CN109251285B - Conjugated microporous polymer based on chlorinated 1,3, 5-tri (4-aldehyde pyridyl) triazine and preparation method thereof - Google Patents
Conjugated microporous polymer based on chlorinated 1,3, 5-tri (4-aldehyde pyridyl) triazine and preparation method thereof Download PDFInfo
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Abstract
The invention provides a conjugated microporous polymer based on chlorinated 1,3, 5-tri (4-aldehyde pyridyl) triazine with a structure shown in formula I, wherein the conjugated microporous polymer prepared by introducing symmetric indacene-1, 3,5,7(2H,6H) -tetraone on the basis of chlorinated 1,3, 5-tri (4-aldehyde pyridyl) triazine is in a sheet structure, is an amorphous material and has ultraviolet absorption performance. The invention provides a preparation method of a conjugated microporous polymer based on chlorinated 1,3, 5-tri (4-aldehyde pyridyl) triazine with a structure shown in formula I, which is simple and feasible and is beneficial to realizing large-scale production.
Description
Technical Field
The invention relates to the technical field of conjugated microporous polymers, in particular to a conjugated microporous polymer based on chlorinated 1,3, 5-tri (4-aldehyde pyridyl) triazine and a preparation method thereof.
Background
With the coming of the information-oriented era and the rapid development of scientific technology, large-scale and super-large-scale integrated circuits come along, and the application of the integrated circuits in the life of people is very popular. In order to match the high-speed development of integrated circuits and the high cruising demand of people, professional, high-performance, large-capacity, light, flexible, economical, durable and fast-charging battery materials are needed, while the development of lithium batteries is in a bottleneck period, and the continuous development cost and the performance improvement ratio are lower because the energy density is close to the physical limit.
In recent years, the organic porous material has attracted close attention of researchers due to the unique structure and performance of the organic porous material, and many researchers invest in the development and research of the organic porous material, find that the organic porous material has great application value in the fields of gas adsorption, separation, heterogeneous catalysis, energy storage and the like, and then in recent years, the outside places a breakthrough for searching a super battery on the novel material.
Organic porous Materials (MOPs) are classified into four types according to their structural characteristics: from microporous Polymers (PIMs), hypercrosslinked polymers (HCPs), covalent organic networks (COFs), and Conjugated Microporous Polymers (CMPs). Since the Cooper group successfully synthesized 3D ppms (paes) with 2D aryl acetylide and aryl bromide/iodide as monomers, more and more researchers have been dedicated to the research of CMPs as a branch of organic porous materials. CMPs have many advantages, such as large specific surface area, low framework density, and stable physical and chemical properties, with the molecules containing open-linked molecular-sized pores.
The construction of structural units according to different chemical reactions, and the development of CMPs with different structures and special properties, become a research hotspot at present.
Disclosure of Invention
The invention aims to provide a conjugated microporous polymer based on 1,3, 5-tri (4-aldehyde pyridyl) triazine chloride and a preparation method thereof, and the conjugated microporous polymer based on 1,3, 5-tri (4-aldehyde pyridyl) triazine chloride provided by the invention has a sheet structure, is an amorphous material and has ultraviolet absorption performance.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a conjugated microporous polymer based on 1,3, 5-tri (4-aldehyde pyridyl) triazine chloride, which takes 1,3, 5-tri (4-aldehyde pyridyl) triazine chloride and symmetrical indacene-1, 3,5,7(2H,6H) -tetraone as monomers, and takes 1,3, 5-tri (4-aldehyde pyridyl) triazine chloride and symmetrical indacene-1, 3,5,7(2H,6H) -tetraone as the molar ratio of 1: (1.3-1.7) and has a structure shown in formula I:
in the formula I, the compound is shown in the specification,
the radicals attached at both ends of the radical being
Three terminal connection of radicalsThe attached group is
The chlorinated 1,3, 5-tri (4-aldehyde pyridyl) triazine has a structure shown in a formula II:
the invention provides a preparation method of a conjugated microporous polymer based on chlorinated 1,3, 5-tri (4-aldehyde pyridyl) triazine in the technical scheme, which comprises the following steps:
cyanuric chloride, 4-pyridine aldehyde and tetrahydrofuran are mixed and subjected to substitution reaction in a protective atmosphere to obtain chlorinated 1,3, 5-tri (4-aldehyde pyridyl) triazine;
mixing the chlorinated 1,3, 5-tri (4-aldehyde pyridyl) triazine, the symmetrical indacene-1, 3,5,7(2H,6H) -tetraone, an organic solvent, an acidic catalyst and water in a protective atmosphere, and carrying out nucleophilic addition-elimination reaction to obtain the conjugated microporous polymer based on the chlorinated 1,3, 5-tri (4-aldehyde pyridyl) triazine with the structure shown in formula I; wherein the molar ratio of the 1,3, 5-tri (4-aldehyde pyridyl) triazine chloride to the sym-indacene-1, 3,5,7(2H,6H) -tetraone is 1: (1.3-1.7).
