KR101016231B1 - Method for preparing porous imprinted polymer particles for the selective separation of heavy metal ions - Google Patents

Abstract

The present invention provides a method for producing a porous stamping polymer particles for selectively separating heavy metal ions, comprising: (S1) preparing a metal salt-acid monomer complex solution by reacting a metal salt solution, an acid monomer and a basic monomer; (S2) preparing a stabilizer aqueous solution; (S3) mixing the metal salt-acid monomer complex solution obtained in step (S1) and the stabilizer aqueous solution obtained in step (S2), and then mixing a porous solvent solution with the mixed solution; (S4) polymerizing the mixed solution mixed in the step (S3) to obtain a polymer containing a metal ion; And (S5) provides a method for producing a porous stamping polymer particles capable of separating heavy metal ions comprising the step of removing metal ions from the polymer obtained in step (S4). The method for producing porous stamping polymer particles according to the present invention is easy to control the number of adsorption sites of heavy metal ions, the adsorption power is very good, can be given arbitrarily according to the intended use, the regeneration effect is very excellent, the reaction It is very economical because it saves time.

Porous stamping polymer, heavy metal ion, separation, metal salt, acid monomer, basic monomer

Description

METHODS FOR PREPARING POROUS IMPRINTED POLYMER PARTICLES FOR THE SELECTIVE SEPARATION OF HEAVY METAL IONS}

The present invention relates to a method for producing a porous stamping polymer particles that can selectively separate heavy metal ions, more specifically, having a high adsorption power and a fast adsorption rate while maintaining the selectivity to a specific heavy metal ion, economical porous stamping polymer particles It relates to a manufacturing method of.

Recently, molecularly imprinted polymers (MIPs) or metal ion imprinted polymers (MIIPs) have been developed which are environmentally friendly in separation concepts and very advantageous for process simplification. Molecular imprinted polymer (MIP) or metal ion-engraved polymer (MIIP) is a template and form by removing the template material after synthesizing the polymer using a monomer that is combined with a suitable template. Refers to a polymer in which the same space exists.

Since only the morphologically identical template can be inserted into the template space and molecules with different conformations than the template material, polymers with template space can be used to separate the template and other molecules. .

This is like the principle that antibodies formed against an antigen selectively interact with the antigen only (Fischer's Lock-and-Key Concept) or that enzymes in vivo only act on a specific substrate (Receptor Theory). It makes sense. A basic process for the preparation of molecular imprinted polymers (MIPs) is disclosed in EP 0190228.

Looking specifically at the first half of the process for preparing a molecule or an ionic angle polymer, the molecular or ionic imprint is a polymerizable functional monomer having a functional group capable of first dissolving a template in a solvent and then binding to a portion of the template material. ) Forms a complex between the template material and the functional unit. Then, in order to maintain the alignment of the functional units combined with the template material, an excess amount of inert units, a cross-linker and a polymerization initiator, are added and polymerized. In this process, the solvent that dissolves the template material plays an important role in determining the properties of the synthesized polymer. In particular, the polar solvent dissolves the polar molecule, which may break the bond between the template and the functional single molecule.

In practice, research on the structural design and manufacturing method of molecules with specific molecular recognition ability has been continuously conducted in relation to the molecular imprinting polymer technology, mostly racemic compound, amino acid Has been applied to the separation of compounds that are difficult to separate. The basic idea to apply the molecular imprinting polymer technology to the selective separation of heavy metal ions has been presented very recently. Currently, research is being conducted in several advanced countries such as the United States, Japan, and Sweden, and the scope of research has been expanded.

The Mosbach group of the University of Lund, Sweden, reported the selective separation effect of several types of similar structural compounds by molecular imprinting. Murray Group of the University of Maryland, U.S., synthesized ion-imprinted polymers to produce Pb (II), Cd (II), Li (II), Na (II), Mg (II), Ca (II), Cu (II), Zn ( II), selective separation characteristics for metal ions such as Hg (II) was reported. Fish Group of Lawrence Berkely Laboratories in the United States confirmed the selective separation of Zn (II) ions using triazacyclononane ligands. Recently, Japan has been conducting research on separation characteristics using metal ion imprinting at Kyushu University.

