CN112898571B

CN112898571B - Porous cross-linked material and preparation method and application thereof

Info

Publication number: CN112898571B
Application number: CN202110127768.5A
Authority: CN
Inventors: 路建美; 徐庆锋
Original assignee: Suzhou University
Current assignee: Suzhou University
Priority date: 2021-01-29
Filing date: 2021-01-29
Publication date: 2022-06-21
Anticipated expiration: 2041-01-29
Also published as: CN112898571A

Abstract

The invention discloses a porous cross-linked material, a preparation method and application thereof, wherein TPC-OTBS n-hexane solution is added into TPC-OSO₂F. Standing the mixed solution of DMF and DBU to obtain cross-linked solvent gel; and adding the crosslinking solvent gel into methanol, stirring and drying to obtain the porous crosslinking material. The gel obtained by the invention can be used for preparing a solid porous organic polymer material with abundant pores through solvent exchange. The surface and internal appearance of the solid material are characterized by SEM and TEM, and the appearance of the solid material is found to be porous, and more pores are formed. The structure of the crosslinked polysulfate is characterized by infrared and nuclear magnetism, the complete reaction of sulfuryl fluoride groups is proved by solid nuclear magnetism fluorine spectrum and XPS element analysis, and the porous structure of the crosslinked polysulfate has better application prospect in the aspect of adsorption; the maximum adsorption capacity of the organic phase to iodine can reach 702 mg/g, and the water phase to bisphenol A has better results, and the maximum adsorption capacity can reach 205 mg/g.

Description

Porous cross-linked material and preparation method and application thereof

Technical Field

The invention belongs to a material preparation technology, and particularly relates to a porous cross-linked material, and a preparation method and application thereof.

Background

The porous organic polymer, as a new organic porous material, has the advantages of strong designability, easy preparation, stable and diversified structure, light weight, excellent adsorption performance and the like compared with an inorganic porous material, and is widely concerned by researchers. Generally, porous organic polymers are mostly crosslinked polymers. The crosslinking method can form a skeleton by using a polymer body, so that pores are formed, and the general size of the pores is often closely related to the structures of a polymer monomer and a crosslinking agent. There have been some examples showing that some porous organic polymer adsorbents successfully synthesized by crosslinking can effectively treat contaminants such as metal ions, organic contaminants, and drug residues such as antibiotics, etc. in water. Persistent Organic Pollutants (POPs) in water bodies are a new type of water environment pollution problem caused by industrial development. Because persistent organic pollutants generally have strong biological toxicity, many of the persistent organic pollutants have mutagenicity and carcinogenicity, are extremely harmful and are difficult to remove by a common biological method. The adsorption technology has the advantages of relatively low cost, simple adsorption and regeneration process, simple operation and no harmful by-products, and is considered to be a water purification technology with wide application prospect. The various advantages of porous organic polymers make them extremely advantageous for the removal of persistent organic pollutants from water bodies.

Disclosure of Invention

The invention has the advantages of convenient chemical synthesis and simple preparation of the monomer with multiple functionality. Firstly, 4',4' ' -trihydroxy triphenylmethane (TPC-OH) is selected as a phenol precursor, sulfuryl fluorination and silicon-oxygen etherification are respectively carried out to form trifunctional monomers TPC-OTBS and TPC-OSO₂And F, standing for the first time to obtain the solvent gel. The present invention for the first time uses multifunctional groups (with a number of functional groups of 3 or more) to prepare crosslinked polysulfates with the aim of using a novel method to synthesize porous organic polymers and apply them for water pollution remediation.

The invention adopts the following technical scheme:

a porous cross-linked material is prepared from cross-linked solvent gel; the crosslinked solvent gel is used for crosslinked solvent gelThe monomer is prepared in the presence of DBU. Specifically, the preparation method of the porous cross-linked material disclosed by the invention comprises the step of adding TPC-OTBS n-hexane solution into TPC-OSO₂F. Standing the mixed solution of DMF and DBU to obtain cross-linked solvent gel; and adding the crosslinking solvent gel into alcohol, stirring and drying to obtain the porous crosslinking material.

The invention discloses a cross-linked solvent gel, which is prepared by adding TPC-OTBS n-hexane solution into TPC-OSO₂F. And (3) standing the mixture of DMF and DBU to obtain the cross-linked solvent gel.

