelength 350 nm) of a 4-hydroxy-1, 5-naphthyridine europium complex prepared according to the present invention, and test samples are complexes prepared using analytically pure absolute ethanol in example 1, complexes prepared using calcium oxide dehydration mother liquor in example 6, and europium complexes prepared using non-dehydration mother liquor in comparative example 1.
Detailed Description
The products, the process of preparation of the invention are further illustrated by the following specific examples, which are not intended to limit the scope of the invention in any way.
A recycling method of a mother solution for preparing 4-hydroxy-1, 5-naphthyridine europium complex comprises the following steps: (1) Mixing the complex preparation mother solution (containing an alcohol solvent, water, salts, a small amount of residual 4-hydroxy-1, 5-naphthyridine europium complex and impurities) with a dehydrating agent according to the mass ratio of 1 (0.05-0.5), and stirring for 10 minutes to 24 hours at a reflux temperature; (2) Cooling to room temperature, filtering and separating dehydrating agent and other insoluble matters to obtain dehydrated mother liquor B, and directly using the dehydrated mother liquor B for preparing europium complexes in the next batch to realize recycling; (3) After mother liquor B is repeatedly reused for 0-5 times, more impurities are accumulated in the mother liquor B, and the mother liquor B can be dehydrated in the mode of the step (1) and then distilled to obtain an anhydrous alcohol solvent (salt and impurities are removed through distillation) for preparing europium complexes in the next batch.
In the invention, the complex mother liquor, the preparation mother liquor and the mother liquor are the same meaning, and refer to the residual liquid after the preparation of the 4-hydroxy-1, 5-naphthyridine europium complex according to the method of Chinese patent 202210338200.2 or 201510130379.2.
< preparation of Complex with New Anhydrous ethanol >
Example 1.
Preparation of europium complex Eu (8 mCND) with absolute ethanol 3 (phen), the europium complex structure of this example is as follows:
to 400g of absolute ethanol, 55.5g (0.3 mol) of 3-cyano-4-hydroxy-8 methyl-1, 5-naphthyridine (H8 mCND), 54.3g (0.3 mol) of organic base-tetramethylammonium hydroxide pentahydrate, 36.6g (0.1 mol) of europium trichloride hexahydrate and 18.0g (0.1 mol) of anhydrous phenanthroline (phen) were added, and the mixture was heated and refluxed for 2 hours. White europium complex solid is formed, while the byproduct-tetramethyl ammonium chloride is dissolved in ethanol. After cooling, direct filtration and separation, ethanol washing and vacuum drying are carried out, 81.4g of white europium complex product is obtained, and the yield is 92.1%. Mass spectrometry (m/z, ESI): calculated 885.1, experimental 886.1[ M+H ]] + . Elemental analysis (mass%): c,55.96 (55.88); h,3.23 (3.13), N,16.95 (17.07), eu (8 mCND) in brackets 3 (phen)·1.0H 2 O theory.
Example 2.
Preparation of europium complex Eu (8 mCND) with absolute ethanol 4 (NMe 4 ) The europium complex structure of this example is as follows:
to 400g of absolute ethanol, 74.0g (0.4 mol) of 3-cyano-4-hydroxy-8 methyl-1, 5-naphthyridine (H8 mCND), 72.4g (0.4 mol) of tetramethyl ammonium hydroxide pentahydrate as an organic base, 36.6g (0.1 mol) of europium trichloride hexahydrate were added, and the mixture was heated under reflux for 6 hours. White europium complex solid is formed, while the byproduct-tetramethyl ammonium chloride is dissolved in ethanol. After cooling, direct filtration and separation, ethanol washing and normal pressure drying at 180 ℃ are carried out, 83.3g of yellowish europium complex product is obtained, and the yield is 85.0%. Mass spectrometry (m/z, ESI): theoretical value 962.8, measured molecular ion peak M/z= 889.1, [ M-NMe 4 ] - . Elemental analysis (mass%): c,53.56 (53.88); h,3.99 (3.91), N,18.35 (18.56), eu (8 mCND) in brackets 4 (NMe 4 )·1.0H 2 O theory.
