Synthesis method of amino-functionalized mesoporous material
By chloromethylation on the phenolic resin mesoporous material and grafting amine groups, the amine functionalized orderly mesoporous material was synthesized, and the problem of insufficient performance in CO2 adsorption was solved, and the effect of significantly improving the CO2 adsorption capacity was achieved.
Patent Information
- Application Number
- CN202411980259.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-31
- Publication Date
- 2025-04-11
AI Technical Summary
Existing micro and mesoporous composites have few research on CO2 adsorption, and the physical adsorption properties of unmodified materials are limited, making it difficult to effectively capture and store CO2.
The phenolic resin mesoporous material is used as the matrix, and the amine group is grafted after chloromethylation to synthesize an amine group functionalized orderly mesoporous material with adjustable nitrogen content.
The CO2 adsorption capacity of the material is improved, the adsorption amount to carbon dioxide is significantly increased, and the carbon dioxide adsorption performance is strong.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of nanomaterials, and in particular to a method for synthesizing an amine-functionalized mesoporous material. Background Art
[0002] The main energy source of modern society is still fossil fuels. The energy generated by the combustion of fossil fuels accounts for 85% of the total energy demand, but the combustion of fossil fuels produces a large amount of CO2, which causes the greenhouse effect. At the same time, CO2, as an important C1 resource, has important applications in industrial synthesis. Selective adsorption and storage of CO2 is of great significance to preventing the deterioration of the greenhouse effect and improving the efficiency of CO2 use.
[0003] Solid adsorbents such as microporous, mesoporous and micro / mesoporous dual-channel materials can capture CO2, but the physical adsorption performance of unmodified materials is limited. Amine functional groups have good affinity for CO2. Introducing alkaline amine functional groups into adsorbents can improve the chemical adsorption performance of adsorbents, improve the capture effect, and facilitate their recycling. According to the different loading methods of amine groups, the modification methods are divided into chemical grafting and physical impregnation. Generally speaking, chemical grafting is the chemical reaction between organic silane and the silanol group on the surface of the carrier to form a covalent bond and be fixed on the carrier; while physical impregnation is the electrostatic interaction between amine substances and materials and adsorption on the surface of the inner channel. However, in recent years, there are still few research reports on the application of amine-modified micro- and mesoporous composite materials in CO2 adsorption. Summary of the invention
[0004] In view of the above technical problems, the present invention provides a method for synthesizing an amine-functionalized mesoporous material.
[0005] Technical solution: A method for synthesizing an amine-functionalized mesoporous material comprises the following steps: S1: Add phenol into a reaction vessel, heat to 40-45°C to melt, add sodium hydroxide solution, dropwise add formaldehyde solution, raise the reaction temperature to 70-75°C and reflux for 2-3h to obtain a phenolic resin precursor; S2: Add dilute hydrochloric acid to the reaction solution to adjust the pH to neutral, remove water by rotary evaporation, dissolve with ethanol, add template F127 and heat to dissolve, mix and stir at room temperature for 0.5-1h, pour on a glass plate and evaporate at room temperature for 8-10h, then transfer to an oven and cure at 110-130°C for 24-48h to obtain an ordered mesoporous phenolic resin; S3: Ordered mesoporous phenolic resin reacts with methyl chloromethyl ether under Lewis acid catalysis to obtain chloromethylated ordered mesoporous phenolic resin; S4: Chloromethylated ordered mesoporous phenolic resin reacts with ethylenediamine (EDA), diethylenetriamine (DETA) or tetraethylenepentamine (TEPA) to generate the amine-functionalized mesoporous material.
[0006] Furthermore, the molar ratio of phenol to formaldehyde in S1 is 1:2-4.
[0007] Furthermore, the mass fraction of the sodium hydroxide solution in S1 is 8-15%, and the added amount is 1.5-2 times the mass of phenol.
[0008] Furthermore, the amount of template F127 added in S2 is 2-3 times the mass of phenol.
[0009] Furthermore, the Lewis acid in S3 is any one of aluminum chloride, zinc chloride and tin chloride.
[0010] Further, the S3 ordered mesoporous phenolic resin is dispersed in anhydrous acetonitrile for reaction, and after the reaction, the solid is filtered and rinsed with anhydrous acetonitrile.
[0011] Furthermore, the molar ratio of methyl chloromethyl ether to phenol in S3 is 1:1.2-1.5.
[0012] Furthermore, the molar ratio of ethylenediamine (EDA), diethylenetriamine (DETA) or tetraethylenepentamine (TEPA) to phenol in S4 is 1:1.2-1.5.
[0013] Furthermore, the reaction of S4 was carried out in anhydrous acetonitrile and heated under reflux for 24 h. After the reaction was completed, it was filtered, ultrasonically dispersed in acetone for 1 h, filtered, and dried at 60°C.
