CN110437464A - A kind of linear imidazole ligands strong electronegativity copper complex and preparation method thereof - Google Patents
A kind of linear imidazole ligands strong electronegativity copper complex and preparation method thereof Download PDFInfo
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- CN110437464A CN110437464A CN201910774279.1A CN201910774279A CN110437464A CN 110437464 A CN110437464 A CN 110437464A CN 201910774279 A CN201910774279 A CN 201910774279A CN 110437464 A CN110437464 A CN 110437464A
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
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Abstract
The invention discloses a kind of linear imidazole ligands strong electronegativity copper complexes and preparation method thereof, belong to polymer self assembles and supramolecular materials technical field.Its chemical formula is [Cu (L)2SiF6], wherein L is Isosorbide-5-Nitrae-diimidazole base benzene ligand.Preparation process of the present invention is simple, at low cost, mild condition, and with the suspension type SiF of strong electronegativity in three-dimensional structure6Root has good absorption property to acetylene, and selectivity is good, can remove the traces of acetylene in ethylene well, meets requirement of the industrialization ethylene polymerization to Ethylene purity.
Description
Technical field
The invention belongs to polymer chemistry, polymer self assembles and supramolecular materials technical fields, and in particular to a kind of line
Property imidazole ligands strong electronegativity copper complex and preparation method thereof.
Background technique
Ethylene is the olefin polymerization industry in one of most widely used industrial chemicals, especially downstream in the world, to ethylene
Purity proposes higher requirement.In the current ethylene produced by naphtha steam cracking technology, acetylene is accounted for as by-product
There is 1% content, but acetylene can poison the catalyst of polymerization reaction makes its inactivation, therefore develops the traces of acetylene removing in ethylene
Technology is most important.The low temperature distillation and Catalytic Hydrogenation Techniques of mainstream extremely consume energy, and metal-organic framework materials have because of it
Special cellular structure, and pore size and duct environment can be adjusted and modified, pole is shown in terms of ethylene purification
Big potentiality [Coordination Chemistry Reviews, 2019,378,87].Studies have shown that by structure design and
Modulation introduces strong electronegative group in metal-organic framework materials, and the hydrogen bond action that can be formed using it with acetylene reaches pole
High acetylene separative efficiency.
Summary of the invention
Performance based on existing metal-organic framework materials in terms of acetylene adsorbing separation is not ideal enough, the purpose of the present invention
It is to design and synthesize the strong electronegativity metal-organic framework materials with novel crystal structure.Another object is to provide its system
Preparation Method.
In order to achieve the above objectives, the technical solution adopted by the present invention are as follows:
The linear imidazole ligands strong electronegativity copper complex, chemical formula are [Cu (L)2SiF6], wherein L is Isosorbide-5-Nitrae-two
Imidazole radicals benzene ligand (I), structural formula is as follows:
The linear imidazole ligands strong electronegativity copper complex crystal belongs to monoclinic system, C2/m space group, and with 6-c
Connection forms pcu topological network, and point symbol is { 4^12.6^3 }, and cell parameter is a=12.755 (4), b=25.512 (7),α=90, β=117.474 (7), γ=90 °,
Preparation method includes the following steps:
(1) it prepares L ligand: Isosorbide-5-Nitrae-dibromobenzene, imidazoles, potassium carbonate and copper sulphate is mixed and grind uniformly, be packed into poly- four
In fluorine liner reactor, baking oven heating reaction is put into after nitrogen purging；After reaction, it is down to room temperature, after suction filtration is washed with water
Retain filter residue, extracted, filtered, revolving obtains ligand L；
(2) by CuSiF6Aqueous solution is added dropwise in test tube bottom, then slow along tube wall with n,N-Dimethylformamide/aqueous mixtures
The n,N-Dimethylformamide solution of L ligand is finally slowly added to test tube, forms three stratum boundaries by the slow test tube that is added as buffer layer
Face solution；
(3) the layering solution by step (2) preparation covers, and is placed at room temperature for reaction, after reaction, is filtered, and washs, and does
It is dry, obtain linear imidazole ligands strong electronegativity copper complex.
Water used is deionized water in step (1) and step (2), and Isosorbide-5-Nitrae-dibromobenzene, imidazoles, potassium carbonate and copper sulphate are preferred
Molar ratio 100:1200:315:2.
CuSiF in step (2)6The concentration of aqueous solution is 0.09~0.12mol/L.
Concentration of the L ligand in N,N-dimethylformamide solution is 0.06~0.08mol/L in step (2).
The volume ratio of N,N-dimethylformamide and water is 1:2~2:1 in buffer solution in step (2).
