CN112574394A - 1,3, 5-tri (4-formylphenyl) benzene-based conjugated microporous polymer and preparation method thereof - Google Patents

1,3, 5-tri (4-formylphenyl) benzene-based conjugated microporous polymer and preparation method thereof Download PDF

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CN112574394A
CN112574394A CN201910925350.1A CN201910925350A CN112574394A CN 112574394 A CN112574394 A CN 112574394A CN 201910925350 A CN201910925350 A CN 201910925350A CN 112574394 A CN112574394 A CN 112574394A
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benzene
formylphenyl
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conjugated microporous
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任世斌
吴建波
许振浩
胡黛玉
韩得满
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Taizhou University
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Abstract

The invention provides a conjugated microporous polymer based on 1,3, 5-tri (4-formylphenyl) benzene and a preparation method thereof, belonging to the technical field of conjugated microporous polymers. The invention mixes 1,3, 5-tri (4-formylphenyl) benzene, symmetrical indacene-1, 3,5,7(2H,6H) -tetraone, organic solvent and acid reagent water solution, and carries out nucleophilic addition reaction in protective atmosphere to obtain the conjugated microporous polymer based on 1,3, 5-tri (4-formylphenyl) benzene. According to the invention, the symmetric indacene-1, 3,5,7(2H,6H) -tetraone is introduced on the basis of 1,3, 5-tri (4-formylphenyl) benzene, and the prepared conjugated microporous polymer is a loose and irregular polymer with a porous structure, has better thermal stability and chemical stability, and can be used as a high polymer material to be applied to the fields of lithium ion electronic materials and the like.

Description

1,3, 5-tri (4-formylphenyl) benzene-based conjugated microporous polymer and preparation method thereof
Technical Field
The invention relates to the technical field of conjugated microporous polymers, in particular to a conjugated microporous polymer based on 1,3, 5-tri (4-formylphenyl) benzene and a preparation method thereof.
Background
Conjugated Microporous Polymers (CMPs) are compounds with a three-dimensional network structure combined through covalent bonds, the compounds are used as one class of organic porous Materials (MOPs), the conjugated microporous polymers have micropores and unique pi-pi conjugated structures, have the advantages of good chemical stability, large specific surface area, adjustability and controllability and the like, and are widely applied in the fields of energy storage, gas storage, catalysts, adsorption, biosensors, light capture and the like in recent years.
However, the prior art has a small number of CMPs and cannot meet the social demand for diversified CMPs.
Disclosure of Invention
The invention aims to provide a 1,3, 5-tri (4-formylphenyl) benzene-based conjugated microporous polymer and a preparation method thereof, and the 1,3, 5-tri (4-formylphenyl) benzene-based conjugated microporous polymer prepared by the method is a loose and irregular polymer with a porous structure and has better thermal stability and chemical stability.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a 1,3, 5-tri (4-formylphenyl) benzene-based conjugated microporous polymer, which comprises the following steps:
mixing 1,3, 5-tri (4-formylphenyl) benzene, symmetrical indacene-1, 3,5,7(2H,6H) -tetraone, an organic solvent and an aqueous solution of an acid reagent, and carrying out nucleophilic addition reaction in a protective atmosphere to obtain the conjugated microporous polymer based on the 1,3, 5-tri (4-formylphenyl) benzene.
Preferably, the molar ratio of 1,3, 5-tris (4-formylphenyl) benzene to sym-indacene-1, 3,5,7(2H,6H) -tetraone is 1: (2.5-3.0).
Preferably, the dosage ratio of the 1,3, 5-tri (4-formylphenyl) benzene, the organic solvent and the acid reagent aqueous solution is 1.3 mmol: (15-25) mL: (1.5-2.5) mL; the concentration of the acidic reagent aqueous solution is 5-7 mol/L.
Preferably, the organic solvent includes at least two of o-dichlorobenzene, n-butanol, toluene and dioxane.
Preferably, the organic solvent is an o-dichlorobenzene-n-butanol mixed solvent or a toluene-dioxane mixed solvent.
