Preparation method and application of triazinyl ionic organic polymer
By preparing triazine-based ionic organic polymer materials as catalysts, the existing catalysts have solved the problem of low catalytic activity, difficulty in separation and pollution of the environment in the catalytic cycloaddition reaction of carbon dioxide and epoxy compounds, and achieved high efficiency and selectivity High and recyclable catalytic effects that meet green chemistry and sustainable development standards.
Patent Information
- Application Number
- CN202411614735.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-13
- Publication Date
- 2025-02-18
AI Technical Summary
Existing catalysts have low catalytic activity, difficulty in separating and polluting the environment in the catalytic cycloaddition reaction of carbon dioxide and epoxy compounds.
Using triazine-based ionic organic polymer material as catalyst, the reaction of triazine-cyanochloride and pyridine or imidazole organic matter under specific conditions is prepared to form a catalyst with multiple active sites and epoxy in an autoclave. The compound reacts with carbon dioxide.
The catalyst exhibits excellent catalytic effect under mild conditions, is highly selective, is easy to separate and recycle, and is free of metal contamination, and meets the standards of green chemistry and sustainable development.
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Figure CN119463170A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to a preparation method of a triazine-based ionic organic polymer material and application of the triazine-based ionic organic polymer material in catalyzing a cycloaddition reaction of carbon dioxide and an epoxy compound, and belongs to the technical field of material chemical engineering. Background Art
[0002] Due to the excessive consumption of fossil energy such as coal, oil and natural gas, the amount of CO2 in the atmosphere has increased dramatically, which has further triggered a series of environmental problems such as extreme weather and greenhouse effect, posing a huge threat to the natural ecological balance of the earth and human survival. However, CO2 is also regarded as a valuable resource that is abundant, low-cost, non-toxic, safe and renewable. Considering the environmental challenges brought by CO2, the capture and chemical conversion of CO2 is considered to be a key means to achieve sustainable development and meet the growing energy demand. Using CO2 as the main raw material can produce high value-added chemicals such as methanol, pharmaceutical intermediates, aromatic monomers and organic carbonates. It is particularly noteworthy that the cycloaddition of CO2 with epoxides to form cyclic carbonates is an organic chemical reaction that meets the standards of green chemistry and sustainable development. This method not only has abundant raw material sources, but also has many advantages such as 100% atom economy. Cyclic carbonates are highly polar and biologically active and are widely used in the chemical industry as fuel additives, lithium battery electrolytes, aprotic solvents and polymer monomers. Therefore, it is particularly important to study how to catalyze the conversion of CO2 into cyclic carbonates with high added value.
[0003] At present, a variety of homogeneous and heterogeneous catalysts have been developed to catalyze the cycloaddition reaction of CO2 and epoxides. Homogeneous catalysts include organic bases, ionic liquids, quaternary ammonium salts, etc. Although they have high catalytic activity, they are difficult to separate, recover and reuse, which limits their wide application in the industrial field. Heterogeneous catalysts such as porous carbon materials, metal oxides, covalent organic frameworks (COFs), metal organic frameworks (MOFs), and porous organic polymers (POPs) have become a hot topic of current research because of their easy separation and recovery, adjustable structure and easy modification. However, the active sites of metal oxides and porous carbon materials are relatively single and their catalytic activity is insufficient. The synthesis steps of MOFs and COFs materials are cumbersome and not conducive to large-scale production. In addition, metal-containing catalysts have the risk of metal leaching, which not only pollutes the environment, but also the residual metals affect the application of cyclic carbonates. Ionic organic polymerization has the advantages of simple synthesis, designable structure, strong stability and no metal pollution, showing good application prospects and potential in the cycloaddition reaction of CO2 and epoxides. Summary of the invention
[0004] In view of the problems that the cycloaddition reaction conditions of carbon dioxide and epoxy compounds are harsh, the traditional catalyst has low catalytic activity, is difficult to separate and pollutes the environment, the present invention provides a preparation method of a triazine-based ionic organic polymer material. The method first adds cyanuric chloride and pyridine organic matter or imidazole organic matter into a three-necked flask, and refluxes for 1-24 hours at 40-120° C. in the presence of a solvent, cools the reaction product to room temperature, separates the solid from the liquid, and washes and dries the solid to obtain the triazine-based ionic organic polymer material.
