CN114478969A - Method for large-scale batch preparation of porous organic cages by using high-pressure homogenization - Google Patents
Method for large-scale batch preparation of porous organic cages by using high-pressure homogenization Download PDFInfo
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Abstract
A method for preparing porous organic cages in large scale by high-pressure homogenization belongs to the technical field of high-molecular organic porous materials. Adding tetracyclic intermediate cyclo-calix [4] arene (C4RACHO) and an amino ligand into a beaker, uniformly mixing, and then adding into a high-pressure homogenizer for homogenizing for a certain time; and after the homogeneous reaction, carrying out suction filtration on the product powder, recycling the filtrate, and washing and drying the product powder to obtain the porous organic cage POCs. Compared with other POCs preparation methods, the high-pressure homogenization method provided by the invention has the advantages of continuous reaction, simplicity in operation, low cost, high yield, environmental friendliness, energy conservation, short reaction time and the like, has large-scale production potential, and can greatly promote the industrial production process of POCs materials.
Description
Technical Field
The invention belongs to the technical field of high-molecular organic porous materials, and particularly relates to a method for large-scale batch preparation of porous organic cages by high-pressure homogenization.
Background
Porous Organic Cages (POCs) are cage-type organic molecules formed by covalent bonds of light elements such as C, H, O, N, B and having a three-dimensional structure. The material has the advantages of rigid skeleton structure, lasting shape, molecular cavities and windows, adjustable pore channel structure, large specific surface area and the like, is widely concerned by researchers, and has wide application prospects in the aspects of adsorption separation, energy storage, sensing, detection, catalysis, gas capture and the like.
At present, the main preparation methods of the porous organic cage are a solvothermal method, a solvothermal/volatilization method, a microwave radiation method, a double-screw extrusion method, a dynamic flow synthesis method and the like, wherein the solvothermal method and the solvothermal/volatilization method are the most common methods.
The porous organic cages are prepared by a solvothermal method or a solvothermal/volatilization method, so that the porous organic cages have good universality on POCs materials, but the method has long synthesis time, harsh reaction conditions, high energy consumption and low product yield, and cannot be used for continuous batch production, a Yuan Qiang teacher topic group obtains a series of POCs materials by the solvothermal/volatilization method, (J.Am.Chem.Soc.2020,142, 18060-18072; Chem.Sci.,2021,12, 13307-13315), and after the reaction system is subjected to high-temperature treatment, the products can be obtained only by volatilizing methanol for a plurality of weeks, so that the method has long energy consumption and is not suitable for industrial production; the microwave method is difficult to realize large-scale production due to the high cost of equipment, the inability of large-scale production, high cost and the like; rebecca l.greenaway et al propose to prepare porous organic cages CC3 by a twin-screw extrusion method, which is not conducive to industrial production due to limited mass transfer, low BET specific surface area of the obtained material, high temperature requirement, high energy consumption (chem.sci.,2020,11, 6582-; although the dynamic flow synthesis method can realize large-scale preparation, continuous production cannot be realized, high-temperature conditions are required in the synthesis process, the energy consumption is high, and the method is not favorable for industrial production of the POCs.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing a porous organic cage by High Pressure Homogenization (HPH), which solves the problems of long synthesis time, complex process, high energy consumption, low yield, incapability of continuous production and the like in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for large-scale batch preparation of porous organic cages by high-pressure homogenization comprises the following steps:
common organic ligands are used as raw materials, and the synthesized POCs comprise but are not limited to imine, borate and other connected porous organic cage materials; the solvent is water or an organic solvent, and the organic solvent comprises but is not limited to one of N, N-dimethylformamide, N-dimethylacetamide, dioxane, ethanol, methanol, acetonitrile, tetrahydrofuran and mesitylene; in the reaction process, catalysts are used or not, for example, the catalysts are used, the catalysts include but are not limited to trifluoroacetic acid, acetic acid and the like, which can synthesize POCs, all reaction raw materials are uniformly mixed, and the porous organic cage is obtained after the homogenization by a high-pressure homogenizer.
