CN116550310B - Chromatographic column based on covalent organic framework and preparation method and application thereof - Google Patents
Chromatographic column based on covalent organic framework and preparation method and application thereof Download PDFInfo
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- CN116550310B CN116550310B CN202310522794.7A CN202310522794A CN116550310B CN 116550310 B CN116550310 B CN 116550310B CN 202310522794 A CN202310522794 A CN 202310522794A CN 116550310 B CN116550310 B CN 116550310B
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000004817 gas chromatography Methods 0.000 claims abstract description 11
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 11
- 150000001298 alcohols Chemical class 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000007822 coupling agent Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 11
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 8
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- 230000006911 nucleation Effects 0.000 claims description 4
- 238000010899 nucleation Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical group C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 229960003638 dopamine Drugs 0.000 claims description 3
- 150000007524 organic acids Chemical group 0.000 claims description 3
- 150000001448 anilines Chemical group 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 238000013375 chromatographic separation Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 238000004587 chromatography analysis Methods 0.000 description 22
- 239000007789 gas Substances 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000013078 crystal Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000796 flavoring agent Substances 0.000 description 10
- 235000019634 flavors Nutrition 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000013482 COF 303 Substances 0.000 description 9
- 230000005526 G1 to G0 transition Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- KUDPGZONDFORKU-UHFFFAOYSA-N n-chloroaniline Chemical compound ClNC1=CC=CC=C1 KUDPGZONDFORKU-UHFFFAOYSA-N 0.000 description 7
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 description 7
- 238000005191 phase separation Methods 0.000 description 7
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical class CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 150000003738 xylenes Chemical class 0.000 description 6
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- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 4
- QMQDJVIJVPEQHE-UHFFFAOYSA-N 2-methoxy-3-(1-methylpropyl) pyrazine Chemical group CCC(C)C1=NC=CN=C1OC QMQDJVIJVPEQHE-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- -1 hydrophobicity Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000005199 trimethylbenzenes Chemical class 0.000 description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229940117389 dichlorobenzene Drugs 0.000 description 3
- 239000005350 fused silica glass Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 3
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- 230000009467 reduction Effects 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical group ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- YAIMUUJMEBJXAA-UHFFFAOYSA-N 2-(2-methylpropyl)pyrazine Chemical compound CC(C)CC1=CN=CC=N1 YAIMUUJMEBJXAA-UHFFFAOYSA-N 0.000 description 2
- RAFHQTNQEZECFL-UHFFFAOYSA-N 2-Ethyl-6-methylpyrazine Chemical compound CCC1=CN=CC(C)=N1 RAFHQTNQEZECFL-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000004816 dichlorobenzenes Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- HCRBXQFHJMCTLF-ZCFIWIBFSA-N ethyl (2r)-2-methylbutanoate Chemical compound CCOC(=O)[C@H](C)CC HCRBXQFHJMCTLF-ZCFIWIBFSA-N 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 150000003216 pyrazines Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- 239000001908 2-ethyl-5-methylpyrazine Substances 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 238000003965 capillary gas chromatography Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 239000001813 ethyl (2R)-2-methylbutanoate Substances 0.000 description 1
- 229940090910 ethyl 2-methylbutyrate Drugs 0.000 description 1
- XTCQUBCCCSJAKJ-UHFFFAOYSA-N ethylbenzene Chemical compound CCC1=CC=CC=C1.CCC1=CC=CC=C1 XTCQUBCCCSJAKJ-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/20—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the sorbent material
- B01D15/206—Packing or coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/22—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the construction of the column
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
- B01D15/38—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving specific interaction not covered by one or more of groups B01D15/265 - B01D15/36
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/286—Phases chemically bonded to a substrate, e.g. to silica or to polymers
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3092—Packing of a container, e.g. packing a cartridge or column
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- B01J2220/86—Sorbents applied to inner surfaces of columns or capillaries
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/025—Gas chromatography
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Abstract
The invention relates to a chromatographic column based on a covalent organic framework, and a preparation method and application thereof, and belongs to the technical field of chromatographic separation. Filling an amino coupling agent solution into a capillary tube for reaction, and then washing and drying to obtain an amino modified capillary tube; (2) Filling 1,3,5, 7-tetra (4-benzaldehyde) -adamantane solution into the amino modified capillary tube for reaction, and then washing and drying to obtain the 1,3,5, 7-tetra (4-benzaldehyde) -adamantane modified capillary tube; (3) Filling the pre-polymerized liquid of the covalent organic framework into the 1,3,5, 7-tetra (4-benzaldehyde) -adamantane modified capillary, standing for 10-30 days, and then introducing the capillary into a gas chromatograph for heating and aging to obtain the chromatographic column based on the covalent organic framework. The chromatographic column based on the covalent organic framework has excellent separation effect in the application of separating isomers, normal paraffins or normal alcohols by gas chromatography.