In the present invention, TPC-OSO₂F. The dosage ratio of DMF, DBU and TPC-OTBS n-hexane solution is (200-210 mg), 1-4.5 mL, 50 mu g and 2.15 mL, preferably (200-210 mg), 3.5-4.2 mL, 50 mu g and 2.15 mL; in the TPC-OTBS n-hexane solution, the dosage ratio of TPC-OTBS to n-hexane is (2.2-2.205 g) to 22 mL; the alcohol is small molecule alcohol, such as methanol; the dosage of the cross-linking solvent gel and the alcohol is not limited, so that the alcohol can submerge the gel, and the stirring and drying are conventional technologies, for example, the drying is carried out at 70-90 ℃ for 10-15 hours, and preferably at 80 ℃ for 12 hours.

A typical process for the synthesis of a crosslinked solvent gel (TPC-cPS-gel) according to the present invention is: scale TPC-OSO₂F, taking DMF (dimethyl formamide) by using a liquid transfer gun in a sample bottle, adding the DMF into the sample bottle as a solvent, dissolving all solids by ultrasound, adding DBU (DBU), performing ultrasound again to dissolve and disperse the DBU uniformly, absorbing a n-hexane solution of TPC-OTBS (Polymethylacetylene-OTBS) prepared in advance by using the liquid transfer gun, and adding the n-hexane solution into the sample bottle along the bottle wall to form a double-layer liquid with obvious layering and clear interface; standing the sample bottle at room temperature, observing the fluidity of the solution by an inclined method, judging the formation of gel (conventional technology), pouring out the upper layer liquid, and taking out the lower layer solvent gel, namely the TPC-cPS-gel. The specific dissolving, dropping and charging involved in the invention are all conventional techniques in the field.

In the invention, TPC-OTBS and TPC-OSO₂The chemical structural formula of F is as follows:

in the invention, 4,4',4' ' -trihydroxy triphenylmethane and tert-butyldimethylsilyl chloride react in the presence of imidazole to prepare TPC-OTBS; further, the molar ratio of 4,4',4' ' -trihydroxy triphenylmethane to tert-butyldimethylsilyl chloride to imidazole is 1: 3-4; the reaction was carried out at room temperature.

In the invention, 4,4',4' ' -trihydroxy triphenylmethane reacts with sulfuryl fluoride in the presence of triethylamine to prepare TPC-OSO₂F; further, the molar ratio of 4,4',4' ' -trihydroxy triphenylmethane to triethylamine is 1: 3-4; the reaction was carried out at room temperature.

The invention discloses the application of the porous cross-linked material as an adsorbent; specifically, the method for adsorbing pollutants by using the porous cross-linked material comprises the following steps of adding the porous cross-linked material into a solution containing pollutants to realize the adsorption of the pollutants; the pollutants comprise iodine, rhodamine B, bisphenol A and tetracycline; the solution may be an aqueous solution or an organic solvent solution.

In the invention, a multifunctional monomer TPC-OSO is synthesized₂F and TPC-OTBS and chemically synthesized cross-linked polysulfate gels are used. At the appropriate concentration, a double liquid phase interfacial extraction reaction is used to form a solvent gel of the crosslinked polysulfate in DMF solution. The obtained gel can prepare a solid porous organic polymer material with abundant macropores through solvent exchange. The surface and internal appearance of the solid material are characterized by SEM and TEM, and the appearance of the solid material is found to be porous, and is more macroporous. XRD and HR-TEM and TEM diffraction confirmed that the polymer was amorphous, with pores probably due to macroscopic gel-beam aggregation and solvent evaporation. The structure of the crosslinked polysulfate is characterized by infrared and nuclear magnetism, and the residue of sulfuryl fluoride groups is confirmed by solid nuclear magnetism fluorine spectrum and XPS element analysis. Meanwhile, the porous structure of the crosslinked polysulfate has better application prospect in the aspect of adsorptionThe maximum adsorption capacity of the organic phase to iodine can reach 702 mg/g, and the adsorption capacity to bisphenol A in the aqueous phase is also good, and the maximum adsorption capacity can reach 205 mg/g.

