KR101777838B1 - Nanoporous Fluorinated Covalent Organic Polymers for Selective Adsorption of Organic Molecules and Method of Preparing Same - Google Patents

Nanoporous Fluorinated Covalent Organic Polymers for Selective Adsorption of Organic Molecules and Method of Preparing Same Download PDF

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KR101777838B1
KR101777838B1 KR1020150180633A KR20150180633A KR101777838B1 KR 101777838 B1 KR101777838 B1 KR 101777838B1 KR 1020150180633 A KR1020150180633 A KR 1020150180633A KR 20150180633 A KR20150180633 A KR 20150180633A KR 101777838 B1 KR101777838 B1 KR 101777838B1
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야부즈 자페르
변지혜
파텔 하스무크
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한국과학기술원
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
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    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
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Abstract

The present invention relates to a fluorine-based porous polymer capable of selectively adsorbing organic molecules and a method for producing the same, and more particularly, to a fluorine-based porous organic polymer polymerized using a fluorine-containing monomer and a method for producing the same. The fluorine-based porous polymer according to the present invention contains micropores and is stable to heat and moisture. In addition, since the polymer has a property of selectively absorbing only water-soluble organic molecules having a size smaller than the pore size among the organic molecules present in the water-soluble phase, it is possible to rapidly and selectively remove the water- And absorbents for water purification.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a fluorine-based porous polymer capable of selectively adsorbing organic molecules and a method for producing the same,

The present invention relates to a fluorine-based porous polymer capable of selectively adsorbing organic molecules and a method for producing the same, and more particularly, to a fluorine-based porous organic polymer polymerized using a fluorine-containing monomer and a method for producing the same.

With the progress of technology, the introduction of new materials and chemicals into industry and agriculture field has led to diversification of pollution sources in wastewater. This new source of pollutants is highly unlikely to be completely removed by conventional water treatment processes due to its high water solubility and small size, so it is likely to enter the human body in the future [US EPA 2010, Treating Contaminants of Emerging Concern: A Literature Review Database ]. Particularly, among the chemicals such as drugs and dyes, the organic molecules charged in the structure are very small in size and can not be separated from water and can be treated only by a high cost of reverse osmosis filtration or a structure decomposition using ozone .

The adsorption technique is the most commonly used method in the water treatment process, and is a technique for separating contaminants and the like on an absorbent having a high specific surface area and a chemical function [J. Nanopart. Res., 2012, 14, 881-887]. At this time, the absorbent used in the water treatment process should have a stable structure on the receiving phase and the contaminant source, and exhibits a high separation / removal efficiency as compared with the pore structure and chemical function suitable for the type of the contaminant source. Recently, a variety of porous structures have been studied and developed for this purpose. Typical examples thereof include metal organic frameworks (MOF), zeolites, polymeric intrinsic microporosity (PIM), covalent organic polymers Polymer, COP). Among them, the porous organic polymer (COP) is easily produced at low cost through the organic polymerization of the two monomers, and has an advantage that it is easy to control the pore and the chemical action function according to the property of the adsorption target molecule [J. Mater. Chem. 2012, 22, 8431]. In addition, it is advantageous to be utilized in water treatment process because it is very stable to heat and moisture due to a strong polymer main chain.

Korean Patent Publication No. 2015-0125790 discloses a volatile organic compound adsorbent. In the present invention, although the aromatic compound is polymerized to form micropores through the aromatic compound bonding structure, since the electrically neutral compound is used, the performance may be deteriorated when the polar compound is adsorbed.

On the other hand, the surface fluorination technique can be applied to photocatalyst [Langmuir, 2008, 24, 7338-7345], gas adsorption [ACS Macro Lett., 2013, 2, 522-526 / Chem. Commun., 2014, 50, 13910-13913] and a water treatment process [Sci. Rep., 2015, 5, 10155]. This is because the high electronegativity, polarity and hydrophobic properties of fluorine ions help to selectively absorb certain molecules. Therefore, when fluoride is contained in the porous polymer, the target molecule present in the water quality can be more selectively and effectively collected. The most efficient technique for introducing fluorine into the polymer chain would be to select a structure containing fluorine in the monomer.

Korean Patent Registration No. 0126991 discloses a chemisorptive membrane and a manufacturing method thereof. In the present invention, nanometer-thick hydrophilic or water-repellent fluorocarbon-based chemisorbed membranes capable of adsorbing organic compounds are described, but since fluorine functional groups are present on the surface of the membranes in which the micropore structure does not exist, Is lowered.