[0014] Beneficial effects: The invention provides a method for synthesizing an amine-functionalized mesoporous material, which uses a phenolic resin mesoporous material as a base material, grafts an amine group after chloromethylation, and finally synthesizes an amine-functionalized ordered mesoporous material with adjustable nitrogen content. The synthesized material has a strong carbon dioxide adsorption capacity. DETAILED DESCRIPTION
[0015] The present invention is described in detail below.
[0016] Embodiment 1: A method for synthesizing an amine-functionalized mesoporous material comprises the following steps: S1: Add 1.0 g of phenol into a reaction container, heat to 40°C to melt, add 1.6 g of 10% sodium hydroxide solution, dropwise add 3.0 g of 37% formaldehyde solution, raise the reaction temperature to 70°C and reflux for 2 h to obtain a phenolic resin precursor; S2: 1 mol / L dilute hydrochloric acid was added dropwise to the reaction solution to adjust the pH to neutral, water was removed by rotary evaporation, and the solution was dissolved with ethanol. 2.5 g of template F127 was added and heated to dissolve the solution. The mixture was mixed and stirred at room temperature for 40 min, poured onto a glass plate and evaporated at room temperature for 8 h, and then transferred to an oven and cured at 120°C for 36 h to obtain an ordered mesoporous phenolic resin. S3: The ordered mesoporous phenolic resin reacts with 0.9 g of methyl chloromethyl ether under the catalysis of AlCl3 to obtain a chloromethylated ordered mesoporous phenolic resin, the reaction solvent is acetonitrile, and after the reaction, the solid is filtered and rinsed with anhydrous acetonitrile; S4: Chloromethylated ordered mesoporous phenolic resin and 0.67 g ethylenediamine (EDA) were refluxed in acetonitrile for 24 h. After the reaction was completed, the resin was filtered and ultrasonically dispersed in acetone for 1 h. After filtering, the resin was dried at 60° C. to obtain the amino-functionalized mesoporous material.
[0017] Embodiment 2: A method for synthesizing an amine-functionalized mesoporous material comprises the following steps: S1: Add 1.0 g of phenol into a reaction container, heat to 40°C to melt, add 1.6 g of 10% sodium hydroxide solution, dropwise add 3.0 g of 37% formaldehyde solution, raise the reaction temperature to 70°C and reflux for 2 h to obtain a phenolic resin precursor; S2: 1 mol / L dilute hydrochloric acid was added dropwise to the reaction solution to adjust the pH to neutral, water was removed by rotary evaporation, and the solution was dissolved with ethanol. 2.5 g of template F127 was added and heated to dissolve the solution. The mixture was mixed and stirred at room temperature for 40 min, poured onto a glass plate and evaporated at room temperature for 8 h, and then transferred to an oven and cured at 120°C for 36 h to obtain an ordered mesoporous phenolic resin. S3: The ordered mesoporous phenolic resin reacts with 0.9 g of methyl chloromethyl ether under the catalysis of SnCl4 to obtain a chloromethylated ordered mesoporous phenolic resin, the reaction solvent is acetonitrile, and after the reaction, the solid is filtered and rinsed with anhydrous acetonitrile; S4: Chloromethylated ordered mesoporous phenolic resin and 1.15 g diethylenetriamine (DETA) were refluxed in acetonitrile for 24 h. After the reaction was completed, the resin was filtered and ultrasonically dispersed in acetone for 1 h. After filtering, the resin was dried at 60° C. to obtain the amino-functionalized mesoporous material.
[0018] Embodiment 3: A method for synthesizing an amine-functionalized mesoporous material comprises the following steps: S1: Add 1.0 g of phenol into a reaction container, heat to 40°C to melt, add 1.6 g of 10% sodium hydroxide solution, dropwise add 3.0 g of 37% formaldehyde solution, raise the reaction temperature to 70°C and reflux for 2 h to obtain a phenolic resin precursor; S2: 1 mol / L dilute hydrochloric acid was added dropwise to the reaction solution to adjust the pH to neutral, water was removed by rotary evaporation, and the solution was dissolved with ethanol. 2.5 g of template F127 was added and heated to dissolve the solution. The mixture was mixed and stirred at room temperature for 40 min, poured onto a glass plate and evaporated at room temperature for 8 h, and then transferred to an oven and cured at 120°C for 36 h to obtain an ordered mesoporous phenolic resin. S3: The ordered mesoporous phenolic resin reacts with 0.9 g of methyl chloromethyl ether under the catalysis of ZnCl2 to obtain a chloromethylated ordered mesoporous phenolic resin, the reaction solvent is acetonitrile, and after the reaction, the solid is filtered and rinsed with anhydrous acetonitrile; S4: Chloromethylated ordered mesoporous phenolic resin and 2.11 g tetraethylenepentamine (TEPA) were refluxed in acetonitrile for 24 h. After the reaction was completed, the resin was filtered and ultrasonically dispersed in acetone for 1 h. After filtering, the resin was dried at 60° C. to obtain the amino-functionalized mesoporous material.