Drawings

FIG. 1 is a nuclear magnetic spectrum of TPC-OTBS;

FIG. 2 is TPC-OSO₂Nuclear magnetic spectrum of F;

FIG. 3 is a schematic diagram of TPC-cPS-gel preparation and implementation;

FIG. 4 is a schematic of the preparation of porous solid TPC-cPS from TPC-cPS-gel by solvent exchange with methanol;

FIG. 5 is an SEM image of TPC-cPS-1 to TPC-cPS-8;

FIG. 6 is a TEM image of TPC-cPS-1 to TPC-cPS-8;

FIG. 7 is an infrared spectrum of TPC-cPS-1 and TPC-cPS-7;

FIG. 8 is a graph of the thermal weight loss of TPC-cPS-7;

FIG. 9 is a DSC of TPC-cPS-7;

FIG. 10 is (a) an XRD spectrum, (b) a high resolution HR-TEM image and (c) a TEM diffraction image of TPC-cPS-7;

FIG. 11 is a graph of the saturated adsorption curves of TPC-cPS-6, TPC-cPS-7 and TPC-cPS-8 to a 2000 ppm iodine in carbon tetrachloride solution;

FIG. 12 is a saturated adsorption curve of TPC-cPS-6, TPC-cPS-7 and TPC-cPS-8 to a 50 ppm bisphenol A aqueous solution;

FIG. 13 shows the removal rates of TPC-cPS-7 by adsorption of a 10ppm iodine solution in carbon tetrachloride and an aqueous solution of bisphenol A, rhodamine B and tetracycline;

FIG. 14 shows TPC-cPS-7¹⁹F-NMR solid nuclear magnetic fluorine spectrum.

Detailed Description

In the prior art, long-chain diaryl polysulfate is synthesized by using bifunctional monomers, and an example of preparing crosslinked polysulfate by using polyfunctional groups (the number of functional groups is 3 or more) is not reported, and a polymer with a porous structure cannot be obtained by using the polyfunctional monomers as raw materials by using the prior art, so that the invention has a great interest in obtaining the solvent gel of the crosslinked polysulfate by limiting the formation conditions and the trend of the solvent gel through a new method. Furthermore, the obtained solvent gel is placed in methanol for solvent exchange, so that the crosslinked polysulfate solid material containing rich macropores (with the aperture of 80-120 nm) can be conveniently obtained, the material has a good effect of removing persistent organic pollutants such as bisphenol A and the like in a water body as an adsorbent, and the porous crosslinked material is added into a solution containing the pollutants to realize the adsorption of the pollutants. Compared with the common organic macroporous material which needs to be prepared by a template method, the synthesis method of the invention completely does not need a template, and macropores can be formed spontaneously during solvent exchange. The work expands the synthesis direction and application scenes of the polysulfate. The raw materials involved in the invention are all commercial products, and the specific operation method and the test method are all conventional methods in the field.

NN-Dimethylformamide (DMF), Tetrahydrofuran (THF), methanol, N-hexane, Dichloromethane (DCM) and Triethylamine (TEA) were purchased from the national drug Consortium group, Inc. 4,4',4' ' -Trihydroxytriphenylmethane was purchased from Shanghai Jiuding chemical technology, Inc. Imidazole, tert-butyldimethylchlorosilane (TBSCl) and 1, 8-Diazabicycloundecene (DBU) were purchased from Chinesia (Tokyo) chemical industry development Co., Ltd. Sulfuryl fluoride gas was purchased from Hangzhou Maoyu electronics chemical Co., Ltd. All the above starting materials and reagents were used as received.

¹H-NMR spectrum was measured using an INOVA 400 MHz high resolution NMR spectrometer with Tetramethylsilane (TMS) as internal standard and CDCl₃Is a solvent.¹³C-NMR and¹⁹the F-NMR spectrum was obtained by measuring 30-40 mg of a solid sample at room temperature with an AVANCEIII/WB-400 solid wide-cavity superconducting NMR spectrometer. The ultraviolet-visible absorption spectrum (UV-vis) was measured using a UV3600 Shimadzu UV-3600 Plus ultraviolet-visible near infrared spectrophotometer (Shimadzu UV-3600 Plus). The concentration of all contaminants is judged by the absorption intensity in the uv spectrum. Infrared spectroscopy (FT-IR) was measured on a VERTEX 70 infrared spectrometer with a diamond ATR accessory. Scanning Electron Microscope (SEM) images were taken by Hitachi S-4700 scanning electron microscope, Hitachi, Japan. TEM image through-the-sunFEI TECNAI G20 transmission electron microscope photographs by national FEI.