As a result of intensive efforts to solve the above problems, the present inventors have synthesized a fluorine-based porous polymer using a fluorine-containing monomer and conducted an adsorption experiment of organic molecules in the aqueous phase using the monomer. As a result, The present inventors confirmed that they selectively adsorbed the fine organic molecules and completed the present invention.

An object of the present invention is to provide a fluorine-based porous polymer capable of selectively adsorbing microorganic molecules having charge in an aqueous phase, and a method for producing the same.

Another object of the present invention is to provide a porous adsorbent comprising the porous polymer and a selective organic molecular adsorbent.

In order to achieve the above object, the present invention provides a fluorine-based porous polymer having a structure represented by Chemical Formula (1), Chemical Formula (2), or Chemical Formula (3).

(Formula 1)

Figure 112015123692766-pat00001

(n is an integer of 100 to 110,000)

(2)

Figure 112015123692766-pat00002

(n is an integer of 100 to 110,000)

(Formula 3)

Figure 112015123692766-pat00003

(n is an integer of 100 to 110,000)

(A) dispersing and heating a monomer containing a fluorine functional group and a hydroxyl group in a solvent and heating the monomer; And (b) adding a base, followed by heating and reacting, and washing and filtering to obtain a product. The present invention also provides a method for producing a polymer having the structure of Formula 1, Formula 2 or Formula 3.

The present invention also provides a porous adsorbent and a selective organic molecular adsorbent comprising a polymer having the structure of Formula 1, Formula 2 or Formula 3.

The fluorine-based porous polymer according to the present invention contains micropores and is stable to heat and moisture. In addition, since the polymer has a property of selectively absorbing only water-soluble organic molecules having a size smaller than the pore size among the organic molecules present in the water-soluble phase, it is possible to rapidly and selectively remove the water- And absorbents for water purification.

1 is a schematic view illustrating synthesis of a fluorine-based porous polymer using tetrafluorohydroquinone according to an embodiment of the present invention.
Fig. 2 shows (a) 1s carbon, (b) 1s oxygen and (c) fluorine 1s as a result of 1s XPS spectrum of a fluorine-based porous polymer using tetrafluorohydroquinone according to an embodiment of the present invention .
FIG. 3 is a 19 F solid-state NMR analysis result of a fluorine-based porous polymer using tetrafluorohydroquinone according to an embodiment of the present invention.
4 is a FTIR spectrum analysis result of a fluorine-based porous polymer using tetrafluorohydroquinone according to an embodiment of the present invention.
5 is a graph showing a heat-weight change curve of a fluorine-based porous polymer using tetrafluorohydroquinone according to an embodiment of the present invention.
6 is a photograph of the surface SEM of the fluorine-based porous polymer using tetrafluorohydroquinone according to an embodiment of the present invention and (b) the result of XRD spectrum analysis.
7 shows (a) an argon adsorption-desorption curve at 87K and (b) a pore distribution curve of a fluorine-based porous polymer using tetrafluorohydroquinone according to an embodiment of the present invention.
8 is a graph showing changes in zeta potential according to pH of a fluorine-based porous polymer aqueous solution using tetrafluorohydroquinone according to an embodiment of the present invention.
9 is a graph showing absorption behavior of microorganic molecules in fluorine-based porous polymer using tetrafluorohydroquinone according to an embodiment of the present invention. (A) Methylene Blue, (b) Rhodamine B, (c) Brilliant Blue G, respectively.
FIG. 10 is a graph showing a change in concentration of fluorine-based porous polymer using (a) tetrafluorohydroquinone and (b) a fluorine-based porous organic polymer using tetrafluorohydroquinone versus a hydrodynamic size of the microorganic molecule Respectively.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.

In the present invention, a fluorine-based polymeric absorbent is prepared by using a monomer containing a fluorine functional group and a hydroxyl group. As a result, it was confirmed that the polymer selectively absorbs only water-soluble organic molecules having micropores, stable to heat and moisture, and having a size smaller than the pore size among the organic molecules existing in the water phase.

Accordingly, in one aspect, the present invention relates to a fluorine-based porous polymer having a structure represented by Chemical Formula (1), Chemical Formula (2), or Chemical Formula (3).