< dehydration of europium Complex mother liquor >
Example 3.
The method for dehydrating the mother liquor adopts calcium oxide. About 500g of the mother solution of the complex produced in example 1 (obtained by filtration) was added to the flask, 100g of calcium oxide powder was added, and the mixture was stirred and heated under reflux for 3 hours. After cooling, the mixture was separated by a flat metal filter press (Φ=300 mm,0.25 μm PP filter), and washed with absolute ethanol (100 g) to obtain about 580g of a dehydrated mother liquor. The 0.25 mu m PP filter membrane can well separate calcium hydroxide fine particles, the filter pressing process is about 1.5 hours, and the mother liquor B after water removal is yellowish clear transparent liquid and can be directly recycled.
Example 4.
About 500g of the mother solution of the complex produced in example 1 (obtained by filtration) was added to the flask, 80g of calcium oxide powder was added, and the mixture was stirred and heated under reflux for 1 hour. Next, absolute ethanol was collected by atmospheric distillation (distillation process continued for 2 hours), yielding about 400g of recovered absolute ethanol which was colorless and transparent.
Example 5.
The method for dehydrating the mother liquor adopts a molecular sieve. About 500g of the complex mother liquor produced in example 2 was charged into a flask, 135g of activated powdery 3A molecular sieve was added, stirred at room temperature for 2 hours, molecular sieve powder was removed using a cup centrifuge, and washed with absolute ethanol (about 150 g) to obtain a dehydrated complex mother liquor. The mother solution of the complex was again placed in a three-necked flask, and the absolute ethanol was collected by distillation to obtain about 600g of recovered absolute ethanol which was colorless and transparent.
And (3) putting the molecular sieve powder obtained by filtering into a muffle furnace, heating for 3 hours at 500 ℃, cooling to about 150 ℃, putting the powder into a drier while the powder is hot, and further cooling to room temperature to obtain the activated molecular sieve. And (3) testing the water content of the mother solution:
qualitatively, it can be judged by adding anhydrous copper sulfate to the alcohol solution. Specifically, anhydrous copper sulfate is gray powder, 0.1g of anhydrous copper sulfate is added into 1mL of alcohol solution, vibration or stirring is carried out, the color change of the anhydrous copper sulfate is observed, the color is not changed within 0.5h, and the water content in the solution is lower than 0.5%; if the color turns blue, the solution contains water.
Quantitatively, it can be measured by a karl fischer moisture meter. The basic principle of titration is that a certain amount of water is needed to participate in the reaction when the sulfur dioxide is oxidized by iodine, and the determination is carried out by the abrupt change of conductivity at the end point. Methanol is used as a working medium, the micro-injector samples 500 mu L each time, and the instrument automatically calculates the titration result. Table 1 shows the results of measuring the moisture content in the alcohol solvents of examples by the Karl Fischer method.
TABLE 1 results of Water content test in alcohol solvents (Karl Fischer method)
As can be seen from Table 1, significant moisture is generated in the complex mother liquor. The reason is that 3-4 parts of water molecules generated by the neutralization reaction of the 4-hydroxy-1, 5-naphthyridine ligand and alkali and the rare earth salt contain crystal water in the preparation process of the complex, so that the water content in the alcohol solvent is increased. In example 1, the water content of the complex mother liquor was 2.88%, and in example 2, the water content of the mother liquor was 3.24%.
By adopting the technical scheme of the invention, the water in the complex mother solution can be effectively removed. In example 3, the water content in the mother liquor B obtained by filtering after dehydration of calcium oxide has been reduced to 0.38%; in example 4, the mother liquor was dehydrated with calcium oxide and distilled to obtain recovered absolute ethyl alcohol with a water content of 0.33%; in example 5, the complex mother liquor was dehydrated by activated molecular sieves and then distilled to obtain recovered ethanol with a water content of 0.54%. The technical scheme of the invention is illustrated that the water in the complex mother liquor can be effectively removed, and the recovered dehydrated alcohol solvent can be obtained through distillation and then put into use.
