CN115947911A - Diketimine-linked covalent organic framework high polymer material and preparation method thereof - Google Patents
Diketimine-linked covalent organic framework high polymer material and preparation method thereof Download PDFInfo
- Publication number
- CN115947911A CN115947911A CN202310193732.6A CN202310193732A CN115947911A CN 115947911 A CN115947911 A CN 115947911A CN 202310193732 A CN202310193732 A CN 202310193732A CN 115947911 A CN115947911 A CN 115947911A
- Authority
- CN
- China
- Prior art keywords
- cof
- dki
- monomer
- butanedione
- diketone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention discloses a covalent organic framework high polymer material connected by diketoimine and a preparation method thereof, relating to the technical field of high polymer organic porous materials. The aromatic ketone/metal salt composite material is prepared by taking an aromatic amine monomer, a diketone monomer and a metal salt as raw materials and acetic acid as a catalyst through a solvothermal reaction in a solvent. The preparation method can successfully prepare the covalent organic framework high polymer material connected by the diketoimine, the preparation process is simple, the raw materials are easy to obtain, and the obtained high polymer material has higher crystallinity and good thermal stability.
Description
Technical Field
The invention belongs to the technical field of high molecular organic porous materials, and particularly relates to a covalent organic framework high molecular material connected by diketone imine and a preparation method thereof.
Background
Functional materials are becoming a trend of scientific research hotspots, and Covalent Organic Frameworks (COFs) are becoming the important focus of functional material research due to the advantages of high crystallinity, stability, functional designability, high specific surface area and the like. The covalent organic framework material is a series of functional crystalline porous materials and is skillfully constructed by organic building units containing light elements through strong covalent bonds. In general, the functional structural diversity of covalent organic framework materials results from their diverse forms of attachment and a wide selective combination of organic building blocks with diverse functions and geometric conformations. Therefore, COFs with customizable structures and designable functions have wide application prospects in various fields such as catalysis, energy storage, gas separation, sensing, photoelectron and the like.
To date, many schiff bases with different properties of linkage, dynamic covalent chemical support, have been reported to react to form imine covalent organic frameworks with reversible bonds, which are of great interest due to their error correcting capabilities and widely applicable mild synthesis conditions. Since the first example of imine COF reports, imine-linked covalent organic frameworks constructed by the dehydrocondensation of amines and aromatic aldehydes have been the focus of research by researchers. In contrast, since aldehydes have higher reactivity, smaller steric hindrance effect during polymerization, and low conjugation, and ketones, particularly aliphatic ketones, are more difficult to construct long-range ordered structural materials than aldehydes, there is no report on covalent organic frameworks of connection methods constructed by aliphatic ketone monomers.
Disclosure of Invention
In view of this, the invention provides a covalent organic framework polymer material connected by diketoimine and a preparation method thereof, the preparation method can successfully prepare the covalent organic framework polymer material in a connection mode constructed by aliphatic ketone monomers, and the obtained polymer material has good thermal stability.
In order to achieve the above object, the present invention provides the following technical solutions: a covalent organic framework polymer material connected by diketone imine has a structural formula shown as follows:
in the formula, R1 is hydrogen, an alkyl substituent or an aromatic ring substituent, R2 is hydrogen, an alkyl substituent or an aromatic ring substituent, or R1 and R2 form an aliphatic ring, an aromatic ring or a heterocyclic ring together; the alkyl substituent comprises methyl, ethyl, n-propyl and isopropyl; the aromatic ring substituent comprises a benzene ring and a pyridine ring.
The invention also provides a preparation method of the covalent organic framework high polymer material connected by the diketone imine, which takes the aromatic amine monomer, the diketone monomer and the metal salt as raw materials and acetic acid as a catalyst to prepare the covalent organic framework high polymer material through solvothermal reaction in a solvent.
Preferably, the solvothermal reaction specifically comprises the following steps:
(1) Uniformly mixing an aromatic amine monomer, a diketone monomer, a metal salt and a catalyst in a solvent to obtain a solid-liquid mixture;
(2) Carrying out three cycles of liquid nitrogen freezing, vacuum degassing and unfreezing on the solid-liquid mixture, and reacting at 100-150 ℃ for 48-120h;
(3) And after the reaction is finished, washing, centrifuging and drying to obtain the covalent organic framework polymer material connected with the diketoimine.
Preferably, the aromatic amine monomer is one of 1,3, 5-tris (4-aminophenyl) benzene, 4',4 ″ - (1, 3, 5-triazine-2, 4, 6-triyl) triphenylamine, 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin, tetrakis- (4-aminophenyl) ethylene and 1,3,6, 8-tetrakis- (p-aminophenyl) -pyrene;
the structural formula of the diketone monomer is shown as a formula a:
formula a
In the formula, R1 is hydrogen, an alkyl substituent or an aromatic ring substituent, R2 is hydrogen, an alkyl substituent or an aromatic ring substituent, or R1 and R2 form an aliphatic ring, an aromatic ring or a heterocyclic ring together; the alkyl substituent comprises methyl, ethyl, n-propyl and isopropyl; the aromatic ring substituent comprises a benzene ring and a pyridine ring;
the metal salt includes, but is not limited to, nickel chloride, ferrous chloride, cobalt chloride, palladium chloride, platinum chloride, zinc chloride, or copper chloride.