(Formula 1)

Figure 112015123692766-pat00004

(n is an integer of 100 to 110,000)

(2)

Figure 112015123692766-pat00005

(n is an integer of 100 to 110,000)

(Formula 3)

Figure 112015123692766-pat00006

(n is an integer of 100 to 110,000)

According to another aspect of the present invention, there is provided a process for producing a fluorine-containing polymer comprising the steps of: (a) dispersing and heating a monomer containing a fluorine functional group and a hydroxyl group in a solvent; And (b) adding a base, followed by heating and reacting, and washing and filtering to obtain a product. The present invention also relates to a process for producing a polymer having the structure represented by Chemical Formula 1, Chemical Formula 2 or Chemical Formula 3.

In the present invention, the monomer containing a fluorine functional group and a hydroxyl group is characterized by being tetrafluorohydroquinone, Octafluoro-4,4'-biphenol or Trifluorophenol can do. A variety of fluorine compounds can be used as monomers to utilize the high electronegativity of fluorine ions. However, it is preferable to use tetrafluorohydroquinone, octafluoro-4,4'-biphenol or trifluoro phenol so that the content of fluorine is high and the condensation polymerization can be simply performed. And more preferably tetrafluorohydroquinone may be used.

In the present invention, the solvent may be selected from the group consisting of N, N-dimethylformamide, acetone, dimethylacetamide, acetonitrile, and n-methylpyrrolidone (n- Methyl Pyrrolidone). ≪ / RTI > The solvent is mixed with a solvent for condensation polymerization of the monomer. The solvent is not limited as long as it is a solvent capable of dissolving the monomer. Preferably, N, N-dimethylformamide, acetone, dimethylacetamide, acetonitrile and n -Methylpyrrolidone, and more preferably N, N-dimethylformamide can be used.

In the present invention, the base may be selected from potassium carbonate (K 2 CO 3 ), sodium carbonate (Na 2 CO 3 ), potassium hydroxide (KOH) and cesium carbonate (Cs 2 CO 3 ). At this time, the base can deprotonate the hydroxyl group to induce a reaction to replace the fluorine. When the base is not added, the fluorine substitution reaction hardly occurs, and the degree of the fluorine substitution reaction may differ depending on the amount of the base to be added, and may also affect the pore size and the amount of fluorine. Therefore, it is preferable that the amount of the introduced base has a constant molar ratio with the amount of the hydroxyl group, more preferably the ratio of the base / hydroxyl group may be 0.2 to 0.4, and most preferably 0.33. When the ratio of the base is more than 0.4, cross-linking is too much to synthesize a non-porous polymer. When the ratio of the base is less than 0.2, polymerization hardly takes place, The surface area can be very low. (K 2 CO 3 ), sodium carbonate (Na 2 CO 3 ), potassium hydroxide (KOH), and cesium carbonate (Cs 2 ) are used as the reaction rate, degree of fluorine substitution and degree of crosslinking may change depending on the strength of the base. CO 3 ), and more preferably, potassium carbonate can be used.

In the present invention, the washing in the step (b) may be carried out by using water, dimethylformamide, acetone, dimethylacetamide, acetonitrile and n-methylpyrrolidone Pyrrolidone). ≪ / RTI > It is preferable to have a washing process to prevent further side reactions after the reaction is completed and to remove unreacted raw materials. In this case, it is preferable to use water or a solvent for dissolving the monomer, more preferably water (most desirably, desalted water).

In the present invention, The heating in step (a) may be performed at 60 to 100 ° C. In the step (a), heating is performed to dissolve the monomer introduced into the solvent. When the temperature is less than 60 ° C, the monomer is difficult to dissolve. When the temperature exceeds 100 ° C, the monomer starts to react or the dissolution rate and the reaction rate are difficult to control. Side reactions may occur. Therefore, the heating in the step (a) is preferably carried out at 60 to 100 ° C, more preferably at 80 ° C. In addition, in order to prevent side reactions during the step (a), it is preferable to perform the reaction in an inert gas atmosphere.

In the present invention, the heating in the step (b) may be performed at a rate of 2 to 10 ° C / min to 120 to 160 ° C. The heating in the step (b) is performed in order to perform condensation polymerization by applying heat to the monomer. The reaction is not carried out at a temperature lower than 120 ° C., and a side reaction occurs at a temperature higher than 160 ° C., resulting in a lower yield. Also, when the heating rate is less than 2 ° C / min, the reaction rate must be slowed to react for a long period of time. At a rate exceeding 10 ° C / min, a side reaction may occur due to rapid heating. Therefore, the heating in the step (b) is preferably carried out at a rate of 2 to 10 ° C / min to 120 to 160 ° C, more preferably at a rate of 5 ° C / min to 145 ° C.