Example one

Synthesis of TPC-OTBS

4,4',4' ' -Trihydroxytriphenylmethane (1.46 g, 5 mmol) and imidazole (1.36 g, 20 mmol) were placed in a 100 mL flask, 20 mL of dichloromethane was added, and the solid was completely dissolved by stirring at room temperature for 15 minutes. Tert-butyldimethylsilyl chloride (3.02 g, 20 mmol) was dissolved in 10 mL of methylene chloride, and the resulting solution was added dropwise to the flask via a constant pressure dropping funnel, and the flask was stirred during the addition, and the addition was completed within 30 minutes. The whole reaction system was further stirred at room temperature for 12 hours. The reaction progress was checked by TLC, after conversion of the starting material, the solid was removed by filtration, the crude product was purified by column chromatography after spin-drying the filtrate, using dichloromethane/petroleum ether as the developing solvent (v/v = 1/2). The pure product was TPC-OTBS as a pure white solid (2.3 g, yield: 72%) and TBS from tert-butyldimethylsilyl chloride (TBSCl). The nuclear magnetic spectrum of the synthesized product is shown in figure 1.¹H NMR (400 MHz, CDCl₃，ppm) δ 6.91 (d, J = 8.0 Hz, 6H), 6.73 (d, J = 8.1 Hz, 6H), 5.33 (d, J = 13.5 Hz, 1H), 0.97 (s, 27H), 0.18 (s, 18H)。

TPC-OSO₂Synthesis of F

4,4',4' ' -Trihydroxytriphenylmethane (1.46 g, 5 mmol) was placed in a 1000 mL flask, 20 mL of dichloromethane was added, stirring was performed at room temperature and triethylamine (2.1 g, 20 mmol) was added, and stirring was continued to dissolve all solids. The flask was sealed, pumped to vacuum with a water pump, and then gassed with sulfuryl fluoride using a 55L gas bag. The entire reaction system was kept sealed and the reaction was continued with stirring at room temperature for 12 hours. Detecting reaction progress by TLC, converting raw material, filtering to remove solid, spin drying filtrate, and collecting crude productColumn chromatography purification is carried out, and the developing solvent is ethyl acetate/petroleum ether (v/v = 1/4). The pure product was TPC-OSO as white fine crystals (2.5 g, yield: 93%)₂F. The nuclear magnetic spectrum of the synthesized product is shown in figure 2.¹H NMR (400 MHz, CDCl₃,ppm) δ 7.28 (d, J = 8.6 Hz, 6H), 7.16 (d, J = 8.7 Hz, 6H), 5.31 (s, 1H)。

Synthesis of TPC-cPS-gel

The synthesis of TPC-cPS-gel is carried out by a typical process, for example, gel synthesis of TPC-cPS-7. 206.5 mg of TPC-OSO were weighed out at room temperature₂F, in a 20 mL sample bottle, measuring 4 mL of DMF (dimethyl formamide) by using a liquid transfer gun, adding the DMF into the sample bottle as a solvent, dissolving all solids by conventional ultrasound, then adding 50 ug of DBU, performing ultrasound again to dissolve and disperse the DBU uniformly, absorbing 2.15 mL of a TPC-OTBS (2.2016 g of TPC-OTBS dissolved in 22mL of n-hexane) solution prepared in advance by using the liquid transfer gun, and adding the solution into the sample bottle along the bottle wall to form a double-layer liquid with obvious layering and clear interface; standing the sample bottle, observing the fluidity of the solution by an inclined method to judge the formation of gel, tracking the concentration of the monomer TPC-OTBS in the n-hexane at the upper layer by TLC to judge the proceeding degree of the reaction, pouring the liquid at the upper layer when the reaction is finished, and taking the solvent gel at the lower layer, namely TPC-cPS-gel, which is a sample 7 in the table 2.

Mixing the TPC-OSO₂Different solvent gels were obtained with varying amounts of F and the remainder, see table 2, sample 1, sample 2, sample 5, sample 6, sample 8.

