CN114196036A - Anion-assisted sulfonyl copper complex and preparation method thereof - Google Patents
Anion-assisted sulfonyl copper complex and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an anion-assisted sulfonyl copper complex and a preparation method thereof, and belongs to the technical field of polymer self-assembly and supramolecular materials. The chemical formula is [ Cu (L)2TiF6]Wherein L is a 1, 1' -sulfonyldiimidazole ligand. The invention has simple preparation process, low cost and mild condition, and the complex is an anion-assisted junctionThe structure has the advantages that the interaction between coordinated anion hexafluorotitanate in the pore channel and acetylene molecules and the size (3.3A) of the pore channel have a synergistic effect on acetylene screening, so that acetylene/ethylene can be efficiently separated, and the purity requirement of industrial polymerization-grade ethylene is met.
Description
Technical Field
The invention belongs to the technical field of high-molecular chemistry, polymer self-assembly and supramolecular materials, and particularly relates to an anion-assisted sulfonyl copper complex and a preparation method thereof.
Background
Ethylene is the core of petrochemical industry, the annual output of the whole world is over hundred million tons, and the product accounts for over 70 percent of petrochemical products and occupies a non-negligible important position in national economy. In the process of ethylene production, the produced trace amount of acetylene can affect the purity of ethylene and easily poison the catalyst for ethylene polymerization, and the acetylene is often separated by a low-temperature process to realize purification, so that the process has huge energy consumption. In recent years, porous materials typified by metal organic framework materials have made a lot of important progress in the field of selective separation of acetylene/ethylene adsorption. The Metal Organic framework material has a special pore channel structure, and can adjust and modify the pore channel Size and the pore channel environment, thereby showing great potential in the acetylene/ethylene separation field [ design Metal-Organic Frameworks for Size-Exclusion-Based Hydrocarbon Separations: Progress and Challenges, adv. Mater.2020,32,2002603 ]. Research shows that the high-efficiency separation of acetylene and ethylene can be realized by utilizing the anion functional group and the metal organic framework material with the size matched with the pore structure. The research and development of new materials are urgently needed at present.
Disclosure of Invention
Based on the fact that the performance of the existing metal organic framework material in the aspect of acetylene adsorption separation is not ideal enough, the invention aims to design and synthesize the metal organic framework material which has anions participating in coordination and is suitable for pore canal size, and the high-efficiency separation of acetylene and ethylene is realized. Another object is to provide a process for the preparation thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
the anion auxiliary sulfonyl copper complex has a chemical formula of [ Cu (L)2TiF6]Wherein L is 1, 1' -sulfonyl diimidazole ligand (I), and the structural formula is shown as follows:
the anion auxiliary sulfonyl copper complex crystal belongs to a trigonal system,
space group having cell parameters of
α＝90°，β＝90°，γ＝120°，
The preparation method comprises the following steps:
(1) mixing Cu (BF)4)2/(NH4)2TiF6Dripping an aqueous solution on the bottom layer of the test tube, slowly adding an N, N-dimethylformamide/methanol/water mixture into the test tube along the tube wall to serve as a buffer layer, and finally slowly adding an N, N-dimethylformamide solution of a 1, 1' -sulfonyl diimidazole ligand (L ligand for short) into the test tube to form a three-layer interface solution; cu (BF)4)2/(NH4)2TiF6The concentration of two reactants in the aqueous solution is 0.10-0.12 mol/L, and the molar ratio is 1: 1;
(2) and (2) covering the layered solution prepared in the step (1), standing at room temperature for reaction, and filtering, washing and drying after the reaction is finished to obtain the sulfonyl copper complex.
The water used in the step (1) is deionized water.
In the step (1), the concentration of the L ligand in the N, N-dimethylformamide solution is 0.09-0.11 mol/L.
The volume ratio of the N, N-dimethylformamide to the methanol to the water in the buffer solution in the step (1) is 2:3: 1.
As a preferable mode, a N, N-dimethylformamide solution, a N, N-dimethylformamide/methanol/water mixture buffer solution and Cu (BF) of the L ligand in the step (1)4)2/(NH4)2TiF6The volume ratio of the aqueous solution is 1:1: 1;
as a preferable mode, the reaction temperature in the step (2) is 25 ℃.