Preferably, the molar ratio of cyanuric chloride to 4-pyridylaldehyde is 1: (2.5-3.5).
Preferably, the temperature of the substitution reaction is 65-75 ℃, and the time is 70-75 h.
Preferably, the acidic catalyst comprises one or more of formic acid, acetic acid and propionic acid.
Preferably, the volume ratio of the organic solvent to the water is (10-20): 1.
preferably, the organic solvent comprises one or more of n-butanol, o-dichlorobenzene, mesitylene and dioxane.
Preferably, the temperature of the nucleophilic addition-elimination reaction is 110-130 ℃, and the time is 70-75 h.
Preferably, the nucleophilic addition-elimination reaction further comprises, after completion:
and (2) carrying out solid-liquid separation on the obtained system after the nucleophilic addition-elimination reaction is finished, sequentially washing and drying the obtained solid material by adopting N, N-dimethylformamide and ethanol, sequentially carrying out Soxhlet extraction on the obtained dried material by adopting methanol and dichloromethane, and drying to obtain the chlorinated 1,3, 5-tri (4-aldehyde pyridyl) triazine-based conjugated microporous polymer with the structure shown in the formula I.
The invention provides a conjugated microporous polymer based on chlorinated 1,3, 5-tri (4-aldehyde pyridyl) triazine with a structure shown in formula I, wherein the conjugated microporous polymer prepared by introducing symmetric indacene-1, 3,5,7(2H,6H) -tetraone on the basis of chlorinated 1,3, 5-tri (4-aldehyde pyridyl) triazine is in a sheet structure, is an amorphous material and has ultraviolet absorption performance.
The invention provides a preparation method of a conjugated microporous polymer based on chlorinated 1,3, 5-tri (4-aldehyde pyridyl) triazine with a structure shown in formula I, which is simple and feasible and is beneficial to realizing large-scale production.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of 1,3, 5-tris (4-formylpyridyl) triazine chloride in example 1;
FIG. 2 is an infrared spectrum of 1,3, 5-tris (4-formylpyridyl) triazine chloride in example 1;
FIG. 3 is a UV spectrum of 1,3, 5-tris (4-formylpyridyl) triazine chloride in example 1;
FIG. 4 is a nuclear magnetic hydrogen spectrum of the symmetrical indacene-1, 3,5,7(2H,6H) -tetraone in example 1;
FIG. 5 is an infrared spectrum of the symmetrical indacene-1, 3,5,7(2H,6H) -tetraone in example 1;
FIG. 6 is an infrared spectrum of a conjugated microporous polymer based on chlorinated 1,3, 5-tris (4-formylpyridyl) triazine having a structure shown in formula I in example 1;
FIG. 7 is a UV spectrum of a conjugated microporous polymer based on chlorinated 1,3, 5-tris (4-formylpyridyl) triazine having the structure shown in formula I in example 1;
FIG. 8 is a thermogravimetric analysis of the conjugated microporous polymer based on chlorinated 1,3, 5-tris (4-formylpyridyl) triazine having the structure shown in formula I in example 1;
FIG. 9 is an XRD scanning analysis of 1,3, 5-tris (4-formylpyridyl) triazine chloride-based conjugated microporous polymer having the structure shown in formula I in example 1;
FIG. 10 is an electron microscope scan of a conjugated microporous polymer based on chlorinated 1,3, 5-tris (4-aldehydiyl) triazine with the structure shown in formula I in example 1.