Preferably, in the o-dichlorobenzene-n-butanol mixed solvent, the volume ratio of o-dichlorobenzene to n-butanol is (2.0-2.5): 1, in the toluene-dioxane mixed solvent, the volume ratio of toluene to dioxane is (3-5): 1.
preferably, the acidic reagent in the aqueous acidic reagent solution comprises formic acid, acetic acid, propionic acid or lactic acid.
Preferably, the temperature of the nucleophilic addition reaction is 115-125 ℃, and the time is 72-80 h.
Preferably, the nucleophilic addition reaction is completed and then comprises post-treatment, and the post-treatment comprises:
and mixing the system obtained after the nucleophilic addition reaction is finished with ethanol, then carrying out solid-liquid separation, drying the obtained solid material, then carrying out Soxhlet extraction on the obtained dried material by adopting methanol, and drying the polymer after the Soxhlet extraction to obtain the 1,3, 5-tri (4-formylphenyl) benzene-based conjugated microporous polymer.
The invention provides a 1,3, 5-tri (4-formylphenyl) benzene-based conjugated microporous polymer prepared by the preparation method in the technical scheme, which has a structure shown in a formula I:
Figure BDA0002218806840000021
in the formula I, the compound is shown in the specification,
Figure BDA0002218806840000031
the radicals attached at both ends of the radical being
Figure BDA0002218806840000032
Figure BDA0002218806840000033
The three-terminal-linked group of the group is
Figure BDA0002218806840000034
The invention provides a preparation method of a 1,3, 5-tri (4-formylphenyl) benzene-based conjugated microporous polymer, which comprises the following steps: mixing 1,3, 5-tri (4-formylphenyl) benzene, symmetrical indacene-1, 3,5,7(2H,6H) -tetraone, an organic solvent and an aqueous solution of an acid reagent, and carrying out nucleophilic addition reaction in a protective atmosphere to obtain the conjugated microporous polymer based on the 1,3, 5-tri (4-formylphenyl) benzene. According to the invention, the symmetric indacene-1, 3,5,7(2H,6H) -tetraone is introduced on the basis of 1,3, 5-tri (4-formylphenyl) benzene, and the prepared conjugated microporous polymer is a loose and irregular polymer with a porous structure, has better thermal stability and chemical stability, and can be used as a high polymer material to be applied to the fields of lithium ion electronic materials and the like.
The preparation method of the 1,3, 5-tri (4-formylphenyl) benzene-based conjugated microporous polymer is simple and easy to implement, and is beneficial to realizing large-scale production.
Drawings
FIG. 1 is an infrared spectrum of 1,3, 5-tris (4-formylphenyl) benzene;
FIG. 2 is a nuclear magnetic hydrogen spectrum of 1,3, 5-tris (4-formylphenyl) benzene;
FIG. 3 is an infrared spectrum of XZH-CMP;
FIG. 4 is a thermogravimetric analysis plot of XZH-CMP;
FIG. 5 is a scanning electron micrograph of XZH-CMP;
FIG. 6 is a UV spectrum of XZH-CMP;
FIG. 7 is an XRD pattern of XZH-CMP.
Detailed Description
The invention provides a preparation method of a 1,3, 5-tri (4-formylphenyl) benzene-based conjugated microporous polymer, which comprises the following steps:
mixing 1,3, 5-tri (4-formylphenyl) benzene, symmetric indacene-1, 3,5,7(2H,6H) -tetraone, an organic solvent and an aqueous solution of an acidic reagent, and carrying out nucleophilic addition reaction in a protective atmosphere to obtain the 1,3, 5-tri (4-formylphenyl) benzene-based conjugated microporous polymer with the structure shown in formula I.
In the present invention, the molar ratio of 1,3, 5-tris (4-formylphenyl) benzene to sym-indacene-1, 3,5,7(2H,6H) -tetraone is preferably 1: (2.5 to 3.0), more preferably 1: (2.5-2.7). In the present invention, the ratio of the amount of 1,3, 5-tris (4-formylphenyl) benzene, the organic solvent and the aqueous solution of the acidic reagent is preferably 1.3 mmol: (15-25) mL: (1.5-2.5) mL, more preferably 1.3 mmol: 20mL of: 2 mL; the concentration of the acidic reagent aqueous solution is preferably 5-7 mol/L. In the present invention, the acidic agent in the acidic agent aqueous solution preferably includes formic acid, acetic acid, propionic acid or lactic acid.