The limitation of different reaction solvents is the primary condition for carrying out the double-liquid phase interfacial polymerization, and the two solvents with large polarity difference are selected as two phases of the interfacial polymerization reaction. To transmit TPC-OSO₂F and a catalyst DBU are dissolved in DMF, then a normal hexane solution of TPC-OTBS is placed on the upper layer of the catalyst, a DMF/normal hexane double-liquid phase reaction system is formed, and the catalyst is placed still for reaction. The occurrence of the reaction was observed at a defined monomer concentration. As shown in FIG. 3, when the reaction time of both phases was not long (2 hours), both phases maintained fluidity, and as the reaction time was prolonged to 24 hours, it was found by the tilt method that the entire DMF layer lost fluidity and formed a gelGlue, at this moment, the concentration of the upper layer solution is analyzed through TLC, the completion of the TPC-OTBS reaction of the monomer can be found, and the TLC is observed to hardly develop color, which indicates that the concentration of the monomer in the n-hexane at the upper layer reaches a very low level and the reaction is completed, and the judgment is the conventional technology in the field; removing the upper solution to obtain gel which is still transparent colloidal solid and has certain mechanical strength, and because the upper solute permeates into the lower layer to react, the gel is not formed at the interface.

Preparation of TPC-cPS porous cross-linked material

Placing the gel (TPC-cPS-7) in methanol (just by flooding), stirring the solution for 1 hour conventionally to allow solvent exchange to occur, removing the catalyst DBU, etc., according to¹³C-NMR and¹⁹F-NMR found that all impurities were removed; and then placing the finally obtained white solid in a vacuum oven to dry for 12 hours at the temperature of 80 ℃ to obtain a white solid porous material, namely TPC-cPS.¹³C NMR (101 MHz, Solid, ppm) δ 149.84, 143.23, 130.98, 121.80, 55.02；¹⁹F NMR (377 MHz, Solid, ppm) δ -122.98。

Placing the gel in the precipitating agent methanol results in solvent exchange, the process is shown in figure 4. The gel was no longer clear and a white polymer solid was produced. As the solvent exchange proceeds, DMF in the whole gel is completely replaced by methanol, catalyst DBU in the gel is also carried away by the methanol, and the gel is solidified and does not have the elasticity of the gel any more, and becomes a white solid. And drying the solid, and observing the surface of the solid through SEM to find that fine holes are distributed on the surface of the solid. The observation of small fragments of the solid by TEM revealed that they had an osteogenic skeleton structure and voids could be formed inside. The polymer is a material with a macroporous structure, and the pore diameter is mostly about 100 nm.

Taking out the gels of the

samples

1, 2, 5, 6 and 8, placing the gels in methanol, electromagnetically stirring, replacing DMF in the gels with methanol, and removing DBU and monomers; the obtained crosslinked polymer solid was dried in a vacuum oven at 80 ℃ for 12 hours to obtain porous crosslinked polysulfates, which were designated as TPC-cPS-1, TPC-cPS-2, TPC-cPS-3, TPC-cPS-6, and TPC-cPS-8, respectively, and the BET test was as shown in Table 1.

TABLE 1 BET data of TPC-cPS-1 to TPC-cPS-8, respectively corresponding to the serial numbers

The surface morphology of the solid small particles was observed by SEM. As shown in FIG. 5, it can be seen that TPC-cPS-1 and TPC-cPS-2 exhibit a dense surface morphology. At higher concentrations, the entire polymer is slightly yellow, rigid plastic; small holes formed on the surface of the crosslinked polysulfate can be observed from TPC-cPS-5 to TPC-cPS-8, and TPC-cPS-6 and TPC-cPS-7 have better shapes, the pore size distribution is uniform and distributed, the strength is high in gel state, and the gel can not be broken by shearing force applied from the outside, such as electromagnetic stirring and the like; TPC-cPS-8 with the minimum concentration has more macroporous defects, is powdery in an aggregation state, is not high in strength in a gel state, and is easy to break by external shearing force such as electromagnetic stirring and the like.

Observation of small solid particles by TEM gave similar results to SEM. As shown in fig. 6, although the TPC-cPS-1, TPC-cPS-2 and TPC-cPS-5 can observe the skeleton formed by the polymer on a macroscopic level, they are extremely dense, and after the concentration is gradually reduced, the pore diameter is increased, macropores begin to appear, and as the concentration is further reduced, the skeleton defect comes more and more, and the skeleton is broken.