As a heavy metal ion separator having a function similar to the present technology, chelated ion exchange resins are manufactured in the United States, Japan, China, and exported to overseas countries. In the US, DOW, a chelate type ionic resin known under the trade name DOWEX is used to separate nickel during the cobalt purification process. Invitrongen in the United States is also used in the nickel separation process under the trade name Probond, which has a separation property for Ni ions. Amberlate, a chelating ion exchange resin from Rohm and Haas of the United States, is being applied to the process of separating metal ions. Chelated ion exchange resins are manufactured and sold under the trade name DIAION at Mitsubishi Chemical in Japan. As described above, the chelate type ion exchange resin manufactured and sold in the United States or Japan is currently applied in various forms in the process, but the selectivity is not so excellent and is limited to the separation of some metal ions.

In connection with this, the present inventors have developed a method for manufacturing a surface-engraved core-shell microspheres that are economically and environmentally advantageous by not only shortening the heavy metal ion separation time but also using no surfactant or stabilizer and registering a patent. (Korea Patent Registration No. 10-0861452).

The present inventors have conducted further studies on the method for selectively separating heavy metal ions. As a result, heavy metal adsorbents are made by using ion-imprinting technology, and thus the number of adsorption sites can be easily adjusted as compared to general ion exchange resins. It has been developed a method for producing a porous stamping polymer particles that can be very excellent, can be given arbitrarily according to the intended use, excellent regeneration effect and economically excellent, which can separate specific heavy metal ions.

An object of the present invention is easy to control the number of adsorption sites of heavy metal ions, very good adsorption power, can be given arbitrarily according to the intended use, excellent regeneration effect, economically excellent porous stamping polymer particles It is to provide a method of manufacturing.

In order to achieve the above object, the present invention is a method of producing a porous stamping polymer particles for selectively separating heavy metal ions, (S1) to prepare a metal salt-acid monomer complex solution by reacting a metal salt solution, an acid monomer and a basic monomer Making; (S2) preparing a stabilizer aqueous solution; (S3) mixing the metal salt-acid monomer complex solution obtained in step (S1) and the stabilizer aqueous solution obtained in step (S2), and then mixing a porous solvent solution with the mixed solution; (S4) polymerizing the mixed solution mixed in the step (S3) to obtain a polymer containing a metal ion; And (S5) provides a method for producing a porous stamping polymer particles capable of separating heavy metal ions comprising the step of removing metal ions from the polymer obtained in step (S4).

The metal salt solution may be prepared by mixing a metal salt and a solvent selected from the group consisting of water, C ₁ to C ₆ alcohols and C ₁ to C ₆ hydrocarbons.

The metal salt may be a salt selected from the group consisting of Cu, Pb, Cd, Li, Na, Mg, Ca, Zn, Hg and Fe.

As the acidic monomer, an acrylate monomer, a styrene monomer or a silane monomer containing a carboxyl group may be used, and more particularly, acrylic acid, methacrylic acid, ethacrylic acid, vinylbenzoic acid, divinylbenzoic acid, ethylene glycol dimethyl methacrylate, and the like. Can be used.

As the basic monomer, a vinylpyridine monomer may be used, and more particularly, one selected from the group consisting of 4-vinylpyridine and 2-vinylpyridine may be used.

The present invention can separate specific heavy metal ions, it is easy to control the number of adsorption sites of heavy metal ions, the adsorption power is very good, can be given arbitrarily according to the intended use, the regeneration effect is very excellent, economical It has the effect of providing a method for producing a very excellent stamping porous polymer particles.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The present invention is a method for producing a porous stamping polymer particles for selectively separating heavy metal ions,

(S1) reacting the metal salt solution, the acid monomer and the basic monomer to prepare a metal salt-acid monomer complex solution;

(S2) preparing a stabilizer aqueous solution;

(S3) mixing the metal salt-acid monomer complex solution obtained in step (S1) and the stabilizer aqueous solution obtained in step (S2), and then mixing a porous solvent solution with the mixed solution;

(S4) polymerizing the mixed solution mixed in the step (S3) to obtain a polymer containing a metal ion; And

(S5) Provides a method for producing a porous stamping polymer particles capable of separating heavy metal ions comprising the step of removing metal ions from the polymer obtained in step (S4).

Hereinafter will be described in detail step by step a method for producing a porous stamping polymer particles capable of separating heavy metal ions according to the present invention.

The step (S1) is a step of preparing a metal salt-acid monomer complex solution by reacting a metal salt solution, an acid monomer and a basic monomer.

