CN111574408A - Method for preparing urea-succinic acid metastable eutectic by limited-domain evaporative crystallization - Google Patents
Method for preparing urea-succinic acid metastable eutectic by limited-domain evaporative crystallization Download PDFInfo
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- CN111574408A CN111574408A CN202010456422.5A CN202010456422A CN111574408A CN 111574408 A CN111574408 A CN 111574408A CN 202010456422 A CN202010456422 A CN 202010456422A CN 111574408 A CN111574408 A CN 111574408A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
- C07C273/14—Separation; Purification; Stabilisation; Use of additives
- C07C273/16—Separation; Purification
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
- C07C55/02—Dicarboxylic acids
- C07C55/10—Succinic acid
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- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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Abstract
The invention relates to a method for preparing urea-succinic acid metastable eutectic by limited-domain evaporative crystallization, which comprises the steps of completely dissolving urea and succinic acid in deionized water according to the molar ratio of 1:1, then soaking porous glass into the obtained solution, filtering after soaking, transferring a filter cake to an air-blast drying oven, and flatly spreading and drying to obtain the urea-succinic acid metastable eutectic. According to the invention, the solution evaporation crystallization is limited in a nanometer space, the growth environment of crystallization nucleation is changed, the conversion rate of the metastable crystal form of urea and succinic acid to the stable crystal form is slowed down, the content of the metastable crystal form in the final product is improved, the operation is simple, the operation temperature is lower, and the repeatability is good.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a method for preparing urea-succinic acid metastable eutectic by limited-domain evaporative crystallization.
Background
The urea crystal is an ultraviolet frequency doubling crystal which is practically applied, has the advantages of large birefringence and small temperature coefficient of refractive index, and can realize stable output of ultraviolet frequency doubling at room temperature. From the perspective of molecular structure, the derivative of urea or the eutectic of urea also has a nonlinear optical effect similar to that of pure urea crystals, and the construction of the eutectic of urea through molecular engineering can help to improve the nonlinear optical effect.
Eutectic crystals are crystals formed of two or more molecules, and the eutectic crystals have recently been drawing attention as a functional material for pharmaceutical, electronic, and organic chemical synthesis applications. The 2:1 eutectic of urea and succinic acid can be directly prepared by a conventional experimental method, and the 1:1 uric acid-succinic acid eutectic is prepared by a spray drying method for the first time by using Sitaram P.Veaga (Crystal Growth & Design,2010,10(8), 3302-doped 3305), which is a metastable Crystal with a Crystal structure different from that of the 2:1 stable eutectic. Vinitha (Brazilian Journal of Physics 2020,50, 192-213) states that stable and metastable eutectics of urea are possible to improve the optical application properties of urea crystals in different ways and to different extents. However, the spray drying process for preparing metastable urea butane diacid eutectic requires higher operating temperature, which may cause thermal reaction of urea.
Because of the excellent physical and chemical properties of eutectic, the preparation method of eutectic has been widely studied, and the preparation of eutectic commonly used at present mainly includes evaporative crystallization, cooling crystallization, melting crystallization, paste crystallization and solid grinding method. Different preparation methods are usually based on different eutectic formation mechanism processes, and a single preparation method is usually limited, so that the development of more preparation methods or auxiliary methods means the improvement of the probability of successfully preparing the eutectic, and in addition, the selection and comparison of more preparation methods are beneficial to the summary of eutectic preparation experience and the research of eutectic mechanism.
Although many methods for preparing the eutectic are available, many eutectic which can be predicted by theory cannot be prepared by the existing experimental method, which is due to the fact that the experimental operation is limited by the difference of physicochemical properties such as solubility, melting point and the like among the components for composing the eutectic, and the preparation method is possibly limited. More preparation methods will provide more opportunities for discovery and acquisition of new co-crystals.
Disclosure of Invention
The invention aims to provide a method for preparing urea-succinic acid metastable eutectic by limited-domain evaporative crystallization under mild conditions.
Aiming at the purposes, the technical scheme adopted by the invention comprises the following steps:
1. completely dissolving urea and succinic acid in deionized water according to a molar ratio of 1:1, controlling the total concentration of the urea and the succinic acid in the solution to be 5-30 g/100g of water, and then soaking porous glass with a nano pore diameter in the obtained solution for 5-10 hours at room temperature.
2. And (3) filtering the solid-liquid mixture obtained in the step (1), flatly paving the obtained filter cake to an air-blast drying oven for drying, wherein the drying temperature is 35-65 ℃, and the drying time is 8-30 hours, so as to obtain the urea-succinic acid metastable eutectic crystal.