Further preferably, the diketone monomer is one of 2, 3-butanedione, 3, 5-dimethylcyclopentane-1, 2-dione, 3, 4-hexanedione, 1, 2-cyclohexanedione, dibenzoyl, 9, 10-phenanthrenequinone, acenaphthenequinone, 1, 2-bis (4-aminophenyl) ethane-1, 2-dione, 2, 3-pentanedione, 1-chloro-2, 3-butanedione, 5-methyl-2, 3-hexanedione, 1, 2-indanedione, 1-phenyl-1, 2-propanedione, 1, 2-naphthoquinone, 6-nitro-2, 3-dihydroxyquinoxaline, bis (2-pyridyl) ethanedione, 1, 10-orthophenanthrolaphenanthrene-5, 6-dione, camphorquinone, 2, 3-dihydroxyquinoxaline, 6, 7-dichloroquinoline-2, 3- (1H, 4H) -dione, and 1, 2-bis (4-bromophenyl) ethane-1, 2-dione.
Preferably, the molar mass ratio of the aromatic amine monomer, the diketone monomer and the metal salt is (1 to 3) to (1.5 to 6).
Preferably, the catalyst is an acetic acid solution.
Preferably, the solvent is one or more of mesitylene, ethanol or isopropanol.
Preferably, the vacuum degassing operation is: and (2) putting the reactor filled with the aromatic amine monomer, the binary ketone monomer, the metal salt, the solvent and the catalyst into liquid nitrogen for 3 to 5min, taking out, connecting a vacuum pump to pump for 3 min, then putting into normal-temperature water until the liquid is completely thawed, and repeating the three steps of putting into liquid nitrogen, taking out, vacuumizing and thawing for three times.
Preferably, the washing is carried out by respectively using 1, 4-dioxane, tetrahydrofuran and ethanol; the drying temperature is 50 to 120 ℃.
The invention has the following beneficial effects:
the invention provides a covalent organic framework high polymer material connected by diketone imine and a preparation method thereof. The preparation method can successfully prepare the covalent organic framework high polymer material connected by the diketoimine, the preparation process is simple, the raw materials are easy to obtain, and the obtained high polymer material has higher crystallinity and good thermal stability.
Drawings
FIG. 1 is an infrared spectrum of DKI-TPB-COF-1 material, TPB and 2, 3-butanedione in example 1;
FIG. 2 is an infrared spectrum of the polymer materials obtained in examples 1 to 6;
FIG. 3 is an X-ray photoelectron spectrum of the polymer materials obtained in examples 1 to 6;
FIG. 4 is an X-ray powder diffraction pattern of the DKI-TPB-COF-1 material of example 1 for experiments, refinements, and simulations of different packing patterns;
FIG. 5 is an X-ray powder diffraction pattern of the polymer materials obtained in examples 1 to 21;
FIG. 6 is a scanning tunnel microscope photograph of the polymer materials obtained in examples 1 to 6;
FIG. 7 is a transmission electron microscope photograph of the polymer materials obtained in examples 1 to 6;
FIG. 8 is a thermogravimetric plot of the polymer materials obtained in examples 1 to 6;
FIG. 9 is an infrared spectrum of DKI-TTA-COF-1 material, TTA and 2, 3-butanedione in example 22;
FIG. 10 is an infrared spectrum of each of the polymers obtained in examples 22 to 27;
FIG. 11 is an X-ray powder diffraction pattern of experiment, refinement, and simulation of different packing patterns of DKI-TTA-COF-1 material of example 22; (ii) a
FIG. 12 is an X-ray powder diffraction pattern of the polymer materials obtained in examples 22 to 27;
FIG. 13 is a scanning tunnel microscope photograph of the polymer materials obtained in examples 22 to 27;
FIG. 14 is a transmission electron microscope photograph of the polymer materials obtained in examples 22 to 27;
FIG. 15 is an X-ray powder diffraction pattern of the polymer materials obtained in examples 28 to 33;
FIG. 16 is an X-ray powder diffraction pattern of the polymer materials obtained in examples 34 to 39;
FIG. 17 is an IR spectrum of DKI-TPE-COF-1 material, TPE and 2, 3-butanedione in example 34;
FIG. 18 is an infrared spectrum of each of the polymeric materials obtained in examples 34 to 39;
FIG. 19 is an X-ray powder diffraction pattern of the polymer materials obtained in examples 40 to 45.
Detailed description of the preferred embodiments
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but rather as a more detailed description of certain aspects, features and embodiments of the invention.
The invention provides a covalent organic framework high polymer material connected by diketone imine, which has the following structural formula:
in the formula, R1 is hydrogen, an alkyl substituent or an aromatic ring substituent, R2 is hydrogen, an alkyl substituent or an aromatic ring substituent, or R1 and R2 form an aliphatic ring, an aromatic ring or a heterocyclic ring together; the alkyl substituent comprises methyl, ethyl, n-propyl and isopropyl; the aromatic ring substituent comprises a benzene ring and a pyridine ring.
The invention also provides a preparation method of the covalent organic framework high polymer material connected by the diketone imine, which takes the aromatic amine monomer, the diketone monomer and the metal salt as raw materials and acetic acid as a catalyst to prepare the covalent organic framework high polymer material through solvothermal reaction in a solvent.
In the present invention, the solvothermal reaction specifically comprises the following steps:
(1) Uniformly mixing an aromatic amine monomer, a diketone monomer, a metal salt and a catalyst in a solvent to obtain a solid-liquid mixture;
(2) Carrying out three cycles of liquid nitrogen freezing, vacuum degassing and unfreezing on the solid-liquid mixture, and reacting at 100-150 ℃ for 48-120h;
(3) And after the reaction is finished, washing, centrifuging and drying to obtain the covalent organic framework polymer material connected with the diketoimine.
The method comprises the following steps of uniformly mixing an aromatic amine monomer, a diketone monomer, a metal salt and a catalyst in a solvent to obtain a solid-liquid mixture, specifically, the mixing step comprises the steps of putting the aromatic amine monomer, the diketone monomer and the metal salt into a reactor, adding the solvent into the reactor, and carrying out ultrasonic treatment for 10min, and then adding the catalyst to obtain the solid-liquid mixture.