In the present invention, the organic solvent preferably includes at least two of o-dichlorobenzene, n-butanol, toluene and dioxane, more preferably an o-dichlorobenzene-n-butanol mixed solvent or a toluene-dioxane mixed solvent, wherein the volume ratio of o-dichlorobenzene to n-butanol in the o-dichlorobenzene-n-butanol mixed solvent is preferably (2.0 to 2.5): in the toluene-dioxane mixed solvent, the volume ratio of toluene to dioxane is preferably (3-5): 1.
the sources of the 1,3, 5-tri (4-formylphenyl) benzene and the symmetric indacene-1, 3,5,7(2H,6H) -tetraone are not specially limited, and the method can adopt commercial products or self-made products. In the embodiment of the present invention, the sym-indacene-1, 3,5,7(2H,6H) -tetraone is preferably commercially available, the 1,3, 5-tris (4-formylphenyl) benzene is preferably self-made, and the preparation method preferably comprises the following steps:
mixing 1,3, 5-tribromobenzene, 4-formylphenylboronic acid, dioxane and anhydrous potassium carbonate, heating to 80-90 ℃ under the protection of nitrogen, adding a tetrakis (triphenylphosphine) palladium catalyst under the condition of magnetic stirring, vacuumizing, and carrying out Suzuki coupling reaction for 45-50 h under the condition of condensation reflux;
after the reaction is finished, carrying out rotary evaporation on the obtained product system, adding ethyl acetate to dissolve the product system after the rotary evaporation is finished, pouring the obtained feed liquid into a separating funnel, adding a saturated sodium chloride solution, shaking the mixture, taking an upper organic layer, drying the organic layer with anhydrous magnesium sulfate overnight, then carrying out suction filtration, carrying out rotary evaporation on the filtrate, mixing the residue with anhydrous ethanol after the rotary evaporation is finished, carrying out ultrasonic treatment, then carrying out suction filtration, drying the obtained filter cake in an oven, purifying the dried product by using dichloromethane as a solvent through a column chromatography method, obtaining a crude product after the rotary evaporation of the obtained purified product, and then carrying out recrystallization purification by using tetrahydrofuran as a solvent to obtain the 1,3, 5-tri (4-formylphenyl) benzene.
In the invention, the preparation process of the 1,3, 5-tri (4-formylphenyl) benzene specifically comprises the following steps:
Figure BDA0002218806840000051
in the present invention, the mixing of the 1,3, 5-tris (4-formylphenyl) benzene, the indacene-1, 3,5,7(2H,6H) -tetrone, the organic solvent and the aqueous solution of the acidic reagent is preferably performed in a protective atmosphere, and more preferably, the 1,3, 5-tris (4-formylphenyl) benzene, the indacene-1, 3,5,7(2H,6H) -tetrone and the organic solvent are mixed under stirring in a protective atmosphere for 15 to 25min, and then the aqueous solution of the acidic reagent is added to mix. 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 reaction is preferably 115-125 ℃, and more preferably 120 ℃; the time is preferably 72 to 80 hours, and more preferably 72 to 75 hours. In the present invention, the nucleophilic addition reaction is preferably carried out in a protective atmosphere; 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 present invention, it is preferable that the nucleophilic addition reaction is completed and then includes a post-treatment, and the post-treatment preferably includes:
and mixing the system obtained after the nucleophilic addition reaction is finished with ethanol, then carrying out solid-liquid separation, drying the obtained solid material, then carrying out Soxhlet extraction on the obtained dried material by adopting methanol, and drying the polymer after the Soxhlet extraction to obtain the 1,3, 5-tri (4-formylphenyl) benzene-based conjugated microporous polymer with the structure shown in the formula I.
The solid-liquid separation mode is not particularly limited, and the technical scheme of solid-liquid separation known to those skilled in the art, such as suction filtration, can be adopted. The drying after the solid-liquid separation is not particularly limited, and the drying can be carried out by heating in an oven.