[0005] The pyridine organic matter is 2,4,6-tris(4-pyridine)-1,3,5-triazine, 1,3,5-tris(4-pyridyl)benzene, 2,4,6-tris(3-pyridyl)-1,3,5-triazine, 1,3,5-tris(4-pyridin-3-ylphenyl)benzene, 1,3,5-tris[4-(pyridin-4-yl)phenyl]benzene, 3,3'-[5'-[3-(3-pyridyl)phenyl][1,1':3',1''-terphenyl]-3,3''-diyl]bipyridine, 1,3,5-tris(pyridine-4-ethynyl) The present invention relates to a kind of organic compound comprising: 1,4-dipyridine-2,5-dimethoxybenzene, 4,4'-di(4-pyridyl)biphenyl, 3,3'-bipyridine, 1-hydroxy-3,5-di(4-pyridylphenyl)benzene, 9,10-bis((E)-2-(pyridin-4-yl)vinyl)anthracene, and the molar ratio of cyanuric chloride to pyridine organic compound is 1:1-5.
[0006] The imidazole organic compounds are 2,4,6-tris(1H-imidazol-1-yl)-1,3,5-triazine, 1,3,5-tris(1H-imidazol-1-yl)benzene, 1,3,5-tris(p-imidazolylphenyl)benzene, 1,3,5-tris(2-methyl-1H-imidazol-1-yl)benzene, 1,3,5-tris((1H-imidazol-1-yl)methyl)benzene, 2,2',2'-(1,3 ,5-phenyltriyl)tri-1H-benzimidazole, 1,3,5-tri(N-imidazolemethyl)-2,4,6-trimethylbenzene, tri-(4-imidazolylphenyl)amine, diimidazolylbenzene, 1,4-bis(2-methyl-1H-imidazol-1-yl)benzene, 1,3-bis(1H-imidazol-1-yl)benzene, 1,3-bis(1-imidazole)propane, 1,3-bis(1-imidazole)propane, 1,1'-(oxydi-4,1-phenylene)bis-1H-imidazole, and the molar ratio of cyanuric chloride to the imidazole organic matter is 1:1-5.
[0007] The solvent is one or more of 1,4-dioxane, N,N-dimethylacetamide, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, ethyl acetate, ethanol, ethylene glycol, dichloromethane, methanol, acetone, benzene, toluene, petroleum ether, hexane, acetonitrile, ethylamine, and acetic acid.
[0008] Another object of the present invention is to apply the triazine-based ionic organic polymer material prepared by the above method to catalyze the cycloaddition reaction of carbon dioxide and epoxy compounds, specifically, the triazine-based ionic organic polymer material (catalyst) and the epoxy compound are sequentially added into a high-pressure reactor (the molar ratio of catalyst:epoxy compound=1:100-1000), and before the CO2 cycloaddition reaction, the autoclave is purified by CO2 (volume concentration 99.99%) three times at room temperature to remove impurities, and then CO2 with a volume concentration of 99.99% is introduced, the initial CO2 pressure is adjusted to 0.1-3MPa, the reaction temperature is set to 60-120°C, the reaction time is 1-48h, and after the reaction is completed, the autoclave temperature is cooled to below 10°C with an ice bath, the residual gas is slowly released, and the catalyst and reaction products are filtered and collected.
[0009] The epoxy compound is one of ethylene oxide, propylene oxide, epichlorohydrin, epibromohydrin, 1,2-butylene oxide, 1,2-epoxyhexane, 1,2-epoxypentane, styrene oxide, glycidyl ether, cyclohexene oxide, 2-benzyl oxirane, 3-chlorophenyl oxirane and 2-vinyl oxirane.
