CN110776665B

CN110776665B - Multifunctional two-dimensional porous polymer hybrid material and preparation method and application thereof

Info

Publication number: CN110776665B
Application number: CN201911071564.3A
Authority: CN
Inventors: 吴丁财; 黄文�; 刘倩彤; 郑冰娜; 符若文
Original assignee: Sun Yat Sen University
Current assignee: Sun Yat Sen University
Priority date: 2019-11-05
Filing date: 2019-11-05
Publication date: 2022-04-12
Anticipated expiration: 2039-11-05
Also published as: CN110776665A

Abstract

The invention provides a multifunctional two-dimensional porous polymer hybrid material, and a preparation method and application thereof. The two-dimensional porous high-molecular hybrid material is prepared by modifying a functional porous polymer on the surface of graphene oxide, and the hybrid material has a two-dimensional sheet shape and a surface microporous structure. After the multifunctional two-dimensional porous polymer hybrid material is assembled into a water filtering layer, the material microcosmically presents a porous structure formed by mutually lapping two-dimensional nano sheets. The multifunctional two-dimensional porous polymer hybrid material provided by the invention has the structural and functional characteristics of two-dimensional graphene oxide and a functional porous organic polymer, has ultrahigh water permeability and high-efficiency pollutant removal performance after being assembled into a water filtering layer, also provides an integrated solution for simultaneously detecting and separating pollutants, and has wide application prospects in the field of environmental management.

Description

Multifunctional two-dimensional porous polymer hybrid material and preparation method and application thereof

Technical Field

The invention relates to the field of two-dimensional nano materials, in particular to a multifunctional two-dimensional porous polymer hybrid material and a preparation method and application thereof.

Background

The porous polymer has the advantages of good porosity, high specific surface area, controllable pore structure, chemical modification and the like, and the porous polymer realizes the aims of easy modification, high absorption, quick separation and the like on the basis of molecular size, charge affinity and chemical bonds. Nevertheless, most adsorbents are still subject to very slow adsorption kinetics, often requiring minutes or even hours to reach equilibrium. The potential for rapid contamination isolation has not been fully exploited due to the synergistic effect of chemical and structural properties. In addition, the regeneration cycle of the adsorbate requires a large amount of energy to be consumed due to the exothermic nature of the adsorption process. Graphene oxide aerogel, on the other hand, is another novel porous environmental control material. The combination of low density and large interconnected macropores makes graphene oxide aerogel an ideal choice for petroleum collection. A large amount of hydrophobic oil and organic solvent have an affinity effect on the reduced graphene oxide flakes. The graphene oxide aerogel has a large mass transfer channel and a high adsorption speed, and is particularly suitable for oil with high viscosity. However, the surface of the reduced graphene oxide has no additional nano-pores, so that the graphene oxide aerogel cannot collect low-concentration pollutants in common wastewater treatment. Therefore, a suitable pore structure and function are required to further expand the application of the graphene oxide aerogel.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provides a multifunctional two-dimensional porous polymer hybrid material, a preparation method and application thereof.

In order to achieve the above purpose, the present application provides the following technical solutions:

in a first aspect, the invention provides a multifunctional two-dimensional porous polymer hybrid material, which is prepared by modifying a functional porous polymer on the surface of graphene oxide.

Preferably, the functional porous polymer is prepared by polymerizing 4-chloromethyl styrene, pre-crosslinking, super-crosslinking pore-forming and modifying organic functional groups.

In a second aspect, the invention provides a preparation method of a multifunctional two-dimensional porous polymer hybrid material, which comprises the following steps:

(1) mixing 4-chloromethyl styrene and a cross-linking agent I, dropwise adding the mixture into an aqueous solution containing graphene oxide, heating to 60-80 ℃, adding an initiator, carrying out reflux reaction for 4-8 hours in an inert atmosphere, washing the mixed solution with ethanol and/or water, carrying out centrifugal separation, and carrying out freeze drying to obtain an intermediate product I;

(2) adding the intermediate product I prepared in the step (1) into glacial acetic acid, uniformly stirring, adding a cross-linking agent II and a catalyst I, reacting for 2-4 h at 70-90 ℃, adding an acetone/hydrochloric acid/water mixed solvent to terminate the reaction, and filtering, washing and freeze-drying to obtain an intermediate product II;

(3) dispersing the intermediate product II prepared in the step (2) in a solvent I, swelling overnight, adding a catalyst II at 65-85 ℃, stirring to react for 12-46 h, adding an acetone/hydrochloric acid/water mixed solvent to terminate the reaction, filtering, washing, and freeze-drying to obtain an intermediate product III;

(4) and (3) mixing the intermediate product III prepared in the step (3) with N- (2-aminoethyl) carbazole, cesium carbonate and anhydrous dimethylformamide, continuously stirring and reacting for 16-32 hours at room temperature in a dark place, washing with dimethylformamide and water, performing centrifugal separation, and then performing freeze drying to obtain the multifunctional two-dimensional porous polymer hybrid material.

Preferably, the first crosslinking agent in step (1) is divinylbenzene.

Preferably, the volume ratio of the 4-chloromethyl styrene to the first crosslinking agent in the step (1) is 10-150: 1 ml/ml.

Further preferably, the mixed solvent of 4-chloromethylstyrene and the cross-linking agent in the step (1) adopts a micro-sampling pumpDropwise adding the solution into an aqueous solution of graphene oxide at a sample injection speed of 4000-5000 mu L.h^-1。

Preferably, the volume-to-mass ratio of the 4-chloromethyl styrene to the graphene oxide in the step (1) is 1: 10-170 ml/mg.

Preferably, the mass-to-volume ratio of the graphene oxide to the water in the step (1) is 1.25-12.5: 1 mg/ml.

Preferably, the initiator in step (1) comprises one or more of azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate.

Preferably, the volume molar ratio of the 4-chloromethyl styrene to the initiator in the step (1) is 1: 0.015-0.02 ml/mmol.

Preferably, the inert atmosphere in step (1) comprises one or more of nitrogen, argon and helium.

Preferably, step (1) is carried out for 8h under an inert atmosphere.

Preferably, the reaction temperature in step (1) is 75 ℃.

Preferably, the mass-to-volume ratio of the intermediate product I and the glacial acetic acid in the step (2) is 1-2: 1 mg/ml.

Preferably, the second crosslinking agent in step (2) comprises one or more of dimethoxymethane and carbon tetrachloride.

Preferably, the mass volume ratio of the intermediate product I and the cross-linking agent II in the step (2) is 1: 9-110 g/ml.

Preferably, the catalyst I in the step (2) comprises one or more of anhydrous ferric trichloride and anhydrous aluminum trichloride.

Preferably, the mass ratio of the first intermediate product to the first catalyst in the step (2) is 1: 100-200 g/g.

Preferably, the reflux temperature in step (2) is 80 ℃.

Preferably, the reaction time in step (2) is 4 h.

Preferably, the volume ratio of the hydrochloric acid to the water to the acetone in the acetone/hydrochloric acid/water mixed solvent in the step (2) is 1:3: 4.

Preferably, the solvent in step (3) includes one or more of 1, 2-dichloroethane, dichloromethane, chloroform and carbon tetrachloride.

Preferably, the mass-to-volume ratio of the intermediate product II to the solvent I in the step (3) is 1: 0.5-50 mg/ml.

Preferably, the second catalyst in the step (3) comprises one or more of anhydrous ferric trichloride and anhydrous aluminum trichloride.

Preferably, the mass ratio of the intermediate product II to the catalyst II in the step (3) is 1: 100-200 g/g.

Preferably, the reflux temperature in step (3) is 75 ℃.

Preferably, the reaction time in step (3) is 24 h.

Preferably, the mass ratio of the intermediate product III to the N- (2-aminoethyl) carbazole in the step (4) is 1.5-2.5: 1 g/g.

