Preparation method and application of ionic organic polymer catalyst
Through a heterogeneous ionic organic polymer catalyst rich in nitrogen atoms, carbon dioxide and epoxy compounds are efficiently converted into cyclic carbonate, solving the problems of low activity of existing catalysts and polluting the environment, and achieving efficient and environmentally friendly industrial production.
Patent Information
- Application Number
- CN202411747612.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-02
- Publication Date
- 2025-02-28
AI Technical Summary
Existing catalysts have low activity in catalyzing the cycloaddition reaction of carbon dioxide and epoxy compounds, complex preparation process and pollute the environment, making it difficult to meet the needs of industrial production.
A heterogeneous ionic organic polymer catalyst rich in nitrogen atoms is used, which is prepared by reacting chlorine-containing organic compounds, 4-aminopyridines and isocyanate or acid chloride organic compounds under specific conditions to form an ionic catalyst with a multi-active center. This catalyst is used for the cycloaddition reaction of carbon dioxide and epoxy compounds without adding a cocatalyst.
It has achieved efficient conversion of carbon dioxide into cyclic carbonate under mild conditions, with high product yield, good selectivity, and easy recovery of catalysts, which is suitable for green industrial production.
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Figure CN119529308A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of organic heterogeneous catalysis, and specifically relates to a preparation method of a multi-active center ion type organic polymer catalyst and its use in catalyzing the cycloaddition of carbon dioxide and epoxy compounds. Background Art
[0002] With the rapid development of the global economy and the continuous growth of energy consumption, the concentration of carbon dioxide in the atmosphere has continued to rise, posing a huge challenge to the earth's ecological environment. Actively utilizing carbon dioxide has become a top priority, which not only helps to reduce greenhouse gas emissions and alleviate the pressure of global climate change, but also achieves an effective cycle of carbon resources. 2 It is difficult to activate, but it is a valuable C1 resource. It can be converted into methane, carbon monoxide, cyclic carbonates and other high value-added chemicals through hydrogenation, reduction, cycloaddition and other reactions. Among them, the conversion of cyclic carbonates with epoxides has attracted much attention. Cyclic carbonates have shown broad application prospects in many fields, such as high-performance lithium-ion battery electrolytes, polar aprotic solvents, and fine chemical intermediates. In order to achieve efficient conversion of carbon dioxide to cyclic carbonates, it is imperative to develop high-performance catalysts.
[0003] Currently, the catalytic CO 2 The types of catalysts for cycloaddition reactions mainly include metal catalysts (Schiff base metal complexes, porphyrin metal complexes), ionic liquid catalysts (imidazole ionic liquids, pyridine ionic liquids, quaternary ammonium salt ionic liquids) and organic catalysts (organic base catalysts, hydrogen bond donor catalysts, organic metal catalysts). Although metal catalysts have high catalytic activity, they often have problems such as high cost, easy deactivation, and environmental unfriendliness. Ionic liquid catalysts have good thermal stability and designability, but their preparation process is complicated, expensive, and difficult to recycle. Organic catalysts are relatively green and environmentally friendly, but most organic catalysts have low catalytic efficiency and low selectivity, which makes it difficult to meet the needs of large-scale industrial production.
[0004] Therefore, in CO 2 Compared with the use of transition metals to activate epoxides in cycloaddition reactions, the use of hydrogen bond donor groups (-OH, -COOH, -NH / -NH 2 Activated epoxides are more environmentally friendly and efficient. Using them with nucleophilic halogen anions can more directly and efficiently promote CO 2 In addition, there are lone pairs of electrons on the nitrogen atom of the nitrogen-containing heterocyclic compound, which makes it both nucleophilic to promote the ring opening of the epoxide and alkaline to adsorb and activate CO. 2Therefore, designing heterogeneous catalysts rich in nitrogen atoms with HBD groups and halogen anions can achieve the conversion of CO under mild conditions. 2 Efficient conversion of epoxides to cyclic carbonates. Summary of the invention
[0005] In view of the problems that the cycloaddition reaction conditions of carbon dioxide and epoxy compounds are harsh, the traditional catalyst has low activity, the preparation process is complicated, and the environment is polluted, the present invention provides a method for preparing an ionic organic polymer catalyst.