Description
Technical Field
The invention belongs to the technical field of chromatographic separation, and particularly relates to a chromatographic column based on a covalent organic framework, and a preparation method and application thereof.
Background
Covalent Organic Frameworks (COFs) have shown great potential in chromatography by virtue of their topological, pore and functional designability as a novel porous organic polymer. In contrast to the conventional commercial stationary phase, COFs may be incorporated into the material including molecular sieves, hydrophobicity, hydrogen bonding the synergy of various forces including pi-pi and C-H, so as to effectively improve the separation performance. Thus, COFs exhibit better isomer and enantiomer separation than conventional commercial stationary phases. However, COFs as a chromatographic stationary phase are essentially polycrystalline. The irregular shape and incomplete crystalline forms of polycrystalline COFs not only limit the separation effect, but also prevent the adjustment of particle size to find the particle size most suitable for chromatographic separation.
Monocrystalline COFs means that the entire crystal consists of the same spatial lattice in three dimensions, resulting in a long-range order of the particles. The complete and regular crystal structure of the single crystal COFs enables the pore blocking and mass transfer resistance of the single crystal COFs to be far smaller than that of the polycrystalline COFs, and the chromatographic separation performance of the single crystal COFs is promoted. Single-crystal COFs have been initially explored for their chromatographic separation performance as liquid chromatography immobilization, but single-crystal COFs have yet to be further studied as a gas chromatography stationary phase. Therefore, the utilization of single-crystal covalent organic frameworks as capillary gas chromatography immobilization for efficient separation of isomers is of great importance.
Disclosure of Invention
Therefore, the invention aims to solve the technical problems of irregular shape, poor crystal form, low separation performance and the like of the polycrystalline COFs in the prior art.
In order to solve the technical problems, the invention provides a chromatographic column based on a covalent organic framework, and a preparation method and application thereof.
It is a first object of the present invention to provide a method for preparing a chromatography column based on a covalent organic framework, comprising the steps of,
(1) Filling an amino coupling agent solution into the capillary tube for reaction, and then washing and drying to obtain an amino modified capillary tube;
(2) Filling 1,3,5, 7-tetra (4-benzaldehyde) -adamantane solution into the amino modified capillary tube in the step (1) for reaction, and then washing and drying to obtain the 1,3,5, 7-tetra (4-benzaldehyde) -adamantane modified capillary tube;
(3) Filling the pre-polymerized liquid of the covalent organic framework into the 1,3,5, 7-tetra (4-benzaldehyde) -adamantane modified capillary tube in the step (2), standing for 10-30 days, and then introducing the capillary tube into a gas chromatograph for heating and aging to obtain the chromatographic column based on the covalent organic framework; the pre-polymerized liquid of the covalent organic framework is prepared by dissolving 1,3,5, 7-tetra (4-benzaldehyde) -adamantane, p-phenylenediamine, a catalyst and a nucleation inhibitor in a solvent.
In one embodiment of the present invention, in step (1), the amino coupling agent is selected from one or more of 3-aminopropyl trimethoxysilane, aminopropyl trimethoxysilane and dopamine.
In one embodiment of the invention, in step (1), the temperature of the reaction is from 30 ℃ to 80 ℃; the reaction time is 4h-18h.
In one embodiment of the invention, in step (2), the temperature of the reaction is 40 ℃ to 100 ℃; the reaction time is 2-12 h.
In one embodiment of the invention, in step (3), the catalyst is selected from organic acids; the nucleation inhibitor is selected from anilines; the solvent is selected from 1, 4-dioxane.
Further, the organic acid is selected from formic acid and/or acetic acid.
In one embodiment of the present invention, in step (3), the molar ratio of 1,3,5, 7-tetrakis (4-benzaldehyde) -adamantane to p-phenylenediamine is 1:2 to 2.2.