In the present invention, the aromatic amine monomer is preferably one of 1,3, 5-tris (4-aminophenyl) benzene, 4',4 ″ - (1, 3, 5-triazine-2, 4, 6-triyl) triphenylamine, 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin, tetrakis- (4-aminophenyl) ethylene and 1,3,6, 8-tetrakis- (p-aminophenyl) -pyrene;
the structural formula of the diketone monomer is shown as a formula a:
In the formula, R1 is hydrogen, an alkyl substituent or an aromatic ring substituent, R2 is hydrogen, an alkyl substituent or an aromatic ring substituent, or R1 and R2 jointly form an aliphatic ring, an aromatic ring or a heterocyclic ring; the alkyl substituent comprises methyl, ethyl, n-propyl and isopropyl; the aromatic ring substituent comprises a benzene ring and a pyridine ring;
the metal salt includes, but is not limited to, nickel chloride, ferrous chloride, cobalt chloride, palladium chloride, platinum chloride, zinc chloride, or copper chloride, preferably nickel chloride, and more preferably nickel chloride hexahydrate.
In the invention, when the aromatic amine is 1,3, 5-tris (4-aminophenyl) benzene (TPB), the reaction route of the aromatic amine, the diketone and the nickel chloride hexahydrate is shown as (a), and the structural formula of the obtained high polymer material is shown as formula i:
route (A)
In the present invention, when the aromatic amine is 4',4' ' - (1, 3, 5-triazine-2, 4, 6-Triyl) Triphenylamine (TTA), the reaction route of the aromatic amine, the diketone and the nickel chloride hexahydrate is shown as (B), and the structural formula of the obtained polymer material is shown as formula II:
route (B)
In the invention, when the aromatic amine is 5,10,15, 20-tetra (4-aminophenyl) porphyrin (TAPP), the reaction route of the aromatic amine, the diketone and the nickel chloride hexahydrate is shown as (C), and the structural formula of the obtained high polymer material is shown as formula III:
route (C)
In the invention, when the aromatic amine is tetra- (4-aminostyrene) (TPE), the reaction route of the aromatic amine, the diketone and the nickel chloride hexahydrate is shown as (D), and the structural formula of the obtained high polymer material is shown as a formula IV:
route (D)
In the present invention, when the aromatic amine is 1,3,6, 8-tetra- (p-aminophenyl) -pyrene (Py), the reaction route of the aromatic amine, the diketone and the nickel chloride hexahydrate is shown as (E), and the structural formula of the obtained polymer material is shown as formula V:
route (E)
In the present invention, the diketone monomer is preferably one of 2, 3-butanedione, 3, 5-dimethylcyclopentane-1, 2-dione, 3, 4-hexanedione, 1, 2-cyclohexanedione, bibenzoyl, 9, 10-phenanthrenequinone, acenaphthenequinone, 1, 2-bis (4-aminophenyl) ethane-1, 2-dione, 2, 3-pentanedione, 1-chloro-2, 3-butanedione, 5-methyl-2, 3-hexanedione, 1, 2-indanedione, 1-phenyl-1, 2-propanedione, 1, 2-naphthoquinone, 6-nitro-2, 3-dihydroxyquinoxaline, bis (2-pyridyl) ethanedione, 1, 10-orthophenanthroline-5, 6-dione, camphorquinone, 2, 3-dihydroxyquinoxaline, 6, 7-dichloroquinoline-2, 1- (h, 4 h) -dione, and 1, 2-bis (4-bromophenyl) ethane-1, 2-dione, and the structural formulae are respectively:
in the invention, the molar mass ratio of the aromatic amine monomer, the diketone monomer and the metal salt is preferably (1 to 3) to (1.5 to 6), and more preferably (1 to 2): (1.5 to 4): (1.5 to 4).
In the invention, the catalyst is preferably an acetic acid solution, more preferably an aqueous acetic acid solution, and the concentration of the aqueous acetic acid solution is preferably 6 to 12mol/L.
In the present invention, the solvent is preferably one or more of mesitylene, ethanol or isopropanol. When the solvent is mesitylene, the invention also adds ethanol solution, the volume ratio of the ethanol solution to the mesitylene is 1.
After obtaining the solid-liquid mixture, the solid-liquid mixture is subjected to three cycles of liquid nitrogen freezing, vacuum degassing and unfreezing, and then the solid-liquid mixture is reacted for 48 to 120h at the temperature of 100 to 150 ℃ preferably, and is reacted for 48 to 72h at the temperature of 110 to 130 ℃ more preferably.
In the present invention, the vacuum degassing operation is: and (2) putting the reactor filled with the aromatic amine monomer, the binary ketone monomer, the metal salt, the solvent and the catalyst into liquid nitrogen for 3 to 5min, taking out, connecting a vacuum pump to pump for 3 min, then putting into normal-temperature water until the liquid is completely thawed, and repeating the three steps of putting into liquid nitrogen, taking out, vacuumizing and thawing for three times.
And after the reaction is finished, washing, centrifuging and drying to obtain the covalent organic framework polymer material connected with the diketoimine.
In the invention, the washing is carried out by respectively using 1, 4-dioxane, tetrahydrofuran and ethanol; the drying temperature is preferably 50 to 120 ℃, and more preferably 70 to 90 ℃.
The following examples are provided to further illustrate the present invention in order to better understand the present invention, but the present invention is not limited to the following examples.