The specific operation mode of the Soxhlet extraction is not specially limited, and the technical scheme of the Soxhlet extraction, which is well known by the technical personnel in the field, can be adopted; in the embodiment of the invention, the Soxhlet extraction temperature is preferably 60-80 ℃, and the time is preferably 12-24 h; the invention adopts anhydrous methanol for Soxhlet extraction, and aims to ensure that solvents and unreacted monomers on the surface of a polymer and in the pore canal are removed fully.
In the present invention, the form of drying the polymer after the soxhlet extraction is preferably vacuum drying, but the vacuum drying is not particularly limited, and the polymer after the soxhlet extraction may be sufficiently dried.
In the present invention, the preparation process of the 1,3, 5-tris (4-formylphenyl) benzene-based conjugated microporous polymer is specifically as follows:
Figure BDA0002218806840000061
the invention provides a 1,3, 5-tri (4-formylphenyl) benzene-based conjugated microporous polymer prepared by the preparation method in the technical scheme, which has a structure shown in a formula I:
Figure BDA0002218806840000062
in the formula I, the compound is shown in the specification,
Figure BDA0002218806840000071
the radicals attached at both ends of the radical being
Figure BDA0002218806840000072
Figure BDA0002218806840000073
The three-terminal-linked group of the group is
Figure BDA0002218806840000074
According to the invention, the symmetric indacene-1, 3,5,7(2H,6H) -tetraone is introduced on the basis of 1,3, 5-tri (4-formylphenyl) benzene, and the prepared conjugated microporous polymer is a loose and irregular polymer with a porous structure, has better thermal stability and chemical stability, and can be used as a high polymer material to be applied to the fields of lithium ion electronic materials and the like.
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 1,3, 5-tri (4-formylphenyl) benzene comprises the following steps:
adding 3.14g of 1,3, 5-tribromobenzene, 4.5g of 4-formylphenylboronic acid, 120mL of dioxane and 3g of anhydrous potassium carbonate into a three-neck flask, heating to 85 ℃ under the protection of nitrogen, adding a tetrakis (triphenylphosphine) palladium catalyst under the condition of magnetic stirring, vacuumizing, and carrying out Suzuki coupling reaction for 48 hours under the condition of condensation reflux;
after the reaction is finished, carrying out rotary evaporation on the obtained product system, adding 40mL of ethyl acetate to dissolve the product system after the rotary evaporation is finished, pouring the obtained feed liquid into a separating funnel, adding 20mL of saturated sodium chloride solution, taking an upper organic layer after shaking, drying the organic layer with anhydrous magnesium sulfate overnight, then carrying out suction filtration, carrying out rotary evaporation on the filtrate, mixing the residue with 30mL of anhydrous ethanol after the rotary evaporation is finished, carrying out ultrasonic treatment, then carrying out suction filtration, drying the obtained filter cake in an oven, purifying the dried product by taking dichloromethane as a solvent through a column chromatography method, obtaining a crude product after the rotary evaporation of the obtained purified product, and then carrying out recrystallization purification by taking tetrahydrofuran as a solvent to obtain the 1,3, 5-tris (4-formylphenyl) benzene.
Preparing a 1,3, 5-tris (4-formylphenyl) benzene-based conjugated microporous polymer having a structure represented by formula I, comprising the steps of:
adding 0.51g of 1,3, 5-tri (4-formylphenyl) benzene, 0.76g of symmetric indacene-1, 3,5,7(2H,6H) -tetraone, 14mL of o-dichlorobenzene and 6mL of n-butanol into a round-bottom flask, magnetically stirring for 20min at normal temperature under the protection of nitrogen, adding 2mL of acetic acid with the concentration of 6mol/L, and carrying out nucleophilic addition reaction for 72H at 120 ℃ under the protection of nitrogen; after the reaction is finished, mixing the obtained product system with 20mL of ethanol, then carrying out suction filtration, placing the obtained filter cake in an oven for drying, then carrying out Soxhlet extraction on the dried material by taking anhydrous methanol as a solvent (the temperature is 70 ℃ and the time is 18 hours), and carrying out vacuum drying on the polymer after the Soxhlet extraction to obtain the conjugated microporous polymer (abbreviated as XZH-CMP) based on 1,3, 5-tri (4-formylphenyl) benzene with the structure shown in formula I.