In one embodiment of the invention, in the step (3), the temperature rise and aging are divided into two stages, wherein the first stage is to raise the temperature to 80-90 ℃ at a rate of 2-2.5 ℃ per minute for 30-40 min; the first stage is to raise the temperature to 220-240 deg.c at the rate of 2-2.5 deg.c/min for 2-3 hr.
In one embodiment of the invention, in step (3), the time of the standing reaction is 14 to 16 days.
It is a second object of the present invention to provide a chromatography column based on a covalent organic framework prepared by the method described.
A third object of the present invention is to provide the use of a chromatography column based on a covalent organic framework as described for separating isomers, normal paraffins or normal alcohols.
A fourth object of the present invention is to provide the use of a chromatography column based on a covalent organic framework as described in the field of gas chromatographic separations.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) The stationary phase in the chromatographic column based on the covalent organic framework is of a single crystal type, and compared with a polymorphic covalent organic framework, the chromatographic column based on the covalent organic framework has a more regular shape, so that the pore blocking phenomenon and the mass transfer resistance are far smaller than those of the polymorphic covalent organic framework, and the separation performance is better.
(2) The single crystal covalent organic framework in the chromatographic column based on the covalent organic framework can be regulated and controlled by the growth time, so that the chromatographic column with the single crystal covalent organic framework with different particle sizes can be obtained by different growth times, and a better separation effect can be obtained.
(3) The chromatographic column based on the covalent organic framework has good analysis effect on common normal alkane, normal alcohol and other substances, and successfully realizes high-efficiency gas chromatographic separation of xylene, dichlorobenzene, pinene, trimethylbenzene, nitrotoluene, chloroaniline and other isomers. The separation performance advantage of the chromatographic column based on the covalent organic framework and the huge separation potential in food flavor substances are fully exhibited.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which:
FIG. 1 is a reaction diagram showing the preparation of SCOF-303 in a capillary tube in example 1 of the present invention.
FIG. 2 is a representation of a capillary chromatography column covalently bonded to bare capillary, SCOF-303 in example 1 of the present invention; wherein a is an X-ray powder diffraction (PXRD) diagram of a bare capillary, SCOF-303, and a capillary chromatographic column covalently bonded with SCOF-303; b is a Fourier transform infrared Spectroscopy (FTIR) diagram of a bare capillary, SCOF-303 covalently bonded capillary chromatographic column; c is a Scanning Electron Microscope (SEM) image of the edge of the SCOF-303 covalently bonded capillary chromatographic column; d is a Scanning Electron Microscope (SEM) image of the SCOF-303 covalently bonded capillary column inner wall.
FIG. 3 is a Scanning Electron Microscope (SEM) image of a bare capillary according to example 1 of the present invention.
FIG. 4 is a gas phase separation isomer chromatogram of SCOF-303 covalently bonded capillary chromatography column of test example 1 of the present invention; wherein a is xylene isomer; b is dichlorobenzene isomer; c is a trimethylbenzene isomer; d is pinene isomer; e is nitrotoluene isomer; f is an isomer of chloroaniline.
FIG. 5 is a gas phase separation isomer chromatogram of a polycrystalline COF-303 covalently bonded capillary column of test example 1 of the present invention; wherein a is xylene isomer; b is dichlorobenzene isomer; c is a trimethylbenzene isomer; d is pinene isomer; e is nitrotoluene isomer; f is an isomer of chloroaniline.
FIG. 6 is a chromatogram of a gas phase separation series of normal paraffins and alcohols for SCOF-303 covalently bonded capillary chromatography column of test 2-3 according to the invention; wherein a is normal alkane; b is an n-alcohol.
FIG. 7 is a chromatogram of alcohol isomers in a gas phase separation food flavor of SCOF-303 covalently bonded capillary chromatography column of test example 4 according to the present invention; wherein a is butanol isomer; b is the pentanol isomer.
FIG. 8 is a chromatogram of ester isomers in a gas phase separation of food flavor using SCOF-303 covalently bonded capillary chromatography column according to test example 5 of the present invention; wherein a is the C 6H12O2 isomer; b is the C 7H14O2 isomer.
FIG. 9 is a chromatogram of pyrazine isomer in SCOF-303 covalently bonded capillary column vapor separation food flavor according to test example 6 of the present invention; wherein a is 2-ethyl-3/5/6-methylpyrazine; b is 2-methoxy-3-sec/isobutyl pyrazine.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
In the present invention, unless otherwise indicated, the capillary used is a fused silica capillary.
