CN109999756B - Beta-keto enamine chiral covalent organic frame material and preparation method and application of bonding capillary gas chromatographic column thereof - Google Patents
Beta-keto enamine chiral covalent organic frame material and preparation method and application of bonding capillary gas chromatographic column thereof Download PDFInfo
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Abstract
The invention discloses a beta-keto enamine chiral covalent organic framework material and a preparation method and application of a bonding capillary gas chromatographic column thereof. The beta-keto enamine chiral covalent organic framework material has the advantages of high thermal stability, large specific surface area and uniform pore size distribution, and can be used for chiral identification and separation. The beta-ketoenamine chiral covalent organic framework material and the bonded beta-ketoenamine chiral covalent organic framework capillary column prepared from the same can realize component separation of a mixed component of straight-chain and branched-chain alkane or a mixed component of ethylbenzene and styrene, and have good application prospect.
Description
Technical Field
The invention relates to the field of covalent organic framework functional materials, in particular to a beta-ketoenamine chiral covalent organic framework material, a preparation method of a bonding capillary gas chromatographic column thereof and application thereof in capillary gas chromatographic separation.
Background
Covalent organic framework materials (COFs) are novel ordered porous crystalline materials formed by covalently bonding small organic molecules containing light elements (C, H, N, O, B, etc.). As one of typical representatives of the novel porous materials, the covalent organic framework material has the characteristics of light weight, low density, adjustable skeleton size, pore channel modification, high ordered permanent porosity, large specific surface area, good thermal stability and chemical stability and the like, and is widely applied to the aspects of gas storage, heterogeneous catalysis, proton conduction, chemical sensors, drug sustained release and the like.
Covalent organic framework materials also have great potential for use in the field of separation science. In recent years, covalent organic frameworks and composites thereof have been used as adsorbents for solid phase extraction, coatings for solid phase microextraction, and novel immobilization reagents for capillary electrochromatography and high performance liquid chromatography, and the like. However, reports on the use of covalent organic framework materials as novel stationary phases for gas chromatographic separations are very rare at present. In particular, beta-ketoenamine chiral covalent organic framework materials have not been reported, and therefore, the research on a preparation method of a novel covalent organic framework material and the application of the novel covalent organic framework material to the separation of capillary gas chromatography are the subjects worth of research.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a novel beta-keto enamine chiral covalent organic framework material. The beta-keto enamine chiral covalent organic framework material has the advantages of high thermal stability, large specific surface area and uniform pore size distribution, and can be used for chiral identification and separation.
The invention also aims to disclose a preparation method of the beta-keto enamine chiral covalent organic framework material.
The invention also aims to disclose a bonded beta-keto enamine chiral covalent organic framework capillary column.
The invention also aims to disclose a preparation method of the bonded beta-keto enamine chiral covalent organic framework capillary column.
The invention also aims to disclose application of the bonded beta-ketoenamine chiral covalent organic framework capillary column.
The above object of the present invention is achieved by the following technical solutions:
a beta-ketoenamine chiral covalent organic framework material has a repeating unit shown in formula (I),
the inventors disclosed in CN109054031A and CN107362785A chiral covalent organic framework materials of hydrazone linkage connection type, which all exhibit the advantages of high thermal stability, large specific surface area and uniform pore size distribution, and revealed that such materials can be applied to high performance liquid chromatography separation, but do not disclose that they can be applied to gas chromatography. The material is a novel beta-keto enamine connection type chiral covalent organic framework material which has a framework structure different from that of a hydrazone bond connection type chiral covalent organic framework material, and the inventor finds that the material can be applied to capillary gas chromatography separation and can realize component separation of a mixed component of straight-chain and branched-chain alkane or a mixed component of ethylbenzene and styrene.
The synthesis method of the beta-keto enamine chiral covalent organic framework material comprises the following steps:
under the protection of inert atmosphere, 2,4, 6-trihydroxy mesitylene aldehyde and chiral precursor (S) -2, 5-bis (2-methylbutoxy) terephthalic acid dihydrazide react in an organic solvent to obtain the chiral covalent organic framework material.
Preferably, after the reaction is finished, collecting the solid obtained by the reaction through suction filtration, and cleaning and drying the solid to obtain the chiral covalent organic framework material.
Preferably, the washing may be performed using an organic solvent, and more preferably, the washing is performed using 1, 4-dioxane and/or tetrahydrofuran, and then the washing is performed using acetone to complete the whole washing process.