[0010] Compared with the prior art, the present invention has the following advantages: (1) The synthesis method of the present invention prepares an organic polymer material with good stability and good structural diversity. The structure of the triazine-based organic polymer contains abundant nitrogen atoms, which enables it to form a Lewis acid-base pair with CO2, thereby improving its adsorption and activation ability for CO2. While being rich in Lewis basic group N active sites, the nucleophilic anion Cl is introduced - Active sites, while forming quaternary ammonium salt structures with imidazole organic monomers and pyridine organic monomers. The synergistic effect of multiple active sites maintains the original catalytic activity of ionic liquids in principle, while overcoming the difficulties of separation and purification, and completing the heterogeneity of homogeneous materials; (2) Under mild conditions of metal-free, catalyst-free, solvent-free, low temperature and low pressure, the material has excellent catalytic effect and high selectivity in the reaction of CO2 and epoxides to prepare cyclic carbonates. It is also easy to separate from the product and can be recycled many times. It has good structural stability and recyclability. In addition, it also has significant catalytic activity towards a series of epoxides.
[0011] (3) The preparation method of the present invention is simple, the reaction conditions are mild, the catalytic efficiency is high, and the materials are easy to recycle. It conforms to the concept of economic, green and sustainable development and shows unique advantages in CO2 conversion and resource utilization, and is easy to realize green industrial production. BRIEF DESCRIPTION OF THE DRAWINGS
[0012] Figure 1 It is a Fourier transform infrared spectrum (FTIR) of the triazine-based ionic organic polymer material of Example 1; wherein TIT is 2,4,6-tris(1H-imidazole-1-yl)-1,3,5-triazine, Cyanuric chloride is cyanuric chloride, and CTP-TIT is a triazine-based ionic organic polymer material; Figure 2 The cyclic carbonate prepared in Example 1 1 H NMR spectra. DETAILED DESCRIPTION
[0013] The present invention is further described in detail below through examples and drawings, but the protection of the present invention is not limited to the described contents. Example 1
[0014] (1) After adding 0.3688 g of cyanuric chloride, 0.5585 g of 2,4,6-tri(1H-imidazol-1-yl)-1,3,5-triazine and 50 mL of 1,4-dioxane in a 250 mL three-necked flask, the three-necked flask was placed in an oil bath and refluxed at 90 °C for 24 h. After the reaction was completed, the flask was cooled to room temperature, the solid was collected by centrifugation, washed three times with 1,4-dioxane, and then placed in a vacuum drying oven at 40 °C for 24 h to obtain a triazine-based ionic organic polymer material (CTP-TIT); Fourier transform infrared spectroscopy (FTIR) was used to characterize the raw materials and the obtained materials. Figure 1 Shown: 3145cm -1 The vibration peak at 1531cm is the stretching vibration of CH of the imidazole ring. These two characteristic absorption peaks appear in the spectra of the target products CTP-TIT and TIT. -1 -1629cm -1 The vibration peak at the range is attributed to the C=N bond of the imidazole ring, indicating the presence of an imidazole ring in the synthesized CTP-TIT. The infrared spectra of CTP-TIT and cyanuric chloride show that the peak at 1315 cm -1 -1649cm -1 The vibration peak (C=N) at the range of 1271 cm-1 is present in both cyanuric chloride and CTP-TIT, indicating the presence of triazine ring in CTP-TIT. -1A new characteristic absorption peak appeared in the reaction, which can be attributed to the characteristic absorption peak of carbon-nitrogen single bond (CN), indicating that cyanuric chloride and TIT reacted to form a CN bond, indicating the successful synthesis of CTP-TIT.