The metal salt solution may be prepared by mixing a metal salt and a solvent. The metal salt may be a salt selected from the group consisting of Cu, Pb, Cd, Li, Na, Mg, Ca, Zn, Hg and Fe as a metal salt containing a metal ion to be selectively separated, more preferably CuSO ₄ can be used.

As a solvent for preparing the metal salt solution by mixing with the metal salt, a solvent selected from the group consisting of water, C ₁ to C ₆ alcohols and C ₁ to C ₆ hydrocarbons may be used.

As the acidic monomer, an acrylate monomer, a styrene monomer or a silane monomer containing a carboxyl group may be used, and more particularly, acrylic acid, methacrylic acid, ethacrylic acid, vinyl benzoic acid, divinylbenzoic acid, and ethylene glycol dimethyl methacrylate. Etc. can be used.

The basic monomer may be a vinylpyridine-based monomer, more particularly selected from the group consisting of 4-vinylpyridine and 2-vinylpyridine. In the present invention, the basic monomer plays a role of assisting the binding of the metal ion and the acidic monomer.

1 is a schematic diagram schematically illustrating a process of forming a metal salt-acid monomer complex by reacting a metal salt solution, an acid monomer and a basic monomer in step (S1). Referring to Figure 1, the carboxyl groups are easily ionized in the acidic monomer (2) and metal ions acid monomer (2) containing a carboxyl group-On (Cu ^{2 +)} coupling the complex (complex) common solution in the formation containing the carboxyl group However, a separate process of forming the metal salt-acidic monomer complex (1) is required, but when the basic monomer (3) is added as in the present invention, the basic monomer is charged with a positive charge (H ⁺ ) from the carboxyl group of the acidic monomer. By dragging and ionizing, the metal salt-acidic monomer complex 1 can be easily formed.

As described above, in the present invention, by using the basic monomer when forming the metal salt-acid monomer complex, the synthesis process of the metal ion-containing monomer and the polymerization process thereof may be performed at once without performing a separate process. As a result, the reaction time can be greatly shortened in the preparation of the porous-marked polymer particles, and it is very economically useful because it can be obtained in high yield.

The ratio of the basic monomers to the acidic monomers used in the step (S1) is preferably 0.01 to 100.

The role of the basic monomer in the present invention is to draw cations from the acidic monomers so that the acid monomers cause ionization. Ionized acidic monomers can easily complex with metal ions. Since the acid monomer used in the present invention has a carboxyl group exhibiting weak acidity, ionization does not occur well. Thus, when basic monomer is added, ionization occurs and complexes with metal ions. When the ratio of the basic monomer to the acid monomer is less than 0.01, the formation of a complex with the metal ion will be difficult since the ionization of the acid monomer hardly occurs due to the lack of the basic monomer which may help the ionization of the acid monomer. On the contrary, when the ratio of the basic monomer to the acidic monomer is greater than 100, the adsorption capacity and selectivity may decrease. This is because the amount of acidic monomers that can form complexes with metal ions is reduced.

The metal salt-acid monomer complex solution in step (S1) may further include a crosslinking agent and an initiator.

As the crosslinking agent, an acrylate monomer, a styrene monomer or a silane-based monomer may be used, and more particularly, ethylene glycol dimethacrylate may be used.

The initiator may be a redox-based initiator or a peroxide-based initiator, and more particularly, azodiisobutyronitrile may be used.

The (S2) step is to prepare a stabilizer aqueous solution.

The stabilizer may be hydroxy ethyl cellulose, modified hydroxy ethyl cellulose, poly (vinyl alcohol), poly (ethylene oxide), polyvinyl methyl ether, polymethacrylic acid and the like.

Step (S3) is a step of mixing the metal salt-acid monomer complex solution obtained in step (S1) and the stabilizer aqueous solution obtained in step (S2), followed by mixing a porous solvent solution (porogenic solvent) in the mixed solution. .

The porous solvent means a solution that induces pore formation during polymer polymerization, and is selected from the group consisting of toluene, benzene, xylene, C ₁ to C ₆ alcohols and C ₁ to C ₆ hydrocarbons. May be used, but is not limited thereto.