As a preferred embodiment, baking oven reaction temperature is 180 DEG C in step (1), and the reaction time is for 24 hours；
As a preferred embodiment, in step (2) L ligand n,N-Dimethylformamide solution, N, N- dimethyl formyl
Amine/aqueous mixtures buffer solution and CuSiF6Aqueous solution volume ratio is 1:2:1；
As a preferred embodiment, reaction temperature is 25 DEG C in step (3).
The invention has the following advantages:
The present invention has synthesized a kind of copper-based three-dimension layer cylindrulite body knot of novel strong electronegativity by binary linearity imidazole ligands
Structure, synthetic method is simple, and yield is up to 80% or more.With the suspension type SiF of strong electronegativity in the complex three-dimensional structure6Root pair
Acetylene has good absorption property, and selectivity is good, can remove the traces of acetylene in ethylene well, realizes to ethylene and acetylene
Separation, meet requirement of the industrialization ethylene polymerization to Ethylene purity, have good application prospect in olefin purification field.
Detailed description of the invention
Fig. 1 is the synthesis schematic diagram of complex of the present invention.
Fig. 2 is the asymmetric cell of complex of the present invention.
Fig. 3 is the ligand L connection figure of ligand object of the present invention.
Fig. 4 is the metal connection figure of ligand object of the present invention.
Fig. 5 is duct figure of the complex of the present invention in c-axis direction.
Fig. 6 is the x-ray diffractogram of powder of complex of the present invention, in figure, the powder x-ray diffraction of 1- complex of the present invention
Figure, 2- simulation drawing.
Fig. 7 is the adsorption isothermal curve of complex of the present invention ethylene and acetylene at a temperature of 298K.
Fig. 8 is complex fixed bed separation test schematic diagram of the present invention.
Fig. 9 be complex of the present invention at a temperature of 298K 99% ethylene/1% acetylene gaseous mixture fixed bed separating property and
Repetitive test curve.
Specific embodiment
Explanation that the present invention will be further explained combined with specific embodiments below, but specific embodiment is not to the present invention
It is limited in any way.Unless stated otherwise, reagent involved in embodiment is reagent commonly used in the art.
Embodiment 1
(1) preparation of ligand L
1,4- dibromobenzene (2.34g, 10mmol), imidazoles (2.86g, 120mmol), potassium carbonate (4.36g, 31.5mmol) and
Copper sulphate (32mg, 0.2mmol) is packed into polytetrafluoro liner reactor after uniformly grinding, nitrogen purging is packed into stainless steel after ten minutes
Reaction kettle, fastening are put into 180 DEG C of baking oven and react 24 hours.After reaction, it is down to room temperature, with water filtering and washing (3*
500mL), inorganic salts and unreacted imidazoles are removed；(3*100mL) is extracted with dichloromethane in above-mentioned filter residue, adds magnesium sulfate (quiet
Set 3-4 hours) the remaining moisture of extraction is dried and removed, it filters, revolving obtains product, yield 83%.
(2) preparation of linear imidazole ligands strong electronegativity copper complex
By the CuSiF of 10mg6It is dissolved in 0.5mL water and is added dropwise in internal diameter 6mm × high 150mm test tube bottom, then by 1mL's
N,N-Dimethylformamide/aqueous mixtures that volume ratio is 1:1 are slowly added to test tube as buffer layer along tube wall, finally will
The L ligand of 7.5mg is equally slowly added to test tube after being dissolved in the n,N-Dimethylformamide solution of 0.5mL, to be divided into apparent
Three layers (see attached drawing 1)；The layering solution test tube of preparation is covered, 25 DEG C are placed at room temperature for 7 days, after reaction, are filtered, are washed
It washs, it is dry, obtain linear imidazole ligands strong electronegativity copper complex, yield 85%.
Comparative example 1
(1) preparation of ligand L
With embodiment 1.
(2) preparation of linear imidazole ligands strong electronegativity copper complex
With embodiment 1, CuSiF6Dosage be 20mg, a large amount of floccules are arranged at test tube bottom, and no crystal is precipitated.
Comparative example 2
(1) preparation of ligand L
With embodiment 1.
(2) preparation of linear imidazole ligands strong electronegativity copper complex
With embodiment 1, buffer solution is 6:3:1 using n,N-Dimethylformamide/ethanol/water volume ratio in step (2)
Mixture, no crystal is precipitated.