In the step 1, the total concentration of urea and succinic acid in the solution is preferably controlled to be 10-15 g/100g of water.
In the step 1, the pore diameter of the porous glass is preferably 30 to 60 nm.
In the step 2, the preferable drying temperature is 45-55 ℃ and the drying time is 10-12 hours.
In the step 2, the further preferable tiled thickness is 2-4 mm.
The invention has the following beneficial effects:
1. according to the invention, the solution evaporation crystallization is limited in the nanometer space, the path of eutectic nucleation is changed, the transformation rate of the metastable crystal form of urea and succinic acid to the stable crystal form is slowed down by limiting the domain space, the content of the metastable crystal form in the final product is improved, the metastable crystal form eutectic of urea and succinic acid is successfully obtained, and the long-term storage of the metastable crystal form eutectic is facilitated.
2. The method has low requirement on experimental conditions, is easy to operate, and has low operation temperature and good repeatability.
3. The method can obtain the eutectic which can not be obtained by the conventional method, is beneficial to finding potential novel eutectic and is beneficial to improving the screening efficiency of the eutectic ligand. The invention can also be used for preparing other eutectics, not only urea and succinic acid eutectic.
Drawings
FIG. 1 is an X-ray diffraction pattern of the metastable eutectic urea-succinate prepared by the limited-domain evaporative crystallization method in example 1.
Detailed Description
The technical solutions of the present invention will be described in detail below with reference to the accompanying drawings and examples, but the scope of the present invention is not limited to these examples.
Example 1
1. Dissolving 0.3g (5mmol) of urea and 0.6g (5mmol) of succinic acid in 6.0g of deionized water, and stirring to obtain a clear solution; then, 80mg of porous glass having a pore diameter of 50nm was immersed in the resultant solution at room temperature for 8 hours.
2. And (3) filtering the solid-liquid mixture obtained in the step (1), flatly paving the obtained filter cake in a blast drying oven, wherein the flatly paving thickness is 3mm, and drying at 45 ℃ for 10 hours to obtain the urea-succinic acid metastable eutectic crystal.
The obtained sample was characterized by an X-ray diffractometer, and the results are shown in FIG. 1. As can be seen from FIG. 1, the obvious metastable eutectic diffraction peaks of 1:1 urea-succinic acid appear at the 2 theta angles of 9.4 degrees, 19.6 degrees and 27.3 degrees respectively, and basically accord with the eutectic XRD diffraction pattern reported in the literature (CrystalGrowth & Design 19(2019)1505-1508) (the background peak is an amorphous peak of porous glass), which indicates that the metastable eutectic of urea-succinic acid is successfully prepared by the method.
Example 2
1. Dissolving 0.3g (5mmol) of urea and 0.6g (5mmol) of succinic acid in 3.0g of deionized water, and stirring to obtain a clear solution; then, 80mg of porous glass having a pore diameter of 50nm was immersed in the resultant solution at room temperature for 5 hours.
2. And (3) filtering the solid-liquid mixture obtained in the step (1), flatly paving the obtained filter cake in a blast drying oven, wherein the flatly paving thickness is 2mm, and drying for 10 hours at the temperature of 35 ℃ to obtain the urea-succinic acid metastable eutectic crystal.
Example 3
1. Dissolving 0.3g (5mmol) of urea and 0.6g (5mmol) of succinic acid in 10.0g of deionized water, and stirring to obtain a clear solution; then, 80mg of porous glass having a pore diameter of 40nm was immersed in the resultant solution at room temperature for 8 hours.
2. And (3) filtering the solid-liquid mixture obtained in the step (1), flatly paving the obtained filter cake in a blast drying oven, wherein the flatly paving thickness is 3mm, and drying at 55 ℃ for 10 hours to obtain the urea-succinic acid metastable eutectic crystal.
Example 4
1. Dissolving 0.3g (5mmol) of urea and 0.6g (5mmol) of succinic acid in 6.0g of deionized water, and stirring to obtain a clear solution; then, 80mg of porous glass having a pore diameter of 60nm was immersed in the resultant solution at room temperature for 8 hours.
2. And (3) filtering the solid-liquid mixture obtained in the step (1), flatly paving the obtained filter cake in a blast drying oven, wherein the flatly paving thickness is 4mm, and drying at 45 ℃ for 10 hours to obtain the urea-succinic acid metastable eutectic crystal.
Example 5
1. Dissolving 0.3g (5mmol) of urea and 0.6g (5mmol) of succinic acid in 12.0g of deionized water, and stirring to obtain a clear solution; then, 80mg of porous glass having a pore diameter of 40nm was immersed in the resultant solution at room temperature for 8 hours.