Preferably, the molar ratio of 2,4, 6-trihydroxy-benzenetricarboxylic acid to the chiral precursor (S) -2, 5-bis (2-methylbutoxy) terephthalic acid dihydrazide is 1: (1-1.5).
Preferably, the organic solvent is 1, 4-dioxane or a volume ratio of 1, 4-dioxane to mesitylene of 1: 1.
Preferably, in the preparation process of the chiral covalent organic framework material, an acid catalyst is added, and the molar weight of the acid catalyst is preferably 1-10 times that of the hydrazide chiral precursor.
Preferably, the acid catalyst is acetic acid. The concentration of the acetic acid is preferably 3-6M.
Preferably, the reaction temperature is 90-110 ℃, and the reaction time is 3-5 days.
A bonded beta-keto enamine chiral covalent organic frame capillary column, the inner wall of the capillary column is fixed with a covalent organic frame stationary phase in a chemical bond mode, the covalent organic frame stationary phase has a repeating unit shown in a formula (I),
the preparation method of the capillary column comprises the following steps:
s1, carrying out amino modification on a capillary tube to obtain an amino-modified capillary tube;
s2, fully mixing 2,4, 6-trihydroxy mesitylene aldehyde, chiral precursor (S) -2, 5-bis (2-methylbutoxy) terephthalic acid dihydrazide and an organic solvent, and blowing inert gas into the mixture to obtain a pre-polymerization solution;
s3, filling the pre-polymerization liquid obtained in the S2 into the amino-modified capillary tube in the S1, sealing, reacting for 3-5 days at 90-110 ℃, removing the solvent after the reaction is finished, and curing the coating of the capillary tube to obtain the bonded beta-keto-enamine chiral covalent organic framework capillary tube.
Preferably, in s1. the amino-modified capillary tube may be prepared as follows:
washing a quartz capillary column with sodium hydroxide solution, deionized water, hydrochloric acid and deionized water in sequence, finally washing until the washing liquid is neutral, then washing with methanol, filling the treated capillary with methanol solution of 3-Aminopropyltriethoxysilane (APTES), sealing two ends of the capillary with rubber plugs, placing in a water bath overnight, washing out residual solvent with methanol, and finally heating and drying the capillary column under the protection of nitrogen, thereby obtaining the amino-modified capillary.
Preferably, the concentration of the sodium hydroxide solution is 1M, the concentration of the hydrochloric acid is 0.1M, and the volume ratio of the methanol solution of the 3-Aminopropyltriethoxysilane (APTES) is 1: 1.
preferably, in S2. the molar ratio of 2,4, 6-trihydroxytrimesic aldehyde to the chiral precursor (S) -2, 5-bis (2-methylbutoxy) terephthalic acid dihydrazide is 1: (1-1.5).
Most preferably, in S2. the molar ratio of 2,4, 6-trihydroxytrimesic aldehyde to the chiral precursor (S) -2, 5-bis (2-methylbutoxy) terephthalic acid dihydrazide is 1: 1.5.
preferably, in S2, the volume ratio of the organic solvent to 1, 4-dioxane or 1, 4-dioxane to mesitylene is 1: 1.
Preferably, in S3, the reaction is controlled at 90 ℃ for 3 days.
The bonded beta-keto enamine chiral covalent organic framework capillary column is applied to gas chromatographic separation.
The bonded beta-keto enamine chiral covalent organic framework capillary column is used for separating components of a mixed component of straight-chain and branched-chain alkane or a mixed component of ethylbenzene and styrene.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a beta-ketoenamine chiral covalent organic framework material, a bonded beta-ketoenamine chiral covalent organic framework capillary column, a preparation method and application thereof. The beta-keto enamine chiral covalent organic framework material has the advantages of high thermal stability, large specific surface area and uniform pore size distribution, and can also realize component separation of a mixed component of straight-chain and branched-chain alkane or a mixed component of ethylbenzene and styrene. The bonded beta-keto enamine chiral covalent organic framework capillary column is prepared by adopting an in-situ growth mode, can be used as a stationary phase of gas chromatography, can realize the component separation of a mixed component of straight-chain and branched-chain alkane or a mixed component of ethylbenzene and styrene, overcomes the defect of complicated preparation of the existing packed column, saves synthetic raw materials, has low cost, is beneficial to popularization and application, and has great production and practice significance.
Drawings
FIG. 1 is a schematic diagram of a preparation process of a beta-ketoenamine chiral covalent organic framework material of the invention.
FIG. 2 is a powder X-ray diffraction pattern of a chiral covalent organic framework material prepared in example 1 of the present invention.