Example 1
Referring to fig. 1, the chromatographic column based on covalent organic frameworks and the preparation method thereof specifically comprise the following steps:
(1) The capillary (10M long x 0.53mm inside diameter) was sequentially treated with 1M sodium hydroxide (NaOH) for 2h,0.1M hydrochloric acid (HCl) for 2h, water until effluent ph=7.0, then methanol for 30min.
(2) The capillary tube was filled with a methanol solution (50%, v/v) of 3-aminopropyl trimethoxysilane (APTES), reacted overnight at 40 ℃, rinsed with methanol, dried with nitrogen flow at 120 ℃ for 2h, further filled with an ethanol solution of 1,3,5, 7-tetrakis (4-benzaldehyde) -adamantane (TFPM) (21.6 mg TFPM in 3mL ethanol), and reacted at 60 ℃ for 2h.
(3) The capillary column was rinsed with methanol to rinse off the residue and dried with a nitrogen stream at 120 ℃ for 2h to obtain TFPM modified capillaries.
(4) TFPM (4.32 mg,0.01 mmol), p-Phenylenediamine (PA) (2.16 mg,0.02 mmol), aqueous acetic acid (0.2 mL, 6M), aniline (0.24 mL,104 eq.) and 1, 4-dioxane (3 mL) were dissolved and mixed well to give a pre-polymerized solution of single crystal COF-303 (SCOF-303), which was rapidly injected into TFPM modified capillaries and reacted at room temperature for 15 days.
(5) After washing off unbound SCOF-303 with ethanol, introducing into a gas chromatograph, aging with programmed temperature rise, maintaining at 80deg.C for 30min, heating to 220deg.C at a rate of 2deg.C/min, and maintaining for 2 hr to obtain SCOF-303 covalently bonded capillary chromatographic column.
Characterization of bare capillary, SCOF-303 covalently bonded capillary chromatography columns was performed and the results are shown in FIGS. 2-3. It can be seen from FIG. 2a that the SCOF-303 powder is similar to the SCOF-303PXRD pattern bonded to the quartz plate, indicating that SCOF-303 grown on the inner walls of the capillaries has a high degree of crystallinity. As can be seen from FIG. 2b, the COF-303 covalently bonded capillary chromatography column has both capillary and FTIR peaks of SCOF-303, further demonstrating the success of the preparation of SCOF-303 covalently bonded capillary chromatography column. As can be seen from FIGS. 2c, 2d and 3, the presence of SCOF-303 particles of regular shape and size covalently bonded to the inner wall of the capillary column of SCOF-303, in contrast to the bare capillary, also demonstrates the success of bonding SCOF-303 to the inner wall of the capillary.
Example 2
The invention relates to a chromatographic column based on a covalent organic framework and a preparation method thereof, which specifically comprise the following steps:
Essentially the same as in example 1, except that fused silica capillaries (0.2 m-100 m) of different lengths were used in step (1), the other conditions were unchanged, and the characterization results of the prepared capillary chromatographic column were similar to those of example 1.
Example 3
The invention relates to a chromatographic column based on a covalent organic framework and a preparation method thereof, which specifically comprise the following steps:
Essentially the same as in example 1, except that fused silica capillaries (0.075 mm-0.53 mm) of different inner diameters were used in step (1), the other conditions were unchanged, and the characterization results of the prepared capillary chromatographic column were similar to example 1.
Example 4
The invention relates to a chromatographic column based on a covalent organic framework and a preparation method thereof, which specifically comprise the following steps:
Essentially the same as in example 1, except that dopamine was used instead of APTES to modify the capillary tube in step (2), the other conditions were unchanged, and the characterization results of the prepared capillary chromatographic column were similar to example 1.
Example 5
The invention relates to a chromatographic column based on a covalent organic framework and a preparation method thereof, which specifically comprise the following steps:
Essentially the same as in example 1, except that aminopropyl trimethoxysilane was used in step (2) instead of APTES to modify the capillary tube, the other conditions were unchanged, and the characterization of the prepared capillary column was similar to example 1.
Example 6
The invention relates to a chromatographic column based on a covalent organic framework and a preparation method thereof, which specifically comprise the following steps:
essentially the same as in example 1, except that the reaction was carried out in step (4) for a different period of time (10-30 days) and the other conditions were unchanged, the characterization results of the capillary chromatography column obtained were similar to those of example 1.