< preparation of europium Complex from dehydrated and recycled mother liquor >
Example 6.
The dehydrated and recycled mother solution B is reused for one time to prepare europium complex Eu (8 mCND) 3 (phen) has a structure shown in formula IV. The preparation method is the same as in example 1, except that the absolute ethanol is changed to that obtained in example 3Is a dehydrated mother liquor B. Finally, 83.5g of yellowish europium complex product was obtained in a yield of 94.4%. Mass spectrometry (m/z, ESI): calculated 885.1, experimental 886.1[ M+H ]] + . Elemental analysis (mass%): c,55.92 (55.88); h,3.20 (3.25), N,17.02 (17.07), eu (8 mCND) in brackets 3 (phen)·1.0H 2 O theory.
Example 7.
And (5) secondary application of the dehydrated and recycled mother liquor B. The mother liquor of the complex obtained in example 6 was dehydrated with calcium oxide in the manner described in example 3. Then the dehydrated mother solution B is reused for preparing europium complex Eu (8 mCND) by the complex 3 (phen) has a structure shown in formula IV.
The preparation method is the same as in example 1, except that the absolute ethanol is changed into dehydrated mother liquor B for secondary application. Finally, 84.2g of yellowish europium complex product was obtained in a yield of 95.2%.
Example 8.
And the mother liquor B after dehydration and reuse is reused for three times. The mother liquor of the complex obtained in example 7 was dehydrated with calcium oxide in the manner described in example 3. Then the dehydrated mother solution B is reused for three times for preparing europium complex Eu (8 mCND) by the complex 3 (phen) has a structure shown in formula IV.
The preparation method is the same as in example 1, except that the dehydrated mother liquor B is changed into dehydrated mother liquor B for three times. Finally, 86.2g of yellowish europium complex product was obtained in a yield of 97.5%.
With the mother solution B, the complex Eu (8 mCND) 3 The yield of (phen) was gradually increased. First preparation, complex yield 92.1% (example 1); the mother liquor B is dehydrated and reused once, and the yield of the complex is 94.4 percent (example 6); the mother liquor B is dehydrated and reused, and the yield of the complex is 95.2 percent (example 7); the mother liquor B was dehydrated and applied three times, and the yield of the complex was 97.5% (example 8). The reason may be that there is a certain product Eu (8 mCND) in the complex mother liquor 3 (phen) (with certain solubility), in the process of mother liquor B, the product is further separated out, and the product yield is improved. When the mother solution B is used for sleeving, the color of the product is yellowish, and the luminous quantum efficiency is highThe (PLQY) test is qualified and is more than 50 percent.
Example 9.
And (3) after dehydration of the mother solution B calcium oxide for multiple times, distilling and recovering absolute ethyl alcohol to prepare the europium complex.
The complex mother liquor obtained in example 8 after three applications had a large accumulation of impurity content, and the solution was reddish brown. The recovered absolute ethanol was obtained by dehydration with the addition of calcium oxide and then distillation in the manner described in example 4. Then used for preparing europium complex Eu (8 mCND) 3 (phen) has a structure shown in formula IV.
The preparation method is the same as in example 1, except that the absolute ethyl alcohol is changed into the recycled dehydrated alcohol obtained by processing mother liquor B for multiple times according to the method of example 4. Finally, 81.5g of white europium complex product was obtained in a yield of 92.1%. Mass spectrometry (m/z, ESI): calculated 885.1, experimental 886.1[ M+H ]] + . Elemental analysis (mass%): c,55.80 (55.88); h,3.20 (3.13), N,17.12 (17.07), eu (8 mCND) in brackets 3 (phen)·1.0H 2 O theory.
Example 10.
And (3) dehydrating the mother liquor molecular sieve, and distilling to recover absolute ethyl alcohol to prepare the europium complex.