[0015] (2) 2 mL of epichlorohydrin and 0.0501 g of a catalyst triazine-based ionic organic polymer material (catalyst: epoxide molar ratio = 1:500) were added sequentially into a 50 mL autoclave. Before the CO2 cycloaddition, the autoclave was purified three times with 99.99% CO2 to remove impurities. Then, 99.99% CO2 was introduced. After the introduction, the inlet and outlet valves were closed. The speed was set to 280 r / min, the temperature was set to 80 °C, the carbon dioxide pressure was set to 0.5 MPa, and the reaction time was set to 6 h. After the reaction was completed, the autoclave was cooled to below 10 °C with an ice bath, and the residual gas was slowly released. Finally, the reaction mixture was filtered to collect the catalyst and the reaction product 3-chloropropylene carbonate. The product yield was 94.3% and the selectivity was 99%. Example 2
[0016] (1) After adding 0.1844 g of cyanuric chloride, 0.3094 g of 1,3,5-tri(4-pyridyl)benzene and 50 mL of 1,4-dioxane into a 250 mL three-necked flask, the three-necked flask was placed in an oil bath and refluxed at 90 °C for 24 h. After the reaction was completed, the flask was cooled to room temperature, and the solid was collected by centrifugation and washed three times with 1,4-dioxane. The solid was then placed in a vacuum drying oven at 40 °C and vacuum dried for 24 h to obtain a triazine-based ionic organic polymer material (CTP-TPB); (2) 2 mL of epichlorohydrin and 0.0502 g of a catalyst triazine-based ionic organic polymer material (catalyst: epoxide molar ratio = 1:500) were added sequentially into a 50 mL autoclave. Before the CO2 cycloaddition, the autoclave was purged three times with 99.99% CO2 by volume, and then 99.99% CO2 by volume was introduced. After the introduction was completed, the inlet and outlet valves were closed, and the speed was set to 280 r / min, the temperature to 100 °C, the carbon dioxide pressure to 1.0 MPa, and the reaction time to 8 h. After the reaction was completed, the autoclave temperature was cooled to below 10 °C with an ice bath, and the residual gas was slowly released. Finally, the reaction mixture was filtered to collect the catalyst and the reaction product 3-chloropropylene carbonate. The product yield was 96.7% and the selectivity was 99%. Example 3
[0017] (1) After adding 0.3688 g of cyanuric chloride, 0.6246 g of 2,4,6-tris(4-pyridine)-1,3,5-triazine and 50 mL of 1,4-dioxane into a 250 mL three-necked flask, the three-necked flask was placed in an oil bath and refluxed at 90 °C for 24 h. After the reaction was completed, the flask was cooled to room temperature, and the sample was collected by centrifugation and washed three times with 1,4-dioxane. The sample was then placed in a vacuum drying oven at 40 °C and vacuum dried for 24 h to obtain a triazine-based ionic organic polymer material (CTP-TPT); (2) 2 mL of epichlorohydrin and 0.0500 g of a catalyst triazine-based ionic organic polymer material (catalyst: epoxide molar ratio = 1:500) were added to a 50 mL autoclave in sequence. Before the CO2 cycloaddition reaction, the autoclave was purified three times with 99.99% CO2 by volume to remove impurities. Then, 99.99% CO2 by volume was introduced. After the introduction was completed, the inlet and outlet valves were closed. The speed was set to 280 r / min, the temperature was set to 100 °C, the carbon dioxide pressure was set to 1.0 MPa, and the reaction time was set to 8 h. After the reaction was completed, the autoclave temperature was cooled to below 10 °C with an ice bath, and the residual gas was slowly released. Finally, the reaction mixture was filtered to collect the catalyst and the reaction product 3-chloropropylene carbonate. The product yield was 94.5% and the selectivity was 99%. 1 The obtained product was characterized by H NMR spectrum. Figure 2 The chemical shifts of the product 3-chloropropylene carbonate were d=5.06ppm, 4.63ppm, 4.43ppm, 3.87ppm, and 3.75ppm, respectively, which determined that CO2 and epichlorohydrin underwent a cycloaddition reaction to produce 3-chloropropylene carbonate. Example 4
[0018] (1) After adding 0.3688 g of cyanuric chloride, 0.5525 g of 1,3,5-tri(1H-imidazole-1-)benzene and 50 mL of 1,4-dioxane into a 250 mL three-necked flask, the three-necked flask was placed in an oil bath and refluxed at 90 °C for 24 h. After the reaction was completed, the flask was cooled to room temperature, and the sample was collected by centrifugation and washed three times with 1,4-dioxane. The sample was then placed in a vacuum drying oven at 40 °C and vacuum dried for 24 h to obtain a triazine-based ionic organic polymer material (CTP-TIB); (2) 2 mL of epichlorohydrin and 0.0501 g of a catalyst triazine-based ionic organic polymer material (catalyst: epoxide molar ratio = 1:500) were added sequentially into a 50 mL autoclave. Before the CO2 cycloaddition, the autoclave was purified three times with 99.99% CO2 to remove impurities. Then, 99.99% CO2 was introduced. After the introduction, the inlet and outlet valves were closed. The speed was set to 280 r / min, the temperature was set to 100 °C, the carbon dioxide pressure was set to 1.0 MPa, and the reaction time was set to 8 h. After the reaction was completed, the autoclave was cooled to below 10 °C with an ice bath, and the residual gas was slowly released. Finally, the reaction mixture was filtered to collect the catalyst and the reaction product 3-chloropropylene carbonate. The product yield was 97.6% and the selectivity was 99%.