Example 1
TPB, nickel chloride hexahydrate and 2, 3-butanedione are placed in a reactor according to a molar weight ratio of 2. After three cycles of freezing by liquid nitrogen, vacuum degassing and unfreezing, heating at 120 ℃ for 72 hours for reaction, wherein the vacuum degassing specifically comprises the steps of putting a reactor filled with the solid-liquid mixture into the liquid nitrogen for 3 to 5 minutes, taking out, connecting a vacuum pump for pumping for 3 minutes, then putting into normal-temperature water until the liquid is completely unfrozen, then repeatedly putting into the liquid nitrogen, taking out, vacuumizing and unfreezing for three times. After the reaction is finished, washing and centrifuging twice by using 1, 4-dioxane, tetrahydrofuran and ethanol respectively, and putting the obtained solid into a vacuum drying oven at 80 ℃ overnight to obtain uniform brown powder. The brown powder obtained was named DKI-TPB-COF-1.
FIG. 1 is an infrared spectrum of DKI-TPB-COF-1 material, TPB and 2, 3-butanedione. From fig. 1, it can be found that the infrared spectrum of the DKI-TPB-COF-1 material is completely different from the infrared spectrum of TPB and 2, 3-butanedione, and the stretching vibration peak of C = O bond in the raw material 2, 3-butanedione disappears, and the absorption peak of imine C = N bond appears, confirming the successful occurrence of condensation reaction.
Fig. 4 shows X-ray powder diffraction patterns of experiment, refinement and simulation of different stacking modes of DKI-TPB-COF-1 material, and it can be found from fig. 4 that DKI-TPB-COF-1 is a covalent organic framework material with high crystallinity, and it can be found that it adopts ABC stacking mode by comparing diffraction peaks of three simulated different stacking modes after refinement. The X-ray powder diffraction peaks at 2theta values of 6.19 degrees, 10.73 degrees, 11.63 degrees, 12.40 degrees, 13.19 degrees and 16.43 degrees respectively belong to R32 space groups
A crystal plane.
Example 2
The same as example 1 except that 2, 3-butanedione was replaced by 3, 5-dimethylcyclopentane-1, 2-dione, and the resulting solid powder was named DKI-TPB-COF-2.
Example 3
The same as example 1 except that 2, 3-butanedione was replaced by 3, 4-hexanedione, the resulting solid powder was named DKI-TPB-COF-3.
Example 4
The same as in example 1 except that 2, 3-butanedione was replaced by 1, 2-cyclohexanedione, the resulting solid powder was named DKI-TPB-COF-4.
Example 5
The same as example 1 except that 2, 3-butanedione was replaced by dibenzoyl, the resulting solid powder was named DKI-TPB-COF-5.
Example 6
The same as example 1 except that 2, 3-butanedione was replaced with 9, 10-phenanthrenequinone, and the resulting solid powder was named DKI-TPB-COF-6.
FIG. 2 is an infrared spectrum diagram of the polymer materials obtained in examples 1 to 6, and it can be seen from FIG. 2 that the six examples of the covalent organic framework materials in examples 1 to 6 all have the same infrared spectrum absorption peak, which proves that the condensation reaction occurs successfully.
FIG. 3 is an X-ray photoelectron spectrum of the polymeric materials obtained in examples 1 to 6, and as can be seen from FIG. 3, the X-ray photoelectron spectrum shows that 2p orbits of Ni elements of the polymeric materials DKI-TPB-COF-1 to DKI-TPB-COF-6 prepared in examples 1 to 6 have two identical peak positions of 856.0eV and 873.4eV, which correspond to the binding energies of 2p3/2 and 2p1/2, respectively. It is directly proved that nickel chloride exists in the covalent organic framework material in the coordination of positive divalent nickel ions.
FIG. 6 is a scanning tunneling microscope image of the polymer materials obtained in examples 1 to 6, as shown in FIG. 6, DKI-TPB-COF-1 and DKI-TPB-COF-3 show irregular shapes, and DKI-TPB-COF-2, DKI-TPB-COF-4, DKI-TPB-COF-5 and DKI-TPB-COF-6 are rod-shaped.
FIG. 7 is a transmission electron microscope image of the polymer materials obtained in examples 1 to 6, and as shown in FIG. 7, significant lattice fringes can be observed in all of the six examples of the covalent organic framework materials in examples 1 to 6, which proves that the polymer materials have high crystallinity. Meanwhile, the lattice fringe spacing can be measured to obtain the perfect correspondence between the lattice spacing of about 1.4nm and the (1 (-) 20) crystal plane.
FIG. 8 is a thermogravimetric graph of the polymer materials obtained in examples 1 to 6, and from FIG. 8, it can be seen that all of DKI-TPB-COF-1 to DKI-TPB-COF-6 are stable at a temperature of less than 400 ℃, which proves that the materials have good thermal stability.
The solid powders obtained in examples 1 to 6 were subjected to metal content test analysis by an inductively coupled plasma emission spectrometer, and the obtained data are shown in table 1, and the listed data can obtain a better match between the content of nickel element and a theoretical calculation value, thereby indirectly confirming an ideal coordination environment of nickel ions in a frame material.
TABLE 1
Example 7
The same as example 1 except that 2, 3-butanedione was replaced with acenaphthenequinone, and the resulting solid powder was named DKI-TPB-COF-7.
Example 8
The same as example 1 except that 2, 3-butanedione was replaced by 1, 2-bis (4-aminophenyl) ethane-1, 2-dione, and the resulting solid powder was named DKI-TPB-COF-8.
Example 9
The same as example 1 except that 2, 3-butanedione was replaced by 2, 3-pentanedione, the resulting solid powder was named DKI-TPB-COF-9.
Example 10
The same as example 1 except that 2, 3-butanedione was replaced with 1-chloro-2, 3-butanedione, and the resulting solid powder was named DKI-TPB-COF-10.
Example 11
The same as example 1 except that 2, 3-butanedione was replaced with 5-methyl-2, 3-hexanedione, the resulting solid powder was named DKI-TPB-COF-11.