Furthermore, ligand raw materials required by synthesizing the POCs are selected from tetra-aldehyde-group cyclopolycalix [4] arene (C4RACHO) and p-phenylenediamine or benzidine.
Further, the molar ratio of the ligand to the solvent is: c4 RACHO: p-phenylenediamine or benzidine: solvent 1: 0.1-10: 50-5000.
Further, the method comprises the step of uniformly mixing the raw materials, wherein the manner of uniformly mixing the raw materials comprises but is not limited to one of mechanical stirring, ultrasonic treatment and heating dissolution.
Further, the homogenization pressure of the high-pressure homogenization reaction is 5-500Mpa, and the homogenization time is 0.01-5000 min.
Further, the external environment of the high-pressure homogenizer is normal temperature and normal pressure, or inert gas atmosphere.
And further, after the high-pressure homogenization reaction is finished, performing suction filtration or centrifugal recovery treatment on the product, recovering the obtained liquid for next synthesis, and washing and drying the obtained solid to obtain the porous organic cage.
Compared with the prior art, the invention has the beneficial effects that:
(1) compared with a solvothermal method, a solvothermal/volatilization method and a microwave method, the high-pressure homogenization method can shorten the 1-week time required by the preparation of the traditional solvothermal/volatilization method to 2 minutes under the effects of a cavity effect, an impact effect and a shear effect, and can obtain POCs (POCs) with crystallinity and Brunauer-Emmett-Teller (BET) specific surface area performance equivalent to those of the solvothermal/volatilization method, and in addition, the solvent used by the high-pressure homogenization method can be recycled, so that continuous production can be realized. The microwave method can not realize continuous production and does not have industrialized production conditions, so that the high-pressure homogenization method has the advantages of environmental protection, energy conservation, short reaction time, simple operation, low cost and capability of realizing continuous production compared with a solvothermal method, a solvothermal/volatilization method and a microwave method.
(2) Compared with a double-screw extrusion method, the method has better mass transfer efficiency, and the obtained product has the advantages of good crystallization performance, high specific surface area, low energy consumption, environmental protection and energy conservation under the action of a cavity effect, an impact effect and a shearing effect of a high-pressure homogenizer.
(3) Compared with a dynamic flow synthesis method, the method has the advantages of low product energy consumption, environmental protection and energy conservation, can be used for continuous production, and has better industrial application potential.
(4) The porous organic cage prepared by the method disclosed by the invention has the same excellent thermal stability and BET specific surface area as POCs materials prepared by a traditional solvothermal method or a solvothermal/volatilization method, overcomes the defects of high energy consumption, poor product crystallinity, low specific surface area, incapability of continuous production and the like of a double-screw extrusion method and a dynamic flow synthesis method, realizes efficient, environment-friendly and energy-saving continuous production of POCs materials in batches, and has important industrial potential. It is worth mentioning that the solvent or catalyst used in the high pressure homogeneous reaction can be recycled. The POCs prepared by the recovered solvent and catalyst mixture still have the same excellent performance. Thus, the process has significant economic advantages. In conclusion, the method for preparing the POCs material through high-pressure homogenization has important significance for promoting the industrial production of the POCs material.
Drawings
Fig. 1 is the porous organic cage of example 1: PXRD atlas of HPH-CPOC-301-2 min;
fig. 2 is the porous organic cage of example 1: infrared spectrum of HPH-CPOC-301-2 min;
fig. 3 is the porous organic cage of example 1: thermogravimetric mapping of HPH-CPOC-301-2 min;
fig. 4 is the porous organic cage of example 1: HPH-CPOC-301-2min nitrogen adsorption pattern;
fig. 5 is the porous organic cage of example 2: PXRD pattern of HPH-CPOC-301;
fig. 6 is the porous organic cage of example 3: PXRD pattern of HPH-CPOC-301;
fig. 7 is the porous organic cage of example 4: PXRD pattern of HPH-CPOC-301;
fig. 8 is the porous organic cage of example 5: PXRD pattern of HPH-CPOC-301;
fig. 9 is the porous organic cage of example 6: PXRD pattern of HPH-CPOC-301;
fig. 10 is the porous organic cage of example 7: PXRD spectrum of HPH-CPOC-302-2 min;
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clear, the present invention is further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting of the invention.