In the present invention, by manufacturing the imprinted polymer particles in a porous structure having a large surface area using a porous agent solution, not only can maintain the selectivity to a specific metal, but also can exhibit a high adsorptive power and fast separation rate, it will show a very excellent effect in the separation process Can be.

The step (S4) is a step of polymerizing the mixed solution mixed in the step (S3) to obtain a polymer containing a metal ion.

Step (S5) is a step of obtaining a porous stamping polymer particles according to the present invention by removing metal ions from the polymer obtained in the step (S4).

The present invention provides a method for producing porous stamping polymer particles for selectively separating copper ions, comprising the steps of: (a) preparing a metal salt-acid monomer complex solution by reacting a copper sulfate solution, a methacrylate monomer and 4-vinylpyridine; (b) preparing a stabilizer aqueous solution using hydroxy ethylcellulose; (c) after mixing the metal salt-acid monomer complex solution obtained in step (a) and the stabilizer aqueous solution obtained in step (b), toluene, azodiisobutyronitrile and ethylene glycol dimethacrylate are added to the mixed solution. Mixing; (d) polymerizing the mixed solution mixed in step (c) to obtain a polymer containing copper ions; And (e) removing the copper ions from the polymer obtained in step (d).

Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

< Example >

Example  One

By dissolving CuSO ₄ 5H ₂ O in water to prepare a Cu ^{2 +} metal liquid solution. Methacrylic acid (MAA, Aldrich, Miwaukee, WI, USA) as acidic monomer, 4-vinylpyridine (4-VP, Aldrich) as basic monomer, ethylene glycol dimethacrylate (EGDMA, Aldrich) as crosslinking agent ) and put as an initiator ah as the acrylonitrile Jody isobutyronitrile (AIBN, Aldrich) in turn was sufficiently stirred for 2 hours to form a complex between Cu ^{2 +} and methacrylic acid. And hydroxy cellulose (HEC) as a stabilizer was added to water and stirred until completely dissolved at about 70 ℃. The solution formed with a complex between Cu ions and an acidic monomer was placed in a 250 ml three-necked flask equipped with a mechanical stirrer. After that, 10 ml of toluene (Aldrich) and a stabilizer aqueous solution were added to the flask as a porous solvent, and nitrogen purged. Stir for minutes. The polymer synthesis reaction was carried out for 6 hours at 70 ℃ at 250 rpm. Nitrogen gas was continuously purged during the polymer synthesis reaction. After the synthesis was completed, in order to remove the unreacted monomer or stabilizer, the mixture was mixed with water / acetone 1: 1 and stirred for 30 minutes. This process was repeated four times. Thereafter, the resultant was dried at 40 ° C. for about one day in a vacuum oven to obtain a copper ion-imprinted polymer. To remove Cu (II) ions in the polymer, it was immersed in HNO ₃ aqueous solution for 40 minutes. The procedure was repeated five times to completely remove the Cu (II) ions. After the Cu (II) ions were removed, the polymer particles were washed with deionized water and dried in a vacuum oven to prepare porous stamping polymer particles, and scanning electron micrographs were taken of the prepared porous stamping polymer particles. 2 is shown. As shown in Figure 2, the size of the porous stamping polymer particles produced according to the present invention is about 250 ㎛ and has a spherical shape. Beads showing a porous structure increases the movement of the metal ion solution while increasing the surface area, thereby increasing the adsorption capacity of the porous stamping polymer. And FT-IR (IFS-66 / s, Bruker, USA) was used to confirm the synthesis of the porous stamping polymer (see Figure 3). Referring to FIG. 3, a peak of Cu—O was observed in a copper ion-containing imprinted polymer (Cu ion-containing MIP) before copper ions were removed at 1610 cm ⁻¹ , but the peak disappeared after copper ions were removed. . It can be seen that copper ions have been removed. The characteristic peak of the pyridine ring was found at 1638 cm ⁻¹ .

Experimental Example 1 Comparison of Surface Area of Porous Marking Polymer and Commercially Used Ion Exchange Resins

The surface area, total pore volume, and pore size of the porous stamping polymer prepared in Example 1 and a commercially available ion exchange resin purchased from Bayer Chemical (Germany) were obtained by using the BET method. As shown in Table 1, the porous stamping polymer prepared in Example 1 has a larger surface area than the three commercially available ion exchange resins, indicating that it has many voids. The total pore volume of the porous stamped polymer prepared in Example 1 was 0.14 cm ³ / g and showed a higher value than other resins. The average pore size of the porous stamping polymer prepared in Example 1 showed a medium value between the other two resins (weak acid resin, chelate resin).