Example 12
The same as example 1 except that 2, 3-butanedione was replaced with 1, 2-indandione, and the resulting solid powder was named DKI-TPB-COF-12.
Example 13
The same as example 1 except that 2, 3-butanedione was replaced with 1-phenyl-1, 2-propanedione, and the resulting solid powder was named DKI-TPB-COF-13.
Example 14
The same as example 1 except that 2, 3-butanedione was replaced with 1, 2-naphthoquinone, the resulting solid powder was named DKI-TPB-COF-14.
Example 15
The procedure is as in example 1, except that 2, 3-butanedione is replaced by 6-nitro-2, 3-dihydroxyquinoxaline, and the solid powder obtained is designated DKI-TPB-COF-15.
Example 16
The same as example 1 except that 2, 3-butanedione was replaced by di (2-pyridyl) ethanedione, the resulting solid powder was named DKI-TPB-COF-16.
Example 17
The same as example 1 except that 2, 3-butanedione was replaced with 1, 10-phenanthroline-5, 6-dione, and the resulting solid powder was named DKI-TPB-COF-17.
Example 18
The same as example 1 except that 2, 3-butanedione was replaced with camphorquinone, the resulting solid powder was named DKI-TPB-COF-18.
Example 19
The same as in example 1 except that 2, 3-butanedione was replaced with 2, 3-dihydroxyquinoxaline, and the resulting solid powder was designated DKI-TPB-COF-19.
Example 20
The same as example 1 except that 2, 3-butanedione was replaced with 6, 7-dichloroquinoline-2, 3- (1H, 4H) -dione, and the resulting solid powder was named DKI-TPB-COF-20.
Example 21
The same as example 1 except that 2, 3-butanedione was replaced with 1, 2-bis (4-bromophenyl) ethane-1, 2-dione, and the resulting solid powder was named DKI-TPB-COF-21.
FIG. 5 is an X-ray powder diffraction pattern of the polymer materials obtained in examples 1 to 21, and as shown in FIG. 5, the polymer materials DKI-TPB-COF-1 to DKI-TPB-COF-21 obtained in examples 1 to 21 have the same diffraction peaks and the same unit cell parameters and stacking patterns as DKI-TPB-COF-1.
Example 22
TTA, nickel chloride hexahydrate and 2, 3-butanedione are placed in a reactor in a molar weight ratio of 1.3. And after three times of circulation of three steps of freezing by liquid nitrogen, vacuum degassing and unfreezing, heating at 120 ℃ for 72 hours for reaction, wherein the vacuum degassing specifically comprises the steps of putting a reactor filled with the solid-liquid mixture into the liquid nitrogen for 3 to 5 minutes, taking out, connecting a vacuum pump for pumping for 3 minutes, then putting into normal-temperature water until the liquid is completely unfrozen, and repeating the three steps of putting into the liquid nitrogen, taking out, vacuumizing and unfreezing for three times. After the reaction is finished, washing and centrifuging twice by using 1, 4-dioxane, tetrahydrofuran and ethanol respectively, and putting the obtained solid in a vacuum drying oven at 80 ℃ overnight to obtain uniform solid powder. The resulting solid powder was named DKI-TTA-COF-1.
FIG. 9 is an infrared spectrum of DKI-TTA-COF-1 material, TTA and 2, 3-butanedione in example 22. From FIG. 9, it can be found that the infrared spectrum of DKI-TTA-COF-1 material is completely different from the infrared spectrum of TTA and 2, 3-butanedione, and the stretching vibration peak of C = O bond in 2, 3-butanedione as the raw material disappears, and the absorption peak of imine C = N bond appears, confirming the successful occurrence of condensation reaction.
FIG. 11 is an X-ray powder diffraction pattern of experiment, refinement and simulation of different packing patterns of DKI-TTA-COF-1 material of example 22. From FIG. 11, it can be seen that DKI-TTA-COF-1 is a covalent organic framework material with high crystallinity, and it can be seen that it adopts ABC packing pattern by comparing the diffraction peaks of three simulated different packing patterns after refinement. The X-ray powder diffraction peaks are respectively assigned to R at 2theta values of 6.34 degrees, 11.00 degrees, 12.71 degrees, 13.15 degrees and 16.83 degrees 32 The (1 (-) 20), (030), (2 (-) 40), (2 (-) 31), and (1 (-) 50) facets of the space group.
Example 23
The same as in example 22 except that 2, 3-butanedione was replaced by 3, 5-dimethylcyclopentane-1, 2-dione, and the resulting solid powder was named DKI-TTA-COF-2.
Example 24
The same as in example 22 except that 2, 3-butanedione was replaced by 3, 4-hexanedione, the resulting solid powder was designated DKI-TTA-COF-3.
Example 25
The same as in example 22 except that 2, 3-butanedione was replaced by 1, 2-cyclohexanedione, the resulting solid powder was designated DKI-TTA-COF-4.
Example 26
The same as in example 22 except that 2, 3-butanedione was replaced by dibenzoyl, the resulting solid powder was named DKI-TTA-COF-5.
Example 27
The same as in example 22 except that 2, 3-butanedione was replaced with 9, 10-phenanthrenequinone, the resulting solid powder was named DKI-TTA-COF-6.
FIG. 10 is an infrared spectrum of the polymer materials obtained in examples 22 to 27, and FIG. 10 shows that the absorption peaks of the infrared spectrum of the covalent organic frameworks in all six examples 22 to 27 are the same, which proves that the condensation reaction occurs successfully.
FIG. 12 is an X-ray powder diffraction pattern of the polymer materials obtained in examples 22 to 27, and as shown in FIG. 12, the diffraction peaks of DKI-TTA-COF-1 to DKI-TTA-COF-6 are the same as those of DKI-TTA-COF-1, and have the same unit cell parameters and stacking patterns as those of DKI-TTA-COF-1.