In combination with SEM and TEM images, it can be seen that the concentration has some influence on the pore size of the finally formed crosslinked polysulfate. The lower the concentration, the larger the pore size, and the more uniform the pore size distribution tends to be under conditions where the concentration can be formed. High concentrations can reduce the pore size and even gradually densify.

In order to investigate the cause of the pore formation, a series of characterizations were performed on the prepared TPC-cPS. First, TPC-cPS-1 and TPC-cPS-7 were infrared-characterized and their infrared spectra showed complete agreement (FIG. 7). It is reasonable to believe that the chemical composition of all TPC-cPS prepared is identical except for DMF volume, depending on the reaction conditions. The results of TAG (fig. 8) and DSC (fig. 9) show that the crosslinked polysulfate has better thermal stability, a 5% weight loss temperature (Td 5%) of 249.25 ℃, no significant DSC heat absorption and release peaks, and meets the general characteristics of crosslinked polymers.

The TPC-cPS-7 was subjected to XRD analysis and TEM diffraction image photographing at the same time. As shown in FIG. 10 (a), no sharp peaks were evident in the XRD pattern of TPC-cPS-7, indicating that there was no regular ordered structure at the molecular level. The high resolution TEM image (fig. 10 b) and TEM diffraction also demonstrated that TPC-cPS-7 had no microscopically ordered structure, which is consistent with BET data, which further demonstrates that the channels in TPC-cPS were not established by a microscopic chemical structure but formed at a macroscopic physical level; the formation of these channels is attributed to aggregation of the gel fiber bundles and volatilization of the solvent.

The porous organic cross-linked polymer skeleton with excellent appearance can be conveniently prepared by adopting a double-liquid-phase interface extraction reaction method for the first time, the adsorption performance of the porous material is further characterized, SEM and TEM images show that TPC-cPS-7 has excellent porous appearance and pore size distribution, and the adsorption performance of the TPC-cPS-7 as an adsorbent in an organic solution is inspected due to the good wettability of the TPC-cPS-7 to an organic solvent: the adsorption performance of a relatively common adsorbed substance, namely iodine simple substance, is inspected, and the TPC-cPS has a good adsorption effect on iodine under a relatively low concentration, so that the concentration of iodine can be reduced to be below 0.1 ppm within half an hour by adsorbing a carbon tetrachloride solution with iodine of 10ppm by using an adsorbent concentration of 1 mg/mL (10 mg of adsorbent is added into a 10 mL solution), the specific concentration exceeds the ultraviolet detection limit, and the removal rate is conventionally considered to reach 100% (fig. 13); in order to examine the adsorption capacity, a carbon tetrachloride solution containing 2000 ppm of iodine was prepared, the concentration of the adsorbent was measured every 15 minutes using 1 mg/mL (10 mg of adsorbent was added to 10 mL of the solution), and the adsorption amount was calculated after 150 minutes of total adsorption. Meanwhile, TPC-cPS-6 and TPC-cPS-8 were similarly tested as a control, and the adsorption amount results are shown in FIG. 11. As can be seen, TPC-cPS-7 in the three adsorbents has the best adsorption effect, the adsorption rate and the adsorption capacity are both the best, and the maximum adsorption capacity can reach 702 mg/g; the adsorption effect of TPC-cPS-8 is slightly inferior to that of TPC-cPS-6. Under the same test, the adsorption effect of TPC-cPS-1, TPC-cPS-2 and TPC-cPS-5 is much worse than that of TPC-cPS-8. The results of iodine adsorption were similar to the morphological results observed by SEM for each sample.