[0006] The preparation method of the ionic organic polymer catalyst of the present invention comprises the following steps: adding a chlorine-containing organic compound, 4-aminopyridine, an isocyanate organic compound or an acyl chloride organic compound into a reactor in sequence, and then adding an organic solvent (selected from 1,4-dioxane, acetonitrile, N,N-dimethylformamide, dimethylformamide, dimethyl sulfoxide, and ethanol), reacting at 80-100° C. for 24 hours, cooling to room temperature, washing the reaction product, and vacuum drying to obtain the ionic organic polymer catalyst.
[0007] The chlorine-containing organic compound is selected from cyanuric chloride, 2,4,6-trichloropyrimidine, 3,6-dichloro-1,2,4,5-tetrazine, 2,4,6,8-tetrachloropyrimido[5,4-d]pyrimidine, 2,4-dichloro-6-(6-chloropyridin-2-yl)-1,3,5-triazine, and 4,5-dichloro-2-methyl-1H-imidazole.
[0008] The isocyanate organic compound is selected from p-phenylene diisocyanate, 4,4'-methylenebis(phenyl isocyanate), and triisocyanate.
[0009] The acyl chloride organic compound is selected from terephthaloyl chloride, 4,4'-biphenyl diacetyl chloride, azobenzene-4,4'-dicarbonyl chloride, and 2,2-bipyridine-5,5-acyl chloride.
[0010] The molar ratio of the chlorine-containing organic compound to 4-aminopyridine is 1:(2-4), and the molar ratio of the chlorine-containing organic compound to the isocyanate organic compound or the acyl chloride organic compound is 1:(1-2).
[0011] Another object of the present invention is to apply the ionic organic polymer catalyst prepared by the above method to the addition reaction of carbon dioxide and epoxy compounds, specifically, the ionic organic polymer catalyst and the epoxy compound are sequentially added to a high-pressure reactor, and then carbon dioxide with a volume concentration of 99.99% is introduced into the high-pressure reactor, and the air in the reactor is replaced 2 to 3 times, and then carbon dioxide with a volume concentration of 99.99% is introduced, and the carbon dioxide pressure is 0.1MPa to 1MPa. The reaction is carried out at 70 to 100°C for 2 to 10 hours, and the temperature is lowered to room temperature. After the reaction is completed, the product is a cyclic carbonate.
[0012] The epoxy compound is selected from epichlorohydrin, epibromohydrin, cyclohexene oxide, propylene oxide, benzyl glycidyl ether, and styrene oxide.
[0013] Compared with the prior art, the present invention has the following advantages: (1) The present invention uses nitrogen-rich organic compounds as the skeleton, introduces hydrogen bond donors and nucleophilic groups by bridging, and forms an ionic organic polymer catalyst and a porous heterogeneous catalyst; (2) This method synthesizes an ionic organic polymer catalyst, which is used for the cycloaddition reaction of epoxy compounds and carbon dioxide to prepare cyclic carbonates without adding a co-catalyst. The reaction conditions are mild, the product yield is high, and the selectivity is good; (3) The present invention adopts a one-step preparation method, which has a simple preparation method, low preparation cost, good catalytic performance, no metal pollution, easy catalyst recovery, and easy to achieve green industrial production. BRIEF DESCRIPTION OF THE DRAWINGS
[0014] Figure 1 is a Fourier transform infrared spectroscopy (FTIR) graph of the multi-active site ionic organic polymer catalyst of Example 1; wherein CPP is an ionic organic polymer catalyst; Figure 2 The cyclic carbonate prepared in Example 1 1 H NMR spectra. DETAILED DESCRIPTION
[0015] The present invention is further described in detail below through examples and drawings, but the described examples are only part of the embodiments of the present invention, rather than all the embodiments, and the protection of the present invention is not limited to the described contents.