Preferably, the mass ratio of the intermediate product III to the cesium carbonate in the step (4) is 1: 4-6 g/g.

Preferably, the mass-to-volume ratio of the intermediate product III to the anhydrous dimethylformamide in the step (4) is 18-22: 1 mg/ml.

Preferably, the reaction time in step (4) is 24 h.

Preferably, the multifunctional two-dimensional porous polymer hybrid material according to the first aspect is prepared by the preparation method of the multifunctional two-dimensional porous polymer hybrid material according to the second aspect.

The principle of the invention is as follows: the invention provides a multifunctional two-dimensional porous polymer hybrid material and a preparation method and application thereof. The method is characterized in that benzyl chloride of microporous polychloromethylstyrene nanosheets GO @ xPCMS is used as an active grafting site, and carbazolyl fluorescent groups are grafted on the surface of GO @ xPCMS through substitution reaction of N- (2-aminoethyl) carbazole on easily-removed chlorine atoms, so that the design and construction of a two-dimensional porous functional material are realized, and a novel multifunctional two-dimensional porous polymer hybrid material is developed. Since self-crosslinking pore-forming is carried out on the surface and inside of the high molecular polymer, the good mechanical property of the graphene/polymer hybrid material is realized, and a porous structure is introduced. And an organic modification strategy is further utilized, so that the fluorescent response and the rapid adsorption function of trace organic molecules in the water body are realized. The water filtering layer formed by assembling the material has a macroporous structure, which is beneficial to the rapid passing of a solvent and the rapid adsorption characteristic of the material, thereby realizing the rapid treatment of pollutants.

In a third aspect, the invention provides an application of the multifunctional two-dimensional porous polymer hybrid material as described in the first aspect in pollutant detection and pollutant adsorption separation.

In a fourth aspect, the invention provides an application of the preparation method of the multifunctional two-dimensional porous polymer hybrid material in pollutant detection and pollutant adsorption separation.

In a fifth aspect, the invention provides a filter material, wherein the filter material is prepared by dispersing the multifunctional two-dimensional porous polymer hybrid material in a solvent, and assembling with a microporous filter membrane as a support membrane.

Preferably, the solvent comprises one or more of water, ethanol, methanol, N-dimethylformamide and acetonitrile.

Preferably, the assembling method comprises one or more of vacuum filtration, positive pressure filtration and coating volatilization.

Preferably, the thickness of the filter material is 10-100 μm.

The invention has the following beneficial effects:

(1) the multifunctional two-dimensional porous high-molecular hybrid material prepared by the invention has unique structures and performances of a functional porous organic polymer and two-dimensional graphene oxide, has a sandwich-like nano structure, has rich pore structures and good pore utilization rate, can reach adsorption balance within 30s, and is obviously superior to the traditional adsorbent;

(2) the water filtering layer assembled by using the multifunctional two-dimensional porous polymer hybrid material can well maintain two-dimensional morphology and a macroporous channel, is not easy to deform or collapse in the filtering process, and ensures high permeability of a solvent;

(3) the micro-size of the multifunctional two-dimensional porous polymer hybrid material prepared by the invention can be adjusted by changing experimental conditions, and the size of micropores can be adjusted by reaction conditions and a crosslinking mode.

Drawings

In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present application, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.

FIG. 1 is a scanning electron microscope photograph of a first multifunctional two-dimensional porous polymer hybrid material provided in example 1 of the present invention;

FIG. 2 is a scanning electron micrograph of an assembled drainage layer of the multifunctional two-dimensional porous polymer hybrid material provided in example 1 of the present invention;

fig. 3 is a diagram (left) of a nitrogen adsorption-desorption isotherm and a pore size distribution diagram (right) of a first multifunctional two-dimensional porous polymer hybrid material provided in example 1 of the present invention;

FIG. 4 is an adsorption curve of the first multifunctional two-dimensional porous polymer hybrid material provided in example 1 of the present invention;

FIG. 5 shows a fluorescence quenching spectrum and a photograph of the first multifunctional two-dimensional porous polymer hybrid material according to embodiment 1 of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.

It is understood that the steps of the sem test include: fixing the multifunctional two-dimensional porous polymer hybrid material on a sample table by using conductive adhesive, and placing the sample table in a vacuum drying oven for drying treatment for 12 h. After the metal spraying treatment, the structural morphology of the sample is observed by an S-4800 cold field emission scanning electron microscope produced by Hitachi high and new technology under the voltage of 10 kV.

It is understood that the steps of the specific surface area and pore size distribution test include: n of the sample was measured by using ASAP2020 adsorption apparatus manufactured by Micromeritics of USA₂Adsorption-desorption isotherms. Weighing 0.02g of multifunctional two-dimensional porous polymer hybrid material sample, and degassing the sample at 250 ℃ in vacuum for 6h before testing. Specific surface area S_BETThe total pore volume is calculated by a BET method, the total pore volume is calculated by a t-polt method, and the full pore size distribution is calculated by a DFT theory.

Example 1

A preparation method of a multifunctional two-dimensional porous polymer hybrid material comprises the following steps:

step (1): mixing 1.5ml of 4-chloromethyl styrene and 0.015ml of divinylbenzene, then slowly pushing and injecting the mixture into 20ml of aqueous solution containing 25mg of graphene oxide by using a trace sample injection pump, heating the mixture to 75 ℃, adding 4.38mg of azobisisobutyronitrile, carrying out reflux reaction for 8 hours at 75 ℃ under inert atmosphere, washing the mixed solution by using ethanol and water, carrying out centrifugal separation, freezing the mixed solution by using liquid nitrogen, and drying the frozen mixed solution in a freeze dryer to obtain an intermediate product I;

step (2): adding 30mg of the intermediate product prepared in the step (1) into 20ml of glacial acetic acid and stirring, adding 2.8ml of dimethoxymethane and 5g of anhydrous FeCl₃Reacting for 4 hours at 80 ℃, adding an acetone/hydrochloric acid/water mixed solvent to terminate the reaction, and filtering, washing and freeze-drying to obtain an intermediate product II;

and (3): dissolving 30mg of the intermediate product prepared in the step (2) in 150ml of dichloroethane, swelling overnight, and adding 5.6g of anhydrous FeCl at 75 DEG C₃Stirring for reaction for 24h, and adding acetone/hydrochloric acid/water mixed solvent to obtain the final productStopping reaction, filtering, washing, freezing and drying to obtain an intermediate product III;

and (4): and (3) mixing 20mg of the intermediate product III prepared in the step (3) with 10mg of N- (2-aminoethyl) carbazole, 110mg of cesium carbonate and 1ml of anhydrous dimethylformamide, continuously stirring for reaction at room temperature in a dark place for 24 hours, washing with dimethylformamide and water, performing centrifugal separation, and then performing freeze drying to obtain the multifunctional two-dimensional porous polymer hybrid material I.

And (5): dispersing the multifunctional two-dimensional porous polymer hybrid material I in water by short-time ultrasonic, taking a polyamide microporous filter membrane as a support membrane, and preparing a water filtering layer by vacuum-assisted suction filtration, wherein the thickness of the water filtering layer is 36 mu m.

To further illustrate the effect of the first multifunctional two-dimensional porous polymer hybrid material prepared in example 1, the following characterization was performed.

Fig. 1 and fig. 2 are scanning electron microscope photographs of the multifunctional two-dimensional porous polymer hybrid material i and the water filtering layer assembled by the multifunctional two-dimensional porous polymer hybrid material i, respectively. As can be seen from FIG. 1, the porous macromolecules on one surface of the multifunctional two-dimensional porous macromolecular hybrid material are uniformly distributed, and the thickness is about 27 nm; as can be seen from figure 2, the drainage layer is composed of multifunctional two-dimensional porous polymer hybrid material nanosheets, can be bent to any angle on the polyamide support membrane, and has good flexibility and mechanical stability.