Example 1
S1, adding C4RACHO (0.5mmol) and p-phenylenediamine (1mmol) into a 250mL beaker at normal temperature and pressure, adding 80mL (578.4mmol) of mesitylene, and carrying out ultrasonic treatment for 5 min;
s2, adding the suspension into a high-pressure homogenizer at normal temperature and normal pressure, and circularly homogenizing and reacting for 2min at the homogenizing pressure of 100 MPa;
s3, after the reaction is finished, taking the reaction suspension by using a beaker, carrying out suction filtration by using a vacuum suction filtration pump to obtain a solid product, collecting the filtrate by using a clean filter flask, recovering and storing the filtrate for later use, drying the obtained solid for 12 hours at the temperature of 150 ℃ to obtain the HPH-CPOC-301-2min prepared by the high-pressure homogenization method, wherein the separation yield is 83%.
FIG. 1 is a PXRD spectrum corresponding to example 1, and it can be seen from the graph that HPH-CPOC-301 obtained by high pressure homogenization is consistent with the main characteristic peak position of CPOC-301 prepared by the solvent thermal/volatilization method reported in the literature (J.Am.chem.Soc.2020,142,18060-18072), which indicates that the porous organic cage prepared by the method has an ordered crystal structure.
FIG. 2 is an IR spectrum corresponding to example 1, from which it can be seen that the main IR characteristic peak of HPH-CPOC-301-2min obtained by high pressure homogenization and CPOC-301 obtained by solvothermal/evaporation method is C-N1289 cm-1、C=C 1582cm-1、C=O 1615cm-1、C=C-H 2955cm-1Equal location consistent, tableThe porous organic cage CPOC-301 is successfully prepared by the method.
Fig. 3 is a thermogravimetric plot corresponding to example 1, and it can be seen from the graph that the thermogravimetric curves of the POCs obtained by the high-pressure homogenization method and the CPOC-301 obtained by the solvothermal/volatilization method are substantially equivalent, which indicates that the POC obtained by the high-pressure homogenization method has thermal stability comparable to that of the conventional solvothermal method.
FIG. 4 shows the nitrogen adsorption pattern corresponding to example 1, from which it can be seen that BET of HPH-CPOC-301-2min obtained by high pressure homogenization is 1865m2(iv)/g BET of CPOC-301 obtained by conventional solvothermal/evaporation method (1962 m)2The/g) is basically equivalent, and the result shows that the POCs prepared by the high-pressure homogenization method have excellent performance equivalent to that of the traditional solvothermal/volatilization method.
Example 2
S1, adding C4RACHO (0.5mmol) and p-phenylenediamine (1mmol) into a 250mL beaker at normal temperature and pressure, adding 80mL (578.4mmol) of mesitylene, and carrying out ultrasonic treatment for 5 min;
s2, adding the suspension into a high-pressure homogenizer at normal temperature and normal pressure, and circularly homogenizing and reacting for 60min at the homogenizing pressure of 50 MPa;
s3, after the reaction is finished, taking the reaction suspension by using a beaker, performing suction filtration to obtain a solid product, recovering and storing the filtrate for later use, and drying the obtained solid at 150 ℃ for 12h to obtain the HPH-CPOC-301 prepared by the high-pressure homogenization method, wherein the separation yield is 81%.
FIG. 5 is a PXRD spectrum corresponding to example 2, and it can be seen from the graph that the main characteristic peak positions of HPH-CPOC-301 obtained by the high-pressure homogenization at a homogenization pressure of 50MPa and a homogenization time of 60min are consistent with those of HPH-CPOC-301 obtained at a homogenization pressure of 100MPa, and the crystallinity is good, which indicates that CPOC-301 with good crystallinity can be obtained by reducing the homogenization pressure and prolonging the homogenization time.