The complex mother liquor obtained in example 2 was dehydrated by adding molecular sieve in the manner described in example 5, and then distilled to obtain recovered absolute ethanol, which was then used for preparing europium complex Eu (8 mCND) 4 (NMe 4 ) The structure is shown as formula V.
The preparation method is the same as in example 2, except that the absolute ethyl alcohol is changed into the recycled dehydrated alcohol obtained by distillation after molecular sieve dehydration. Finally, 84.5g of light yellow europium complex is obtained and dried at 180 ℃, and the product yield is 86.2%. Mass spectrometry (m/z, ESI): theoretical value 962.8, measured molecular ion peak M/z= 889.1, [ M-NMe 4 ] - . Elemental analysis (mass%): c,53.56 (53.88); h,3.99 (3.91), N,18.35 (18.56), eu (8 mCND) in brackets 4 (NMe 4 )·1.0H 2 O theory.
Comparative example 1.
Complex mother liquorThe europium complex Eu (8 mCND) is prepared without dehydration and is directly recycled 3 (phen) has a structure shown in formula IV. The preparation was carried out in the same manner as in example 1, except that the absolute ethanol was replaced by the mother liquor of the complex produced in example 1. 78.5g of yellowish europium complex product is obtained in 89% yield. Mass spectrometry (m/z, ESI): calculated 885.1, experimental 886.1[ M+H ]] + 。
Comparative example 2.
The mother solution of the complex is not dehydrated and is directly recycled to prepare europium complex Eu (8 mCND) 4 (NMe 4 ) The structure is shown as formula V. The preparation was carried out in the same manner as in example 2, except that absolute ethanol was replaced by the mother liquor of the complex produced in example 2. 73.5g of yellowish europium complex product is obtained with a yield of 75%. Mass spectrometry (m/z, ESI): theoretical value 962.8, measured molecular ion peak M/z= 889.1, [ M-NMe 4 ] - 。
The water in the mother liquor also results in the product Eu (8 mCND) 4 (NMe 4 ) The yield is lower. The complex Eu (8 mCND) prepared with absolute ethanol in example 2 4 (NMe 4 ) The yield was 85%, and comparative example 2 used aqueous ethanol to prepare the complex, the yield was reduced to 75%. The possible reasons are that the water molecules cause ligand hydrolysis, so that the proportion is inaccurate, and the generation of the complex is influenced.
Example 11.
Characterization of photophysical Properties of products
(1) Excitation and emission spectra
The excitation and emission spectra are tested by using an Edinburgh FLS1000 fluorescence spectrometer, the excitation light source is a xenon lamp, and the detector is a photomultiplier. And proper amount of europium complex powder is placed in the quartz sample cell, and the excitation slit and the emission slit are both 0.5nm. The emission spectrum was tested at an ultraviolet excitation wavelength of 350nm.
(2) Photoluminescence quantum efficiency
Photoluminescence quantum efficiency is the absolute quantum efficiency measured by the integrating sphere of the FLS1000 spectrometer. Scanning a background signal in a range of 340-750 nm by taking 350nm as an excitation wavelength and taking a blank quartz cell as a reference, and placing a proper amount of europium complex powder in a quartz sample cell to scan an absorption and luminescence signal of a sample; processing the spectrograms of the two scans, wherein the difference value of the areas of spectrum integral peaks in the range of 340-360 nm is the absorption value of excitation light, and the difference value of the areas of spectrum integral peaks in the range of 500-750 nm is the luminous intensity value; the ratio between the luminous intensity value and the absorption value is the photoluminescence quantum efficiency.
The test results are shown in fig. 1 and table 2. FIG. 1 is a graph showing the comparison of the luminescence intensities of europium complexes prepared in example 1, example 6 and comparative example 1, with an excitation wavelength of 350nm. Example 1A 4-hydroxy-1, 5-naphthyridine europium complex was prepared using purchased analytically pure absolute ethanol (water content 0.16%), example 6 a complex was prepared using calcium oxide dehydrated mother liquor B (water content 0.38%) and comparative example 1 a complex was prepared directly using a non-dehydrated aqueous mother liquor (water content 2.88%). Example 6 has similar luminous intensity (the curves of which are highly coincident and are basically indistinguishable from each other as seen in fig. 1) to the product of example 1, and is higher than the luminous intensity of the product of comparative example 1, which shows that the dehydrated mother liquor B can prepare a product with acceptable luminous efficiency.