The left picture in FIG. 3 is N₂Adsorption-desorption isotherm diagram, the right diagram is the pore size distribution diagram. As can be seen from FIG. 3, the BET specific surface area of the obtained first multifunctional two-dimensional porous polymer hybrid material is 152m²/g。

FIG. 4 is a pollutant adsorption curve of the first multifunctional two-dimensional porous polymer hybrid material.

FIG. 5 is a diagram of the quenching change of the fluorescence emission spectrum of the multifunctional two-dimensional porous polymer hybrid material with the dropping of the pollutant (DNT), and a built-in picture is a photograph of the color change of the material with the dropping of the pollutant (DNT) under the irradiation of an ultraviolet lamp.

Example 2

step (1): mixing 0.5ml of 4-chloromethyl styrene and 0.005ml of divinylbenzene, then slowly pushing and injecting the mixture into 20ml of aqueous solution containing 25mg of graphene oxide by using a trace sample injection pump, heating the mixture to 75 ℃, adding 1.46mg of azobisisobutyronitrile, carrying out reflux reaction for 8 hours at 75 ℃ under an inert atmosphere, washing the mixed solution by using ethanol and water, carrying out centrifugal separation, freezing the mixed solution by using liquid nitrogen, and drying the frozen mixed solution in a freeze dryer to obtain an intermediate product I;

and (3): dissolving 30mg of the intermediate product prepared in the step (2) in 150ml of dichloroethane, swelling overnight, and adding 5.6g of anhydrous FeCl at 75 DEG C₃Stirring for reaction for 24h, adding an acetone/hydrochloric acid/water mixed solvent to terminate the reaction, and filtering, washing and freeze-drying to obtain an intermediate product III;

and (4): and (3) mixing 20mg of the intermediate product III prepared in the step (3) with 10mg of N- (2-aminoethyl) carbazole, 110mg of cesium carbonate and 1ml of anhydrous dimethylformamide, continuously stirring for reaction at room temperature in a dark place for 24 hours, washing with dimethylformamide and water, performing centrifugal separation, and then performing freeze drying to obtain the multifunctional two-dimensional porous polymer hybrid material II.

And (5): dispersing the multifunctional two-dimensional porous polymer hybrid material II in water by short-time ultrasonic dispersion, taking a polyamide microporous filter membrane as a support membrane, and preparing a water filtering layer by vacuum-assisted suction filtration, wherein the thickness of the water filtering layer is 23 mu m.

Example 3

step (1): mixing 1.0ml of 4-chloromethyl styrene and 0.010ml of divinylbenzene, then slowly pushing and injecting the mixture into 20ml of aqueous solution containing 25mg of graphene oxide by using a trace sample injection pump, heating the mixture to 75 ℃, adding 2.92mg of azobisisobutyronitrile, carrying out reflux reaction for 8 hours at 75 ℃ under inert atmosphere, washing the mixed solution by using ethanol and water, carrying out centrifugal separation, freezing the mixed solution by using liquid nitrogen, and drying the frozen mixed solution in a freeze dryer to obtain an intermediate product I;

and (4): and (3) mixing 20mg of the intermediate product III prepared in the step (3) with 10mg of N- (2-aminoethyl) carbazole, 110mg of cesium carbonate and 1ml of anhydrous dimethylformamide, continuously stirring for reaction at room temperature in a dark place for 24 hours, washing with dimethylformamide and water, performing centrifugal separation, and performing freeze drying to obtain the multifunctional two-dimensional porous polymer hybrid material III.

And (5): dispersing the multifunctional two-dimensional porous polymer hybrid material tee in water by short-time ultrasonic dispersion, taking a polyamide microporous filter membrane as a support membrane, and preparing a water filtering layer by vacuum-assisted suction filtration, wherein the thickness of the water filtering layer is 29 mu m.

Example 4

step (1): mixing 2.0ml of 4-chloromethyl styrene and 0.020ml of divinylbenzene, adding the mixture into 20ml of aqueous solution containing 25mg of graphene oxide, heating the mixture to 75 ℃ after mixing, adding 5.84mg of azobisisobutyronitrile, carrying out reflux reaction for 8 hours at 75 ℃ under the inert atmosphere, washing the mixed solution with ethanol and water, carrying out centrifugal separation, freezing the mixed solution with liquid nitrogen, and drying the frozen mixed solution in a freeze dryer to obtain an intermediate product I;

step (2): adding 30mg of the intermediate product prepared in the step (1) into the mixtureTo 20ml of glacial acetic acid and stirred, 2.8ml of dimethoxymethane and 5g of anhydrous FeCl are added₃Reacting for 4 hours at 80 ℃, adding an acetone/hydrochloric acid/water mixed solvent to terminate the reaction, and filtering, washing and freeze-drying to obtain an intermediate product II;

and (4): and (3) mixing 20mg of the intermediate product III prepared in the step (3) with 10mg of N- (2-aminoethyl) carbazole, 110mg of cesium carbonate and 1ml of anhydrous dimethylformamide, continuously stirring for reaction at room temperature in a dark place for 24 hours, washing with dimethylformamide and water, performing centrifugal separation, and performing freeze drying to obtain the multifunctional two-dimensional porous polymer hybrid material IV.

And (5): dispersing the multifunctional two-dimensional porous polymer hybrid material into water by short-time ultrasonic dispersion, and preparing a water filtering layer by using a polyamide microporous filtering membrane as a supporting membrane and performing vacuum-assisted suction filtration, wherein the thickness of the water filtering layer is 38 mu m.

Example 5

step (1): mixing 2.5ml of 4-chloromethyl styrene and 0.025ml of divinylbenzene, adding the mixture into 20ml of aqueous solution containing 25mg of graphene oxide, heating the mixture to 75 ℃ after mixing, adding 7.3mg of azobisisobutyronitrile, carrying out reflux reaction for 8 hours at 75 ℃ under the inert atmosphere, washing the mixed solution with ethanol and water, carrying out centrifugal separation, freezing the mixed solution with liquid nitrogen, and drying the frozen mixed solution in a freeze dryer to obtain an intermediate product I;

step (ii) of(3): dissolving 30mg of the intermediate product prepared in the step (2) in 150ml of dichloroethane, swelling overnight, and adding 5.6g of anhydrous FeCl at 75 DEG C₃Stirring for reaction for 24h, adding an acetone/hydrochloric acid/water mixed solvent to terminate the reaction, and filtering, washing and freeze-drying to obtain an intermediate product III;

and (4): and (3) mixing 20mg of the intermediate product III prepared in the step (3) with 10mg of N- (2-aminoethyl) carbazole, 110mg of cesium carbonate and 1ml of anhydrous dimethylformamide, continuously stirring for reaction at room temperature in a dark place for 24 hours, washing with dimethylformamide and water, performing centrifugal separation, and performing freeze drying to obtain the multifunctional two-dimensional porous polymer hybrid material V.

And (5): dispersing the multifunctional two-dimensional porous polymer hybrid material in water by short-time ultrasonic dispersion, taking a polyamide microporous filter membrane as a support membrane, and preparing a water filtering layer by vacuum-assisted suction filtration, wherein the thickness of the water filtering layer is 43 mu m.

Effect example 1

In order to further illustrate the beneficial effects of the present invention, nitrogen adsorption-desorption isotherms were performed on the multifunctional two-dimensional porous polymer hybrid materials prepared in examples 1 to 5, and the results are shown in table 1.