The invention has the following beneficial effects:
the invention synthesizes a novel anion auxiliary sulfonyl three-dimensional crystal structure through the bidentate sulfonyl nitrogen ligand, the synthesis method is simple, and the yield reaches more than 82%. The three-dimensional structure of the complex is an anion distribution pore channel structure and an anion auxiliary structure, and the coordination anion hexafluorotitanate participating in the pore channel interacts with acetylene molecules and has the pore channel size
Has synergistic effect on acetylene screening, can efficiently separate acetylene/ethylene and meet the purity requirement of industrial polymerization-grade ethylene.
Drawings
FIG. 1 is an asymmetric unit of a complex of the present invention.
FIG. 2 is a diagram of the ligand L linkage of the ligand of the present invention.
FIG. 3 is a metal connection diagram of the ligand of the present invention.
FIG. 4 shows a diagram of channels in the c-direction and a spiral structure of secondary pores of the complex of the present invention.
FIG. 5 is a powder X-ray diffraction pattern at varying temperatures for a complex of the present invention.
FIG. 6 is a graph showing the isothermal adsorption of acetylene and ethylene at a temperature of 298K for the complex of the present invention.
FIG. 7 is a graph showing the separation performance of the complex of the present invention in a fixed bed of 1% acetylene/99% ethylene mixed gas at 298K and 333K.
Detailed Description
The present invention will be further explained with reference to specific examples, which are not intended to limit the present invention in any way. Unless otherwise indicated, all reagents referred to in the examples are those commonly used in the art.
Example 1
(1) Preparation of anion-assisted sulfonyl copper complex
20 μ L of Cu (BF)4)245 wt% aqueous solution and 10mg (NH)4)2SiF6Dissolving in 0.5mL of water, dropwise adding into the bottom layer of a test tube with the inner diameter of 6mm multiplied by the height of 150mm, slowly adding 0.5mL of N, N-dimethylformamide/methanol/water mixture with the volume ratio of 2:3:1 into the test tube along the tube wall to serve as a buffer layer, finally dissolving 10mg of L ligand in 0.5mL of N, N-dimethylformamide solution, and slowly adding into the test tube to divide into three distinct layers; and (3) covering the prepared layered solution in a test tube, standing at 25 ℃ for 10 days at room temperature, and after the reaction is finished, filtering, washing and drying to obtain the anion auxiliary sulfonyl copper complex with the yield of 84%.
The crystal unit cell parameters are as follows:
comparative example 1
(1) Preparation of anion-assisted sulfonyl copper complex
30 μ L of Cu (BF)4)245 wt% aqueous solution and 25mg (NH)4)2SiF6Dissolving in 0.5mL of water, dropwise adding into the bottom layer of a test tube with the inner diameter of 6mm multiplied by the height of 150mm, slowly adding 0.5mL of N, N-dimethylformamide/methanol/water mixture with the volume ratio of 2:3:1 into the test tube along the tube wall to serve as a buffer layer, finally dissolving 10mg of L ligand in 0.5mL of N, N-dimethylformamide solution, and slowly adding into the test tube to divide into three distinct layers; the prepared layered solution is covered on a test tube, the test tube is placed at room temperature of 25 ℃ for 10 days, and after the reaction is finished, a large amount of colorless precipitate is formed at the bottom of the test tube, and no crystal is separated out.
Comparative example 2
(1) Preparation of anion-assisted sulfonyl copper complex
20 μ L of Cu (BF)4)245 wt% aqueous solution and 10mg (NH)4)2SiF6Dissolving in 0.5mL of water, adding dropwise into the bottom layer of a test tube with inner diameter of 6mm and height of 150mm, slowly adding 0.5mL of N, N-dimethylformamide/water mixture with volume ratio of 1:1 into the test tube along the tube wall as buffer layer, and finally adding into the test tubeDissolving 10mg of L ligand in 0.5mL of N, N-dimethylformamide solution, and slowly adding into the test tube to obtain three distinct layers; the prepared layered solution was capped and left at room temperature of 25 ℃ for 10 days, and no crystal was precipitated after the reaction was completed.