Detailed Description
The invention provides a conjugated microporous polymer based on 1,3, 5-tri (4-aldehyde pyridyl) triazine chloride, which takes 1,3, 5-tri (4-aldehyde pyridyl) triazine chloride and symmetrical indacene-1, 3,5,7(2H,6H) -tetraone as monomers, and takes 1,3, 5-tri (4-aldehyde pyridyl) triazine chloride and symmetrical indacene-1, 3,5,7(2H,6H) -tetraone as the molar ratio of 1: (1.3-1.7) and has a structure shown in formula I:
in the formula I, the compound is shown in the specification,
the radicals attached at both ends of the radical being
The three-terminal-linked group of the group is
The chlorinated 1,3, 5-tri (4-aldehyde pyridyl) triazine has a structure shown in a formula II:
the invention provides a preparation method of a conjugated microporous polymer based on chlorinated 1,3, 5-tri (4-aldehyde pyridyl) triazine in the technical scheme, which comprises the following steps:
cyanuric chloride, 4-pyridine aldehyde and tetrahydrofuran are mixed and subjected to substitution reaction in a protective atmosphere to obtain chlorinated 1,3, 5-tri (4-aldehyde pyridyl) triazine;
mixing the chlorinated 1,3, 5-tri (4-aldehyde pyridyl) triazine, the symmetrical indacene-1, 3,5,7(2H,6H) -tetraone, an organic solvent, an acidic catalyst and water in a protective atmosphere, and carrying out nucleophilic addition-elimination reaction to obtain the conjugated microporous polymer based on the chlorinated 1,3, 5-tri (4-aldehyde pyridyl) triazine with the structure shown in formula I; wherein the molar ratio of the 1,3, 5-tri (4-aldehyde pyridyl) triazine chloride to the sym-indacene-1, 3,5,7(2H,6H) -tetraone is 1: (1.3-1.7).
The method mixes cyanuric chloride, 4-pyridine aldehyde and tetrahydrofuran, and carries out substitution reaction in protective atmosphere to obtain chlorinated 1,3, 5-tri (4-aldehyde pyridyl) triazine. In the present invention, the molar ratio of cyanuric chloride to 4-pyridylaldehyde is preferably 1: (2.5-3.5). The invention has no special limitation on the mixture of the cyanuric chloride, the 4-pyridine aldehyde and the tetrahydrofuran, and adopts the technical scheme of material mixing which is well known by the technical personnel in the field; in the present invention, the mixing is preferably performed under stirring conditions. In the invention, the temperature of the substitution reaction is preferably 65-75 ℃, and more preferably 70 ℃; the time is preferably 70-75 h, and more preferably 72 h. The type of the protective gas for providing the protective atmosphere is not particularly limited in the present invention, and a protective gas known to those skilled in the art, such as nitrogen, may be used. In the embodiment of the invention, the cyanuric chloride, the 4-pyridine aldehyde and the tetrahydrofuran are mixed, stirred for 1.5-2.5 hours, materials are fully mixed and initially reacted, and then the reaction is carried out for 70-75 hours at 65-75 ℃ in a protective atmosphere.
After the substitution reaction is finished, the invention preferably performs solid-liquid separation on the obtained system, washes the obtained solid material by adopting tetrahydrofuran and ethanol in sequence, and dries to obtain the chlorinated 1,3, 5-tri (4-aldehyde pyridyl) triazine. The solid-liquid separation mode is not particularly limited, and the technical scheme of solid-liquid separation known to those skilled in the art can be adopted, such as reduced pressure suction filtration. The drying method is not particularly limited, and the materials can be sufficiently dried by adopting a drying technical scheme well known to those skilled in the art.