FIG. 13 is a scanning tunneling microscope photograph of the polymeric materials obtained in examples 22 to 27, and as shown in FIG. 13, DKI-TTA-COF-1 to DKI-TTA-COF-6 show a random morphology.
FIG. 14 is a transmission electron microscope photograph showing the polymer materials obtained in examples 22 to 27, and as can be seen from FIG. 14, a clear lattice fringe was observed, demonstrating a higher crystallinity. Meanwhile, the lattice space of about 1.4nm can be perfectly corresponding to the (1 (-) 20) crystal plane through measuring the lattice fringe space.
Example 28
TAPP, nickel chloride hexahydrate and 2, 3-butanedione are put into a reactor according to a molar weight ratio of 1.5. After three cycles of freezing by liquid nitrogen, vacuum degassing and unfreezing, heating at 120 ℃ for 72 hours for reaction, wherein the vacuum degassing specifically comprises the steps of putting a reactor filled with the solid-liquid mixture into the liquid nitrogen for 3 to 5 minutes, taking out, connecting a vacuum pump for pumping for 3 minutes, then putting into normal-temperature water until the liquid is completely unfrozen, then repeatedly putting into the liquid nitrogen, taking out, vacuumizing and unfreezing for three times. After the reaction is finished, washing and centrifuging twice by using 1, 4-dioxane, tetrahydrofuran and ethanol respectively, and putting the obtained solid into a vacuum drying oven at 80 ℃ overnight to obtain uniform solid powder. The resulting solid powder was named DKI-TAPP-COF-1.
Example 29
The same as in example 28 except that 2, 3-butanedione was replaced by 3, 5-dimethylcyclopentane-1, 2-dione, and the resulting solid powder was named DKI-TAPP-COF-2.
Example 30
The same as in example 28 except that 2, 3-butanedione was replaced by 3, 4-hexanedione, the resulting solid powder was designated DKI-TAPP-COF-3.
Example 31
The same as in example 28 except that 2, 3-butanedione was replaced by 1, 2-cyclohexanedione, the resulting solid powder was designated DKI-TAPP-COF-4.
Example 32
The same as in example 28 except that 2, 3-butanedione was replaced by dibenzoyl, the resulting solid powder was named DKI-TAPP-COF-5.
Example 33
The same as in example 28 except that 2, 3-butanedione was replaced with 9, 10-phenanthrenequinone, and the resulting solid powder was named DKI-TAPP-COF-6.
FIG. 15 shows X-ray powder diffractograms of the polymeric materials obtained in examples 28 to 33, and it can be seen from FIG. 15 that DKI-TAPP-COF-1 to DKI-TAPP-COF-6 are covalent organic framework materials having high crystallinity.
Example 34
The TPE, nickel chloride hexahydrate and 2, 3-butanedione are placed in a reactor according to a molar weight ratio of 1.7. And after three times of circulation of three steps of freezing by liquid nitrogen, vacuum degassing and unfreezing, heating at 120 ℃ for 72 hours for reaction, wherein the vacuum degassing specifically comprises the steps of putting a reactor filled with the solid-liquid mixture into the liquid nitrogen for 3 to 5 minutes, taking out, connecting a vacuum pump for pumping for 3 minutes, then putting into normal-temperature water until the liquid is completely unfrozen, and repeating the three steps of putting into the liquid nitrogen, taking out, vacuumizing and unfreezing for three times. After the reaction is finished, washing and centrifuging twice by using 1, 4-dioxane, tetrahydrofuran and ethanol respectively, and putting the obtained solid in a vacuum drying oven at 80 ℃ overnight to obtain uniform solid powder. The resulting solid powder was named DKI-TPE-COF-1.
Fig. 17 is an infrared spectrum of DKI-TPE-COF-1 material, TPE and 2, 3-butanedione in example 34, and it can be found from fig. 17 that the infrared spectrum of the DKI-TPE-COF-1 material is completely different from the infrared spectrum of the TPE and 2, 3-butanedione raw materials, and the stretching vibration peak of C = O bond in the raw material 2, 3-butanedione disappears, and the absorption peak of imine C = N bond appears, thus confirming the successful occurrence of condensation reaction.
Example 35
The same as in example 34, except that 2, 3-butanedione was replaced by 3, 5-dimethylcyclopentane-1, 2-dione, and the resulting solid powder was named DKI-TPE-COF-2.
Example 36
The same as in example 34, except that 2, 3-butanedione was replaced by 3, 4-hexanedione, the resulting solid powder was designated DKI-TPE-COF-3.
Example 37
The same as in example 34, except that 2, 3-butanedione was replaced by 1, 2-cyclohexanedione, the resulting solid powder was designated DKI-TPE-COF-4.
Example 38
The same as example 34, except that 2, 3-butanedione was replaced by dibenzoyl, the resulting solid powder was named DKI-TPE-COF-5.
Example 39
The same as example 34, except that 2, 3-butanedione was replaced with 9, 10-phenanthrenequinone, and the resulting solid powder was named DKI-TPE-COF-6.
FIG. 16 is an X-ray powder diffraction pattern of the polymeric materials obtained in examples 34 to 39, and from FIG. 16, it can be seen that DKI-TPE-COF-1 to DKI-TPE-COF-6 are covalent organic framework materials with high crystallinity.
FIG. 18 is an infrared spectrum of the polymer materials obtained in examples 34 to 39. As can be seen from FIG. 18, the six examples of the covalent organic framework materials in examples 34 to 39 all have the same infrared spectrum absorption peak, which proves that the condensation reaction occurs successfully.