The complex prepared by the invention has the acetylene adsorption capacity of 50.2mL/g under the conditions of 298K and 1bar, and ethane is basically not adsorbed (shown in figure 6). In view of this, the separation performance of the complex 1% acetylene/99% ethylene mixed gas was tested by a fixed bed separation apparatus, and the acetylene breakthrough time was 90 minutes at a temperature of 298K (fig. 7). Compared with similar materials in the literature, the complex has the advantages that the adsorption amount of acetylene is equivalent to that of the similar materials, and the adsorption amount of ethylene is lower, so that the complex shows excellent acetylene/ethylene separation performance.
*Angew.Chem.Int.Ed.2020,59,18927–18932(doi:10.1002/anie.202009446)。
Claims (6)
1. A sulfonyl copper complex, which is characterized in that the chemical formula is [ Cu (L) ]2TiF6]Wherein L is 1, 1' -sulfonyl diimidazole ligand (I), and the structural formula is shown as follows:
the sulfonyl copper complex crystal belongs to a trigonal system, R
A c-space group having unit cell parameters a =22.194(6) a, b =22.194(6) a, c =29.291(8) a, α =90 °, β =90 °, γ =120 °, V =12495.4 a3。
2. The sulfonyl copper complex material of claim 1 assembled from the channel structure shown in figure 4.
3. A process for preparing a copper sulfonyl complex according to claim 1 by the steps of:
(1) mixing Cu (BF)4)2/(NH4)2TiF6Dripping the aqueous solution on the bottom layer of the test tube, adding the N, N-dimethylformamide/methanol/water mixture into the test tube along the tube wall to serve as a buffer layer, and finally adding the N, N-dimethylformamide solution of the 1, 1' -sulfonyl diimidazole ligand into the test tube to form a three-layer interface solution; cu (BF)4)2/(NH4)2TiF6The concentration of the two reactants in the aqueous solution is 0.10-0.12 mol/L, and the molar ratio is 1: 1;
(2) and (2) covering the layered solution prepared in the step (1), standing at room temperature for reaction, and filtering, washing and drying after the reaction is finished to obtain the sulfonyl copper complex.
4. The method for preparing a sulfonyl copper complex according to claim 3, wherein the concentration of the 1, 1' -sulfonyl diimidazole ligand in the N, N-dimethylformamide solution in the step (1) is 0.09 to 0.11 mol/L.
5. The method for producing a copper sulfonyl complex according to claim 3 wherein in the step (1), a solution of 1, 1' -sulfonyl diimidazole ligand in N, N-dimethylformamide, a buffer solution of N, N-dimethylformamide/methanol/water mixture and Cu (BF) are used4)2/(NH4)2TiF6The volume ratio of the aqueous solution is 1:1: 1.
6. The method for producing a sulfonyl copper complex according to claim 3, wherein the volume ratio of N, N-dimethylformamide, methanol and water in the buffer solution in the step (1) is 2:3: 1.
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| US20150190779A1 (en) * | 2014-01-07 | 2015-07-09 | University Of South Florida | Functionalized Porous Organic Polymers for Olefin/Paraffin Separations |
| US20150231600A1 (en) * | 2012-09-03 | 2015-08-20 | The University Of Liverpool | Metal-organic frameworks |
| CN109438722A (en) * | 2018-08-08 | 2019-03-08 | 江苏科技大学 | Based on manganese base luminescent metal organic framework material and its preparation method and application |
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|---|---|---|---|---|
| US20150231600A1 (en) * | 2012-09-03 | 2015-08-20 | The University Of Liverpool | Metal-organic frameworks |
| US20150190779A1 (en) * | 2014-01-07 | 2015-07-09 | University Of South Florida | Functionalized Porous Organic Polymers for Olefin/Paraffin Separations |
| CN109438722A (en) * | 2018-08-08 | 2019-03-08 | 江苏科技大学 | Based on manganese base luminescent metal organic framework material and its preparation method and application |
| CN110437464A (en) * | 2019-08-21 | 2019-11-12 | 商丘师范学院 | A kind of linear imidazole ligands strong electronegativity copper complex and preparation method thereof |
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