In the aqueous phase, TPC-cPS is found to have good removal effect on some dyes and persistent organic pollutants as an adsorbent. Rhodamine B, bisphenol A and tetracycline aqueous solutions are respectively prepared, and when the organic concentration is 10ppm, the removal rates of 100%, 93% and 70% for rhodamine B, bisphenol A and tetracycline respectively can be respectively achieved by adopting the adsorbent concentration of 1 mg/mL (figure 13). Bisphenol A is selected as a research object of saturated adsorption capacity of TPC-cPS in an aqueous phase. Similarly, TPC-cPS-6 and TPC-cPS-8 were compared with TPC-cPS-7. Using a 50 ppm concentration of bisphenol A in water (25 mg bisphenol A in 500 mL deionized water), and again using a 1 mg/mL concentration of adsorbent (10 mg adsorbent was added to 10 mL solution), the solution point concentration was measured every 15 minutes for a total of 120 minutes of adsorption, and the adsorption capacity was calculated and shown in the graph. Likewise, TPC-cPS-7 still has good effect, the general trend is similar to the adsorption of iodine, but the saturation is reached in shorter time, which shows that the adsorption efficiency of bisphenol A is obviously higher. Also, the three samples began to exhibit a larger difference. The maximum adsorption amount of TPC-cPS-7 can reach 205 mg/g, but the worst TPC-cPS-8 only has 151 mg/g, which is obviously different from the result of iodine adsorption.

First in the TPC-cPS infrared test (FIG. 7), there was a peak of the absorption of sulfur fluorine bonds by vibration, indicating that sulfur fluorine bonds still remained in the product. Further, TPC-cPS-7 was subjected to¹⁹F-NMR solid nuclear magnetic fluorine spectrum tests (fig. 14) prove the presence of fluorine, the chemical shift of which corresponds to the chemical shift of fluorine in the sulfuryl fluoride group in solid nuclear magnetic, XPS elemental analysis also proves the presence of elements, and it is considered that to some extent, sulfuryl fluoride groups are retained in the crosslinked polymer, which may serve as a provider of driving force for adsorption.

Comparative example 1

Synthesis of TPC-cPS-gel TPC-OSO from example one₂The amounts of F and DMF were varied and the remainder was unchanged, no solvent gel was obtained, see Table 2,

samples

9 and 10.

Table 2 amount of monomers and solvent used in the reaction of example one and comparative example one

As shown in Table 2, TPC-OSO was applied in 8 concentration gradients₂F and 50 ug DBU were dissolved in eight DMF solvents of different volumes, and an equal volume of TPC-OTBS in n-hexane solution was added to the upper layer to carry out the same reaction. As a result of the reaction, when the concentration is small (sample 8), it is difficult to maintain good gel morphology and strength, and the gel can be broken by applying a weak shearing force (stirring at 300rpm by using a conventional electromagnetic stirrer), and the strength is not high; whereas comparative sample 9 and sample 10, both formed no gel; the rest gel has good strength and can not be broken by the stirring of the electromagnetic stirring particles.

Claims

1. A porous cross-linked material, characterized in that the porous cross-linked material is prepared from a cross-linked solvent gel; the cross-linked solvent gel is prepared from a monomer for cross-linked solvent gel in the presence of DBU; the monomers for the crosslinking solvent gel are TPC-OTBS and TPC-OSO₂F; the TPC-OTBS and the TPC-OSO₂The chemical structural formula of F is as follows:

the preparation method of the porous cross-linked material comprises the following steps of adding TPC-OTBS n-hexane solution into TPC-OSO₂F. Standing the mixed solution of DMF and DBU to obtain cross-linked solvent gel; adding the crosslinking solvent gel into alcohol, stirring and drying to obtain a porous crosslinking material; wherein TPC-OSO₂F、DThe dosage ratio of the MF, DBU and TPC-OTBS n-hexane solution is (200-210 mg) to (1-4.5 mL) to 50 mu g to 2.15 mL; in the TPC-OTBS n-hexane solution, the dosage ratio of TPC-OTBS to n-hexane is (2.2-2.205 g) to 22 mL.

2. The porous crosslinked material of claim 1, wherein 4,4',4 "-trihydroxytriphenylmethane is reacted with t-butyldimethylsilyl chloride in the presence of imidazole to prepare TPC-OTBS; preparation of TPC-OSO by reacting 4,4',4' ' -trihydroxy triphenylmethane with sulfuryl fluoride in the presence of triethylamine₂F。

3. The porous crosslinked material of claim 1, wherein the drying is performed at 70-90 ℃ for 10-15 hours.

4. Use of the porous cross-linked material of claim 1 for adsorbing contaminants.

5. A method for adsorbing pollutants by using the porous cross-linked material as claimed in claim 1, which comprises the step of adding the porous cross-linked material into a solution containing pollutants to realize the adsorption of the pollutants.

6. The method of claim 5, wherein the contaminants comprise iodine, rhodamine B, bisphenol A, tetracycline.