TABLE 1 pore Structure data of different multifunctional two-dimensional porous Polymer hybrid materials

Sample name	Morphology of	BET specific surface area (m)²/g)
			Two-dimensional porous polymer hybrid material I	Good nano flaky network morphology	152
Two-dimensional porous polymer hybrid material II	Good nano flaky network morphology	52
			Two-dimensional porous polymer hybrid material III	Good nano flaky network morphology	119
Two-dimensional porous polymer hybrid material IV	Good nano flaky network morphology	103
			Two-dimensional porous polymer hybrid material V	Without good nano-sheet network morphology	-

The results show that: the influence of the use amount of the 4-chloromethylstyrene and the divinylbenzene in the step (1) on the specific surface area and the morphology of the product is larger, the amount of the polymer formed on the surface of the graphene oxide by the polymer can be increased along with the increase of the concentration of the reaction monomer, and the BET specific surface area is increased. However, with the increase of the concentration of the monomer for promoting the reaction, the monomer can generate self-polymerization and cannot be coated on the surface of the graphene, and the BET specific surface area is reduced. The monomer and the catalyst are directly added into a reaction system, and the monomer can not be directly self-polymerized to form a polymer film on the surface of the graphene uniformly without being slowly dripped.

Example 6

step (1): mixing 1.5ml of 4-chloromethyl styrene and 0.015ml of divinylbenzene, then slowly pushing and injecting the mixture into 20ml of aqueous solution containing 25mg of graphene oxide by using a trace sample injection pump, heating the mixture to 75 ℃, adding 4.38mg of azobisisobutyronitrile, carrying out reflux reaction for 4 hours at 75 ℃ under the inert atmosphere, washing the mixed solution by using ethanol and water, carrying out centrifugal separation, freezing the mixed solution by using liquid nitrogen, and drying the frozen mixed solution in a freeze dryer to obtain an intermediate product I;

and (4): and (3) mixing 20mg of the intermediate product III prepared in the step (3) with 10mg of N- (2-aminoethyl) carbazole, 110mg of cesium carbonate and 1ml of anhydrous dimethylformamide, continuously stirring for reaction at room temperature in a dark place for 24 hours, washing with dimethylformamide and water, performing centrifugal separation, and then performing freeze drying to obtain the multifunctional two-dimensional porous polymer hybrid material VI.

And (5): dispersing the multifunctional two-dimensional porous polymer hybrid material II in water by short-time ultrasonic dispersion, taking a polyamide microporous filter membrane as a support membrane, and preparing a water filtering layer by vacuum-assisted suction filtration, wherein the thickness of the water filtering layer is 30 mu m.

Example 7

step (1): mixing 1.5ml of 4-chloromethylstyrene and 0.015ml of divinylbenzene, then slowly pushing and injecting the mixture into 20ml of aqueous solution containing 25mg of graphene oxide by using a trace sample injection pump, heating the mixture to 75 ℃, adding 4.38mg of azodiisobutyramidine hydrochloride, carrying out reflux reaction for 6 hours at 75 ℃ under an inert atmosphere, washing the mixed solution by using ethanol and water, carrying out centrifugal separation, freezing by using liquid nitrogen, and drying in a freeze dryer to obtain an intermediate product I;

and (4): and (3) mixing 20mg of the intermediate product III prepared in the step (3) with 10mg of N- (2-aminoethyl) carbazole, 110mg of cesium carbonate and 1ml of anhydrous dimethylformamide, continuously stirring for reaction at room temperature in a dark place for 24 hours, washing with dimethylformamide and water, performing centrifugal separation, and then performing freeze drying to obtain the multifunctional two-dimensional porous polymer hybrid material VII.

And (5): dispersing the multifunctional two-dimensional porous polymer hybrid material seven in water by short-time ultrasonic, taking a polyamide microporous filter membrane as a support membrane, and preparing a water filtering layer by vacuum-assisted suction filtration, wherein the thickness of the water filtering layer is 32 mu m.

Example 8

step (1): mixing 1.5ml of 4-chloromethyl styrene and 0.015ml of divinylbenzene, then slowly pushing and injecting the mixture into 20ml of aqueous solution containing 25mg of graphene oxide by using a trace sample injection pump, heating the mixture to 60 ℃, adding 4.38mg of azobisisobutyronitrile, carrying out reflux reaction for 8 hours at the temperature of 60 ℃ under inert atmosphere, washing the mixed solution by using ethanol and water, carrying out centrifugal separation, freezing the mixed solution by using liquid nitrogen, and drying the mixed solution in a freeze dryer to obtain an intermediate product I;

and (4): and (3) mixing 20mg of the intermediate product III prepared in the step (3) with 10mg of N- (2-aminoethyl) carbazole, 110mg of cesium carbonate and 1ml of anhydrous dimethylformamide, continuously stirring for reaction at room temperature in a dark place for 24 hours, washing with dimethylformamide and water, performing centrifugal separation, and then performing freeze drying to obtain the multifunctional two-dimensional porous polymer hybrid material VIII.

And (5): dispersing the multifunctional two-dimensional porous polymer hybrid material eight in water by short-time ultrasonic, taking a polyamide microporous filter membrane as a support membrane, and preparing a water filtering layer by vacuum-assisted suction filtration, wherein the thickness of the water filtering layer is 31 mu m.

Example 9

step (1): mixing 1.5ml of 4-chloromethyl styrene and 0.015ml of divinylbenzene, then slowly pushing and injecting the mixture into 20ml of aqueous solution containing 25mg of graphene oxide by using a trace sample injection pump, heating the mixture to 75 ℃, adding 4.38mg of azobisisobutyronitrile, carrying out reflux reaction for 8 hours at 75 ℃ under inert atmosphere, washing the mixed solution by using ethanol and water, carrying out centrifugal separation, freezing the mixed solution in a refrigerator, and drying the mixed solution in a freeze dryer to obtain an intermediate product I;

and (3): intermediate product II prepared in the step (2)30mg dissolved in 150ml dichloroethane, swollen overnight, 5.6g of anhydrous FeCl added at 75 deg.C₃Stirring for reaction for 24h, adding an acetone/hydrochloric acid/water mixed solvent to terminate the reaction, and filtering, washing and freeze-drying to obtain an intermediate product III;

and (4): and (3) mixing 20mg of the intermediate product III prepared in the step (3) with 10mg of N- (2-aminoethyl) carbazole, 110mg of cesium carbonate and 1ml of anhydrous dimethylformamide, continuously stirring for reaction at room temperature in a dark place for 24 hours, washing with dimethylformamide and water, performing centrifugal separation, and then performing freeze drying to obtain the multifunctional two-dimensional porous polymer hybrid material.

And (5): dispersing the multifunctional two-dimensional porous polymer hybrid material nine in water by short-time ultrasonic, taking a polyamide microporous filter membrane as a support membrane, and preparing a water filtering layer by vacuum-assisted suction filtration, wherein the thickness of the water filtering layer is 41 mu m.

Effect example 2

In order to further illustrate the beneficial effects of the present invention, nitrogen adsorption-desorption isotherms were performed on the multifunctional two-dimensional porous polymer hybrid materials prepared in examples 6 to 9, and the results are shown in table 2.

TABLE 2 pore structure data of different multifunctional two-dimensional porous polymer hybrid materials

Sample name	Morphology of	BET specific surface area (m)²/g)
			Two-dimensional porous polymer hybrid material I	Good nano flaky network morphology	152
Two-dimensional porous polymer hybrid material VI	Good nano flaky network morphology	98
			Two-dimensional porous polymer hybrid material seven	Good nano flaky network morphology	127
Two-dimensional porous polymer hybrid material eight	Good nano sheet network structure	113
			Two-dimensional porous polymer hybrid material	Good nano flaky network morphology	135

The results show that: in the step (1), the polymerization time has a large influence on the specific surface area of the product, and when the polymerization time is prolonged, the amount of the polymer forming high molecules on the surface of the graphene can be increased, so that the specific surface area is increased. The reaction temperature can accelerate the polymerization reaction, and when the temperature is lower, the reaction rate is reduced. And the BET specific surface area of the obtained product is smaller by freezing in a refrigerator.

