CN115322201B - Macrocyclic column aromatic compound, and preparation method and application thereof - Google Patents
Macrocyclic column aromatic compound, and preparation method and application thereof Download PDFInfo
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- 150000001491 aromatic compounds Chemical class 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- -1 cyclic aliphatic compound Chemical class 0.000 claims abstract description 11
- 230000005526 G1 to G0 transition Effects 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 11
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 9
- 229920002866 paraformaldehyde Polymers 0.000 claims description 9
- 238000004817 gas chromatography Methods 0.000 claims description 8
- UWMCHDDHXMFKMA-UHFFFAOYSA-N (2,5-dimethoxyphenyl)methanamine Chemical compound COC1=CC=C(OC)C(CN)=C1 UWMCHDDHXMFKMA-UHFFFAOYSA-N 0.000 claims description 6
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000006482 condensation reaction Methods 0.000 claims description 5
- 238000013375 chromatographic separation Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000000926 separation method Methods 0.000 abstract description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 4
- 230000002950 deficient Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 74
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 37
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 13
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000002955 isolation Methods 0.000 description 4
- 150000002678 macrocyclic compounds Chemical class 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical class COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
-
- 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
- B01D15/265—Adsorption chromatography
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
The invention discloses a macrocyclic aromatic compound, a preparation method and application thereof. The large-ring column aromatic compound has a symmetrical structure of a nano-size electron-deficient cavity, has good solubility in common organic solvents such as dichloromethane, chloroform, acetone and DMF, and has good thermal stability, and when the large-ring column aromatic compound is used as a stationary phase of a gas chromatographic column to separate an aromatic compound from a cyclic aliphatic compound, the separation efficiency is high, the separation temperature is low, the material residence time is short, and the packed column has the advantages of simple preparation method, high stability and reusability. The preparation method of the large ring column aromatic compound is simple, has low cost and can realize large-scale production.
Description
Technical Field
The invention relates to a column aromatic hydrocarbon, in particular to a macrocyclic column aromatic hydrocarbon compound, and also relates to a preparation method and application thereof, belonging to the field of organic synthesis.
Background
Since the first discovery of crown ethers in 1967 c.j.petersen, supramolecular chemistry has received great attention, particularly in the development and creation of new synthetic macrocyclic compounds with specific host-guest properties. Synthetic macrocyclic hosts such as calixarenes, resorcinol aromatics, cyclotriveratenes, column aromatics, and the like have been widely studied and applied to supramolecular self-assembly, molecular machines, stimuli-responsive materials, adsorptive separations, and the like.
Light hydrocarbons, i.e., C1-C9 hydrocarbons, such as benzene (PhH), cyclohexane (Cy), toluene (Tol) and methylcyclohexane (MCy) are important chemical feedstocks and solvents for use in large amounts in the petrochemical industry. PhH and Tol hydrogenation can produce Cy and MCy, respectively, but still a trace amount of unreacted residual starting material cannot be avoided. The separation of the unreacted mixture of PhH and Cy or Tol and MCy is critical to the production of high grade PhH, cy, tol and MCy feedstock chemicals for further conversion to more useful commodity products. However, the subtle differences in boiling points and similar physical properties of PhH and Cy, tol and MCy make it almost impossible to separate them by conventional distillation processes. Thus, the isolation of these benzene derivatives is considered one of the most critical separations that can change the world.
In recent years, various synthetic macrocyclic compounds have been developed which can efficiently and energy-effectively separate high-purity cyclic aliphatic compounds from the corresponding aromatic compounds, but their synthesis is relatively complicated, yield is relatively low, and separation means are relatively cumbersome. Chromatography is one of the most effective methods for separating complex mixtures. However, the use of synthetic macrocycles in chromatography has been rarely explored, and in particular the synthesis of functional macrocycles capable of separating PhH/Cy or Tol/MCy in chromatography remains a great challenge.
Disclosure of Invention
Based on the problems of difficult separation, low separation efficiency and the like of the prior PhH/Cy or Tol/MCy, the first aim of the invention is to provide a macrocyclic aromatic compound which can effectively separate the PhH/Cy or Tol/MCy.
The second aim of the invention is to provide a preparation method of the macrocyclic aromatic compound, which is simple and easy to implement, has higher yield and low production cost, and can realize mass production.
The third object of the present invention is to provide an application of a macrocyclic aromatic compound as a chromatographic stationary phase for separating and purifying aromatic compounds and cyclic aliphatic compounds, which has excellent separation efficiency, low separation temperature, high stability of the prepared packed column and reusability.
In order to achieve the above technical object, the present invention provides a macrocyclic aromatic compound having a structure represented by formula 1:
the compound is a 3,3', 4' -biphenyl tetracarboxylic diimide extended macrocyclic column aromatic compound, has a symmetrical structure of a nanoscale electron-deficient cavity, shows good solubility in common organic solvents such as dichloromethane, chloroform, acetone, DMF and the like, and has good thermal stability.