Comparative example 1
The gas chromatographic column based on the polycrystalline covalent organic framework and the preparation method thereof specifically comprise the following steps:
(1) The capillary (10M long x 0.53mm inside diameter) was sequentially treated with 1M sodium hydroxide (NaOH) for 2h,0.1M hydrochloric acid (HCl) for 2h, water until effluent ph=7.0, then methanol for 30min.
(2) The capillary tube was filled with a methanol solution (50%, v/v) of 3-aminopropyl trimethoxysilane (APTES), reacted overnight at 40 ℃, rinsed with methanol, dried with nitrogen flow at 120 ℃ for 2h, further filled with an ethanol solution of 1,3,5, 7-tetrakis (4-benzaldehyde) -adamantane (TFPM) (21.6 mg TFPM in 3mL ethanol), and reacted at 60 ℃ for 2h.
(3) The capillary column was rinsed with methanol to rinse off the residue and dried with a nitrogen stream at 120 ℃ for 2h to obtain TFPM modified capillaries.
(4) TFPM (21.6 mg,0.05 mmol), p-phenylenediamine (PA, 16.3mg,0.10 mmol), aqueous acetic acid (0.2 mL, 6M), N, N-dimethylacetamide/tetrahydrofuran (DMAC/THF, v/v=1/2, 2.0 mL) were dissolved and mixed uniformly to give a pre-polymerized solution of polycrystalline COF-303, which was rapidly injected into TFPM modified capillaries and reacted at 90℃for 1 day.
(5) After washing off unbound polycrystalline COF-303 with ethanol, introducing into a gas chromatograph, aging with programmed temperature rise, maintaining at 80deg.C for 30min, heating to 220deg.C at a rate of 2deg.C/min, and maintaining for 2 hr to obtain polycrystalline COF-303 covalent bonding capillary chromatographic column.
Test example 1
(1) The SCOF-303 prepared in example 1 was used to gas phase separate xylene, dichlorobenzene, trimethylbenzene, pinene, nitrotoluene, and chloroaniline isomers using a covalently-bonded capillary chromatography column. The SCOF-303 covalent bonding capillary chromatographic column (10 m multiplied by 0.53 mm) is used as a gas chromatographic stationary phase, and six groups of isomers are subjected to constant temperature separation under different N 2 flow rates and different temperature conditions, and the result is shown in figure 4. As can be seen from FIG. 4, the baseline separation of six isomers can be realized on SCOF-303 covalently bonded capillary chromatographic column, the xylene isomer condition is that the temperature is 260 ℃, the flow rate of N 2 is 120cm s -1, the separation degree is 2.55-3.63, and the column efficiency is 5131-7879 plates/meter; The dichlorobenzene isomer condition is that the temperature is 280 ℃, the flow rate of N 2 is 120cm s -1, the separation degree is 3.29-3.52, and the column efficiency is 4163-5581 plates/meter; the trimethylbenzene isomer condition is that the temperature is 280 ℃, the flow rate of N 2 is 160cm s -1, the separation degree is 3.40-6.80, and the column efficiency is 1642-2410 plates/m; The pinene isomer condition is that the temperature is 220 ℃, the flow rate of N 2 is 60cm s -1, the separation degree is 1.30, and the column efficiency is 1199-1250 plates/meter; the conditions of the nitrotoluene isomer are that the temperature is 280 ℃, the flow rate of N 2 is 120cm s -1, the separation degree is 1.68-11.75, and the column efficiency is 5945-7028 plates/meter; The condition of chloroaniline isomer is that the temperature is 260 ℃, the flow rate of N 2 is 120cm s -1, the separation degree is 3.11-3.65, and the column efficiency is 3468-4937 plates/meter.