Example 10

step (2): adding 30mg of the intermediate product prepared in the step (1) into 20ml of glacial acetic acid and stirring, adding 2.8ml of dimethoxymethane and 5g of anhydrous FeCl₃Reacting for 4 hours at 70 ℃, adding an acetone/hydrochloric acid/water mixed solvent to terminate the reaction, and filtering, washing and freeze-drying to obtain an intermediate product II;

And (5): dispersing the multifunctional two-dimensional porous polymer hybrid material in water by short-time ultrasonic dispersion, taking a polyamide microporous filter membrane as a support membrane, and preparing a water filtering layer by vacuum-assisted suction filtration, wherein the thickness of the water filtering layer is 35 mu m.

Example 11

step (2): adding 30mg of the intermediate product prepared in the step (1) into 20ml of glacial acetic acid and stirring, adding 2.8ml of dimethoxymethane and 5g of anhydrous FeCl₃Reacting for 2 hours at 80 ℃, adding an acetone/hydrochloric acid/water mixed solvent to terminate the reaction, and filtering, washing and freeze-drying to obtain an intermediate product II;

step (4): and (3) mixing 20mg of the intermediate product III prepared in the step (3) with 10mg of N- (2-aminoethyl) carbazole, 110mg of cesium carbonate and 1ml of anhydrous dimethylformamide, continuously stirring for reaction at room temperature in a dark place for 24 hours, washing with dimethylformamide and water, performing centrifugal separation, and then performing freeze drying to obtain the multifunctional two-dimensional porous polymer hybrid material eleven.

And (5): dispersing the multifunctional two-dimensional porous polymer hybrid material eleven in water by short-time ultrasonic, taking a polyamide microporous filter membrane as a support membrane, and preparing a water filtering layer by vacuum-assisted suction filtration, wherein the thickness of the water filtering layer is 33 microns.

Example 12

step (2): adding 30mg of the intermediate product prepared in the step (1) into 20ml of glacial acetic acid, stirring, and adding 5g of anhydrous FeCl₃Reacting for 4 hours at 80 ℃, adding an acetone/hydrochloric acid/water mixed solvent to terminate the reaction, and filtering, washing and freeze-drying to obtain an intermediate product II;

and (3): dissolving 30mg of the intermediate product II prepared in the step (2) in 150ml of the intermediate product IIIn ethyl chloride, swell overnight, add 5.6g of anhydrous FeCl at 75 deg.C₃Stirring for reaction for 24h, adding an acetone/hydrochloric acid/water mixed solvent to terminate the reaction, and filtering, washing and freeze-drying to obtain an intermediate product III;

and (4): and (3) mixing 20mg of the intermediate product III prepared in the step (3) with 10mg of N- (2-aminoethyl) carbazole, 110mg of cesium carbonate and 1ml of anhydrous dimethylformamide, continuously stirring for reaction at room temperature in a dark place for 24 hours, washing with dimethylformamide and water, performing centrifugal separation, and then performing freeze drying to obtain the multifunctional two-dimensional porous polymer hybrid material twelve.

And (5): dispersing the multifunctional two-dimensional porous polymer hybrid material twelve in water by short-time ultrasound, taking a polyamide microporous filter membrane as a support membrane, and preparing a water filtering layer by vacuum-assisted suction filtration, wherein the thickness of the water filtering layer is 32 mu m.

Example 13

step (2): 30mg of the intermediate product obtained in step (1) was dissolved in 150ml of dichloroethane, swollen overnight, and 5.6g of anhydrous FeCl was added at 75 deg.C₃Stirring to react for 24h, adding an acetone/hydrochloric acid/water mixed solvent to terminate the reaction, and filtering, washing and freeze-drying to obtain an intermediate product II;

and (3): and (3) mixing 20mg of the intermediate product II prepared in the step (3) with 10mg of N- (2-aminoethyl) carbazole, 110mg of cesium carbonate and 1ml of anhydrous dimethylformamide, continuously stirring for reaction at room temperature in a dark place for 24 hours, washing with dimethylformamide and water, performing centrifugal separation, and then performing freeze drying to obtain the multifunctional two-dimensional porous polymer hybrid material thirteen.

And (4): dispersing the multifunctional two-dimensional porous polymer hybrid material thirteen in water by short-time ultrasonic, taking a polyamide microporous filter membrane as a support membrane, and preparing a water filtering layer by vacuum-assisted suction filtration, wherein the thickness of the water filtering layer is 21 mu m.

Effect example 3

To further illustrate the beneficial effects of the present invention, nitrogen adsorption-desorption isotherms were performed on the multifunctional two-dimensional porous polymer hybrid materials prepared in examples 9 to 12, and the results are shown in table 3.

TABLE 3 pore structure data of different multifunctional two-dimensional porous polymer hybrid materials

Sample name	Morphology of	BET specific surface area (m)²/g)
			Two-dimensional porous polymer hybrid material I	Good nano flaky network morphology	152
Two-dimensional porous polymer hybrid material	Good nano flaky network morphology	127
			Two-dimensional porous polymer hybrid material eleven	Good nano flaky network morphology	131
Twelve-dimensional porous high-molecular hybrid material	Good nano flaky network morphology	129
			Two-dimensional porous polymer hybrid material thirteen	Does not form good nano flaky network morphology	-

The results show that: the control of the reaction time and temperature of the pre-crosslinking step in the step (2) has certain influence on the appearance and the specific surface area of the multifunctional two-dimensional porous polymer hybrid material; due to the existence of the step (2), the sheet network structure of the two-dimensional porous polymer hybrid material is well maintained, and the product structure obtained through the pre-crosslinking step is not damaged; the addition of dimethoxymethane (FDA) external crosslinking agent leads to a higher BET specific surface.

Example 14

and (3): dissolving 30mg of the intermediate product prepared in the step (2) in water150ml of dichloroethane, swollen overnight, 5.6g of anhydrous FeCl added at 65 ℃₃Stirring for reaction for 24h, adding an acetone/hydrochloric acid/water mixed solvent to terminate the reaction, and filtering, washing and freeze-drying to obtain an intermediate product III;

and (4): and (3) mixing 20mg of the intermediate product III prepared in the step (3) with 10mg of N- (2-aminoethyl) carbazole, 110mg of cesium carbonate and 1ml of anhydrous dimethylformamide, continuously stirring for reaction at room temperature in a dark place for 24 hours, washing with dimethylformamide and water, performing centrifugal separation, and freeze-drying to obtain the multifunctional two-dimensional porous polymer hybrid material fourteen.

And (5): dispersing the multifunctional two-dimensional porous polymer hybrid material fourteen in water by short-time ultrasound, taking a polyamide microporous filter membrane as a support membrane, and preparing a water filtering layer by vacuum-assisted suction filtration, wherein the thickness of the water filtering layer is 32 mu m.

Example 15

and (3): dissolving 30mg of the intermediate product prepared in the step (2) in 150ml of dichloroethane, swelling overnight, and adding 4.6g of anhydrous AlCl at 75 DEG C₃Stirring for reaction for 24h, adding an acetone/hydrochloric acid/water mixed solvent to terminate the reaction, and filtering, washing and freeze-drying to obtain an intermediate product III;

and (4): and (3) mixing 20mg of the intermediate product III prepared in the step (3) with 10mg of N- (2-aminoethyl) carbazole, 110mg of cesium carbonate and 1ml of anhydrous dimethylformamide, continuously stirring for reaction at room temperature in a dark place for 24 hours, washing with dimethylformamide and water, performing centrifugal separation, and then performing freeze drying to obtain the multifunctional two-dimensional porous polymer hybrid material fifteen.

And (5): dispersing the multifunctional two-dimensional porous macromolecular hybrid material fifteen in water by short-time ultrasonic, taking a polyamide microporous filter membrane as a support membrane, and preparing a water filtering layer by vacuum-assisted suction filtration, wherein the thickness of the water filtering layer is 25 mu m.