BET surface area
(m ² / g) Total void volume
(cm ³ / g) Average pore size
(nm) Example 1
(Cu (Ⅱ) -MIP) 60.5 0.14 9.16 Strong acid resin 0.013 N / D N / D Weakly acidic resin 1.57 0.000138 2.07 Chelate resin 8.58 0.047 21.4

* Strong acid resin (SR): Lewatit monoplus S 100

* Weak acid resin (WR): Lewatit CNP 80

Chelating resin (CR): Lewatit TP 207

< Experimental Example  2> adsorption and selectivity experiment

Adsorption and selectivity experiments were carried out in two ways: batch type and column type.

(1) batch type Batch type ) Adsorption and Selectivity Experiment

0.1 g of the porous stamped polymer particles prepared in Example 1 were immersed in an aqueous solution of 5 cm ³ containing Cu (NO ₃ ) ₂ , Ni (NO ₃ ) ₂ , and Zn (NO ₃ ) ₂ . Each metal ion concentration was changed from 0.05 to 0.5 mM. The pH was adjusted to the desired value between 1.0 and 6.0 by adding 100 mM acetic / sodium acetate solution and 100 mM nitric acid solution. The mixture was sonicated for 3 minutes and stirred at room temperature for 5 to 60 minutes. The particles were filtered using a polyethylene membrane (Sumplep LCR 25-LG, Nippon Millipore, Ltd., Japan). Metal ions adsorbed on the particles were measured using a Hitachi 180-70 polarized Zeeman atomic absorption spectrophotometer (AAS, Hitachi, Japan). The adsorption capacity (μmol / g) was calculated by the difference in the concentration of metal ions in the solution at the beginning and at the end. The experiment was repeated three times and pH measurement was performed using a LI-120 digital pH meter (ELICO, India). This selective separation force for the excellent Cu ^{2 +} was measured relative to metals, such as ^{Mg 2 +, Ni 2 +,} Zn 2 +.

* Results and Analysis

One) pH Analysis of Adsorption Capacity of Porous Imprinted Polymer

Adsorption force Q is defined by the following equation.

Q = total amount of adsorbed metal ions / weight of imprinted polymer particles used

Figure 4 is a graph showing the adsorption capacity of the porous stamping polymer with a change in pH (initial concentration 10 ppm). Increasing pH increases the ionization of the polymer terminal carboxyl groups. Therefore, it forms a complex of adjacent carboxyl groups and copper ions. As shown in FIG. 4, the sorption amount of metal ions increases as pH increases, indicating that ionization of carboxyl groups present at the host molecule ends plays an important role in adsorption of metal ions. Since the protonation of carboxyl group occurs, sorption capacity is lowest at pH below 2.0. Porous imprinted polymer particles bearing Cu (II) have a higher adsorption capacity for Cu (II) ions than other metal ions in the entire pH range.

2) Analysis of Adsorption Capacity of Porous Marking Polymer According to Particle Size

5 is a graph showing the adsorption capacity of the porous stamping polymer particles according to the particle size. Referring to Figure 5 it can be seen that as the particle size decreases the adsorption capacity of the porous stamping polymer increases. This is because the surface area increased as the particle size became smaller. If the surface area is increased, it can be easily in contact with the metal ion.

3) adsorption rate ( Adsorption kinetics ) Measure

Figure 6 is a graph measuring the adsorption rate for the metal ion of the porous stamping polymer prepared in Example 1. The adsorption equilibrium was reached within 10 minutes, showing a rapid adsorption rate at the beginning of the adsorption process. The Cu ^{2 +} ions, and the amount is about 50 μmol / g suction to the porous imprinted polymers were compared to other ions ^{(Ni 2 +, Zn 2 +} ). Thus, rapid adsorption process is due to the ion complex formation rate is high, and Cu ^{2 +} Cu ^{2 +} affinity of the geometrical place in the extraction. Where the template is removed in the polymer, it leaves a chemofunctional group of similar size, shape, and template. Spaces of the desired shape are formed and promote interaction with the imprinted copper ions. In order to determine the reusability of the porous polymer particles with Cu (II) imprinted, the adsorption-desorption process was repeated 10 times using the same porous imprinted polymer. There was no change in the amount of adsorption during this iteration, which means that the porous stamping polymer particles imprinted with Cu (II) can be reused.