(2) The polycrystalline COF-303 prepared in comparative example 1 was used to gas phase separate isomers of xylene, dichlorobenzene, trimethylbenzene, pinene, nitrotoluene, chloroaniline, etc., by covalent bonding to a capillary chromatography column. The polycrystalline COF-303 covalent bonding capillary chromatographic column (10 m multiplied by 0.53 mm) is used as a gas chromatographic stationary phase, and six groups of isomers are subjected to constant temperature separation under different N 2 flow rates and different temperature conditions, and the result is shown in figure 5. As can be seen from FIG. 5, the baseline separation of six isomers was not achieved on SCOF-303 covalently bonded capillary chromatographic columns, and the xylene isomers were at a temperature of 220℃and a flow rate of N 2 of 20cm s -1, a degree of separation of 1.17-2.03, and a column efficiency of 1566-2781 plates/meter; The dichlorobenzene isomer condition is that the temperature is 240 ℃, the flow rate of N 2 is 20cm s -1, the separation degree is 0.54-3.00, and the column efficiency is 3286-3972 plates/meter; the trimethylbenzene isomer is prepared by the steps of heating to 240 ℃, flowing at the speed of N 2 for 20cm s -1, separating at 1.47-3.24, and performing column effect of 804-1152 plates/m; The pinene isomer condition is that the temperature is 160 ℃, the flow rate of N 2 is 20cm s -1, the separation degree is 1.37, and the column efficiency is 458-528 plates/meter; the conditions of the nitrotoluene isomer are that the temperature is 280 ℃, the flow rate of N 2 is 120cm s -1, the separation degree is 1.66-6.22, and the column efficiency is 1022-2219 plates/meter; The condition of chloroaniline isomer is that the temperature is 240 ℃, the flow rate of N 2 is 120cm s -1, the separation degree is 2.41-3.01, and the column efficiency is 1075-1537 plates/meter. The separation time of the polycrystalline COF-303 capillary column in the separation of six isomers is longer, the separation degree is poorer, and the column efficiency is lower.
Test example 2
The SCOF-303 prepared in example 1 was used to separate a series of normal paraffins including pentane, hexane, heptane, octane, nonane, decane, etc. from a gas phase by means of a covalently bonded capillary chromatographic column. The result of using SCOF-303 covalently bonded capillary chromatographic column (10 m×0.53 mm) as gas chromatographic stationary phase, N 2 flow rate 180cm s -1, constant temperature 240 ℃ to end of separation is shown in FIG. 6 a. As can be seen from FIG. 6a, the results obtained a baseline separation of 6 normal paraffins having a broader boiling point range on a SCOF-303 covalently bonded capillary chromatography column.
Test example 3
The SCOF-303 prepared in example 1 was used to covalently bond to a capillary column for gas phase separation of a series of normal alcohols including propanol, butanol, pentanol, hexanol, heptanol, and the like. The result of using SCOF-303 covalently bonded capillary chromatographic column (10 m×0.53 mm) as gas chromatographic stationary phase, N 2 flow rate 180cm s -1, constant temperature 220 ℃ to end of separation is shown in FIG. 6 b. As can be seen from FIG. 6b, the results indicate that the five normal alcohols are completely separated on the SCOF-303 covalently bonded capillary chromatographic column.
Test example 4
The alcohol isomers in the food flavor, including the isomers in the food flavor such as butanol, pentanol, etc., were gas-phase separated using the SCOF-303 covalently bonded capillary column prepared in example 1, and the results are shown in FIG. 7. As can be seen from FIG. 7, baseline separation of 2 isomers was achieved on SCOF-303 covalently bonded capillary chromatography column, butanol isomer at 120℃and N 2 flow rate of 20cm s -1, separation of 1.58; the pentanol isomer conditions were 160℃and N 2 flow rate of 20cm s -1 and degree of separation of 2.08.
Test example 5
The ester isomers in the food flavor were gas-phase separated by using the SCOF-303 prepared in example 1 and the isomers in the food flavor including ethyl butyrate, ethyl 2-methylbutyrate and the like were separated by using a capillary column chromatography, and the results are shown in FIG. 8. As can be seen from FIG. 8, the baseline separation of 2 isomers was achieved on SCOF-303 covalently bonded capillary chromatographic column, with the C 6H12O2 isomer condition being 240℃and N 2 flow rate of 120cm s -1, and the degree of separation of 2.12-2.67; the C 7H14O2 isomer condition is that the temperature is 260 ℃, the flow rate of N 2 is 120cm s -1, and the separation degree is 4.19-9.26.