Example 16

and (3): dissolving 30mg of the intermediate product prepared in the step (2) in 150ml of dichloroethane, swelling overnight, and adding 5.6g of anhydrous FeCl at 75 DEG C₃Stirring to react for 12h, adding an acetone/hydrochloric acid/water mixed solvent to terminate the reaction, and filtering, washing and freeze-drying to obtain an intermediate product III;

and (4): and (3) mixing 20mg of the intermediate product III prepared in the step (3) with 10mg of N- (2-aminoethyl) carbazole, 110mg of cesium carbonate and 1ml of anhydrous dimethylformamide, continuously stirring for reaction at room temperature in a dark place for 24 hours, washing with dimethylformamide and water, performing centrifugal separation, and performing freeze drying to obtain the multifunctional two-dimensional porous polymer hybrid material sixteen.

And (5): dispersing the multifunctional two-dimensional porous polymer hybrid material sixteen in water by short-time ultrasonic, taking a polyamide microporous filter membrane as a support membrane, and preparing a water filtering layer by vacuum-assisted suction filtration, wherein the thickness of the water filtering layer is 28 microns.

Example 17

and (3): dissolving 30mg of the intermediate product prepared in the step (2) in 150ml of carbon tetrachloride, swelling overnight, and adding 5.6g of anhydrous FeCl at 75 DEG C₃Stirring for reaction for 24h, adding an acetone/hydrochloric acid/water mixed solvent to terminate the reaction, and filtering, washing and freeze-drying to obtain an intermediate product III;

and (4): and (3) mixing 20mg of the intermediate product III prepared in the step (3) with 10mg of N- (2-aminoethyl) carbazole, 110mg of cesium carbonate and 1ml of anhydrous dimethylformamide, continuously stirring for reaction at room temperature in a dark place for 24 hours, washing with dimethylformamide and water, performing centrifugal separation, and freeze-drying to obtain the multifunctional two-dimensional porous polymer hybrid material seventeen.

And (5): dispersing the seventeen multifunctional two-dimensional porous polymer hybrid material in water by short-time ultrasonic, taking a polyamide microporous filter membrane as a support membrane, and preparing a water filtering layer by vacuum-assisted suction filtration, wherein the thickness of the water filtering layer is 32 mu m.

Effect example 4

In order to further illustrate the beneficial effects of the present invention, nitrogen adsorption-desorption isotherms were performed on the multifunctional two-dimensional porous polymer hybrid materials prepared in examples 13 to 16, and the results are shown in table 4.

TABLE 4 pore structure data of different multifunctional two-dimensional porous polymer hybrid materials

Sample name	Morphology of	BET specific surface area (m)²/g)
			Two-dimensional porous polymer hybrid material I	Good nano flaky network morphology	152
Fourteen two-dimensional porous high-molecular hybrid materials	Good nano flaky network morphology	108
			Fifteen-dimensional porous high-molecular hybrid material	Good nano flaky network morphology	149
Sixteen two-dimensional porous high-molecular hybrid material	Good nano-sheetNetwork-like morphology	105
			Seventeen two-dimensional porous polymer hybrid material	Most of the nano flaky network morphology is kept good	98

The results show that: the control of the catalyst, the solvent, the reaction time and the temperature in the hypercrosslinking step in the step (3) has certain influence on the appearance and the specific surface area of the multifunctional two-dimensional porous polymer hybrid material; dispersing the pre-crosslinked product in 1, 2-dichloroethane to obtain a polymer nano network with good nano network morphology, wherein the solvent adopts carbon tetrachloride, and part of the nano sheet structure is damaged; the selection of the aluminum trichloride and the ferric trichloride is not very different; the reduction in the reaction time and the reduction in the temperature lead to a reduction in the BET specific surface area of the product.

Example 18

step (1): mixing 1.5ml of 4-chloromethyl styrene and 0.015ml of divinylbenzene, then slowly pushing and injecting the mixture into 20ml of aqueous solution containing 250mg of graphene oxide by using a trace sample injection pump, heating the mixture to 75 ℃, adding 4.38mg of azobisisobutyronitrile, carrying out reflux reaction for 8 hours at 75 ℃ under inert atmosphere, washing the mixed solution by using ethanol and water, carrying out centrifugal separation, freezing the mixed solution by using liquid nitrogen, and drying the frozen mixed solution in a freeze dryer to obtain an intermediate product I;

and (3): dissolving the intermediate product (30 mg) prepared in the step (2) in 150ml of dichloroethyleneIn an alkane, swollen overnight, 5.6g of anhydrous FeCl added at 75 deg.C₃Stirring for reaction for 24h, adding an acetone/hydrochloric acid/water mixed solvent to terminate the reaction, and filtering, washing and freeze-drying to obtain an intermediate product III;

and (4): and (3) mixing 20mg of the intermediate product III prepared in the step (3) with 10mg of N- (2-aminoethyl) carbazole, 110mg of cesium carbonate and 1ml of anhydrous dimethylformamide, continuously stirring for reaction at room temperature in a dark place for 24 hours, washing with dimethylformamide and water, performing centrifugal separation, and then performing freeze drying to obtain the multifunctional two-dimensional porous polymer hybrid material eighteen.

And (5): dispersing the multifunctional two-dimensional porous polymer hybrid material in water by short-time ultrasonic dispersion, taking a polyamide microporous filter membrane as a support membrane, and preparing a water filtering layer by vacuum-assisted suction filtration, wherein the thickness of the water filtering layer is 16 mu m.

Example 19

step (1): mixing 1.5ml of 4-chloromethyl styrene and 0.015ml of divinylbenzene, then slowly pushing and injecting the mixture into 20ml of aqueous solution containing 125mg of graphene oxide by using a trace sample injection pump, heating the mixture to 75 ℃, adding 4.38mg of azobisisobutyronitrile, carrying out reflux reaction for 8 hours at 75 ℃ under inert atmosphere, washing the mixed solution by using ethanol and water, carrying out centrifugal separation, freezing the mixed solution by using liquid nitrogen, and drying the frozen mixed solution in a freeze dryer to obtain an intermediate product I;

and (4): and (3) mixing 20mg of the intermediate product III prepared in the step (3) with 10mg of N- (2-aminoethyl) carbazole, 110mg of cesium carbonate and 1ml of anhydrous dimethylformamide, continuously stirring for reaction at room temperature in a dark place for 24 hours, washing with dimethylformamide and water, performing centrifugal separation, and performing freeze drying to obtain the nineteen multifunctional two-dimensional porous polymer hybrid material.

And (5): nineteen multifunctional two-dimensional porous polymer hybrid materials are dispersed in water through transient ultrasonic, a polyamide microporous filter membrane is used as a support membrane, and a water filtering layer is prepared through vacuum-assisted suction filtration, wherein the thickness of the water filtering layer is 36 microns.

Effect example 5

To further illustrate the beneficial effects of the present invention, nitrogen adsorption-desorption isotherms were performed on the multifunctional two-dimensional porous polymer hybrid materials prepared in examples 18 and 19, and the results are shown in table 5.

TABLE 5 pore structure data of different multifunctional two-dimensional porous polymer hybrid materials

Sample name	Morphology of	BET specific surface area (m)²/g)
			Two-dimensional porous polymer hybrid material I	Good nano flaky network morphology	152
Eighteen two-dimensional porous high-molecular hybrid material	Good nano flaky network morphology	59
			Nineteen-dimensional porous polymer hybrid material	Good nano flaky network morphology	105

The results show that: the concentration of the graphene aqueous solution in the step (1) has certain influence on the appearance and the specific surface area of the multifunctional two-dimensional porous polymer hybrid material; the high concentration is beneficial to forming a good sheet structure, but the specific surface area of the two-dimensional porous polymer hybrid material is reduced due to the excessively high concentration; at low concentrations, two-dimensional porous materials with good sheet morphology cannot be formed.