As can be seen from Table 2, in examples 6 to 9, europium complex Eu (8 mCND) prepared using calcium oxide dehydration mother liquor 3 (phen) the luminous efficiency of the product remained between 52% and 58%, similar to that of the complex prepared with analytically pure absolute ethanol in example 1 (58%); in comparative example 1, the Eu (8 mCND) complex was directly prepared using the aqueous mother liquor 3 (phen) has a significantly reduced luminous efficiency of only 43%.
In example 10, europium complex Eu (8 mCND) prepared by distilling molecular sieve dehydration mother liquor to recover ethanol 4 (NMe 4 ) The luminous efficiency of the product was 70%, similar to that of the complex prepared using analytically pure absolute ethanol in example 2 (72%); in comparative example 2, the Eu (8 mCND) complex was directly prepared using the aqueous mother liquor 4 (NMe 4 ) The luminous efficiency is obviously reduced to only 49%.
TABLE 2 characterization of the luminescence properties of europium complexes
The results in Table 2 show that moisture accumulation (water content of 2.8-3.3% in single reaction) occurs during the preparation of the complex, and if the water content is multiplied by multiple times, the presence of a large amount of water molecules can lead to dissociation and hydrolysis of the 4-hydroxy-1, 5-naphthyridine ligand, resulting in reduced luminous efficiency and even reduced yield of the product. After the preparation mother liquor is dehydrated by the method, the dehydrated mother liquor and the obtained alcohol solvent are recycled for preparation, the obtained complex has higher yield, and the luminous efficiency of the product is not affected.
The technical scheme of the invention provides a dehydration recycling method of 4-hydroxy-1, 5-naphthyridine europium complex mother solution, and the dehydration method can effectively remove the moisture in the mother solution by adopting calcium oxide or molecular sieve, so that the repeated application of the mother solution is realized, the luminous efficiency of the product is not obviously changed, and the requirement of industrial production is met. The invention dewaters and recycles the mother liquor, and simultaneously recovers the alcohol solvent, reduces the discharge of waste liquid and lowers the production cost.
The above-described embodiments are merely preferred embodiments of the present invention, and it should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the inventive concept of the present invention.

Claims (11)

  1. The recycling method of the preparation mother liquor of the 4-hydroxy-1, 5-naphthyridine europium complex is characterized in that the 4-hydroxy-1, 5-naphthyridine europium complex is prepared according to the method of Chinese patent 202210338200.2 or 201510130379.2, and complex preparation mother liquor is generated; the complex preparation mother solution consists of an aqueous alcohol solvent, salts, a small amount of residual 4-hydroxy-1, 5-naphthyridine europium complex and impurities;
    the recycling method comprises the following steps:
    1) Dehydrating: the complex preparation mother liquor and the dehydrating agent are mixed according to the mass ratio of 1: mixing in the proportion of 0.05-0.5, stirring at room temperature-reflux temperature for 10 min-24 h;
    2) Separation and/or distillation: cooling the dehydrated preparation mother liquor obtained in the step 1) to room temperature, and then separating a dehydrating agent and other insoluble matters to obtain dehydrated mother liquor B which is used for preparing europium complexes in the next batch, thereby realizing the recycling of the preparation mother liquor of 4-hydroxy-1, 5-naphthyridine europium complexes; or directly distilling the dehydrated preparation mother liquor to obtain an anhydrous alcohol solvent, and using the anhydrous alcohol solvent for preparing europium complexes in the next batch to realize the recycling of the preparation mother liquor of 4-hydroxy-1, 5-naphthyridine europium complexes;
    the structure of the 4-hydroxy-1, 5-naphthyridine europium complex is shown as formula I or II:
    in the formulas I and II, R 1 、R 2 、R 3 、R 4 、R 5 Any one selected from hydrogen atoms, halogen atoms, cyano groups, methyl groups, ethyl groups, trifluoromethyl groups and pentafluoroethyl groups; l is a neutral ligand, x=1 to 3; m is any one of positive monovalent alkali metal ions and quaternary ammonium ions;
    the neutral ligand is a nitrogen-containing aromatic heterocyclic ligand, a methyl or phenyl substituted nitrogen-containing aromatic heterocyclic ligand, a nitrogen-containing aromatic heterocyclic-N-oxide ligand, a methyl or phenyl substituted nitrogen-containing aromatic heterocyclic-N-oxide ligand, or a methyl or phenyl substituted phosphono ligand.