After 1,3, 5-tri (4-aldehyde pyridyl) triazine chloride is obtained, the invention mixes the 1,3, 5-tri (4-aldehyde pyridyl) triazine chloride, symmetrical indacene-1, 3,5,7(2H,6H) -tetraone, organic solvent, acid catalyst and water in protective atmosphere to carry out nucleophilic addition-elimination reaction to obtain the conjugated microporous polymer based on 1,3, 5-tri (4-aldehyde pyridyl) triazine chloride with the structure shown in formula I; wherein the molar ratio of the 1,3, 5-tri (4-aldehyde pyridyl) triazine chloride to the sym-indacene-1, 3,5,7(2H,6H) -tetraone is 1: (1.3-1.7). In the present invention, the acidic catalyst preferably includes one or more of formic acid, acetic acid and propionic acid.
In the invention, the volume ratio of the organic solvent to the water is preferably (10-20): 1, more preferably (13-17): 1. in the invention, the organic solvent can increase the solubility of the reaction raw materials, and the water can adjust the polarity of the reaction system to ensure the smooth reaction.
In the present invention, the organic solvent preferably includes one or more of n-butanol, o-dichlorobenzene, mesitylene and dioxane.
The source of the symmetrical indacene-1, 3,5,7(2H,6H) -tetraone is not particularly limited in the invention, and the symmetrical indacene-1, 3,5,7(2H,6H) -tetraone can be prepared by a method well known to a person skilled in the art. In an embodiment of the present invention, the preparation method of the symmetric indacene-1, 3,5,7(2H,6H) -tetraone specifically includes the following steps:
mixing pyromellitic anhydride, ethyl acetoacetate and triethylamine under the stirring condition, heating in a water bath to 60-65 ℃, adding acetic anhydride into the obtained mixture, and heating in an oil bath to 98-102 ℃ for refluxing for 2-2.5 h; after the reaction is finished, cooling to room temperature, then cooling for 12-15 h at 0-5 ℃ to obtain light brown precipitates, carrying out vacuum filtration on the obtained materials, washing with acetic anhydride and diethyl ether respectively to obtain orange precipitates, and drying; and (3) mixing the dried product according to the proportion of 1: adding distilled water in a proportion of 100 for dissolving, dropwise adding concentrated sulfuric acid into the obtained material under the ice-water bath condition, continuously dropwise adding 1-2 mL of concentrated sulfuric acid when the solution turns brown, washing the obtained material with ethanol, and drying; and mixing the dried product with 120mL of acetonitrile, reacting for 3-3.5H under the condition of stirring at 90-95 ℃, filtering the obtained material under reduced pressure, washing the obtained solid material with acetonitrile, and drying to obtain the symmetrical indacen-1, 3,5,7(2H,6H) -tetrone.
In the invention, the 1,3, 5-tri (4-aldehyde pyridyl) triazine chloride, the sym-indacene-1, 3,5,7(2H,6H) -tetraone, the organic solvent, the acid catalyst and the water are preferably mixed in a protective atmosphere, the 1,3, 5-tri (4-aldehyde pyridyl) triazine chloride, the sym-indacene-1, 3,5,7(2H,6H) -tetraone and the organic solvent are stirred and mixed for 5-15 min, and then the aqueous solution of the acid catalyst is added into the obtained mixed material.
The type of the protective gas for providing the protective atmosphere is not particularly limited in the present invention, and a protective gas known to those skilled in the art, such as nitrogen, may be used.
In the invention, the temperature of the nucleophilic addition-elimination reaction is preferably 110-130 ℃, and more preferably 120 ℃; the time is preferably 70-75 h, and more preferably 72 h.