Example 20

step (2): adding 30mg of the intermediate product obtained in the step (1) into 20ml of glacial acetic acid, stirring, adding 3.1ml of carbon tetrachloride and 4g of anhydrous AlCl₃Reacting for 4 hours at 80 ℃, adding an acetone/hydrochloric acid/water mixed solvent to terminate the reaction, and filtering, washing and freeze-drying to obtain an intermediate product II;

and (4): and (3) mixing 20mg of the intermediate product III prepared in the step (3) with 10mg of N- (2-aminoethyl) carbazole, 110mg of cesium carbonate and 1ml of anhydrous dimethylformamide, continuously stirring for reaction at room temperature in a dark place for 24 hours, washing with dimethylformamide and water, performing centrifugal separation, and freeze-drying to obtain the multifunctional two-dimensional porous polymer hybrid material Twenty.

And (5): the multifunctional two-dimensional porous polymer hybrid material twenty is dispersed in water through transient ultrasonic, a polyamide microporous filter membrane is used as a support membrane, and a water filtering layer is prepared through vacuum-assisted suction filtration, wherein the thickness of the water filtering layer is 25 mu m.

Effect example 6

To further illustrate the beneficial effects of the present invention, nitrogen adsorption-desorption isotherms were performed on the multifunctional two-dimensional porous polymeric hybrid material prepared in example 20, and the results are shown in table 6.

TABLE 6 pore structure data of different multifunctional two-dimensional porous polymer hybrid materials

Sample name	Morphology of	BET specific surface area (m)²/g)
			Two-dimensional porous polymer hybrid material I	Good nano flaky network morphology	152
Two-dimensional porous polymer hybrid material twenty	Good nano flaky network morphology	139

The results show that: the carbon tetrachloride selected in the step (2) can be used as a cross-linking agent to prepare the multifunctional two-dimensional porous polymer hybrid material.

Example 21

step (2): adding 30mg of the intermediate product prepared in the step (1) into 20ml of glacial acetic acid and stirring, adding 0.28ml of dimethoxymethane and 5g of anhydrous FeCl₃Reacting for 4 hours at 80 ℃, adding an acetone/hydrochloric acid/water mixed solvent to terminate the reaction, and filtering, washing and freeze-drying to obtain an intermediate product II;

and (4): and (3) mixing 20mg of the intermediate product III prepared in the step (3) with 10mg of N- (2-aminoethyl) carbazole, 110mg of cesium carbonate and 1ml of anhydrous dimethylformamide, continuously stirring for reaction at room temperature in a dark place for 24 hours, washing with dimethylformamide and water, performing centrifugal separation, and then performing freeze drying to obtain the multifunctional two-dimensional porous polymer hybrid material twenty one.

And (5): the preparation method comprises the steps of dispersing a multifunctional two-dimensional porous polymer hybrid material twenty one in water through transient ultrasonic, taking a polyamide microporous filter membrane as a support membrane, and preparing a water filtering layer through vacuum-assisted suction filtration, wherein the thickness of the water filtering layer is 12 microns.

Example 22

step (2): adding 30mg of the intermediate product prepared in the step (1) into 20ml of glacial acetic acid, stirring, adding 28ml of dimethoxymethane and 5g of anhydrous FeCl₃Reacting for 4 hours at 80 ℃, adding an acetone/hydrochloric acid/water mixed solvent to terminate the reaction, and filtering, washing and freeze-drying to obtain an intermediate product II;

and (4): and (3) mixing 20mg of the intermediate product III prepared in the step (3) with 10mg of N- (2-aminoethyl) carbazole, 110mg of cesium carbonate and 1ml of anhydrous dimethylformamide, continuously stirring for reaction at room temperature in a dark place for 24 hours, washing with dimethylformamide and water, performing centrifugal separation, and performing freeze drying to obtain the multifunctional two-dimensional porous polymer hybrid material twenty-two.

And (5): the multifunctional two-dimensional porous polymer hybrid material twenty-two is dispersed in water by short-time ultrasonic dispersion, a polyamide microporous filter membrane is used as a support membrane, and a water filtering layer is prepared by vacuum-assisted suction filtration, wherein the thickness of the water filtering layer is 24 mu m.

Effect example 7

To further illustrate the advantageous effects of the present invention, nitrogen adsorption-desorption isotherms were performed on the multifunctional two-dimensional porous polymeric hybrid materials prepared in examples 21 and 22, and the results are shown in table 7.

TABLE 7 pore structure data of different multifunctional two-dimensional porous polymer hybrid materials

Sample name	Morphology of	BET specific surface area (m)²/g)
			Two-dimensional porous polymer hybrid material I	Good nano flaky network morphology	152
Twenty-one of two-dimensional porous high molecular hybrid material	Good nano flaky network morphology	61
			Two-dimensional porous polymer hybrid material twenty-two	Good nano flaky network morphology	156

The results show that: the dosage of the cross-linking agent in the step (2) has important influence on the specific surface area of the multifunctional two-dimensional porous polymer hybrid material. Too little cross-linking agent can result in insufficient pore-forming amount and greatly reduced specific surface area.

Example 23

and (3): dissolving 30mg of the intermediate product prepared in the step (2) in 15ml of dichloroethane, swelling overnight, and adding 5.6g of anhydrous FeCl at 75 DEG C₃Stirring for reaction for 24h, adding an acetone/hydrochloric acid/water mixed solvent to terminate the reaction, and filtering, washing and freeze-drying to obtain an intermediate product III;

and (4): and (3) mixing 20mg of the intermediate product III prepared in the step (3) with 10mg of N- (2-aminoethyl) carbazole, 110mg of cesium carbonate and 1ml of anhydrous dimethylformamide, continuously stirring for reaction at room temperature in a dark place for 24 hours, washing with dimethylformamide and water, performing centrifugal separation, and performing freeze drying to obtain the multifunctional two-dimensional porous polymer hybrid material twenty-three.

And (5): the multifunctional two-dimensional porous polymer hybrid material Twenty-three is dispersed in water by short-time ultrasonic dispersion, a polyamide microporous filter membrane is used as a support membrane, and a water filtering layer is prepared by vacuum-assisted suction filtration, wherein the thickness of the water filtering layer is 23 mu m.

Example 24

and (3): dissolving 30mg of the intermediate product prepared in the step (2) in 1500ml of dichloroethane, swelling overnight, and adding anhydrous FeCl at 75 DEG C₃Stirring for reaction for 24h, adding an acetone/hydrochloric acid/water mixed solvent to terminate the reaction, and filtering, washing and freeze-drying to obtain an intermediate product III;

and (4): and (3) mixing 20mg of the intermediate product III prepared in the step (3) with 10mg of N- (2-aminoethyl) carbazole, 110mg of cesium carbonate and 1ml of anhydrous dimethylformamide, continuously stirring for reaction at room temperature in a dark place for 24 hours, washing with dimethylformamide and water, performing centrifugal separation, and performing freeze drying to obtain the twenty-four multifunctional two-dimensional porous polymer hybrid material.

And (5): the multifunctional two-dimensional porous polymer hybrid material Twenty-four is dispersed in water by short-time ultrasonic dispersion, a polyamide microporous filter membrane is used as a support membrane, and a water filtering layer is prepared by vacuum-assisted suction filtration, wherein the thickness of the water filtering layer is 23 mu m.

Effect example 8

To further illustrate the beneficial effects of the present invention, nitrogen adsorption-desorption isotherms were performed on the multifunctional two-dimensional porous polymeric hybrid materials prepared in examples 23 and 24, and the results are shown in table 8.

TABLE 8 pore structure data of different multifunctional two-dimensional porous polymer hybrid materials

The results show that: the dosage of the first solvent in the step (3) has an important influence on the specific surface area of the multifunctional two-dimensional porous polymer hybrid material. Too little solvent is used, which leads to insufficient swelling in the crosslinking stage of the material, reduced porosity and large downward sliding of the specific surface area.