In the present invention, the step (b) may further include a step of drying at 100 to 150 ° C for 4 to 10 hours in a vacuum atmosphere. When the reaction is completed after the step (b), a polymer is obtained as a precipitate on the solution. Therefore, it is preferable to carry out a drying process to remove the solvent and obtain the polymer. In this case, it is preferable to heat-dry in the air because it takes a lot of time to dry naturally in the air, and it is preferable to dry in a vacuum atmosphere in order to avoid pyrolysis and side reaction at high temperature.

In the present invention, structural analysis was also conducted using the polymer. As a result, the BET (Brunauer-Emmett-Teller) specific surface area of the polymer showed an adsorption curve of a material having a typical micropore.

Accordingly, the present invention relates to a porous adsorbent comprising a polymer of the above formula (1), (2) or (3).

In the present invention, water-soluble micro-molecular absorption experiments were also conducted using the polymer. As a result, it was confirmed that the molecule adsorbed on the structure was smaller than the micropores in the polymer.

Accordingly, the present invention relates to a selective adsorbent of organic molecules containing a polymer of the above general formula (1), (2) or (3) from another viewpoint.

In the present invention, the organic molecular-selective adsorbent may be characterized by selectively adsorbing molecules having a positive or negative charge to the structure, the size of which is 1 nm or less in an aqueous solution. Since the adsorbent is adsorbed in the pores, molecules smaller than the pore size can be selectively adsorbed. Therefore, molecules of 1 nm or less smaller than the pore size can be selectively adsorbed, and molecules having a positive charge or negative charge can be selectively adsorbed to the structure.

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for illustrating the present invention and that the scope of the present invention is not construed as being limited by these embodiments.

Example  1: Preparation of fluorine-based porous polymer

0.5 g of tetrafluorohydroquinone was dissolved in 15 ml of N, N-dimethylformamide (DMF) solvent, and the temperature was raised to 80 ° C in an inert gas atmosphere and stirred. 0.25 g of anhydrous K 2 CO 3 is slowly poured into the solution and then the mixture is heated to 145 ° C. at a rate of about 5 ° C./min and stirred for 24 hours. After the reaction, about 100 ml of demineralized water is poured into the mixture cooled to room temperature and stirred for 4 hours. The obtained precipitate is filtered, washed with demineralized water and acetone to wash off impurities remaining in the precipitate, and dried in a vacuum atmosphere at 120 캜 for 6 hours to obtain a brown powder. (Yield: 72%) wherein the formula is as shown in Fig.

Experimental Example  1: Structure analysis of fluorine-based porous polymer

The structures of the polymers obtained in the examples were analyzed using XPS, NMR, FTIR and elemental analysis. The carbon 1s XPS spectrum (Fig. 2 (a)) of the fluorine polymer shows three peaks with binding energies of 284.6 eV, 286.6 eV, and 286.9 eV, which correspond to aromatic sp2 carbon, ether CO bond, and CF covalent bond . The oxygen 1s XPS spectrum (Fig. 2 (b)) shows three peaks with binding energies of 531.5 eV, 532.8 eV and 534.1 eV, respectively, which are peaks due to unreacted hydroxyl, ether COC and CO groups. The peak of 687.6 eV that appears in the fluorine 1s XPS (Figure 2 (c)) is the peak due to the CF covalent bond. According to 19 F solid-state NMR (FIG. 3), it can be seen that the CF covalent bonds present in the polymer structure chain are arranged on three different positions on the aromatic ring on average. The formation of an ether group according to the nucleophilic substitution reaction is also revealed in the FTIR spectrum (FIG. 4). Peak present in 1030cm -1 on the IR spectrum is the peak due to the movements of the ether function, a peak of 3670cm -1 and 740cm -1 are in accordance with a hydroxyl group, and CF covalent bond. Therefore, it can be seen that this polymer formed by the self-polymerization of a single monomer contains an ether group as a linking group and contains fluorine as a covalent bond. Since the ratio of fluorine to hydroxyl groups in the tetrafluorohydroquinone monomer is 2, the number of hydroxyl groups is relatively small, and fluorine remains in a large amount after the substitution reaction. As a result of the elemental analysis, the fluorine polymer had an experimental ratio similar to that of the theoretical element ratio, and showed a high fluorine content of about 21.5% (Table 1).

element C N H O F Estimated value (%) 47.08 - - 15.68 37.24 Experimental value (%) 50.05 0.92 0.87 26.73 21.51

Experimental Example  2: Thermal durability of fluorine-based porous polymer

The thermal durability of the adsorbent is very important for recycling the adsorbent after regeneration in the water treatment process. In order to confirm the thermal stability of the fluorine polymer, weight change of the structure due to heating in air and nitrogen atmosphere was measured using the thermogravimetry (FIG. 5). The polymer exhibited a weight change of about 3% at about 300 ° C in both air and nitrogen conditions, due to the desorption of simple solvents or moisture. The structure was very stable up to 300 ℃ in air and nitrogen atmosphere, and it was confirmed that the structure gradually collapsed at above temperature. Therefore, the polymer is expected to be structurally stable even when exposed to wastewater environment and high regeneration temperature.

Experimental Example  3: Size and shape of fluorine-based porous polymer

SEM and XRD techniques were used to analyze the size and shape of the polymer. The polymer observed through SEM photographs was observed as porous particles in the form of agglomerated compacts (Fig. 6 (a)). In this case, the size of the particles is expected to be several tens to several hundreds of microns or more and can be separated from the solution by a simple filtration technique after dispersing in an aqueous liquid. According to the XRD spectrum of the polymer (Fig. 6 (b)), the polymer is an amorphous polymer having no crystallinity, which appears to be due to the random polymerization property of the monomer's self-polymerization reactivity.

Experimental Example  4: Pore structure of fluorine-based porous polymer

The specific surface area and pore structure of the polymer were determined through adsorption and desorption of argon (Fig. 7). BET (Brunauer-Emmett-Teller) specific surface area of the fluorinated polymer is 479m 2 g - 1, and showed the absorption curve of material having a typical micro-pores. The fluoropolymer has a very uniform and narrow pore distribution with a pore volume of 0.185 cm 3 g -1 and an average pore size of 0.51 nm (Fig. 7 (b)). It is considered unusual for the fluoropolymer to exhibit such a uniform pore distribution in spite of a random polymerization reaction, and that the small-sized monomer is connected to the short ether group. The uniform pores of the fluoropolymer are important factors for the absorption of organic molecules in the water.

Experimental Example  5: Absorption Behavior of Water-Soluble Microorganic Molecules in Fluorine-Based Porous Polymers

The properties of the polymer surface dispersed in aqueous solution will be very important for organic molecule absorption. Then, the fluorine polymer was dispersed in the aqueous solution prepared under different pH conditions, and the zeta potential was measured (FIG. 8). The zeta potential at pH 5-9 is about -40 mV, indicating that the polymer stably exists in aqueous solution at pH 5 ~ 9 and its surface is negative. On the other hand, at pH 3 and pH 11, the zeta potential values were slightly increased to -10 mV and -20 mV, respectively. This indicates that a small amount of hydroxyl groups in the structure are quantized or dequantized in a somewhat higher acidity and basicity, It is because it is canceled. Therefore, it is expected that the fluoropolymer can be used in actual water treatment process because it shows very stable and negative surface at pH 5 ~ 9.

Based on the properties of the fluoropolymer, the absorption behavior of the organic molecules in the water was measured. For the convenience of the measurement, the adsorbed target was selected from the group of the water-soluble dyes having charge in the structure in different sizes. Three structures of Methylene Blue, MB, Rhodamine B, RDB and Brilliant Blue G (BBG) were applied in the adsorption experiment. The initial concentrations of the three dyes were set to the same value of 50 μM, and the dye concentration before and after treatment with the polymer was measured as the value of the maximum absorption wavelength of the UV-vis spectrum. When three dyes were treated with a fluorine polymer for 3 hours, there was a large difference in the degree of absorption depending on the size of the dye molecule. Methylene blue having the smallest molecular size absorbed about 60% during the first hour and all the molecules were absorbed and removed within 3 hours (Fig. 9 (a)). Rhodamine B and Brilliant Blue G, which have relatively large molecular sizes, And no absorption behavior was observed after the treatment (Fig. 9 (b), (c)). The difference in the absorption ability of the fluoropolymer to the water-soluble organic molecule is due to the molecular sieve effect due to the narrow pore distribution of the fluoropolymer. A fluoropolymer having an average pore size of about 0.51 nm has a very uniform pore size. When the size of the organic molecule is larger than the pore size, the polymer is not absorbed into the polymer.

Experimental Example  6: Absorption Behavior of Water-Soluble Microorganic Molecules of Fluorine-Based Porous Polymers

As the fluorine polymer selectively absorbs water - soluble organic molecules, the absorption behavior for molecules that are not charged to the structure in organic molecules having small sizes was measured. Bisphenol A (BPA) is a neutral molecule with a similar hydrodynamic size to MB but no charge to the structure. As a result of measuring the absorption behavior of the fluoropolymer polymer with respect to BPA at a concentration of 50 μM, it was found that the degree of absorption with MB of the same size was very different (FIG. 10 (a)). In the case of MB molecule absorption, fine size molecules are adsorbed smoothly due to the interaction between the charge (ammonium ion) of MB molecule and fluorine. On the other hand, since neutral BPA has no interaction with fluorine polymer surface, The efficiency is low.

On the other hand, in the case of a much smaller organic molecule, the fluorine polymer exhibits a fast absorption regardless of the charge of the structure. 4-Nitrophenol (4-NP) has a very small hydrodynamic size in the aqueous phase, and the charge of the structure changes depending on the pH condition. 4-NP is present as a neutral molecule in weakly acidic (pH 4, named 4-NP-a) but becomes weaker in weak base (named pH 9, 4-NP-b) due to deprotonation of hydroxyl group. 4-NP-a and 4-NP-b were absorbed and removed at a high rate in the adsorption experiment using the fluorine polymer, and 99% and 97% absorption efficiency was shown within 30 minutes, respectively (Fig. 10 (a)). This is because as the size of the organic molecule becomes very small, it approaches and absorbs the pores before interaction with the fluorine existing on the surface of the polymer. The selective absorption behavior of the fluorine polymer was confirmed more clearly when the hydrodynamic size of the acceptance phase of the organic molecule was compared with the surface area distribution of the fluorine polymer (Fig. 10 (b)). In the case of RDB and BBG, which are not adsorbed to the fluorine polymer, their size is located outside the surface distribution area, which is consistent with the phenomenon that absorption is not achieved. On the other hand, MB shows a smaller molecular size than that of a region having a large surface area, so that it is absorbed relatively smoothly, and a smaller size of 4-NP is more easily absorbed into the polymer. However, BPA having a size similar to MB has a very small degree of absorption depending on the absence of interaction with fluorine.

While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments, will be. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (9)

Fluorine-based porous polymer having the structure of formula (1), (2) or (3)
(Formula 1)
Figure 112015123692766-pat00007

(n is an integer of 100 to 110,000)
(2)
Figure 112015123692766-pat00008

(n is an integer of 100 to 110,000)
(Formula 3)
Figure 112015123692766-pat00009

(n is an integer of 100 to 110,000)

A method for producing the fluorine-based porous polymer according to claim 1, comprising the steps of:
(a) dispersing and heating a monomer containing a fluorine functional group and a hydroxyl group in a solvent and heating; And
(b) adding a base, and then heating and reacting to obtain a polymer of Formula 1, Formula 2 or Formula 3.

The method according to claim 2, wherein the step (b)
(c) washing and filtration to obtain a polymer of Formula 1, Formula 2 or Formula 3
Based porous polymer. ≪ RTI ID = 0.0 > 11. < / RTI >

The method of claim 2, wherein the fluorine functional group and the monomer containing a hydroxyl group are selected from the group consisting of tetrafluorohydroquinone, octafluoro-4,4'-biphenol, A method for producing a fluorine-based porous polymer characterized by being Trifluorophenol

The process for producing a fluorine-based porous polymer according to claim 2, wherein the heating temperature in step (a) is 60 to 100 ° C.

3. The method of claim 2, wherein the heating in step (b) is carried out at a rate of 2 to 10 ° C / min to 120 to 160 ° C.

A porous adsorbent comprising the fluorine-based porous polymer of claim 1

A selective adsorbent for organic molecules comprising the fluorine-based porous polymer of claim 1.

The selective adsorbent of organic molecules according to claim 8, characterized in that the adsorbent selectively adsorbs molecules having a size of 1 nm or less in an aqueous solution and having a positive or negative charge in the structure.

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JP2003502465A (en) 1999-06-10 2003-01-21 プロメティック、バイオサイエンシーズ、インコーポレーテッド Method for producing fluorinated polymer adsorbent particles
US20050020839A1 (en) 2003-06-17 2005-01-27 Go Masuda Fluorinated bis(phthalic anhydride) and method for producing the same

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JP2003502465A (en) 1999-06-10 2003-01-21 プロメティック、バイオサイエンシーズ、インコーポレーテッド Method for producing fluorinated polymer adsorbent particles
US20050020839A1 (en) 2003-06-17 2005-01-27 Go Masuda Fluorinated bis(phthalic anhydride) and method for producing the same

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