After the nucleophilic addition-elimination reaction is completed, the system obtained after the nucleophilic addition-elimination reaction is preferably subjected to solid-liquid separation, the obtained solid material is washed and dried by sequentially adopting N, N-dimethylformamide and ethanol, the obtained dried material is subjected to Soxhlet extraction and drying by sequentially adopting methanol and dichloromethane, and the conjugated microporous polymer based on chlorinated 1,3, 5-tri (4-aldehyde pyridyl) triazine with the structure shown in formula I is obtained. The solid-liquid separation mode is not particularly limited, and the technical scheme of solid-liquid separation known to those skilled in the art can be adopted, such as reduced pressure suction filtration. The washing method of the present invention is not particularly limited, and a washing method known to those skilled in the art may be used. The drying after washing is not particularly limited in the present invention, and the material can be sufficiently dried by a drying technical scheme well known to those skilled in the art. The invention has no special limitation on the Soxhlet extraction, and the technical scheme of the Soxhlet extraction known by the technical personnel in the field can be adopted; the invention adopts methanol and dichloromethane to carry out Soxhlet extraction on the obtained dry material, and aims to ensure that the solvent and unreacted monomers on the surface of the polymer and in the pore canal are fully removed. In the invention, the drying after the Soxhlet extraction is preferably vacuum drying, and the temperature of the vacuum drying is preferably 40-60 ℃, and more preferably 50 ℃; the time is preferably 12 to 24 hours, and more preferably 15 to 20 hours.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation of chlorinated 1,3, 5-tris (4-formylpyridyl) triazines comprises the following steps:
1.1723g of cyanuric chloride, 1.964g of 4-pyridylaldehyde and 80mL of tetrahydrofuran are mixed, stirred for 2 hours and then reacted for 72 hours at 70 ℃ in a protective atmosphere; and carrying out reduced pressure suction filtration on the obtained system, sequentially adopting tetrahydrofuran and ethanol to wash and dry the obtained solid material to obtain the chlorinated 1,3, 5-tri (4-aldehyde pyridyl) triazine.
Preparation of sym-indacene-1, 3,5,7(2H,6H) -tetraone comprising the steps of:
4.9810g of pyromellitic anhydride, 9.0mL of ethyl acetoacetate and 28.0mL of triethylamine are mixed under the stirring condition, the mixture is heated to 60 ℃ in a water bath, 75.0mL of acetic anhydride is added into the mixture, and the mixture is heated to 100 ℃ in an oil bath and refluxed for 2 hours; cooling to room temperature after the reaction is finished, then cooling for 12 hours at the temperature of 0 ℃ to obtain a light brown precipitate, carrying out vacuum filtration on the obtained material, washing with acetic anhydride and diethyl ether respectively to obtain an orange precipitate, and drying; and (3) mixing the dried product according to the proportion of 1: adding distilled water at a ratio of 100 for dissolving, dropwise adding concentrated sulfuric acid into the obtained material under the ice-water bath condition, continuously dropwise adding 1mL of concentrated sulfuric acid when the solution turns brown, washing the obtained material with ethanol, and drying; and mixing the dried product with 120mL of acetonitrile, reacting for 3H under the condition of stirring at 90 ℃, filtering the obtained material under reduced pressure, washing the obtained solid material with the acetonitrile, and drying to obtain 2.3725g of the symmetrical indacen-1, 3,5,7(2H,6H) -tetraone with the yield of 48.5%.
Preparing a conjugated microporous polymer based on chlorinated 1,3, 5-tris (4-formylpyridyl) triazine having the structure shown in formula I, comprising the following steps:
0.5138g of 1,3, 5-tris (4-aldehyde pyridyl) triazine chloride, 0.3526g of symmetrical indacene-1, 3,5,7(2H,6H) -tetraone, 12mL of N-butanol and 28mL of o-dichlorobenzene are mixed under the protection of nitrogen, then 4mL of acetic acid aqueous solution (prepared from 1.4mL of acetic acid and 2.6mL of water) is added into the obtained mixed material, the mixture is stirred and mixed for 20min, the reaction is carried out for 72H at 120 ℃, the obtained system is subjected to vacuum filtration, the obtained solid material is washed and dried by sequentially adopting N, N-dimethylformamide and ethanol, and the obtained dried material is subjected to Soxhlet extraction by adopting methanol and dichloromethane, so that the conjugated microporous polymer (BHY-CMP) based on 1,3, 5-tris (4-aldehyde pyridyl) triazine chloride with the structure shown in formula I is obtained.