Example 25

step (1): mixing 1.5ml of 4-chloromethyl styrene and 0.15ml of divinylbenzene, then slowly pushing and injecting the mixture into 20ml of aqueous solution containing 25mg of graphene oxide by using a trace sample injection pump, heating the mixture to 75 ℃, adding 4.38mg of azobisisobutyronitrile, carrying out reflux reaction for 8 hours at 75 ℃ under an inert atmosphere, washing the mixed solution by using ethanol and water, carrying out centrifugal separation, freezing the mixed solution by using liquid nitrogen, and drying the frozen mixed solution in a freeze dryer to obtain an intermediate product I;

and (4): and (3) mixing 20mg of the intermediate product III prepared in the step (3) with 10mg of N- (2-aminoethyl) carbazole, 110mg of cesium carbonate and 1ml of anhydrous dimethylformamide, continuously stirring for reaction at room temperature in a dark place for 24 hours, washing with dimethylformamide and water, performing centrifugal separation, and performing freeze drying to obtain the twenty five multifunctional two-dimensional porous polymer hybrid material.

And (5): twenty five multifunctional two-dimensional porous polymer hybrid materials are dispersed in water through transient ultrasonic, a polyamide microporous filter membrane is used as a support membrane, and a water filtering layer is prepared through vacuum-assisted suction filtration, wherein the thickness of the water filtering layer is 24 microns.

Example 26

step (1): mixing 1.5ml of 4-chloromethyl styrene and 0.01ml of divinylbenzene, then slowly pushing and injecting the mixture into 20ml of aqueous solution containing 25mg of graphene oxide by using a trace sample injection pump, heating the mixture to 75 ℃, adding 4.38mg of azobisisobutyronitrile, carrying out reflux reaction for 8 hours at 75 ℃ under inert atmosphere, washing the mixed solution by using ethanol and water, carrying out centrifugal separation, freezing the mixed solution by using liquid nitrogen, and drying the frozen mixed solution in a freeze dryer to obtain an intermediate product I;

and (4): and (3) mixing 20mg of the intermediate product III prepared in the step (3) with 10mg of N- (2-aminoethyl) carbazole, 110mg of cesium carbonate and 1ml of anhydrous dimethylformamide, continuously stirring for reaction at room temperature in a dark place for 24 hours, washing with dimethylformamide and water, performing centrifugal separation, and performing freeze drying to obtain the twenty-six multifunctional two-dimensional porous polymer hybrid material.

And (5): dispersing twenty six multifunctional two-dimensional porous polymer hybrid materials in water by short-time ultrasonic, taking a polyamide microporous filter membrane as a support membrane, and preparing a water filtering layer by vacuum-assisted suction filtration, wherein the thickness of the water filtering layer is 20 microns.

Effect example 9

To further illustrate the advantageous effects of the present invention, nitrogen adsorption-desorption isotherms were performed on the multifunctional two-dimensional porous polymeric hybrid materials prepared in examples 25 and 26, and the results are shown in table 9.

TABLE 9 pore Structure data of different multifunctional two-dimensional porous Polymer hybrid materials

Sample name	Morphology of	BET specific surface area (m)²/g)
			Two-dimensional porous polymer hybrid material I	Good nano flaky network morphology	152
Twenty-five of two-dimensional porous high molecular hybrid material	Good nano flaky network morphology	156
			Twenty-six of two-dimensional porous high molecular hybrid material	Good nano flaky network morphology	126

The results show that: the dosage of the divinylbenzene in the step (1) has important influence on the nano-morphology of the multifunctional two-dimensional porous polymer hybrid material. When the volume ratio of the 4-chloromethylstyrene to the divinylbenzene is 10-150: 1, a good nano-sheet network morphology can be formed, and if the amount of the divinylbenzene is continuously reduced, the pre-crosslinking degree of an intermediate product is insufficient, so that the good sheet network morphology cannot be maintained.

Application example 1

In order to further illustrate the beneficial effects of the invention, the first multifunctional two-dimensional porous polymer hybrid material prepared in example 1 is used as an adsorbing material. As shown in FIG. 4, at a temperature of 298K, the poly-two-dimensional porous polymer hybrid material can reach adsorption equilibrium in 30 seconds by adsorbing dinitrotoluene aqueous solution with the concentration of 100ppm, and the removal rate is as high as 85%. The result shows that the multifunctional two-dimensional porous polymer hybrid material has good adsorption performance on polar organic steam.

Application example 2

To further illustrate the beneficial effects of the present invention, the multifunctional two-dimensional porous polymer hybrid material prepared in example 1 is used as a contamination response detection material. By using a portable ultraviolet lamp under the excitation of 254nm wavelength, the fluorescence response behavior of the material to the aromatic compound is directly tested, and as can be seen from fig. 5, the multifunctional two-dimensional porous polymer hybrid material is blue light; after the electron-deficient aromatic compound dinitrotoluene is added into the solution, the fluorescence of the multifunctional two-dimensional porous polymer hybrid material solution is directly quenched, and no fluorescence can be observed under the irradiation of an ultraviolet lamp. Therefore, the multifunctional two-dimensional porous polymer hybrid material can show a specific response action for the electron-deficient aromatic compound, and the fluorescence of the electron-deficient aromatic compound is quenched. The response performance of fluorescence on aromatic compounds is explored for the multifunctional two-dimensional porous polymer hybrid material I. 2ml of the solution is added, and the concentration is 0.1 mg/ml^-1H of multifunctional two-dimensional porous polymer hybrid material I with pH value of 7₂O&DMSO

The solution is a detection system. Separately preparing a certain concentration of H of dinitrotoluene₂O and DMSO (V)_H2O:V_DMSO1:1) to the systemAdding 20 μ l of the above solution to increase the concentration of aromatic compound by 1 × 10^-4And M. Dinitrotoluene is an aromatic compound with electron deficiency in the benzene ring.

Finally, it should be noted that: it should be understood that the above examples are only for clearly illustrating the present application and are not intended to limit the embodiments. Other variations and modifications in light of the above teachings may occur to those skilled in the art. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of this invention may be made without departing from the spirit or scope of the invention.

Claims

1. The preparation method of the multifunctional two-dimensional porous polymer hybrid material is characterized by comprising the following steps of:

(4) mixing the intermediate product III prepared in the step (3) with N- (2-aminoethyl) carbazole, cesium carbonate and anhydrous dimethylformamide, continuously stirring and reacting for 16-32 hours at room temperature in a dark place, washing with dimethylformamide and water, performing centrifugal separation, and then performing freeze drying to obtain the multifunctional two-dimensional porous polymer hybrid material;

wherein, the first crosslinking agent in the step (1) is divinylbenzene; the initiator in the step (1) comprises one or more of azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate; the second cross-linking agent in the step (2) comprises one or more of dimethoxymethane and carbon tetrachloride; the first catalyst in the step (2) comprises one or more of anhydrous ferric trichloride and anhydrous aluminum trichloride; the first solvent in the step (3) comprises one or more of 1, 2-dichloroethane, dichloromethane, chloroform and carbon tetrachloride; and (3) the second catalyst comprises one or more of anhydrous ferric trichloride and anhydrous aluminum trichloride.

2. A multifunctional two-dimensional porous polymer hybrid material, which is prepared by the preparation method of the multifunctional two-dimensional porous polymer hybrid material of claim 1.

3. The multifunctional two-dimensional porous polymer hybrid material as claimed in claim 2, and its application in pollutant detection and pollutant adsorption separation.

4. A filter material, which is prepared by dispersing the multifunctional two-dimensional porous polymer hybrid material as claimed in claim 2 in a solvent and assembling the multifunctional two-dimensional porous polymer hybrid material with a microporous filter membrane as a support membrane.