Test example 6
The results of gas phase separation of pyrazine isomers in food flavor substances, including isomers in food flavor substances such as 2-ethyl-6-methyl pyrazine and 2-methoxy-3-sec-butyl pyrazine, using the SCOF-303 prepared in example 1 are shown in FIG. 9. As can be seen from FIG. 9, the 2 isomers all achieved baseline separation on SCOF-303 covalently bonded capillary chromatographic column, 2-ethyl-3/5/6-methylpyrazine at a temperature of 260℃and a N 2 flow rate of 80cm s -1, and a separation degree of 2.04-11.06; the conditions for 2-methoxy-3-sec/isobutyl pyrazine were a temperature of 280℃and a flow rate of N 2 of 120cm s -1 and a degree of separation of 2.65.
Test example 7
The reproducibility of the SCOF-303 covalently bonded capillary chromatography column was studied using xylene isomers as analytes and the results are shown in Table 1:
TABLE 1
As can be seen from Table 1, the relative standard deviation in the day (8 times) and the relative standard deviation in the day (8 days) (RSD) were 0.03% -0.06% and 0.27% -0.39%, respectively, indicating good reproducibility of the SCOF-303 covalently bonded capillary chromatography column.
Test example 8
The stability of the SCOF-303 covalently bonded capillary chromatography column was studied using xylene isomers as analytes and the results are shown in Table 2:
TABLE 2
| Analyte(s) | Column efficiency reduction (%) | Capacity factor reduction (%) |
| Ethylbenzene (ethylbenzene) | 2.0 | 1.2 |
| Para-xylene | 0.2 | 1.4 |
| Meta-xylene | 1.9 | 1.0 |
| Ortho-xylene | 0.7 | 1.0 |
As can be seen from Table 2, the column efficiency and capacity factor reductions were 0.2% -1.9% and 1.0% -1.4%, respectively, indicating good reproducibility of the SCOF-303 covalently bonded capillary chromatography column.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (9)
1. A gas chromatographic column based on a covalent organic framework is characterized in that the preparation method of the gas chromatographic column based on the covalent organic framework comprises the following steps,
(1) Filling an amino coupling agent solution into the capillary tube for reaction, and then washing and drying to obtain an amino modified capillary tube;
(2) Filling 1,3,5, 7-tetra (4-benzaldehyde) -adamantane solution into the amino modified capillary tube in the step (1) for reaction, and then washing and drying to obtain the 1,3,5, 7-tetra (4-benzaldehyde) -adamantane modified capillary tube;
(3) Filling the pre-polymerized liquid of the covalent organic framework into the 1,3,5, 7-tetra (4-benzaldehyde) -adamantane modified capillary tube in the step (2), standing for 10-30 days, and then introducing the capillary tube into a gas chromatograph for heating and ageing to obtain the gas chromatographic column based on the covalent organic framework; the pre-polymerized liquid of the covalent organic framework is prepared by dissolving 1,3,5, 7-tetra (4-benzaldehyde) -adamantane, p-phenylenediamine, a catalyst and a nucleation inhibitor in a solvent.
2. The covalent organic framework based gas chromatography column of claim 1, wherein in step (1) the amino coupling agent is selected from one or more of 3-aminopropyl trimethoxysilane, aminopropyl trimethoxysilane and dopamine.
3. The covalent organic framework based gas chromatography column of claim 1, wherein in step (1), the temperature of the reaction is 30-80 ℃; the reaction time is 4h-18h.
4. The covalent organic framework based gas chromatography column of claim 1, wherein in step (2), the temperature of the reaction is 40-100 ℃; the reaction time is 2-12 h.
5. The covalent organic framework based gas chromatography column according to claim 1, wherein in step (3) the catalyst is selected from organic acids; the nucleation inhibitor is selected from anilines; the solvent is selected from 1, 4-dioxane.
6. The covalent organic framework based gas chromatography column of claim 1, wherein in step (3), the molar ratio of 1,3,5, 7-tetrakis (4-benzaldehyde) -adamantane to p-phenylenediamine is 1:2-2.2.
7. The covalent organic framework-based gas chromatography column of claim 1, wherein in step (3), the elevated temperature aging is divided into two stages, the first stage being an elevated temperature to 80-90 ℃ at a rate of 2-2.5 ℃/min for 30-40 min; the first stage is to raise the temperature to 220-240 deg.c at the rate of 2-2.5 deg.c/min for 2-3 hr.
8. Use of a gas chromatography column based on a covalent organic framework according to any one of claims 1-7 for separating isomers, normal paraffins or normal alcohols.
9. Use of a gas chromatography column based on a covalent organic framework according to any one of claims 1-7 in the field of gas chromatography separation.
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