  2. 2. The method for recycling a preparation mother liquor of 4-hydroxy-1, 5-naphthyridine europium complex according to claim 1, wherein the water content in the preparation mother liquor is less than 10% in terms of mass ratio.
  3. 3. The method for recycling the preparation mother liquor of the 4-hydroxy-1, 5-naphthyridine europium complex according to claim 1, wherein the alcohol solvent in the preparation mother liquor is any one or combination of ethanol, methanol and n-butanol in any proportion.
  4. 4. The method for recycling a preparation mother liquor of 4-hydroxy-1, 5-naphthyridine-based europium complex according to claim 1, wherein the impurities in the preparation mother liquor include ligand oxides contained in the 4-hydroxy-1, 5-naphthyridine-based ligand, and complexes generated by binding of iron ions with the ligand.
  5. 5. The method for recycling a mother liquor for preparing 4-hydroxy-1, 5-naphthyridine europium complex according to claim 1, wherein the salt structure in the mother liquor is represented by the general formula MX, wherein M is an alkali metal ion or a quaternary ammonium ion, and X is a chloride ion, an acetate ion or a nitrate ion; the salt is cation and trivalent europium salt EuX in alkali MOH in ligand preparation process 3 y(H 2 The anions of O) are combined to form the product; wherein y represents the amount of water of crystallization in the trivalent europium salt and y=1 to 6.
  6. 6. The method for recycling a mother liquor for preparing 4-hydroxy-1, 5-naphthyridine europium complex according to claim 1, wherein the dehydrating agent is calcium oxide or molecular sieve.
  7. 7. The method for recycling a mother liquor for preparing 4-hydroxy-1, 5-naphthyridine europium complex according to claim 1, wherein in the step 1), the mass ratio of the mother liquor for preparing complex to the dehydrating agent is 1:0.1 to 0.3.
  8. 8. The method for recycling the mother liquor for preparing 4-hydroxy-1, 5-naphthyridine europium complex according to claim 1, wherein after the mother liquor B is recycled for 0-5 times, the mother liquor B after the recycling can be dehydrated in the manner of the step 1), and then distilled to obtain the anhydrous alcohol solvent for preparing europium complex in the next batch for further recycling.
  9. 9. The method for recycling a mother liquor for preparing 4-hydroxy-1, 5-naphthyridine europium complex according to claim 6, wherein the calcium oxide is industrial grade or analytically pure anhydrous calcium oxide powder.
  10. 10. The method for recycling a mother liquor for preparing 4-hydroxy-1, 5-naphthyridine europium complex according to claim 6, wherein the molecular sieve is any one or any combination of any two of a dehydrated and activated 3A molecular sieve and a 4A molecular sieve in any proportion, and the state is granular or powder.
  11. 11. The method for recycling a mother liquor for preparing 4-hydroxy-1, 5-naphthyridine europium complex according to claim 1, wherein in the step 2), the separation mode of the dehydrating agent and other insoluble matters is sedimentation type centrifugation or static pressure filtration.
CN202311558796.8A 2023-11-21 2023-11-21 Recycling method of 4-hydroxy-1, 5-naphthyridine europium complex preparation mother solution Pending CN117551117A (en)

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