[0016] Example 1 (1) 8 mmol (1.4753 g) of cyanuric chloride, 12 mmol (1.9216 g) of p-phenylene diisocyanate, and 24 mmol (2.2588 g) of 4-aminopyridine were added to a 250 mL three-necked flask in sequence, and then 150 mL of 1,4-dioxane was added. The three-necked flask was placed in an oil bath and heated at 100 °C for 24 h. After the reaction, the solid product was centrifuged and washed clean with ethanol, and then dried in a vacuum drying oven at 60 °C for 24 h to obtain an ionic organic polymer catalyst (CPP); The obtained catalyst was characterized by Fourier transform infrared spectroscopy (FTIR). Figure 1 As shown: belongs to 3437cm in 4-aminopyridine -1 Office (-NH 2 stretching vibration of the group) and 2271cm in p-phenylene diisocyanate-1 The stretching vibration of the -N=C=O group disappears obviously, and the -1 The stretching vibration absorption peak of -C=O group appears at 1238cm -1 The stretching vibration absorption peak of NCN appears at 845 cm, indicating that the urea group is successfully formed. -1 The characteristic transmission band belonging to the C-Cl group disappears, and is replaced by 1184cm -1 C=N + The stretching vibration absorption peak is 1680-1300cm -1 Within the range are the characteristic transmission bands of triazine ring, benzene ring and pyridine ring, all of which indicate that the triazine ring is successfully connected to 4-aminopyridine.
[0017] (2) 25 mmol of epichlorohydrin and 0.05 g of an ionic organic polymer catalyst were added to a 100 mL autoclave in sequence; then, carbon dioxide with a volume concentration of 99.99% was introduced into the autoclave, and the introduction was repeated three times. Then, carbon dioxide with a volume concentration of 99.99% was introduced into the autoclave again; 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 80°C, the carbon dioxide pressure was set to 0.5 MPa, the reaction time was set to 8 h, and 3-chloropropylene carbonate was obtained after cooling. The product yield was 95%, the selectivity was 99%, and the reaction temperature was 140 °C. 1 The obtained product was characterized by H NMR spectrum. Figure 2 In the figure, the chemical shifts of the product 3-chloropropylene carbonate are d=5.06ppm, 4.63ppm, 4.43ppm, 3.87ppm, and 3.75ppm, respectively, which confirms that carbon dioxide and epichlorohydrin undergo a cycloaddition reaction to produce 3-chloropropylene carbonate.
[0018] Example 2 (1) 8 mmol (1.4753 g) of cyanuric chloride, 12 mmol (2.4363 g) of terephthaloyl chloride, and 24 mmol (2.2588 g) of 4-aminopyridine were added in sequence into a 250 mL three-necked flask, and then 150 mL of 1,4-dioxane was added. The three-necked flask was placed in an oil bath and heated at 100 °C for 24 h. After the reaction, the solid product was washed by centrifugation with ethanol, and then dried in a vacuum drying oven at 60 °C for 24 h to obtain an ionic organic polymer catalyst. (2) 25 mmol of epibromopropane and 0.05 g of an ionic organic polymer catalyst were added to a 100 mL autoclave in sequence; then, carbon dioxide with a volume concentration of 99.99% was introduced into the autoclave, and the introduction was repeated three times. Then, carbon dioxide with a volume concentration of 99.99% was introduced into the autoclave again; 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 70°C, the carbon dioxide pressure was set to 1 MPa, the reaction time was set to 10 h, and 3-bromopropylene carbonate was obtained after cooling, with a product yield of 91% and a selectivity of 99%.
[0019] Example 3 (1) 8 mmol (2.1592 g) of 2,4,6,8-tetrachloropyrimido[5,4-d]pyrimidine, 16 mmol (2.5621 g) of p-phenylene diisocyanate, and 32 mmol (3.0117 g) of 4-aminopyridine were added in sequence into a 250 mL three-necked flask, and then 150 mL of 1,4-dioxane was added. The three-necked flask was placed in an oil bath and heated at 100°C for 24 h. After the reaction was completed, the solid product was centrifuged and washed clean with ethanol, and then dried in a vacuum drying oven at 60°C for 24 h to obtain an ionic organic polymer catalyst. (2) The ionic organic polymer catalyst was applied to the addition reaction of epichlorohydrin and carbon dioxide, and the implementation method was the same as that of Example 1 to obtain 3-chloropropylene carbonate, with a product yield of 96% and a selectivity of 99%.