The prepared 1,3, 5-tri (4-aldehyde pyridyl) triazine chloride is characterized by comprising the following specific steps:
FIG. 1 is a nuclear magnetic hydrogen spectrum of chlorinated 1,3, 5-tris (4-aldehyde pyridyl) triazine, and it can be seen from FIG. 1 that the absorption peaks at δ ≈ 7.2 are proton peaks at positions 1, 6, and 11 in the compound, the absorption peaks at δ ≈ 1.0 are proton peaks at positions 2,4, 7, 9, 12, and 15 in the compound, the absorption peaks at δ ≈ 0.1 are proton peaks at positions 3,5, 8, 10, 13, and 14 in the compound, and the remaining peaks are impurity peaks. It was confirmed that the compound obtained in this example was indeed 1,3, 5-tris (4-formylpyridyl) triazine chloride.
FIG. 2 shows 1,3, 5-tris (4-Aldehyde pyridyl) triazine, from figure 2, in 3116cm-1The absorption peak of the benzene ring conforms to the absorption frequency range of C-H expansion and contraction in the benzene ring and is 2783cm-1The absorption peak of the compound conforms to the absorption frequency range of aldehyde group C-H and is 1722cm-1The absorption peak of the aldehyde group is in accordance with the absorption frequency range of C ═ O stretching vibration in the aldehyde group and is 1593cm-1The absorption peak of (A) is in accordance with the absorption frequency range of C ═ C in benzene ring, at 840cm-1The absorption peak of the compound conforms to the absorption frequency range of C-C in benzene ring and is 1400cm-1The absorption peak in (A) is consistent with the absorption frequency range of C-N. It was confirmed that the compound obtained in this example was indeed 1,3, 5-tris (4-formylpyridyl) triazine chloride.
FIG. 3 is a graph showing the ultraviolet spectrum of 2,4, 6-tris (4-formylphenoxy) -1,3, 5-triazine, and it can be seen from FIG. 3 that the spectral absorption of the compound is in the ultraviolet-visible range.
The prepared symmetric indacene-1, 3,5,7(2H,6H) -tetraone is characterized as follows:
FIG. 4 is a nuclear magnetic hydrogen spectrum of the symmetric indacene-1, 3,5,7(2H,6H) -tetraone, and it can be seen from FIG. 4 that the proton peaks at positions 2 and 4 in the compound are shown near position delta 7.3, the proton peaks at positions 1 and 3 in the compound are shown near position delta 1.6, and the rest of the peaks are impurity peaks. It was confirmed that the compound obtained in this example was indeed the symmetric indacene-1, 3,5,7(2H,6H) -tetraone.
FIG. 5 is an infrared spectrum of 1,3,5,7(2H,6H) -tetrone of symmetric indacene, as shown in FIG. 5, at 1726cm-1The absorption peak of (A) is in accordance with the absorption frequency range of C ═ O, and is at 1354cm-1The absorption peak of the benzene ring conforms to the absorption frequency range of C ═ C expansion and contraction in the benzene ring, and is 978cm-1The absorption peak corresponds to the absorption frequency range of the C-C absorption peak in the benzene ring. It was confirmed that the compound obtained in this example was indeed the symmetric indacene-1, 3,5,7(2H,6H) -tetraone.
The prepared conjugated microporous polymer (BHY-CMP) based on chlorinated 1,3, 5-tri (4-aldehyde pyridyl) triazine with the structure shown in formula I is characterized as follows:
FIG. 6 is a diagram of a chlorinated 1,3, 5-tris (4-formylpyridyl) tris base having the structure shown in formula IThe infrared spectrum of the conjugated microporous polymer of oxazine is shown in FIG. 6, where the polymer is 2600.35cm-1The characteristic peak of aldehyde group disappears, and the peak is 1678.53cm-1The absorption peak of C ═ C double bond of olefin is shown. It was confirmed that the compound obtained in this example was indeed a conjugated microporous polymer based on chlorinated 1,3, 5-tris (4-formylpyridyl) triazine having the structure shown in formula I.