Example 3
S1, adding C4RACHO (0.5mmol) and p-phenylenediamine (1mmol) into a 250mL beaker at normal temperature and pressure, adding 70mL (506.1mmol) of mesitylene, and performing ultrasonic treatment for 5 min;
s2, adding the suspension into a high-pressure homogenizer at normal temperature and normal pressure, and circularly homogenizing and reacting for 2min at the homogenizing pressure of 100 MPa;
s3, after the reaction is finished, taking the reaction suspension by using a beaker, carrying out suction filtration to obtain a solid product, recovering and storing the filtrate for later use, and drying the obtained solid at 150 ℃ for 12h to obtain the HPH-CPOC-301 prepared by the high-pressure homogenization method, wherein the separation yield is 80%.
FIG. 6 is a PXRD pattern corresponding to example 3, and it can be seen that HPH-CPOC-301 with good crystallinity can be obtained when the amount of mesitylene added as solvent is adjusted from 80ml in example 1 to 70ml, indicating that CPOC-301 with good crystallinity can be obtained by adjusting the amount of solvent added.
Example 4
S1, adding C4RACHO (0.5mmol) and p-phenylenediamine (1mmol) into a 250mL beaker at normal temperature and pressure, adding 80mL (578.4mmol) of mesitylene obtained in example 1 by suction filtration, and carrying out ultrasonic treatment for 5 min;
s2, adding the suspension into a high-pressure homogenizer at normal temperature and normal pressure, and circularly homogenizing and reacting for 2min at the homogenizing pressure of 100 MPa;
s3, after the reaction is finished, taking the reaction suspension by using a beaker, carrying out suction filtration to obtain a solid product, recovering and storing the filtrate for later use, drying the obtained solid at 150 ℃ for 12h to obtain the HPH-CPOC-301 prepared by the high-pressure homogenization method, wherein the separation yield is 82%.
FIG. 7 is the PXRD pattern corresponding to example 4. it can be seen that CPOC-301 prepared by using the solvent obtained by suction filtration in example 1 can still obtain CPOC-301 with good crystallinity, indicating that the solvent can be recycled.
Example 5
S1, adding C4RACHO (0.5mmol) and p-phenylenediamine (1mmol) into a 250mL beaker at normal temperature and pressure, adding 80mL (578.4mmol) of mesitylene obtained in example 4 by suction filtration, and carrying out ultrasonic treatment for 5 min;
s2, adding the suspension into a high-pressure homogenizer at normal temperature and normal pressure, and circularly homogenizing and reacting for 2min at the homogenizing pressure of 100 MPa;
s3, after the reaction is finished, taking the reaction suspension by using a beaker, performing suction filtration to obtain a solid product, recovering and storing the filtrate for later use, and drying the obtained solid at 150 ℃ for 12h to obtain the HPH-CPOC-301 prepared by the high-pressure homogenization method, wherein the separation yield is 81%.
FIG. 8 is a PXRD pattern corresponding to example 5, and it can be seen from the figure that CPOC-301 with good crystallinity can be obtained by using the solvent used for homogenization twice, which shows that the solvent has good recyclability and is beneficial to industrial production.
Example 6
S1, adding C4RACHO (0.5mmol) and p-phenylenediamine (1mmol) into a 250mL beaker at normal temperature and pressure, adding 80mL (578.4mmol) of mesitylene, and carrying out ultrasonic treatment for 5 min;
s2, in order to investigate the influence of inert gas atmosphere on synthesis, changing the feed inlet of a homogenizer from normal temperature and normal pressure to inert (nitrogen) gas atmosphere, adding the suspension into a high-pressure homogenizer, and circularly homogenizing and reacting for 2min at the homogenizing pressure of 100 MPa;
s3, after the reaction is finished, taking the reaction suspension by using a beaker, carrying out suction filtration by using a vacuum suction filtration pump to obtain a solid product, collecting the filtrate by using a clean filter flask, recovering and storing the filtrate for later use, drying the obtained solid for 12 hours at the temperature of 150 ℃ to obtain the HPH-CPOC-301-2min prepared by the high-pressure homogenization method, wherein the separation yield is 84%.