FIG. 3 is a Fourier infrared spectrum of chiral covalent organic framework material (a) prepared in example 1 of the present invention, as well as 2,4, 6-trihydroxytrimesic aldehyde (b) and chiral hydrazide precursor (c).
FIG. 4 is a thermogravimetric analysis plot of the chiral covalent framework material prepared in example 1 of the present invention.
FIG. 5 is a nitrogen sorption desorption temperature line for chiral covalent framework material prepared in example 1 of the present invention.
FIG. 6 is a plot of the pore size distribution of chiral covalent framework material prepared in example 1 of the present invention.
FIG. 7 is a scanning electron microscope image of the cross section of a capillary column of a bonded beta-ketoenamine chiral covalent organic framework prepared in example 2 of the present invention.
FIG. 8 is a chromatogram of the separation of linear and branched alkanes, ethylbenzene and styrene using a capillary column with chiral covalent organic frameworks of bonded β -ketoenamines prepared in example 2 of the present invention.
Detailed description of the invention
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, it being understood that the preferred embodiments described herein are merely for purposes of illustration and understanding, and are not intended to limit the invention. The instruments and reagents used in the examples are all commercially available conventional instruments and reagents, unless otherwise specified.
Example 1: synthesis of beta-keto enamine chiral covalent organic frame material
Chiral precursor (S) -2, 5-bis (2-methylbutoxy) terephthalic acid dihydrazide (22.0mg,0.06mmol), 2,4, 6-trihydroxy-mesitylene-furfural (8.4mg,0.04mmol), 0.5mL dioxane, and 0.5mL mesitylene were placed in a pressure-resistant reaction flask, mixed well and then 0.1mL 3M acetic acid solution was added. The pressure-resistant reaction flask was replaced with argon three times, then quickly sealed with a sealing cap, and then placed in an oven preheated to 110 ℃ for reaction for 3 days. After the reaction is finished, the mixture is cooled to room temperature, solid is collected by suction filtration, washed by 1, 4-dioxane, tetrahydrofuran and acetone in sequence, and finally placed and dried in vacuum to obtain orange yellow solid powder 25mg, wherein the yield is 84%.
The performance measurement results of the beta-ketoenamine chiral covalent organic framework material containing hydroxyl functional groups provided in this example are as follows:
(1) x-ray powder diffraction measurement
Fig. 2 is an X-ray powder diffraction pattern of the chiral covalent organic framework material prepared in this example, wherein 3.4, 6.8 and 26.8 degrees are characteristic diffraction peaks of the chiral covalent organic framework material, which indicates that the chiral covalent organic framework material has better crystallinity.
(2) Fourier Infrared Spectrometry
FIG. 3 is a Fourier infrared spectrum of the chiral covalent organic framework material prepared in this example. Wherein a is chiral covalent organic framework material, b is 2,4, 6-trihydroxy mesitylene formaldehyde, and c is chiral hydrazide precursor.
(3) Thermogravimetric analysis
Fig. 4 is a thermogravimetric analysis curve of the chiral covalent organic framework material prepared in this example under a nitrogen atmosphere, and the result shows that the chiral covalent organic framework material has high thermal stability and can be stabilized to about 350 ℃.
(5) Nitrogen desorption and pore size distribution testing
Fig. 5 is a nitrogen desorption isotherm of the chiral covalent framework material provided in this example, and fig. 6 is a corresponding pore size distribution curve. Nitrogen adsorption and desorption tests show that the obtained chiral covalent framework material has higher BET specific surface area (681 m)2In g), and the pore size distribution curve shows that the material has uniform pore size distribution and is concentrated at 1.59 nm.
Example 2: preparation of bonded beta-keto enamine chiral covalent organic frame capillary column
(1) Pretreatment of a capillary column: a quartz capillary column (10 m.times.0.32 mm) was washed with 1M sodium hydroxide solution for 2 hours, washed with deionized water for 30 minutes, then washed with 0.1M hydrochloric acid for 2 hours, then washed with deionized water until the eluate became neutral, then washed with methanol for 30 minutes, and then the treated capillary was filled with a methanol solution (50%, v/v) of 3-Aminopropyltriethoxysilane (APTES), both ends of the capillary were sealed with rubber stoppers and placed in a 40 ℃ water bath overnight, then the residual solvent was washed out with methanol, and finally heated to 120 ℃ under nitrogen protection and kept for 6 hours to dry the capillary column, thus obtaining an amino-modified capillary for use.