The invention also provides a preparation method of the macrocyclic aromatic compound, which comprises the steps of carrying out imidization reaction on 2, 5-dimethoxy benzylamine and 3,3', 4' -biphenyl tetracarboxylic dianhydride to obtain an intermediate, and carrying out condensation reaction on the intermediate and paraformaldehyde to obtain the macrocyclic aromatic compound;
the intermediate has a structure shown in formula 2:
the method has the advantages of simple preparation process, mild conditions and higher product yield, and is beneficial to large-scale production.
As a preferable scheme, the molar ratio of the 2, 5-dimethoxy benzylamine to the 3,3', 4' -biphenyl tetracarboxylic dianhydride is 2-2.5:1. In the reaction process, the molar ratio of the 2, 5-dimethoxy benzylamine to the 3,3', 4' -biphenyl tetracarboxylic dianhydride is controlled in a proper range, so that the problems of sufficient reaction, fewer product impurities, incomplete reaction, low product yield, raw material waste and the like can be ensured.
As a preferable scheme, the imidization reaction temperature is 100-120 ℃ and the time is 8-16 h. In the imidization reaction process, the temperature and the time are required to be controlled in a proper range, the reaction temperature is too low or the reaction time is too short, the incomplete reaction can be caused, the yield is reduced, and otherwise, the reaction temperature is too high or the reaction time is too long, the comprehensive efficiency is reduced, the energy consumption is increased, and the resource is wasted.
As a preferable scheme, the molar ratio of the intermediate to the paraformaldehyde is 1:3-5. The molar ratio of the intermediate to the paraformaldehyde is controlled within a specific range to ensure the synthesis efficiency, and if the molar ratio of the intermediate to the paraformaldehyde is too low, incomplete reaction can be caused, and the yield is reduced; if the molar ratio of the intermediate to the paraformaldehyde is too high, the paraformaldehyde is wasted, and the production cost is increased.
As a preferable scheme, the temperature of the condensation reaction is 50-80 ℃ and the time is 8-12 h. In the condensation reaction process, the reaction temperature and time are controlled in a proper range, so that the reaction efficiency can be improved, the reaction time is too short, the reaction is incomplete, the yield is reduced, and the energy consumption is increased and even byproducts are generated due to too high temperature and too long time.
The invention also provides application of the macrocyclic aromatic compound, which is applied as a chromatographic stationary phase. The application of the macrocyclic aromatic compound in the chromatograph can realize the separation of complex mixtures, broaden the application range of the macrocyclic aromatic and improve the application value thereof.
As a preferred embodiment, the solid phase is used as a stationary phase for gas chromatography to separate aromatic compounds from cyclic aliphatic compounds. As a more preferred embodiment, the aromatic compound and the cyclic aliphatic compound are benzene/cyclohexane or toluene/methylcyclohexane. Since the macrocyclic aromatic compounds have electron-deficient holes, they introduce non-covalent interactions such as C-H. Pi., C-H. O and charge transfer interactions, which facilitate separation of structurally similar molecules, particularly aromatic and cycloaliphatic compounds. The packed column prepared from the macrocyclic aromatic compound has high stability, can be reused, has less required macrocyclic aromatic load, and has low separation temperature, short retention time of separated materials and high separation efficiency.
As a preferable mode, in the gas chromatographic separation process, the volume ratio of the aromatic compound to the cyclic aliphatic compound is controlled to be 1-9: 1 range.
As a preferable mode, the column temperature of the gas chromatography is 35-50 ℃. In the chromatographic separation process, the column temperature needs to be regulated in a proper range to achieve the optimal separation efficiency, and the separation of raw materials is not facilitated due to the fact that the column temperature is too high or too low.
Compared with the prior art, the invention has the following advantages:
(1) The preparation method is simple, low in cost and high in yield, and can realize large-scale production.
(2) The macrocyclic aromatic compound has a symmetrical structure with a nanoscale electron-deficient cavity, which is beneficial to separating molecules with similar structures, in particular aromatic and cycloaliphatic compounds.
(3) When the packed column is used as a gas chromatography stationary phase for separating aromatic compounds and cyclic aliphatic compounds, the preparation method of the packed column is simple, the column length can be shortened to 1 meter, the stability is high, the packed column can be repeatedly used, the required loading amount of the macrocyclic column aromatic compounds is less, the separation temperature is low, the retention time of separation materials is short, and the separation efficiency is high.
Drawings
FIG. 1 is a macrocyclic aromatic compound produced in example 1 1 H NMR。
FIG. 2 is a macrocyclic aromatic compound prepared in example 1 13 C NMR。
FIG. 3 is a thermogravimetric analysis of the macrocyclic aromatic compound prepared in example 1.