[0019] Test example: The amino-functionalized mesoporous materials prepared in Examples 1-3 and the ordered mesoporous phenolic resin obtained in S2 of Example 1 were used as comparative examples. They were vacuumed at 100° C. for 10 hours using a common oil pump, and the vacuum degree was less than 10 - 3 mmHg; at 25°C and 0-1 atmospheres, the CO2 adsorption capacity of the amine-functionalized mesoporous material was tested on a Micrometrics ASAP2420 gas adsorption instrument, and the adsorption amount is shown in Table 1.
[0020] Table 1: It can be seen from the above table that the amine-functionalized mesoporous materials prepared in Examples 1-3 have a significantly increased CO2 adsorption capacity compared to the ordered mesoporous phenolic resin, proving that the CO2 adsorption capacity of the material is increased after the amine grafting. Examples 1-3 are grafted with ethylenediamine, diethylenetriamine and tetraethylenepentamine respectively. The number of primary amine groups is the same for the three, and the number of secondary amines gradually increases. After the number of secondary amines increases, the CO2 adsorption capacity increases to a certain extent, but the increase is small. The possible reason is that the reactant chain length increases, and the probability of the primary amines at both ends reacting increases, resulting in a decrease in the number of free primary amines.
[0021] Although the present invention has been disclosed as above in terms of preferred embodiments, they are not intended to limit the present invention. Anyone skilled in the art can make various changes or modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be based on the scope of protection defined by the claims of this application.
Claims
1. A method for synthesizing an amine-functionalized mesoporous material, characterized in that: The following steps are involved: S1: Add phenol into a reaction vessel, heat to 40-45°C to melt, add sodium hydroxide solution, dropwise add formaldehyde solution, raise the reaction temperature to 70-75°C and reflux for 2-3h to obtain a phenolic resin precursor; S2: Add dilute hydrochloric acid to the reaction solution to adjust the pH to neutral, remove water by rotary evaporation, dissolve with ethanol, add template F127 and heat to dissolve, mix and stir at room temperature for 0.5-1h, pour on a glass plate and evaporate at room temperature for 8-10h, then transfer to an oven and cure at 110-130°C for 24-48h to obtain an ordered mesoporous phenolic resin; S3: Ordered mesoporous phenolic resin reacts with methyl chloromethyl ether under Lewis acid catalysis to obtain chloromethylated ordered mesoporous phenolic resin; S4: Chloromethylated ordered mesoporous phenolic resin reacts with ethylenediamine (EDA), diethylenetriamine (DETA) or tetraethylenepentamine (TEPA) to generate the amine-functionalized mesoporous material.
2. The method for synthesizing an amine-functionalized mesoporous material according to claim 1, characterized in that: The molar ratio of phenol to formaldehyde in S1 is 1:2-4.
3. The method for synthesizing an amine-functionalized mesoporous material according to claim 2, characterized in that: The mass fraction of the sodium hydroxide solution in S1 is 8-15%, and the added amount is 1.5-2 times the mass of phenol.
4. A method for synthesizing an amine-functionalized mesoporous material according to any one of claims 1 to 3, characterized in that: The amount of template F127 added in S2 is 2-3 times the mass of phenol.
5. The method for synthesizing an amine-functionalized mesoporous material according to claim 4, characterized in that: The Lewis acid in S3 is any one of aluminum chloride, zinc chloride and tin chloride.
6. The method for synthesizing an amine-functionalized mesoporous material according to claim 5, characterized in that: S3 ordered mesoporous phenolic resin was dispersed in anhydrous acetonitrile for reaction. After the reaction, the solid was filtered and rinsed with anhydrous acetonitrile.
7. The method for synthesizing an amine-functionalized mesoporous material according to claim 5 or 6, characterized in that: The molar ratio of methyl chloromethyl ether to phenol in S3 is 1:1.2-1.
5.
8. The method for synthesizing an amine-functionalized mesoporous material according to claim 7, characterized in that: The molar ratio of ethylenediamine (EDA), diethylenetriamine (DETA) or tetraethylenepentamine (TEPA) to phenol in S4 is 1:1.2-1.
5.
9. The method for synthesizing an amine-functionalized mesoporous material according to claim 8, characterized in that: The reaction of S4 was carried out in anhydrous acetonitrile and heated under reflux for 24 h. After the reaction was completed, it was filtered, ultrasonically dispersed in acetone for 1 h, filtered, and dried at 60°C.