Example 40
Py, nickel chloride hexahydrate and 2, 3-butanedione are put into a reactor according to a molar weight ratio of 1.2. And after three times of circulation of three steps of freezing by liquid nitrogen, vacuum degassing and unfreezing, heating at 120 ℃ for 72 hours for reaction, wherein the vacuum degassing specifically comprises the steps of putting a reactor filled with the solid-liquid mixture into the liquid nitrogen for 3 to 5 minutes, taking out, connecting a vacuum pump for pumping for 3 minutes, then putting into normal-temperature water until the liquid is completely unfrozen, and repeating the three steps of putting into the liquid nitrogen, taking out, vacuumizing and unfreezing for three times. After the reaction is finished, washing and centrifuging twice by using 1, 4-dioxane, tetrahydrofuran and ethanol respectively, and putting the obtained solid into a vacuum drying oven at 80 ℃ overnight to obtain uniform solid powder. The resulting solid powder was named DKI-Py-COF-1.
Example 41
The same as in example 40 except that 2, 3-butanedione was replaced by 3, 5-dimethylcyclopentane-1, 2-dione, and the resulting solid powder was named DKI-Py-COF-2.
Example 42
The same as in example 40 except that 2, 3-butanedione was replaced by 3, 4-hexanedione, the resulting solid powder was named DKI-Py-COF-3.
Example 43
The same as in example 40 except that 2, 3-butanedione was replaced by 1, 2-cyclohexanedione, the resulting solid powder was designated DKI-Py-COF-4.
Example 44
The same as in example 40 except that 2, 3-butanedione was replaced by dibenzoyl, the resulting solid powder was named DKI-Py-COF-5.
Example 45
The same as in example 40 except that 2, 3-butanedione was replaced with 9, 10-phenanthrenequinone, and the resulting solid powder was named DKI-Py-COF-6.
FIG. 19 is an X-ray powder diffraction pattern of the polymer materials obtained in examples 40 to 45, and it can be seen from FIG. 19 that DKI-Py-COF-1 to DKI-Py-COF-6 are covalent organic framework materials having high crystallinity.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A covalent organic framework polymer material connected by diketone imine is characterized in that the structural formula is as follows:
in the formula, R1 is hydrogen, an alkyl substituent or an aromatic ring substituent, R2 is hydrogen, an alkyl substituent or an aromatic ring substituent, or R1 and R2 jointly form an aliphatic ring, an aromatic ring or a heterocyclic ring; the alkyl substituent comprises methyl, ethyl, n-propyl and isopropyl; the aromatic ring substituent comprises a benzene ring and a pyridine ring.
2. The preparation method of the covalent organic framework high polymer material connected by the diketone imine as claimed in claim 1, characterized in that the covalent organic framework high polymer material is prepared by taking an aromatic amine monomer, a diketone monomer and a metal salt as raw materials and acetic acid as a catalyst through a solvothermal reaction in a solvent.
3. The preparation method according to claim 2, characterized in that the solvothermal reaction comprises in particular the following steps:
uniformly mixing an aromatic amine monomer, a diketone monomer, a metal salt and a catalyst in a solvent to obtain a solid-liquid mixture;
performing three cycles of liquid nitrogen freezing, vacuum degassing and thawing on the solid-liquid mixture, and reacting at 100-150 ℃ for 48-120h;
(3) And after the reaction is finished, washing, centrifuging and drying to obtain the covalent organic framework polymer material connected with the diketoimine.
4. The production method according to claim 2 or 3, wherein the aromatic amine monomer is one of 1,3, 5-tris (4-aminophenyl) benzene, 4',4 ″ - (1, 3, 5-triazine-2, 4, 6-triyl) triphenylamine, 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin, tetrakis- (4-aminophenyl) ethylene and 1,3,6, 8-tetrakis- (p-aminophenyl) -pyrene;
the structural formula of the diketone monomer is shown as a formula a:
In the formula, R1 is hydrogen, an alkyl substituent or an aromatic ring substituent, R2 is hydrogen, an alkyl substituent or an aromatic ring substituent, or R1 and R2 form an aliphatic ring, an aromatic ring or a heterocyclic ring together; the alkyl substituent comprises methyl, ethyl, n-propyl and isopropyl; the aromatic ring substituent comprises a benzene ring and a pyridine ring;
the metal salt comprises nickel chloride, ferrous chloride, cobalt chloride, palladium chloride, platinum chloride, zinc chloride or copper chloride.
5. The method according to claim 4, wherein the diketone monomer is one of 2, 3-butanedione, 3, 5-dimethylcyclopentane-1, 2-dione, 3, 4-hexanedione, 1, 2-cyclohexanedione, dibenzoyl, 9, 10-phenanthrenequinone, acenaphthenequinone, 1, 2-bis (4-aminophenyl) ethane-1, 2-dione, 2, 3-pentanedione, 1-chloro-2, 3-butanedione, 5-methyl-2, 3-hexanedione, 1, 2-indanedione, 1-phenyl-1, 2-propanedione, 1, 2-naphthoquinone, 6-nitro-2, 3-dihydroxyquinoxaline, bis (2-pyridyl) ethanedione, 1, 10-orthophenanthrene-5, 6-dione, camphorquinone, 2, 3-dihydroxyquinoxaline, 6, 7-dichloroquinoline-2, 3- (1H, 4H) -dione, and 1, 2-bis (4-bromophenyl) ethane-1, 2-dione.
6. The preparation method according to claim 2 or 3, wherein the molar mass ratio of the aromatic amine monomer, the diketone monomer and the metal salt is (1 to 3): (1.5 to 6): 1.5 to 6).