FIG. 4 is a GC chromatogram of a gas chromatography column separating PhH/Cy or Tol/MCy, wherein (a) and (c) are corresponding GC chromatograms of a bare packed column of unsupported macrocyclic aromatic compounds; (b) (d) is the GC chromatogram corresponding to the 1:1 ratio of the raw materials in example 2.
FIG. 5 is a GC chromatogram of example 2 for isolation of PhH/Cy or Tol/MCy.
FIG. 6 is a GC chromatogram of example 3 for isolation of PhH/Cy or Tol/MCy.
FIG. 7 is a GC chromatogram of example 4 for isolation of PhH/Cy or Tol/MCy.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Melting points were determined using a WRR melting point tester and were uncorrected. 1 H NMR， 13 The C NMR spectrum was recorded on a Bruker DMX400 NMR spectrometer. Single crystal X-ray data were measured by a direct method using Bruker SMART APEX II. Thermogravimetric analysis (TGA) was performed using a Q5000IR analyzer (TA Instruments) and an automated vertical overhead thermobalance, using N2 as a shielding gas, and the sample was heated at a rate of 10 ℃/min.
Example 1
The following is a preparation step of a macrocyclic aromatic compound:
(1) 2, 5-Dimethoxybenzylamine (2.01 g,12 mmol) and 3,3', 4' -biphenyltetracarboxylic dianhydride (1.47 g,5 mmol) were dissolved in dry DMF (35 mL) in a sealed tube and then heated on an oil bath at 110℃for 12 hours, after cooling to room temperature, the reaction mixture was poured into water and the resulting yellowish green precipitate was washed with water and then dried in vacuo to give 2.22g of intermediate. The intermediate is yellow solid with a melting point of more than 300 ℃;1H Nuclear magnetic resonance (400 MHz, chloroform-d) δ8.11 (s, 2H), 7.99 (d, J=7.9 Hz, 4H), 6.81 (d, J=9.9 Hz, 2H), 6.76 (d, J=6.7 Hz, 4H), 4.92 (s, 4H), 3.83 (s, 6H), 3.73 (s, 6H); 13C Nuclear magnetic resonance (101 MHz, CDCl 3) delta 167.53, 153.47, 151.37, 145.18, 133.37, 132.94, 131.94, 125.18, 124.18, 122.20, 115.15, 112.56, 111.49, 56.11, 55.73, 37.07.
(2) Intermediate (1.18 g,2.0 mmol) and paraformaldehyde (180 mg,6.0 mmol) were added to dichloromethane (150 mL) and boron trifluoride diethyl etherate (0.3 mL,2.4 mmol) was added to the mixture, the reaction was stopped by adding 150mL of water after stirring at 60℃for 12 hours, the organic layer was separated, dried over anhydrous magnesium sulfate, the solvent was removed in vacuo, and the residue was separated by silica gel column chromatography (column packing 100-200 mesh silica gel, eluent: 1:15 ethyl acetate/DCM) to give 544mg of a macrocyclic aromatic compound as a yellow-green solid, calculated as 45% yield. The macrocyclic column aromatic compound has a melting point >300 ℃, 1H nuclear magnetic resonance (400 MHz, chloroform-d) delta 7.96 (s, 4H), 7.86 (t, j=5.9 hz, 8H), 6.90 (s, 4H), 6.69 (s, 4H), 4.85 (s, 8H), 3.87 (s, 4H), 3.76 (s, 12H), 3.69 (s, 12H); its 13C nuclear magnetic resonance (101 mhz, cdcl 3) delta 167.56, 167.19, 151.26, 144.92, 133.32, 132.68, 131.86, 129.86, 123.88, 122.17, 121.80, 114.26, 113.50, 56.30, 56.11, 37.36, 30.20.
As shown in FIG. 3, the macrocyclic aromatic compound prepared by the present invention hardly experiences weight loss below 400 ℃, indicating good thermal stability.
Example 2
The macrocyclic aromatic compound (100 mg) prepared in example 1 was first dissolved in 15mL of chloroform, then 2g of 40-60 mesh red support 6201 was added, the above mixture was dried under vacuum, and the residue was dried at 120 ℃ for another 4 hours. The carrier loaded with the macrocyclic aromatic compound was packed into a stainless steel column 1.0 meter long and 2.0 millimeter inside diameter. During packing, the column is continuously tapped and the packing is compacted, and then a packed column containing macrocyclic column aromatic compounds is obtained. The column was packed into a column box and activated at 120℃for 12 hours. Benzene/cyclohexane (PhH/Cy) or toluene/methylcyclohexane (Tol/MCy) was separated on a Fuli 9790II gas chromatography system, the carrier gas flow rate was controlled to 25ml/min, the sample injection volume was controlled to 0.1uL, the volume ratio of benzene to cyclohexane (PhH/Cy) or toluene to methylcyclohexane (Tol/MCy) was controlled to be 1:9,1:4,1:1,4:1,9:1, respectively, and when the raw material to be separated was benzene/cyclohexane (PhH/Cy), the column temperature was controlled to be 35 ℃; when the starting material to be separated was toluene/methylcyclohexane (Tol/MCy), the column temperature was controlled to 50 ℃.