Complex produced by the present invention under the conditions of 298K and 1bar, acetylene adsorbance be 75mL/g, and ethylene substantially without
It adsorbs (attached drawing 7).In consideration of it, testing 99% ethylene of complex/1% acetylene mixing by fixed bed separator (attached drawing 8)
The separating property of gas, at a temperature of 298K, acetylene break through is 90 minutes, and after 10 circulations, performance has no decaying (attached drawing
9).Discovery is compared with analog material in document, although complex of the present invention is slightly lower to acetylene adsorbance, is had benefited to second
Alkene is almost without absorption, so that complex of the present invention shows extremely excellent ethylene/acetylene separating property, and property after 10 circulations
It can have no decaying, stability of material is more meaningful for industrial application.
*Angew.Chem.Int.Ed.2018,57,16067-16071(doi:10.1002/anie.201809884)。
Claims (5)
1. a kind of linear imidazole ligands copper complex, which is characterized in that its chemical formula is [Cu (L)2SiF6], wherein L is Isosorbide-5-Nitrae-two
Imidazole radicals benzene ligand (I), structural formula is as follows:
The linear imidazole ligands copper complex crystal belongs to monoclinic system, C2/m space group, and connects to form pcu with 6-c
Topological network, point symbol be { 4^12.6^3 }, cell parameter be a=12.755 (4), b=25.512 (7),α=90, β=117.474 (7), γ=90 °,
2. the method for preparation linear imidazole ligands copper complex as described in claim 1, which is characterized in that as follows
It realizes:
(1) it prepares L ligand: Isosorbide-5-Nitrae-dibromobenzene, imidazoles, potassium carbonate and copper sulphate is mixed and grind uniformly, be packed into polytetrafluoro
It serves as a contrast in reactor, baking oven heating reaction is put into after nitrogen purging；After reaction, it is down to room temperature, is retained after suction filtration is washed with water
Filter residue is extracted, and filtering, revolving obtains ligand L；
(2) by CuSiF6Aqueous solution dropwise addition slowly adds in test tube bottom, then by n,N-Dimethylformamide/aqueous mixtures along tube wall
Enter test tube as buffer layer, the n,N-Dimethylformamide solution of L ligand is finally slowly added to test tube, it is molten to form three bed boundarys
Liquid；CuSiF6The concentration of aqueous solution is 0.09~0.12mol/L；
(3) the layering solution by step (2) preparation covers, and is placed at room temperature for reaction, after reaction, is filtered, and washs, dry,
Obtain linear imidazole ligands copper complex.
3. linear imidazole ligands copper complex preparation method as claimed in claim 2, which is characterized in that L ligand in step (2)
Concentration in N,N-dimethylformamide solution is 0.06~0.08mol/L.
4. linear imidazole ligands copper complex preparation method as claimed in claim 2, which is characterized in that L ligand in step (2)
N,N-dimethylformamide solution, N,N-dimethylformamide/aqueous mixtures buffer solution and CuSiF6Aqueous solution volume ratio
For 1:2:1.
5. linear imidazole ligands copper complex preparation method as claimed in claim 2, which is characterized in that buffering in step (2)
The volume ratio of N,N-dimethylformamide and water is 1:2~2:1 in layer solution.
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| CN114196036A (en) * | 2021-12-20 | 2022-03-18 | 商丘师范学院 | Anion-assisted sulfonyl copper complex and preparation method thereof |
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| CN105131044A (en) * | 2015-09-22 | 2015-12-09 | 商丘师范学院 | Trinuclear n-heterocyclic carbene-palladium compound, synthetic method and application |
| WO2016043122A1 (en) * | 2014-09-16 | 2016-03-24 | 国立大学法人静岡大学 | Coordination polymer compound, porous material, anion remover, and anion removal method |
| CN108772103A (en) * | 2018-05-24 | 2018-11-09 | 南京工业大学 | A kind of bimetallic MOF catalyst and preparation method and application |
| CN110128451A (en) * | 2019-05-14 | 2019-08-16 | 安徽理工大学 | Copper metal organic coordination compound and its preparation method and application based on diphenyl ether ligand |
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Patent Citations (5)
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| CN102241695A (en) * | 2011-05-16 | 2011-11-16 | 汕头大学 | Akin molecular sieve metal double imidazoles porous coordination polymer and preparation method thereof |
| WO2016043122A1 (en) * | 2014-09-16 | 2016-03-24 | 国立大学法人静岡大学 | Coordination polymer compound, porous material, anion remover, and anion removal method |
| CN105131044A (en) * | 2015-09-22 | 2015-12-09 | 商丘师范学院 | Trinuclear n-heterocyclic carbene-palladium compound, synthetic method and application |
| CN108772103A (en) * | 2018-05-24 | 2018-11-09 | 南京工业大学 | A kind of bimetallic MOF catalyst and preparation method and application |
| CN110128451A (en) * | 2019-05-14 | 2019-08-16 | 安徽理工大学 | Copper metal organic coordination compound and its preparation method and application based on diphenyl ether ligand |
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