7. The production method according to claim 2 or 3, characterized in that the catalyst is an acetic acid solution.
8. The method according to claim 2 or 3, wherein the solvent is one or more of mesitylene, ethanol, or isopropanol.
9. The method of claim 3, wherein the vacuum degassing operation is: and (2) putting the reactor filled with the aromatic amine monomer, the binary ketone monomer, the metal salt, the solvent and the catalyst into liquid nitrogen for 3 to 5min, taking out, connecting a vacuum pump to pump for 3 min, then putting into normal-temperature water until the liquid is completely thawed, and repeating the three steps of putting into liquid nitrogen, taking out, vacuumizing and thawing for three times.
10. The production method according to claim 3, wherein the washing is washing with 1, 4-dioxane, tetrahydrofuran and ethanol, respectively; the drying temperature is 50 to 120 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310193732.6A CN115947911B (en) | 2023-02-28 | 2023-02-28 | Diketimine-linked covalent organic framework polymer material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310193732.6A CN115947911B (en) | 2023-02-28 | 2023-02-28 | Diketimine-linked covalent organic framework polymer material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115947911A true CN115947911A (en) | 2023-04-11 |
| CN115947911B CN115947911B (en) | 2023-05-23 |
Family
ID=85891177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310193732.6A Active CN115947911B (en) | 2023-02-28 | 2023-02-28 | Diketimine-linked covalent organic framework polymer material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115947911B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117946355A (en) * | 2024-03-27 | 2024-04-30 | 中国科学技术大学 | Preparation method and application of asymmetric self-supporting covalent organic framework film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021245559A1 (en) * | 2020-06-01 | 2021-12-09 | King Abdullah University Of Science And Technology | Conductive two-dimensional (2d) covalent organic frameworks (cofs) and method of making an electrode material |
| CN115487866A (en) * | 2021-06-18 | 2022-12-20 | 浙江大学 | Covalent organic framework material coupled nano metal catalyst and preparation method thereof |
-
2023
- 2023-02-28 CN CN202310193732.6A patent/CN115947911B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021245559A1 (en) * | 2020-06-01 | 2021-12-09 | King Abdullah University Of Science And Technology | Conductive two-dimensional (2d) covalent organic frameworks (cofs) and method of making an electrode material |
| CN115487866A (en) * | 2021-06-18 | 2022-12-20 | 浙江大学 | Covalent organic framework material coupled nano metal catalyst and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| HUI CHEN等: ""A Visible-Light-Harvesting Covalent Organic Framework Bearing Single Nickel Sites as a Highly Efficient Sulfur–Carbon Cross-Coupling Dual Catalyst"", 《ANGEW. CHEM. INT. ED.》 * |
| RUI SHEN等: ""A porphyrin porous organic polymer with bicatalytic sites for highly efficient one-pot tandem catalysis"", 《CHEM. COMMUN.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117946355A (en) * | 2024-03-27 | 2024-04-30 | 中国科学技术大学 | Preparation method and application of asymmetric self-supporting covalent organic framework film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115947911B (en) | 2023-05-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Synthesis of bipyridine-based covalent organic frameworks for visible-light-driven photocatalytic water oxidation | |
| Li et al. | Chemically robust covalent organic frameworks: progress and perspective | |
| Chen et al. | Designed synthesis of a 2D porphyrin‐based sp2 carbon‐conjugated covalent organic framework for heterogeneous photocatalysis | |
| US20220395821A1 (en) | Covalent organic frameworks and applications as photocatalysts | |
| CN115947911A (en) | Diketimine-linked covalent organic framework high polymer material and preparation method thereof | |
| CN113087923B (en) | Azine-connected benzotrithienyl covalent organic framework material and preparation method and application thereof | |
| Liu et al. | Coordination polymers with a pyridyl–salen ligand for photocatalytic carbon dioxide reduction | |
| CN109517187B (en) | Preparation method of covalent triazine framework polymer under open system | |
| Wu et al. | Arylboron functional covalent organic frameworks for synergistic photocatalytic hydrogen evolution | |
| CN113881004B (en) | Three-dimensional metal porphyrin-based covalent organic framework material with stp topological network structure, and preparation method and application thereof | |
| CN113912844A (en) | Triazine ring connection-based aromatic two-dimensional organic framework nano material and preparation method thereof | |
| Zhong et al. | Oligo (phenylenevinylene)‐based covalent organic frameworks with Kagome lattice for boosting photocatalytic hydrogen evolution | |
| Zhang et al. | Room temperature synthesis of polythioamides from multicomponent polymerization of sulfur, pyridine-activated alkyne, and amines | |
| Nagai | Covalent organic frameworks | |
| Kaliyappan et al. | Synthesis and characterization of a new metal chelating polymer and derived Ni (II) and Cu (II) polymer complexes | |
| Paquette et al. | Synthesis, characterization, and preceramic properties of π‐conjugated polymers based on Ni (II) complexes of goedken's macrocycle | |
| Li et al. | Superstructure‐Induced Hierarchical Assemblies for Nanoconfined Photocatalysis | |
| CN102702521A (en) | Macromolecule triazine charring agent with main chain containing piperazidine structure, and preparation method thereof | |
| CN112961299A (en) | Covalent-organic framework material and preparation method thereof | |
| CN110204738B (en) | Covalent organic framework material based on 1,3, 5-tri (4-aldehyde pyridyl) triazine and preparation method thereof | |
| Gal et al. | An ionic conjugated polymer from the catalyst-free polymerization of 2-ethynylpyridine using 3, 4, 5-trimethoxybenzoyl chloride | |
| CN109651620B (en) | Nickel metal coordination polymer and preparation method thereof | |
| CN114456337B (en) | Preparation method of ionic porous organic cage material applied to radioactive iodine adsorption under high-temperature and low-concentration conditions | |
| Altarawneh et al. | New Microporous Thiophene-Pyridine Functionalized Imine-Linked Polymer for Carbon-Dioxide Capture | |
| Zhuang et al. | Hydrazone‐Linked Covalent Organic Frameworks |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |