Fluorine-containing superhydrophobic porous hypercrosslinked polymer material and application thereof

Abstract

The application belongs to the field of super-hydrophobic materials, and particularly relates to a fluorine-containing super-hydrophobic porous super-crosslinked polymer material and application thereof. The fluorine-containing super-hydrophobic porous super-crosslinked polymer material is prepared by a Friedel-Crafts reaction of a compound with rich pi electrons and capable of undergoing the Friedel-Crafts reaction as a monomer and tetrafluoro-p-dibromobenzene as a crosslinking agent. The contact angle of the fluorine-containing super-hydrophobic porous super-crosslinked polymer material prepared by the application can reach 160 degrees or more, and the super-hydrophobic performance can be maintained under harsh conditions such as strong acid, strong base and high temperature. The fluorine-containing super-hydrophobic porous super-crosslinked polymer material prepared by the application has uniform internal pore diameter and large specific surface area, can separate various emulsified oils, and the separation efficiency can be as high as 99% or more. After 10 cycles of recycling and use, the oil-water separation effect of the fluorine-containing super-hydrophobic porous super-crosslinked polymer material can still be maintained.

Description

Technical Field

[0001] This invention relates to the field of superhydrophobic materials technology, specifically to a fluorine-containing superhydrophobic porous hypercrosslinked polymer material and its applications. Background Technology

[0002] With rapid industrial development, the separation and removal of trace oily mixtures in water has become a major challenge for environmental pollution control. Traditional separation methods such as centrifugation and gravity sedimentation suffer from significant drawbacks, including low efficiency and high energy consumption. Superhydrophobic materials with significantly low surface energy (water contact angle greater than 150°) demonstrate the potential for green and efficient separation of oil-water mixtures and removal of organic pollutants from water. Developing superhydrophobic porous materials is one of the effective ways to solve the aforementioned separation problems.

[0003] Superhydrophobic materials should possess a porous physical structure with low surface energy and chemical properties. Due to the low surface energy of fluoropolymers, researchers have recently developed various fluorinated functionalized porous materials for oil-water separation and the removal of organic pollutants from water, such as metal-organic frameworks (CN 111333854 A), covalent organic frameworks (Journal of Hazardous Materials 411(2021):125190.), and aerogels (AIChE Journal 68.6(2022):e17619.). However, metal-organic frameworks are unstable in water, leading to pore structure collapse. The preparation of covalent organic framework materials requires expensive raw materials and harsh reaction conditions, while the adsorption capacity of activated carbon decreases with prolonged use.

[0004] Hypercrosslinked porous polymers are formed by weaving monomers and crosslinking agents into a polymer network with a stable structure and a large specific surface area through Friedel-Crafts reaction. This structure gives them excellent chemical and thermal stability. Hypercrosslinked polymers have advantages such as simple synthesis, broad monomer selectivity, no need for specially designed linking functional groups, low cost of solvents and catalysts, and large-scale production capability. Summary of the Invention

[0005] To address the problems of unstable porous material structures and harsh reaction conditions in existing technologies, this invention provides fluorinated superhydrophobic porous hypercrosslinked polymer materials, their preparation methods, and applications. This invention embeds low surface energy fluorinated functional groups into the hypercrosslinked porous organic polymer structure, endowing the material with superhydrophobic properties. The superhydrophobic porous hypercrosslinked porous organic polymer of this invention can play an important role in oil-water separation and the removal of organic pollutants from water.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention provides a fluorine-containing superhydrophobic porous supercrosslinked polymer material, wherein the polymer material is prepared by reacting a tetrafluorobenzyl dibromo as a crosslinking agent with a π-electron-rich compound that is a monomer and capable of undergoing a Friedel-Crafts reaction.

[0008] The compounds rich in π electrons and capable of undergoing Friedel-Crafts reactions include: triphenylbenzene, triphenylene, tetraphenylmethane, octaphenylsilsesquioxane, triphenylamine, triphenylphosphine, polycyclic aromatic hydrocarbons, and other aromatic compounds, as shown in the reaction formulas. Figure 7 As shown.

[0009] The chemical formula of the polycyclic aromatic hydrocarbon compound is:

[0010] Wherein, R is one or more phenyl groups. In a specific embodiment, the polycyclic aromatic hydrocarbon compound is naphthalene.

[0011] Preferably, the solvent that can be used in the above reaction is one of dichloromethane, dichloroethane, chloroform, chlorobenzene, and nitrobenzene.

[0012] Preferably, the above reaction uses either aluminum trichloride or ferric trichloride as a catalyst.

[0013] Preferably, the molar ratio of crosslinking agent, monomer, and catalyst in the above reaction is (3-4):(1-4):(2-18). The amount of solvent used is 30-120 mL per 1 mmol of crosslinking agent.

[0014] Preferably, the above reaction is carried out in an inert gas environment.

[0015] The above reaction includes the following specific steps:

[0016] (1) Mix the crosslinking agent and monomer evenly in an inert gas in a solvent, and add aluminum trichloride or ferric trichloride catalyst.

[0017] (2) Under an inert gas environment, the obtained reaction solution is heated to 20-80℃ and reacted for 12-40 hours, and then filtered, washed and dried in sequence to obtain the final product.

[0018] In step (2), the washing process uses dichloromethane and methanol in sequence.

[0019] The drying process described in step (2) involves drying the product at 40–80°C until the product quality remains constant.

[0020] The fluorinated superhydrophobic porous hypercrosslinked polymer material prepared by this invention has a specific surface area of ​​200–400 m². 2 / g, microporous surface area accounts for more than 75% of the total surface area, and pore volume is 0.2-0.6cm³. 3With a pore size of 1–10 nm, this adsorbent can be used as an adsorbent for the separation of emulsified or non-emulsified oils. For non-emulsified oils, current separation methods include gravity separation and flotation skimming, which are energy-intensive and have low separation efficiency in practical applications. The method of this invention solves these problems. Under conditions of a surfactant content of 288.8 g / L, an oil content of 20 g / L, and a separation time of 2 minutes, this adsorbent achieves separation efficiencies exceeding 99.4% for 2% V / V oil-in-water solutions (the "oil" consists of dichloromethane (DCM), n-hexane, cyclohexane (CYH), dimethyl sulfoxide (DMSO), ethyl acetate, dichloroethane (DCE), chlorobenzene (CB), petroleum ether (PE), or xylene) stable with anionic, cationic, and neutral surfactants.

[0021] The application of the fluorinated superhydrophobic porous supercrosslinked polymer material in emulsified oil separation is specifically carried out by placing the fluorinated superhydrophobic porous supercrosslinked polymer material into the emulsified oil, vortexing for 2 minutes, and then filtering to obtain a pure aqueous phase.

[0022] The fluorinated superhydrophobic porous supercrosslinked polymer material can be dried and reused after adsorption, and its separation efficiency is still over 99% after 10 consecutive separations of emulsified oil.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] The two structural units of the fluorinated superhydrophobic porous hypercrosslinked polymer material of the present invention have low surface energy, and have the advantages of inexpensive and readily available raw materials, simple preparation process, and ability to meet actual production needs.

[0025] The fluorinated superhydrophobic porous hypercrosslinked polymer material prepared by this invention can achieve a contact angle of over 160° and maintain stable hydrophobic properties under harsh conditions such as strong acid, strong alkali and high temperature.

[0026] The fluorinated superhydrophobic porous hypercrosslinked polymer material prepared by this invention has a uniform internal pore size and a large specific surface area (200-400 m²). 2 / g, microporous surface area accounts for more than 75% of the total surface area, and pore volume is 0.2-0.6cm³. 3 / g, with a pore size of 1-10nm), it can separate various emulsified oils (such as oil-in-water mixtures containing organic pollutants) with a separation efficiency of over 99%. After 10 cycles of recycling, it can still maintain its original oil-water separation effect. Attached Figure Description

[0027] Figure 1 This is a scanning electron microscope image of the polymer material prepared in Example 1;

[0028] Figure 2 (A) is the carbon NMR spectrum of the polymer material prepared in Example 1; (B) is the fluorine NMR spectrum of the polymer material prepared in Example 1.

[0029] Figure 3 The contact angle diagrams are for the polymer materials obtained in Examples 1, 2, and 3.

[0030] Figure 4 This is a schematic diagram of the separation process of CTAB-stabilized O / W dichloromethane / water emulsion oil by the polymer material prepared in Example 1;

[0031] Figure 5 (A) Image of the demulsification of O / W dichloromethane / water emulsion stabilized by the polymer material of Example 1 of the present invention with CTAB (hexadecyltrimethylammonium bromide); (B) Image during demulsification; (C) Image after demulsification and separation; (D) Microscopic image of the emulsion; (E) Microscopic image after demulsification and separation; (F) Microscopic image of oil droplet size distribution in the emulsion stabilized by surfactant.

[0032] Figure 6 Images of the demulsification of O / W emulsions of other organic solvents / water stabilized by the polymer material HCP-1 of Example 1 of this invention with CTAB (hexadecyltrimethylammonium bromide); (A, E, I, M, Q) images before, during and after the demulsification process; (B, F, J, N, R) microscopic images of the emulsion; (C, G, K, O, S) microscopic images after demulsification and separation; (D, H, LPT) microscopic images of oil droplet size distribution in the emulsion stabilized by surfactant.

[0033] Figure 7 This is the reaction formula of the present invention. Detailed Implementation

[0034] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of the embodiments of this invention will be clearly described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of this invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0035] Example 1

[0036] A fluorinated superhydrophobic porous hypercrosslinked polymer material is disclosed, which is used as an adsorbent for the separation of emulsified or non-emulsified oils. The preparation method of this polymer material specifically includes the following steps:

[0037] (1) Add 100 mL of dichloromethane, 3 mmol (0.93 g) of tetrafluoro-p-dibromobenzyl, and 2 mmol (0.588 g) of triphenylbenzene to a three-necked flask and stir for 30 minutes under nitrogen atmosphere to ensure thorough dispersion.

[0038] (2) Add 1.2g of ferric chloride to the reaction solution of step (1), mix well, heat to 80℃ under nitrogen atmosphere, and react for 30 hours; after the product cools to room temperature, filter it using a vacuum filtration flask and wash the obtained filter cake three times with dichloromethane and methanol in sequence, and dry it in a 60℃ oven for 6 hours to constant weight to obtain the fluorine-containing superhydrophobic porous supercrosslinked polymer material HCP-2, the structural formula of which is shown below:

[0039]

[0040] The water contact angle of the fluorinated superhydrophobic porous hypercrosslinked polymer material, measured using a water contact angle meter, was 170.9°. Figure 3 The superhydrophobic powder has an adsorption capacity of 2.8 g / g for dichloromethane, meaning that each gram of the prepared superhydrophobic powder can adsorb 2.8 grams of dichloromethane. The adsorption capacity is calculated as follows: the prepared fluorine-containing superhydrophobic porous hypercrosslinked polymer powder is immersed in an organic solvent, then separated to obtain saturated superhydrophobic powder. The adsorption capacity is obtained by subtracting the mass of the material before adsorption from the mass of the material after adsorption and dividing by the mass of the material before adsorption.

[0041] Figure 1 The image shows a scanning electron microscope (SEM) image of the fluorine-containing superhydrophobic porous hypercrosslinked polymer material prepared in Example 1. As can be seen from the image, the polymer material has a very rich and uniform pore structure. Figure 2 The images show the carbon NMR spectrum and fluorine NMR spectrum of the prepared fluorine-containing superhydrophobic porous supercrosslinked polymer material.

[0042] Example 2

[0043] A fluorinated superhydrophobic porous hypercrosslinked polymer material is disclosed, which is used as an adsorbent for the separation of emulsified or non-emulsified oils. The preparation method of this polymer material specifically includes the following steps:

[0044] (1) Add 100 mL of dichloromethane, 3 mmol (0.93 g) of tetrafluoro-p-dibromobenzyl, and 2 mmol (0.508 g) of triptene to a three-necked flask and stir for 30 minutes under nitrogen atmosphere to ensure full dispersion.

[0045] (2) Add 1.2g of ferric chloride to the reaction solution of step (1), mix well, heat to 80℃ under nitrogen atmosphere, and react for 30 hours; after the product cools to room temperature, filter it using a vacuum filtration flask and wash the obtained filter cake three times with dichloromethane and methanol in sequence, and dry it in a 60℃ oven for 6 hours to constant weight to obtain the fluorine-containing superhydrophobic porous supercrosslinked polymer material HCP-4, the structural formula of which is shown below:

[0046] .

[0047] The water contact angle of the fluorinated superhydrophobic porous hypercrosslinked polymer material, measured using a water contact angle meter, was 162.7°. Figure 3 Its adsorption capacity for dichloromethane is 2.8 g / g.

[0048] Example 3

[0049] A fluorinated superhydrophobic porous hypercrosslinked polymer material is disclosed, which is used as an adsorbent for the separation of emulsified or non-emulsified oils. The preparation method of this polymer material specifically includes the following steps:

[0050] (1) Add 100 mL of dichloromethane, 4 mmol (1.033 g) of tetrafluoro-p-dibromobenzyl, and 4 mmol (1.28 g) of tetraphenylmethane to a three-necked flask and stir for 30 minutes under nitrogen atmosphere to ensure thorough dispersion.

[0051] (2) Add 1.2g of ferric chloride to the reaction solution of step (1), mix well, heat to 80℃ under nitrogen atmosphere, and react for 30 hours; after the product cools to room temperature, filter it using a vacuum filtration flask and wash the obtained filter cake three times with dichloromethane and methanol in sequence, and dry it in a 60℃ oven for 6 hours to constant weight to obtain the fluorine-containing superhydrophobic porous supercrosslinked polymer material HCP-5, the structural formula of which is shown below:

[0052] .

[0053] The water contact angle of the fluorinated superhydrophobic porous hypercrosslinked polymer material, measured using a water contact angle meter, was 164.7°. Figure 3 Its adsorption capacity for dichloromethane is 2.5 g / g.

[0054] Example 4

[0055] A fluorinated superhydrophobic porous hypercrosslinked polymer material is disclosed, which is used as an adsorbent for the separation of emulsified or non-emulsified oils. The preparation method of this polymer material specifically includes the following steps:

[0056] (1) Add 100 mL of dichloromethane, 4 mmol (1.033 g) of tetrafluoro-p-dibromobenzyl, and 4 mmol (0.512 g) of naphthalene to a three-necked flask and stir for 30 minutes under nitrogen atmosphere to ensure thorough dispersion.

[0057] (2) Add 1.2g of ferric chloride to the reaction solution of step (1), mix well, heat to 80℃ under nitrogen atmosphere, and react for 30 hours; after the product cools to room temperature, filter it using a vacuum filtration flask and wash the obtained filter cake three times with dichloromethane and methanol in sequence, and dry it in a 60℃ oven for 6 hours to constant weight to obtain the fluorine-containing superhydrophobic porous supercrosslinked polymer material HCP-6, the structural formula of which is shown below:

[0058] .

[0059] The water contact angle of the fluorinated superhydrophobic porous hypercrosslinked polymer material, as measured by a water contact angle meter, was 135.7°, and its adsorption capacity for dichloromethane was 1.3 g / g.

[0060] Example 5

[0061] A fluorinated superhydrophobic porous hypercrosslinked polymer material is disclosed, which is used as an adsorbent for the separation of emulsified or non-emulsified oils. The preparation method of this polymer material specifically includes the following steps:

[0062] (1) Add 100 mL of dichloromethane, 4 mmol (1.033 g) of tetrafluoro-p-dibromobenzyl, and 1 mmol (1.344 g) of octaphenyl sesquioxane to a three-necked flask and stir for 30 minutes under nitrogen atmosphere to ensure thorough dispersion.

[0063] (2) Add 1.2g of ferric chloride to the reaction solution of step (1), mix well, heat to 80℃ under nitrogen atmosphere, and react for 30 hours; after the product cools to room temperature, filter it using a vacuum filtration flask and wash the obtained filter cake three times with dichloromethane and methanol in sequence, and dry it in a 60℃ oven for 6 hours to constant weight to obtain the fluorine-containing superhydrophobic porous supercrosslinked polymer material HCP-7, the structural formula of which is shown below:

[0064] .

[0065] The water contact angle of the fluorinated superhydrophobic porous hypercrosslinked polymer material, as measured by a water contact angle meter, was 161.4°, and its adsorption capacity for dichloromethane was 1.4 g / g.

[0066] Example 6

[0067] A fluorinated superhydrophobic porous hypercrosslinked polymer material is disclosed, which is used as an adsorbent for the separation of emulsified or non-emulsified oils. The preparation method of this polymer material specifically includes the following steps:

[0068] (1) Add 100 mL of dichloromethane, 3 mmol (0.93 g) of tetrafluoro-p-dibromobenzyl, and 2 mmol (0.524 g) of triphenylphosphine to a three-necked flask and stir for 30 minutes under nitrogen atmosphere to ensure thorough dispersion.

[0069] (2) Add 1.2g of ferric chloride to the reaction solution of step (1), mix well, heat to 80℃ under nitrogen atmosphere, and react for 30 hours; after the product cools to room temperature, filter it using a vacuum filtration flask and wash the obtained filter cake three times with dichloromethane and methanol in sequence, and dry it in a 60℃ oven for 6 hours to constant weight to obtain the fluorine-containing superhydrophobic porous supercrosslinked polymer material HCP-1, the structural formula of which is shown below:

[0070] .

[0071] The water contact angle of the fluorinated superhydrophobic porous hypercrosslinked polymer material, as measured by a water contact angle meter, was 153.7°, and its adsorption capacity for dichloromethane was 1.14 g / g.

[0072] Example 7

[0073] A fluorinated superhydrophobic porous hypercrosslinked polymer material is disclosed, which is used as an adsorbent for the separation of emulsified or non-emulsified oils. The preparation method of this polymer material specifically includes the following steps:

[0074] (1) Add 100 mL of dichloromethane, 3 mmol (0.93 g) of tetrafluoro-p-dibromobenzyl, and 2 mmol (0.502 g) of triphenylamine to a three-necked flask and stir for 30 minutes under nitrogen atmosphere to ensure thorough dispersion.

[0075] (2) Add 1.2g of ferric chloride to the reaction solution of step (1), mix well, heat to 80℃ under nitrogen atmosphere, and react for 30 hours; after the product cools to room temperature, filter it using a vacuum filtration flask and wash the obtained filter cake three times with dichloromethane and methanol in sequence, and dry it in a 60℃ oven for 6 hours to constant weight to obtain the fluorine-containing superhydrophobic porous supercrosslinked polymer material HCP-3, the structural formula of which is shown below:

[0076] .

[0077] The water contact angle of the fluorinated superhydrophobic porous hypercrosslinked polymer material, as measured by a water contact angle meter, was 151.3°, and its adsorption capacity for dichloromethane was 1.05 g / g.

[0078] Comparative Example 1

[0079] A method for preparing an oil adsorbent specifically includes the following steps:

[0080] (1) Add 100 mL of dichloromethane, 3 mmol (150 μL) of dimethoxymethane and 2 mmol (0.588 g) of triphenylbenzene to a three-necked flask and stir for 30 minutes under nitrogen atmosphere to ensure thorough dispersion.

[0081] (2) Add 1.2g of ferric chloride to the reaction solution in step (1), mix well, heat to 80°C under nitrogen atmosphere, and react for 30 hours; after the product cools to room temperature, filter it using a vacuum filtration flask and wash the obtained filter cake three times with dichloromethane and methanol in sequence, and dry it in a 60°C oven for 6 hours to constant weight to obtain the adsorbent.

[0082] The water contact angle of the adsorbent, as measured by a water contact angle meter, was 77°, and its adsorption capacity for dichloromethane was 0.59 g / g.

[0083] Application examples

[0084] 288.8g of surfactant cetyltrimethylammonium bromide (CTAB) was dispersed in 1000g of water. After complete dissolution, 20g of dichloromethane was added, and the mixture was stirred continuously at room temperature for 2 hours at a stirring speed of 2000rpm to obtain CTAB-stabilized O / W dichloromethane / water emulsion.

[0085] like Figure 4 As shown, 0.5 g of the adsorbent prepared in Examples 1-7 and Comparative Example 1 was directly added to 200 mL of an oil-water mixture (O / W dichloromethane / water emulsion oil), shaken evenly, and filtered after 2 minutes. A control group (without any adsorbent) was also set up. The oil content of the resulting solution was determined by visible light microscopy. The separation efficiency after 10 separations was also studied, and the results are as follows:

[0086] The separation efficiency of the control group 1 for CTAB-stabilized emulsified oil was 0.3%, while the separation efficiency of the adsorbent in Example 1 for CTAB-stabilized O / W dichloromethane / water emulsified oil was 99.6%. Furthermore, the separation efficiency of this adsorbent after 10 consecutive separations of the aforementioned emulsified oil was 99.3%; among which, Figure 5 Figures A through 5E show the changes in the adsorbent of CTAB-stabilized O / W dichloromethane / water emulsion oil before and after adsorption in Example 1. As can be seen from the figures, the oil droplets in the emulsion oil basically disappear after adsorption.

[0087] The adsorbent in Example 2 achieved a separation efficiency of 99.8% for CTAB-stabilized O / W dichloromethane / water emulsions. Furthermore, the adsorbent achieved a separation efficiency of 99.7% after 10 consecutive separations of the aforementioned emulsion.

[0088] The adsorbent in Example 3 achieved a separation efficiency of 99.7% for CTAB-stabilized O / W dichloromethane / water emulsions. Furthermore, the adsorbent achieved a separation efficiency of 99.5% after 10 consecutive separations of the aforementioned emulsion.

[0089] The adsorbent in Example 4 achieved a separation efficiency of 99.4% for CTAB-stabilized O / W dichloromethane / water emulsions. Furthermore, the adsorbent achieved a separation efficiency of 99.3% after 10 consecutive separations of the aforementioned emulsion.

[0090] The adsorbent in Example 5 achieved a separation efficiency of 99.6% for CTAB-stabilized O / W dichloromethane / water emulsions. Furthermore, the adsorbent achieved a separation efficiency of 99.4% after 10 consecutive separations of the aforementioned emulsion.

[0091] The adsorbent of Example 6 achieved a separation efficiency of 99.8% for CTAB-stabilized O / W dichloromethane / water emulsions. Furthermore, the adsorbent achieved a separation efficiency of 99.4% after 10 consecutive separations of the aforementioned emulsion.

[0092] The adsorbent of Example 7 achieved a separation efficiency of 99.7% for CTAB-stabilized O / W dichloromethane / water emulsions. Furthermore, the adsorbent achieved a separation efficiency of 99.5% after 10 consecutive separations of the aforementioned emulsion.

[0093] The adsorbent in Comparative Example 1 achieved a separation efficiency of 13.2% for CTAB-stabilized O / W dichloromethane / water emulsions. Furthermore, the adsorbent achieved a separation efficiency of 8.1% after 10 consecutive separations of the aforementioned emulsion.

[0094] The adsorbent of Example 1 was used to separate CTAB-stabilized O / W chlorobenzene / water emulsion oil, with a separation efficiency of 99.5%. After 10 consecutive separations of the aforementioned emulsion oil, the separation efficiency of the adsorbent was 99.4%.

[0095] The adsorbent of Example 1 was used to separate CTAB-stabilized O / W dichloroethane / water emulsion oil, achieving a separation efficiency of 99.6%. After 10 consecutive separations of the aforementioned emulsion oil, the separation efficiency of the adsorbent was 99.5%.

[0096] The adsorbent of Example 1 was used to separate CTAB-stable O / W xylene / water emulsion oil, with a separation efficiency of 99.8%. The separation efficiency of the adsorbent after 10 consecutive separations of the aforementioned emulsion oil was 99.7%.

[0097] The adsorbent of Example 1 was used to separate CTAB-stabilized O / W petroleum ether / water emulsions, achieving a separation efficiency of 99.5%. After 10 consecutive separations of the aforementioned emulsion, the adsorbent achieved a separation efficiency of 99.4%.

[0098] The adsorbent of Example 1 was used to separate CTAB-stabilized O / W n-hexane / water emulsion oil, with a separation efficiency of 99.6%. The separation efficiency of the adsorbent after 10 consecutive separations of the aforementioned emulsion oil was 99.4%.

[0099] The adsorbent of Example 1 was used to separate CTAB-stabilized O / W cyclohexane / water emulsion oil, achieving a separation efficiency of 99.7%. After 10 consecutive separations of the aforementioned emulsion oil, the separation efficiency of the adsorbent was 99.5%.

[0100] Figure 6 The graph shows the changes in the adsorbent of Example 1 before and after adsorption of the above-mentioned CTAB-stable O / W organic pollutants (chlorobenzene, dichloroethane, xylene, petroleum ether, and n-hexane / water emulsion). As can be seen from the graph, the oil droplets of the emulsion basically disappeared after adsorption.

[0101] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A fluorinated superhydrophobic porous hypercrosslinked polymer material, characterized in that, The polymer material is prepared by reacting a π-electron-rich compound that is capable of Friedel-Crafts reaction with a tetrafluoro-p-dibromobenzyl as a crosslinking agent under the action of a catalyst. The π-electron-rich compound capable of Friedel-Crafts reaction is selected from: triphenylbenzene, triphenylene, tetraphenylmethane, octaphenylsilsesquioxane, triphenylamine, triphenylphosphine, or naphthalene.

2. The fluorinated superhydrophobic porous hypercrosslinked polymer material according to claim 1, characterized in that, The catalyst is aluminum trichloride or ferric trichloride.

3. The fluorinated superhydrophobic porous hypercrosslinked polymer material according to claim 1, characterized in that, The molar ratio of crosslinking agent, monomer and catalyst in the reaction is (3-4):(1-4):(2-18).

4. The fluorinated superhydrophobic porous hypercrosslinked polymer material according to claim 1, characterized in that, The reaction is carried out in an inert gas environment.

5. The fluorinated superhydrophobic porous hypercrosslinked polymer material according to claim 1, characterized in that, The reaction operation steps include: (1) The crosslinking agent and monomer are stirred and mixed evenly in an inert gas in a solvent, and the catalyst is added to obtain a reaction solution; (2) Under an inert gas environment, the obtained reaction solution is heated to 20-80℃ and reacted for 12-40 hours, and then filtered, washed and dried in sequence to obtain the final product.

6. The fluorinated superhydrophobic porous hypercrosslinked polymer material according to claim 5, characterized in that, The solvent in step (1) is one of dichloromethane, dichloroethane, trichloromethane, chloroform, chlorobenzene, and nitrobenzene.

7. The application of the fluorinated superhydrophobic porous hypercrosslinked polymer material according to any one of claims 1-5 in the separation of emulsified oil, characterized in that, The emulsified oil is an oil-in-water solution stabilized by a surfactant.

8. The application according to claim 7, characterized in that, The oil-in-water mixture is made of dichloromethane, n-hexane, cyclohexane, dimethyl sulfoxide, ethyl acetate, dichloroethane, chlorobenzene, petroleum ether, or xylene.

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