[0019] Example 5 (1) The preparation of triazine-based ionic organic polymer material is the same as in Example 1; (2) The triazine-based ionic organic polymer materials were used for the following cycloaddition reactions. The conditions were the same as those in Example 1, except that the epoxides used and the reaction temperatures were different. The relevant data are listed below: .
Claims
1. A method for preparing a triazine-based ionic organic polymer material, characterized in that: Using cyanuric chloride and pyridine organic matter or imidazole organic matter as raw materials, after reflux reaction at 40-120°C for 1-24 hours in the presence of a solvent, the reaction product is cooled to room temperature, the solid-liquid is separated, and the solid is washed and dried to obtain a triazine-based ionic organic polymer material.
2. The method for preparing the triazine-based ionic organic polymer material according to claim 1, characterized in that: Pyridine organic compounds are 2,4,6-tris(4-pyridyl)-1,3,5-triazine, 1,3,5-tris(4-pyridyl)benzene, 2,4,6-tris(3-pyridyl)-1,3,5-triazine, 1,3,5-tris(4-pyridin-3-ylphenyl)benzene, 1,3,5-tris[4-(pyridin-4-yl)phenyl]benzene, 3,3'-[5'-[3-(3-pyridyl)phenyl][1,1':3',1''-terphenyl]-3,3''-diyl]bipyridine, 1,3,5 -Tris(pyridin-4-ethynyl)benzene, N,N',N''-tri(4-pyridinyl)-1,3,5-benzenetricarboxamide, 1,3,5-trimethyl-2,4,6-tri(4-pyridinyl)benzene, tri(4-pyridinyl)amine, 1,4-bipyridine-2,5-dimethoxybenzene, 4,4'-di(4-pyridinyl)biphenyl, 3,3'-bipyridine, 1-hydroxy-3,5-di(4-pyridinylphenyl)benzene, 9,10-bis((E)-2-(pyridin-4-yl)vinyl)anthracene.
3. The method for preparing the triazine-based ionic organic polymer material according to claim 1, characterized in that: Imidazole organic compounds include 2,4,6-tri(1H-imidazol-1-yl)-1,3,5-triazine, 1,3,5-tri(1H-imidazol-1-yl)benzene, 1,3,5-tri(p-imidazolylphenyl)benzene, 1,3,5-tri(2-methyl-1H-imidazol-1-yl)benzene, 1,3,5-tri((1H-imidazol-1-yl)methyl)benzene, 2,2',2'-(1,3, 1,3-bis(1-imidazole)propane, 1,3-bis(1-imidazole)propane, 1,1'-(oxydi-4,1-phenylene)bis-1H-imidazole.
4. The method for preparing the triazine-based ionic organic polymer material according to claim 1, characterized in that: The solvent is one or more of 1,4-dioxane, N,N-dimethylacetamide, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, ethyl acetate, ethanol, ethylene glycol, dichloromethane, methanol, acetone, benzene, toluene, petroleum ether, hexane, acetonitrile, ethylamine and acetic acid.
5. The method for preparing the triazine-based ionic organic polymer material according to claim 1, characterized in that: The molar ratio of cyanuric chloride to pyridine organic matter is 1:1-5, and the molar ratio of cyanuric chloride to imidazole organic matter is 1:1-5.
6. Use of the triazine-based ionic organic polymer material prepared by the method for preparing the triazine-based ionic organic polymer material according to any one of claims 1 to 5 in catalyzing the cycloaddition reaction of carbon dioxide and epoxy compounds.
7. The use according to claim 6, characterized in that: The epoxy compound is one of ethylene oxide, propylene oxide, epichlorohydrin, epibromohydrin, 1,2-butylene oxide, 1,2-epoxyhexane, 1,2-epoxypentane, styrene oxide, glycidyl ether, cyclohexene oxide, 2-benzyl oxirane, 3-chlorophenyl oxirane and 2-vinyl oxirane.