FIG. 9 is a PXRD spectrum corresponding to example 6, and it can be seen from the graph that HPH-CPOC-301 obtained by high pressure homogenization under inert gas atmosphere is consistent with the main characteristic peak position of CPOC-301 prepared by solvent thermal/volatilization method (J.Am.chem.Soc.2020,142,18060-18072) reported in example 1 and literature, which indicates that the porous organic cage prepared by the method also has an ordered crystal structure.
Example 7
S1, adding C4RACHO (0.5mmol) and benzidine (1mmol) into a 250mL beaker at normal temperature and pressure, adding 80mL (578.4mmol) of mesitylene, and carrying out ultrasonic treatment for 5 min;
s2, adding the suspension into a high-pressure homogenizer at normal temperature and normal pressure, and circularly homogenizing and reacting for 2min at the homogenizing pressure of 100 MPa;
s3, after the reaction is finished, taking the reaction suspension by using a beaker, carrying out suction filtration by using a vacuum suction filtration pump to obtain a solid product, collecting the filtrate by using a clean filter flask, recovering and storing the filtrate for later use, drying the obtained solid for 12 hours at the temperature of 150 ℃ to obtain the HPH-CPOC-301-2min prepared by the high-pressure homogenization method, wherein the separation yield is 81%.
FIG. 10 is a PXRD spectrum corresponding to example 7, and it can be seen from the graph that the main characteristic peak positions of HPH-CPOC-302 obtained by high pressure homogenization and CPOC-302 obtained by the solvent thermal/volatilization method reported in the literature (J.Am.chem.Soc.2020,142,18060-18072) are substantially consistent, which indicates that the porous organic cage prepared by the method also has an ordered crystal structure.
The invention adopts a high-pressure homogenization method to prepare the POCs material, and greatly improves the preparation efficiency of the POCs on the premise of keeping the thermal stability and the specific surface area of the POCs material. Compared with a solvothermal method, a solvothermal/volatilization method and a microwave method, the high-pressure homogenization method has the advantages of green and environment-friendly preparation process, simple synthesis operation, high efficiency and low cost; compared with a double-screw extrusion method, the method has better mass transfer efficiency of raw materials, thereby obtaining better polymerization degree and specific surface area and ensuring the performance of the obtained POCs. Compared with a dynamic flow synthesis method, the method has the advantages of lower energy consumption, continuous production and the like, and in addition, the method can realize that the used solvent can be recycled for many times, and completely meets the requirements of industrial production in the aspects of scale and cost. In conclusion, the high-pressure homogenization method provides great guarantee for the industrial production of the POCs from various aspects of production cost, environmental protection, product performance and the like.
The embodiments described above are presented to enable those skilled in the art to make and use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art: including, but not limited to, modifying all ligands capable of synthesizing POCs, modifying the solvents used for the ligands, modifying the reaction ligand ratios, solvent ratios, catalyst amounts, etc., modifying the homogenization pressure, time, temperature, etc., and applying the general principles described herein to other embodiments without undue inventive effort. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should, in light of the present disclosure, appreciate that various modifications and changes can be made without departing from the scope of the invention.
Claims (7)
1. A method for large-scale batch preparation of porous organic cages by high-pressure homogenization is characterized by comprising the following steps:
common organic ligands are used as raw materials, and the synthesized POCs comprise but are not limited to imine, borate and other connected porous organic cage materials; the solvent is water or an organic solvent, and the organic solvent comprises but is not limited to one of N, N-dimethylformamide, N-dimethylacetamide, dioxane, ethanol, methanol, acetonitrile, tetrahydrofuran and mesitylene; in the reaction process, catalysts are used or not, for example, the catalysts are used, the catalysts include but are not limited to trifluoroacetic acid, acetic acid and the like, which can synthesize POCs, all reaction raw materials are uniformly mixed, and the porous organic cage is obtained after the homogenization by a high-pressure homogenizer.