The 1,3, 5-tri (4-formylphenyl) benzene prepared is characterized by the following details:
FIG. 1 is an infrared spectrum of 1,3, 5-tris (4-formylphenyl) benzene at 1593.52cm, as can be seen from FIG. 1-1The absorption peak at (A) corresponds to the absorption peak of C ═ C of the carbon-carbon double bond in the benzene ring, and is 792.74cm-1The absorption peak corresponds to the absorption peak of C-C single bond in benzene ring, which is 1687.72cm-1The CHO absorption peak shows that the prepared compound is actually 1,3, 5-tri (4-formylphenyl) benzene.
FIG. 2 is a nuclear magnetic hydrogen spectrum of 1,3, 5-tris (4-formylphenyl) benzene, and it can be seen from FIG. 2 that the absorption peak at δ ≈ 10.11 is the proton peak at products 1, 11, 18; the absorption peak at δ ≈ 8.02 is the proton peak at products 2, 3, 10, 12, 15, 17; the absorption peak at δ ≈ 7.91 is the proton peak at products 6, 7, 8; the absorption peak at δ ≈ 7.87 is the proton peak at products 4, 5, 9, 13, 14, 16; peaks appearing elsewhere are impurity peaks. Thus, the prepared compound is 1,3, 5-tri (4-formylphenyl) benzene.
The XZH-CMP prepared by the method is characterized by comprising the following specific steps:
FIG. 3 is an infrared spectrum of XZH-CMPAs can be seen from FIG. 3, the length of the groove is 1577.77cm-1The absorption peak at (A) corresponds to the absorption peak of C ═ C of the carbon-carbon double bond in the benzene ring, 792.74cm-1The absorption peak corresponds to the absorption peak of the carbon-carbon single bond C-C in the benzene ring, which is 1685.79cm-1The peak is the absorption peak of C ═ O at 1022.27cm-1The absorption peak is the bending vibration in the C-H bond face of the C ═ C-CH olefin double bond, and the rest are the miscellaneous peaks. Compared with the infrared spectrum of the 1,3, 5-tri (4-formylphenyl) benzene, the disappearance of the aldehyde group on the 1,3, 5-tri (4-formylphenyl) benzene and the increase of 1022.27cm can be seen-1The absorption peak at (b) is the bending vibration in the C — H bond plane on the C ═ C — CH olefin double bond, indicating that the direction and the result of the nucleophilic addition reaction are consistent with those expected and the degree of the reaction is relatively complete.
FIG. 4 is a thermogravimetric analysis chart of XZH-CMP, and it can be seen from FIG. 4 that the mass of the XZH-CMP sample is reduced by 3.5% in the first temperature variation interval, i.e. the interval of 0-70 deg.C, which indicates that the XZH-CMP sample originally contains a certain amount of H2O, moisture evaporates in the case of heating, and a phenomenon occurs in which the quality of the sample is degraded. And (3) continuing heating, wherein the temperature is increased from 70 ℃ to 280 ℃, and the quality of the XZH-CMP sample does not change remarkably in the temperature range, which indicates that the XZH-CMP sample does not decompose at the stage, namely the material structure of the sample is not changed, the sample is maintained to be stable and not decompose, and the thermal stability of the sample at the stage is good. The temperature continued to rise from 280 c to 785.5 c, at which stage there was a significant reduction in the mass of the sample, indicating that the sample had decomposed at elevated temperatures above 280 c.
FIG. 5 is a scanning electron micrograph of XZH-CMP (high-magnification scanning electron micrograph on the left side and low-magnification scanning electron micrograph on the right side), and it can be seen from FIG. 5 that XZH-CMP is a loose, random polymer with a porous structure.
FIG. 6 is a graph of the UV spectrum of XZH-CMP, and it can be seen from FIG. 6 that the XZH-CMP has an absorption band extending from 200nm to 600nm, indicating that the XZH-CMP has UV-visible absorption properties.
FIG. 7 is an XRD pattern of XZH-CMP, and it can be seen from FIG. 7 that no sharp peak is present in the XRD pattern of XZH-CMP, and the area of the peak is small, so that XZH-CMP does not have a regular structure of crystals, but is a porous and irregular substance, and the same result as that obtained in FIG. 5 is obtained.