2. And (3) filtering the solid-liquid mixture obtained in the step (1), flatly paving the obtained filter cake in a blast drying oven, wherein the flatly paving thickness is 4mm, and drying for 10 hours at 65 ℃ to obtain the urea-succinic acid metastable eutectic crystal.
Claims (5)
1. A method for preparing urea-succinic acid metastable eutectic by limited-domain evaporative crystallization is characterized by comprising the following steps:
(1) completely dissolving urea and succinic acid in deionized water according to a molar ratio of 1:1, controlling the total concentration of the urea and the succinic acid in the solution to be 5-30 g/100g of water, then soaking porous glass with a nano pore diameter in the obtained solution, and soaking for 5-10 hours at room temperature;
(2) and (2) filtering the solid-liquid mixture obtained in the step (1), flatly paving the obtained filter cake to an air-blast drying oven for drying, wherein the drying temperature is 35-65 ℃, and the drying time is 8-30 hours, so as to obtain the urea-succinic acid metastable eutectic crystal.
2. The method for preparing the metastable eutectic of urea-succinic acid by the limited-domain evaporative crystallization of claim 1, wherein the metastable eutectic of urea-succinic acid is prepared by the following steps: in the step (1), the total concentration of urea and succinic acid in the solution is controlled to be 10-15 g/100g of water.
3. The method for preparing the metastable eutectic of urea-succinic acid by the limited-domain evaporative crystallization of claim 1, wherein the metastable eutectic of urea-succinic acid is prepared by the following steps: in the step (1), the aperture of the porous glass is 30-60 nm.
4. The method for preparing the metastable eutectic of urea-succinic acid by the limited-domain evaporative crystallization of claim 1, wherein the metastable eutectic of urea-succinic acid is prepared by the following steps: in the step (2), the drying temperature is 45-55 ℃, and the drying time is 10-12 hours.
5. The method for preparing metastable eutectic of urea-succinic acid by evaporation crystallization in limited area according to claim 1 or 4, characterized in that: in the step (2), the tiling thickness is 2-4 mm.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4146730A (en) * | 1975-12-25 | 1979-03-27 | Asahi Kasei Kogyo Kabushiki Kaisha | Method for obtaining glutaric acid, succinic acid, and adipic acid from an acid mixture comprising them |
| CN105566096A (en) * | 2015-12-18 | 2016-05-11 | 江西科技师范大学 | Technique for separating and purifying succinic acid from microbial fermentation liquid |
| CN105696066A (en) * | 2015-10-26 | 2016-06-22 | 西北大学 | Method for preparing eutectic by sheeting process |
| CN105732457A (en) * | 2016-04-01 | 2016-07-06 | 江西科技师范大学 | Method for preparing succinimide with succinic acid fermentation liquor |
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- 2020-05-26 CN CN202010456422.5A patent/CN111574408B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4146730A (en) * | 1975-12-25 | 1979-03-27 | Asahi Kasei Kogyo Kabushiki Kaisha | Method for obtaining glutaric acid, succinic acid, and adipic acid from an acid mixture comprising them |
| CN105696066A (en) * | 2015-10-26 | 2016-06-22 | 西北大学 | Method for preparing eutectic by sheeting process |
| CN105566096A (en) * | 2015-12-18 | 2016-05-11 | 江西科技师范大学 | Technique for separating and purifying succinic acid from microbial fermentation liquid |
| CN105732457A (en) * | 2016-04-01 | 2016-07-06 | 江西科技师范大学 | Method for preparing succinimide with succinic acid fermentation liquor |
Non-Patent Citations (5)
| Title |
|---|
| A. SELVAM等: "Growth and characterization of Urea succinic acid (USA) single crystal by using slow evaporation process", 《DER PHARMA CHEMICA》 * |
| AMJAD ALHALAWEH等: "1:1 and 2:1 Urea-Succinic Acid Cocrystals: Structural Diversity,Solution Chemistry, and Thermodynamic Stability", 《CRYSTAL GROWTH & DESIGN》 * |
| CATHERYN L. JACKSON和GREGORY B. MCKENNA: "Vitrification and Crystallization of Organic Liquids Confined to Nanoscale Pores", 《CHEM. MATER.》 * |
| QI JIANG和MICHAEL D. WARD: "Crystallization under nanoscale confinement", 《CHEM. SOC. REV.》 * |
| QIUSHUO YU等: "Jumping into Metastable 1:1 Urea-Succinic Acid Cocrystal Zone by Freeze-Drying", 《CRYST. GROWTH DES.》 * |
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