(2) Under the condition of ice-water bath, 2,4, 6-trihydroxy-mesitylene-triformal (4.2mg,0.02mmol), chiral precursor (S) -2, 5-bis (2-methylbutoxy) terephthalic acid dihydrazide (11mg,0.03mmol) and l.0mL of 1, 4-dioxane/mesitylene (1/1, v/v) are placed in a pressure-resistant reaction bottle, fully mixed, and the obtained mixture is aerated with argon for 15-20 minutes to obtain a clear prepolymerization solution. And (3) quickly filling the prepolymerization solution into the amino-modified capillary column obtained in the step (1), sealing two ends of the capillary with rubber plugs, and placing the capillary in a 90 ℃ oven for reaction for 72 hours. And after the reaction is finished, washing the capillary column by using 1, 4-dioxane to remove residues, blowing nitrogen for 2 hours to remove the organic solvent, and finally, carrying out temperature programming aging on the capillary to solidify the coating so as to finally prepare the bonding type beta-keto enamine chiral covalent organic framework gas chromatography capillary column.
The performance of the bonded beta-ketoenamine chiral gas chromatography capillary column prepared in this example was determined as follows:
(1) scanning electron microscope assay
FIG. 7 is a scanning electron microscope image of a cross section of a capillary column of the chiral covalent organic framework gas chromatography of the bonded β -ketoenamine class prepared in this example, showing that a coating layer having a thickness of about 3 μm is bonded on the inner wall of the capillary.
(2) Gas chromatography separation test
FIG. 8 is a capillary column of chiral covalent organic framework gas chromatography of bonded beta-keto enamine prepared in this example, which is used to separate straight-chain alkane including n-C6-C14, n-octane and isooctane, benzene and cyclohexane, and benzene and styrene. Wherein FIG. 8(a) is a separation spectrum of linear alkanes C6-C14; FIG. 8(b) is a graph showing the separation of n-octane and iso-octane; FIG. 8(c) is a separation spectrum of benzene and cyclohexane; FIG. 8(d) is a graph showing the separation of ethylbenzene and styrene. As can be seen from fig. 8, the chromatographic column of the present invention achieves baseline separation for the above mixed components, which illustrates that the capillary column for bonded β -ketoenamine chiral covalent organic framework gas chromatography prepared in this embodiment has a better separation performance.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (2)
1. The application of bonded beta-ketoenamine chiral covalent organic framework capillary column in the separation of the components of ethylbenzene and styrene by gas chromatography; the inner wall of the bonded beta-keto enamine chiral covalent organic framework capillary column is fixed with a covalent organic framework stationary phase in a chemical bond mode, the covalent organic framework stationary phase has a repeating unit shown in a formula (I),
2. the use according to claim 1, wherein said bonded β -ketoenamine chiral covalent organic framework capillary column is prepared by a process comprising the steps of:
s1, carrying out amino modification on a capillary tube to obtain an amino-modified capillary tube;
s2, fully mixing 2,4, 6-trihydroxy mesitylene aldehyde, chiral precursor (S) -2, 5-bis (2-methylbutoxy) terephthalic acid dihydrazide and an organic solvent, and blowing inert gas into the mixture to obtain a pre-polymerization solution;
s3, filling the pre-polymerization liquid obtained in the S2 into the amino-modified capillary tube in the S1, sealing, reacting for 3-5 days at 90-110 ℃, removing the solvent after the reaction is finished, and curing the coating of the capillary tube to obtain the bonded beta-keto-enamine chiral covalent organic framework capillary tube.
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| CN111774036B (en) * | 2020-07-01 | 2021-11-02 | 江南大学 | Covalent organic framework doped liquid chromatography monolithic column and preparation method thereof |
| CN113030354B (en) * | 2021-03-12 | 2022-06-21 | 兰州大学 | Capillary column with COF-LZU8 coating and room-temperature in-situ preparation method thereof |
| CN115304729A (en) * | 2021-05-08 | 2022-11-08 | 中国科学院化学研究所 | High-crystallinity chiral two-dimensional covalent organic framework material and preparation method thereof |
| CN114192118B (en) * | 2021-11-16 | 2022-09-23 | 江南大学 | Bonded three-dimensional covalent organic framework chromatographic column and separation application thereof |
| CN113929921B (en) * | 2021-11-24 | 2022-12-20 | 青岛理工大学 | Covalent organic framework material with sulfydryl functionalized beta-keto enamine structure and preparation method and application thereof |
| CN114349975B (en) * | 2022-02-22 | 2023-01-06 | 国科大杭州高等研究院 | Covalent organic framework material containing imine bond and beta ketoenamine bond simultaneously and preparation method and application thereof |
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