FIG. 7 is a UV spectrum of a conjugated microporous polymer based on chlorinated 1,3, 5-tris (4-aldehyde pyridyl) triazine with a structure shown in formula I, and it can be seen from FIG. 7 that the spectral absorption of the target polymer is concentrated in the range of 401 to 872nm compared with that of the monomer chlorinated 1,3, 5-tris (4-aldehyde pyridyl) triazine, which indicates that the polymer obtained by polymerizing the monomer with symmetric indacene-1, 3,5,7(2H,6H) -tetraone can achieve full spectral absorption.
FIG. 8 is a thermogravimetric analysis chart of a conjugated microporous polymer based on chlorinated 1,3, 5-tris (4-aldehyde pyridyl) triazine with the structure shown in formula I, and it can be seen from FIG. 8 that the weight loss rate of the polymer is 55.3%; specifically, in the temperature rise process of 17-100 ℃, the weight loss rate is 15.1%, which is mainly caused by the loss of surface adsorbed water and structural water; starting at 100 ℃, the sample mass decreased rapidly with a weight loss of about 40%, indicating that the polymer structure had collapsed and the structure was damaged in this temperature range.
Fig. 9 is an XRD scanning analysis chart of the conjugated microporous polymer based on 1,3, 5-tris (4-aldehyde pyridyl) triazine chloride having the structure shown in formula I, and it can be seen from fig. 9 that the conjugated microporous polymer provided by the present invention has no distinct strong peak, is an amorphous structure, and belongs to an amorphous material.
FIG. 10 is an electron microscope scanning image of a conjugated microporous polymer based on 1,3, 5-tris (4-aldehydiyl) triazine chloride having a structure shown in formula I, and it can be seen from FIG. 10 that the conjugated microporous polymer provided by the present invention has a lamellar structure.
From the above examples, it is clear that the conjugated microporous polymer based on 1,3, 5-tris (4-aldehyde pyridyl) triazine chloride provided by the present invention has a sheet structure, is an amorphous material, has ultraviolet absorption performance, and can be applied to the fields of photocatalysis and the like.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A conjugated microporous polymer based on 1,3, 5-tri (4-aldehyde pyridyl) triazine chloride takes 1,3, 5-tri (4-aldehyde pyridyl) triazine chloride and symmetrical indacene-1, 3,5,7(2H,6H) -tetraone as monomers, and the molar ratio of 1,3, 5-tri (4-aldehyde pyridyl) triazine chloride to symmetrical indacene-1, 3,5,7(2H,6H) -tetraone is 1: (1.3-1.7) and has a structure shown in formula I:
in the formula I, the compound is shown in the specification,
the radicals attached at both ends of the radical being
The three-terminal-linked group of the group is
The chlorinated 1,3, 5-tri (4-aldehyde pyridyl) triazine has a structure shown in a formula II:
2. a process for the preparation of a conjugated microporous polymer based on chlorinated 1,3, 5-tris (4-formylpyridyl) triazine as claimed in claim 1, comprising the steps of:
cyanuric chloride, 4-pyridine aldehyde and tetrahydrofuran are mixed and subjected to substitution reaction in a protective atmosphere to obtain chlorinated 1,3, 5-tri (4-aldehyde pyridyl) triazine;
mixing the chlorinated 1,3, 5-tri (4-aldehyde pyridyl) triazine, the symmetrical indacene-1, 3,5,7(2H,6H) -tetraone, an organic solvent, an acidic catalyst and water in a protective atmosphere, and carrying out nucleophilic addition-elimination reaction to obtain the conjugated microporous polymer based on the chlorinated 1,3, 5-tri (4-aldehyde pyridyl) triazine with the structure shown in formula I; wherein the molar ratio of the 1,3, 5-tri (4-aldehyde pyridyl) triazine chloride to the sym-indacene-1, 3,5,7(2H,6H) -tetraone is 1: (1.3-1.7).