In addition, red carrier 6201 without loading large ring column aromatic compound is used as gas chromatographic column packing to form bare packed column as reference group, and the volume ratio of corresponding raw materials is controlled to be 1:1, and other conditions are unchanged in sequence.
As shown in fig. 4, when the volume ratio of benzene to cyclohexane (PhH/Cy) or toluene to methylcyclohexane (Tol/MCy) was 1:1, the bare packed column could not separate PhH/Cy or Tol/MCy (a/c), whereas example 2 effectively separated PhH/Cy or Tol/MCy (b/d) using a packed column loaded with a macrocyclic column aromatic compound, and the retention times of cyclohexane (Cy) and benzene (PhH) were 0.67 and 1.84 minutes, respectively; the retention times of methylcyclohexane (MCy) and toluene (Tol) were 0.76 and 2.42 minutes, respectively. While FIG. 5 shows that increasing the volume ratio of PhH to Cy from 1:1 to 4:1 or 9:1, the separation efficiency is essentially unchanged (a); likewise, increasing the volume ratio of Tol to MCy from 1:1 to 4:1 or 9:1, the separation efficiency is also substantially unchanged (b).
Example 3
On the basis of example 2,5 feed separations were repeated: the volume ratio of benzene to cyclohexane (PhH/Cy) or toluene to methylcyclohexane (Tol/MCy) was controlled to be 1:1, and the other conditions were kept unchanged.
As shown in FIG. 6, even after 5 times of repeated use, the retention time of benzene and cyclohexane (PhH/Cy) or toluene and methylcyclohexane (Tol/MCy) did not change significantly, indicating that the packed column prepared by using the macrocyclic aromatic compound of the present invention has high recycling rate.
Example 4
On the basis of example 2, benzene/cyclohexane (PhH/Cy) or toluene/methylcyclohexane (Tol/MCy) was separated by gas chromatography using the packed column after half a month, 1 month, and 2 months, respectively, and the volume ratio of benzene to cyclohexane (PhH/Cy) or toluene to methylcyclohexane (Tol/MCy) was controlled to be 1:1, while the other conditions remained unchanged.
As can be seen from FIG. 7, after 2 months, the packed column has higher stability when the packed column is prepared from the macrocyclic aromatic compound of the present invention, as shown by the fact that the corresponding retention time is not significantly changed when the packed column is used for gas chromatographic separation of benzene and cyclohexane (PhH/Cy) or toluene and methylcyclohexane (Tol/MCy).
Claims (10)
1. A macrocyclic aromatic compound, characterized in that the compound has the structure of formula 1:
2. a process for the preparation of a macrocyclic aromatic compound as defined in claim 1, characterized in that: imidizing 2, 5-dimethoxy benzylamine and 3,3', 4' -biphenyl tetracarboxylic dianhydride to obtain an intermediate, and performing condensation reaction on the intermediate and paraformaldehyde to obtain the product;
the intermediate has a structure shown in formula 2:
3. the method for producing a macrocyclic aromatic compound according to claim 2, characterized in that: the molar ratio of the 2, 5-dimethoxy benzylamine to the 3,3', 4' -biphenyl tetracarboxylic dianhydride is 2-2.5:1.
4. A process for the preparation of a macrocyclic aromatic compound as claimed in claim 2 or 3, characterized in that: the imidization reaction is carried out at a temperature of 100-120 ℃ for 8-16 h.
5. A process for the preparation of a macrocyclic aromatic compound as claimed in claim 2 or 3, characterized in that: the molar ratio of the intermediate to the paraformaldehyde is 1:3-5.
6. The method for producing a macrocyclic aromatic compound according to claim 2, characterized in that: the temperature of the condensation reaction is 50-80 ℃ and the time is 8-12 h.
7. Use of a macrocyclic aromatic compound as claimed in claim 1, characterized in that: as chromatographic stationary phase.
8. The use of a macrocyclic aromatic compound as defined in claim 7, wherein: as a stationary phase for gas chromatography for separating aromatic compounds and cyclic aliphatic compounds.
9. The use of a macrocyclic aromatic compound as defined in claim 8, wherein: in the gas chromatographic separation process, the volume ratio of the aromatic compound to the cyclic aliphatic compound is controlled to be 1-9: 1 range.
10. Use of a macrocyclic aromatic compound according to claim 8 or 9, characterized in that: the column temperature of the gas chromatography is 35-50 ℃.
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