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 (10)

1. A method for preparing a 1,3, 5-tris (4-formylphenyl) benzene-based conjugated microporous polymer, comprising the steps of:
mixing 1,3, 5-tri (4-formylphenyl) benzene, symmetrical indacene-1, 3,5,7(2H,6H) -tetraone, an organic solvent and an aqueous solution of an acid reagent, and carrying out nucleophilic addition reaction in a protective atmosphere to obtain the conjugated microporous polymer based on the 1,3, 5-tri (4-formylphenyl) benzene.
2. The process according to claim 1, wherein the molar ratio of 1,3, 5-tris (4-formylphenyl) benzene to sym-indacene-1, 3,5,7(2H,6H) -tetraone is 1: (2.5-3.0).
3. The method according to claim 2, wherein the 1,3, 5-tris (4-formylphenyl) benzene, the organic solvent and the aqueous acidic reagent solution are used in a ratio of 1.3 mmol: (15-25) mL: (1.5-2.5) mL; the concentration of the acidic reagent aqueous solution is 5-7 mol/L.
4. The production method according to claim 1 or 3, wherein the organic solvent comprises at least two of o-dichlorobenzene, n-butanol, toluene and dioxane.
5. The method according to claim 4, wherein the organic solvent is a mixed solvent of o-dichlorobenzene and n-butanol or a mixed solvent of toluene and dioxane.
6. The preparation method according to claim 5, wherein in the o-dichlorobenzene-n-butanol mixed solvent, the volume ratio of o-dichlorobenzene to n-butanol is (2.0-2.5): 1, in the toluene-dioxane mixed solvent, the volume ratio of toluene to dioxane is (3-5): 1.
7. the method according to claim 1 or 3, wherein the acidic reagent in the aqueous acidic reagent solution comprises formic acid, acetic acid, propionic acid or lactic acid.
8. The preparation method according to claim 1, wherein the temperature of the nucleophilic addition reaction is 115-125 ℃ and the time is 72-80 h.
9. The method of claim 1 or 8, further comprising a post-treatment after completion of the nucleophilic addition reaction, the post-treatment comprising:
and mixing the system obtained after the nucleophilic addition reaction is finished with ethanol, then carrying out solid-liquid separation, drying the obtained solid material, then carrying out Soxhlet extraction on the obtained dried material by adopting methanol, and drying the polymer after the Soxhlet extraction to obtain the 1,3, 5-tri (4-formylphenyl) benzene-based conjugated microporous polymer.
10. The 1,3, 5-tri (4-formylphenyl) benzene-based conjugated microporous polymer prepared by the preparation method of any one of claims 1 to 9, which is characterized by having a structure shown in a formula I:
Figure FDA0002218806830000021
in the formula I, the compound is shown in the specification,
Figure FDA0002218806830000022
the radicals attached at both ends of the radical being
Figure FDA0002218806830000023
Figure FDA0002218806830000024
The three-terminal-linked group of the group is
Figure FDA0002218806830000025
CN201910925350.1A 2019-09-27 2019-09-27 1,3, 5-tri (4-formylphenyl) benzene-based conjugated microporous polymer and preparation method thereof Pending CN112574394A (en)

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CN108892759A (en) * 2018-06-07 2018-11-27 台州学院 A kind of conjugation microporous polymer and preparation method thereof
CN109251285A (en) * 2018-09-21 2019-01-22 台州学院 Conjugation microporous polymer and preparation method thereof based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine
CN109320734A (en) * 2018-10-29 2019-02-12 福州大学 A kind of spherical shape covalent organic framework material and its preparation method and application
CN110218301A (en) * 2019-07-15 2019-09-10 台州学院 One kind being based on the organic microporous polymer of conjugation and preparation method thereof of 1,3,5- tri- (4- Fonnylphenyl) benzene

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108892759A (en) * 2018-06-07 2018-11-27 台州学院 A kind of conjugation microporous polymer and preparation method thereof
CN109251285A (en) * 2018-09-21 2019-01-22 台州学院 Conjugation microporous polymer and preparation method thereof based on 1,3,5- tri- (4- aldehyde radical pyridyl group) triazine
CN109320734A (en) * 2018-10-29 2019-02-12 福州大学 A kind of spherical shape covalent organic framework material and its preparation method and application
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