3. The method according to claim 2, wherein the molar ratio of cyanuric chloride to 4-pyridylaldehyde is 1: (2.5-3.5).
4. The preparation method according to claim 2 or 3, wherein the temperature of the substitution reaction is 65-75 ℃ and the time is 70-75 h.
5. The method of claim 2, wherein the acidic catalyst comprises one or more of formic acid, acetic acid, and propionic acid.
6. The preparation method according to claim 2, wherein the volume ratio of the organic solvent to the water is (10-20): 1.
7. the method according to claim 2 or 6, wherein the organic solvent comprises one or more of n-butanol, o-dichlorobenzene, mesitylene, and dioxane.
8. The method according to claim 2, wherein the nucleophilic addition-elimination reaction is carried out at a temperature of 110 to 130 ℃ for 70 to 75 hours.
9. The method of claim 2, further comprising, after completion of the nucleophilic addition-elimination reaction:
and (2) carrying out solid-liquid separation on the obtained system after the nucleophilic addition-elimination reaction is finished, sequentially washing and drying the obtained solid material by adopting N, N-dimethylformamide and ethanol, sequentially carrying out Soxhlet extraction on the obtained dried material by adopting methanol and dichloromethane, and drying to obtain the chlorinated 1,3, 5-tri (4-aldehyde pyridyl) triazine-based conjugated microporous polymer with the structure shown in the formula I.
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| CN111484602B (en) * | 2019-01-28 | 2023-01-06 | 台州学院 | 1,3,6,8-tetra (p-formylphenyl) pyrene-based conjugated microporous polymer and preparation method thereof |
| CN109880086B (en) * | 2019-03-11 | 2020-07-03 | 北京理工大学 | Ionized nano-porous organic network polymer and preparation method and application thereof |
| CN109942814B (en) * | 2019-03-14 | 2021-07-02 | 东华大学 | Pyridyl-containing conjugated microporous polymer and preparation method and application thereof |
| CN110204738B (en) * | 2019-07-15 | 2021-06-04 | 台州学院 | Covalent organic framework material based on 1,3, 5-tri (4-aldehyde pyridyl) triazine and preparation method thereof |
| CN112574395A (en) * | 2019-09-27 | 2021-03-30 | 台州学院 | Conjugated microporous polymer based on 2,4, 6-tri (4-formylphenyl) pyrimidine and preparation method thereof |
| CN112574370B (en) * | 2019-09-27 | 2022-10-04 | 台州学院 | Three-dimensional hydroxyl-containing covalent organic framework material and preparation method thereof |
| CN112574407B (en) * | 2019-09-27 | 2023-01-06 | 台州学院 | 2,4,6-tri (4-aldehyde phenyl) -1,3,5-triazine-based conjugated microporous polymer and preparation method thereof |
| CN112574394A (en) * | 2019-09-27 | 2021-03-30 | 台州学院 | 1,3, 5-tri (4-formylphenyl) benzene-based conjugated microporous polymer and preparation method thereof |
| CN113024778B (en) * | 2019-12-25 | 2023-10-17 | 东莞伏安光电科技有限公司 | N-type polymer prepared based on aldol condensation and preparation method and application thereof |
| CN111848891A (en) * | 2020-08-12 | 2020-10-30 | 台州学院 | Covalent organic polymer based on 2,4, 6-tri (4-formylphenyl) pyrimidine and preparation method thereof |
| CN111793196B (en) * | 2020-08-12 | 2022-04-12 | 台州学院 | Tetra- (4-aldehyde- (1, 1-biphenyl)) methane-based conjugated organic microporous polymer and preparation method thereof |
| CN112961299A (en) * | 2021-02-06 | 2021-06-15 | 台州学院 | Covalent-organic framework material and preparation method thereof |
| CN115433331B (en) * | 2022-08-12 | 2023-10-31 | 南昌大学 | Preparation method of alkene-linked covalent organic framework and photocatalytic application thereof |
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