2. The method for large-scale mass production of porous organic cages by high pressure homogenization according to claim 1, wherein the ligand raw materials for synthesizing POCs are selected from tetra-aldehyde-group-intermediate cyclo-calix [4] arene (C4RACHO) and p-phenylenediamine or benzidine.
3. The method for large-scale mass production of porous organic cages by high-pressure homogenization according to claim 1, wherein the molar ratio of the ligand to the solvent is: c4 RACHO: p-phenylenediamine or benzidine: solvent 1: 0.1-10: 50-5000.
4. The method for preparing a porous organic cage using high pressure homogenization according to claim 1, wherein the method for preparing the porous organic cage using high pressure homogenization in large-scale batch comprises a step of uniformly mixing the raw materials in a manner including but not limited to one of mechanical stirring, ultrasonic treatment and heating dissolution.
5. The method for mass production of porous organic cages using high pressure homogenization according to claim 1, wherein the homogenization pressure of the high pressure homogenization reaction is 5 to 500Mpa, and the homogenization time is 0.01 to 5000 min.
6. The method for mass production of porous organic cages by high pressure homogenization according to claim 1, wherein the external environment of the high pressure homogenizer is at normal temperature and pressure or under inert gas atmosphere.
7. The method for mass production of porous organic cages by high pressure homogenization according to claim 1, wherein after the high pressure homogenization reaction is finished, the product is recovered by suction filtration or centrifugation, the obtained liquid is recovered for the next synthesis, and the obtained solid is washed and dried to obtain the porous organic cages.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114887665A (en) * | 2022-07-14 | 2022-08-12 | 北京理工大学 | Intelligent catalyst, preparation method and application |
CN115403721A (en) * | 2022-09-21 | 2022-11-29 | 西安交通大学 | Preparation method and application of covalent organic framework material for lithium isotope separation |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104558515A (en) * | 2015-01-21 | 2015-04-29 | 安徽建筑大学 | Preparation method of porous polymer |
CN110835359A (en) * | 2018-08-17 | 2020-02-25 | 中国科学院大连化学物理研究所 | P, N-containing porous organic cage ligand, complex catalyst and application |
CN113024828A (en) * | 2021-03-09 | 2021-06-25 | 南开大学 | Method for preparing covalent organic framework material by utilizing high-pressure homogenization |
CN113461959A (en) * | 2021-07-01 | 2021-10-01 | 南开大学 | Method for preparing metal organic framework material by high-pressure homogenization |
-
2022
- 2022-02-11 CN CN202210127476.6A patent/CN114478969A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104558515A (en) * | 2015-01-21 | 2015-04-29 | 安徽建筑大学 | Preparation method of porous polymer |
CN110835359A (en) * | 2018-08-17 | 2020-02-25 | 中国科学院大连化学物理研究所 | P, N-containing porous organic cage ligand, complex catalyst and application |
CN113024828A (en) * | 2021-03-09 | 2021-06-25 | 南开大学 | Method for preparing covalent organic framework material by utilizing high-pressure homogenization |
CN113461959A (en) * | 2021-07-01 | 2021-10-01 | 南开大学 | Method for preparing metal organic framework material by high-pressure homogenization |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114887665A (en) * | 2022-07-14 | 2022-08-12 | 北京理工大学 | Intelligent catalyst, preparation method and application |
CN114887665B (en) * | 2022-07-14 | 2022-09-16 | 北京理工大学 | Intelligent catalyst, preparation method and application |
CN115403721A (en) * | 2022-09-21 | 2022-11-29 | 西安交通大学 | Preparation method and application of covalent organic framework material for lithium isotope separation |
CN115403721B (en) * | 2022-09-21 | 2023-11-17 | 西安交通大学 | Preparation method and application of covalent organic framework material for lithium isotope separation |
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