[0020] Example 4 (1) 8 mmol (2.1592 g) of 2,4,6,8-tetrachloropyrimido[5,4-d]pyrimidine, 16 mmol (3.2484 g) of terephthaloyl chloride, and 32 mmol (3.0117 g) of 4-aminopyridine were added in sequence into a 250 mL three-necked flask, and then 150 mL of 1,4-dioxane was added. The three-necked flask was placed in an oil bath and heated at 100°C for 24 h. After the reaction was completed, the solid product was centrifuged and washed clean with ethanol, and then dried in a vacuum drying oven at 60°C for 24 h to obtain an ionic organic polymer catalyst; (2) The ionic organic polymer catalyst was applied to the addition reaction of epichlorohydrin and carbon dioxide, and the implementation method was the same as that of Example 1 to obtain 3-chloropropylene carbonate, with a product yield of 96% and a selectivity of 99%.
[0021] Example 5 In a 250 mL three-necked flask, 6 mmol (0.905 g) of 3,6-dichloro-1,2,4,5-tetrazine, 4 mol (1.4694 g) of triisocyanate, and 12 mol (1.5057 g) of 4-aminopyridine were added in sequence, and then 150 mL of acetonitrile was added. The three-necked flask was placed in an oil bath pot and heated at 100° C. for 24 h. After the reaction was completed, the solid product was centrifuged and washed clean with ethanol, and then placed in a vacuum drying oven at 60° C. for 24 h to obtain an ionic organic polymer catalyst; 25 mmol of benzyl glycidyl ether and 0.05 g of an ionic organic polymer catalyst were added to a 100 mL autoclave in sequence; then, carbon dioxide with a volume concentration of 99.99% was introduced into the autoclave, and the introduction was repeated three times, and then carbon dioxide with a volume concentration of 99.99% was introduced into the autoclave again; 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 MPa, the reaction time was set to 8 h, and 4-benzyloxymethyl-1,3-dioxolane-2-one was obtained after cooling, with a product yield of 91% and a selectivity of 99%.
Claims
1. A method for preparing an ionic organic polymer catalyst, characterized in that: Chlorine-containing organic compounds, 4-aminopyridine, isocyanate organic compounds or acyl chloride organic compounds are added to the reactor in sequence, and then an organic solvent is added. After reacting at 80-100° C. for 24 hours, the mixture is cooled to room temperature, and the reaction product is washed and vacuum dried to obtain an ionic organic polymer catalyst.
2. The method for preparing an ionic organic polymer catalyst according to claim 1, characterized in that: The chlorine-containing organic compound is selected from cyanuric chloride, 2,4,6-trichloropyrimidine, 3,6-dichloro-1,2,4,5-tetrazine, 2,4,6,8-tetrachloropyrimido[5,4-d]pyrimidine, 2,4-dichloro-6-(6-chloropyridin-2-yl)-1,3,5-triazine, and 4,5-dichloro-2-methyl-1H-imidazole.
3. The method for preparing an ionic organic polymer catalyst according to claim 1, characterized in that: The isocyanate organic compound is selected from p-phenylene diisocyanate, 4,4'-methylenebis(phenyl isocyanate), and triisocyanate.
4. The method for preparing an ionic organic polymer catalyst according to claim 1, characterized in that: The acyl chloride organic compound is selected from terephthaloyl chloride, 4,4'-biphenyldiacetyl chloride, azobenzene-4,4'-dicarbonyl chloride, and 2,2-bipyridine-5,5-acyl chloride.
5. The method for preparing an ionic organic polymer catalyst according to claim 1, characterized in that: The organic solvent is selected from 1,4-dioxane, acetonitrile, N,N-dimethylformamide, dimethylformamide, dimethyl sulfoxide, and ethanol.
6. The method for preparing an ionic organic polymer catalyst according to claim 1, characterized in that: The molar ratio of the chlorine-containing organic compound to 4-aminopyridine is 1:(2-4), and the molar ratio of the chlorine-containing organic compound to the isocyanate organic compound or the acyl chloride organic compound is 1:(1-2).
7. Use of the ionic organic polymer catalyst prepared by the method for preparing the ionic organic polymer catalyst according to any one of claims 1 to 6 in catalyzing the addition reaction of carbon dioxide and epoxy compounds.
8. The use according to claim 7, characterized in that: The epoxy compound is selected from epichlorohydrin, epibromohydrin, cyclohexene oxide, propylene oxide, benzyl glycidyl ether, and styrene oxide.