4) Analysis of Adsorption Capacity of Porous Marking Polymer According to Initial Metal Ion Concentration

Example 1 using a porous imprinted polymer was prepared in the adsorption test in progress for ^{Cu 2 +, Ni 2+, Zn} 2 + ions on an aqueous solution at pH 6.2. The results are shown in Fig. As shown in FIG. 7, the amount of adsorbed metal ions per unit mass of the porous marking polymer particles increased as the concentration of the initial metal ion increased. Adsorption was completed at approximately 235 μmol metal ion concentration. Adsorption of Cu ^{2 +} ions exhibited a still higher results than the other metal ions the maximum absorption capacity was 235 μmol / g.

5) Comparison of Adsorption Characteristics with Commercialized Ion Exchange Resins

The adsorption characteristics of the porous stamping polymer prepared in Example 1 and the commercially available ion exchange resin were compared and shown in FIG. 8. Three types of commercialized ion exchange resins were purchased from Bayer Chemical (Germany) to compare their properties. Three commercially available ion exchange resins were Lewatit monoplus S 100, a strong acid resin (SR), Lewatit CNP 80, a weak acid resin (WR), and finally a chelating resin (CR). Lewatit TP 207. Of the three ion exchange resins, chelate resins adsorbed the most nickel and zinc ions as well as copper ions. On the other hand, the porous stamping polymer prepared in Example 1 has a smaller amount of adsorption to metal ions than three kinds of ion exchange resins, but the amount of copper ions adsorbed is very high compared to other ions. Based on these results, it can be seen that they have a stronger affinity for copper ions than commercially available ion exchange resins.

6) Selectivity Analysis

The selectivity of the commercially available ion exchange resin and the porous stamping polymer prepared in Example 1 were compared. The selectivity of three commercially available ion exchange resins was compared. The selectivity of the porous stamping polymer for copper ions was compared by experiments to adsorb copper ions in various metal ions. The distribution ratio D, the selection coefficient α and the relative selection coefficient α are calculated using the following equation.

The distribution ratio D is calculated according to the following equation.

In Equation 2, v represents the volume of solution (ml),

m represents the mass (g) of the polymer particles,

C _A represents the initial concentration (umol / l) of the metal ion,

C _B represents the final concentration of metal ions (umol / l).

When present with other kinds of metal ions, the copper ion selection coefficient α can be obtained through the result of an equilibrium state according to Equation 3 below.

In Equation 3 D _Cu represents the distribution ratio of Cu ^{+ 2,}

D _M represents a distribution ratio of other metal ions.

Comparing the selection coefficient of the polymers imprinted with the metal ions and the relative selection coefficients of the polymers not imprinted with each other can evaluate the imprinting effect with selectivity. The relative selection coefficient α can be obtained from Equation 4 below.

In Equation 4, α _i and α _n represent the relative coefficients of the polymer (MIIP) and the non-MIIP (engraved with metal ions), respectively.

As shown in Table 2, the distribution ratio (D) for copper ions of the porous stamping polymer prepared in Example 1 was very large, but the distribution ratio for other ions (Ni, Zn) was very small. Indicated.

The relative selectivity coefficient α represents adsorption affinity with respect to the adsorption recognition site for the imprinted copper ions. As a result, the correlation coefficients Cu (II) / Ni (II) and Cu (II) / Zn (II) of the porous polymers with copper ions were 42.48 and 43.48 times, respectively.

D _Cu D _Ni D _Zn α (D _Cu / D _Ni ) α (D _Cu / D _Zn ) Example 1
(Cu (Ⅱ) -MIP) 23.48 0.54 0.554 43.48 42.38 Strong acid resin 49.5 46.80 47.8 1.06 1.04 Weakly acidic resin 32.48 6.70 9.69 4.85 3.35 Chelate resin 52.59 48.7 47.22 1.08 1.11

* Strong acid resin (SR): Lewatit monoplus S 100

* Weak acid resin (WR): Lewatit CNP 80

Chelating resin (CR): Lewatit TP 207

7) Langmuir adsortion isotherm Using Adsorption amount (Q _max )decision

Adsorption behavior of porous stamped polymers can be analyzed using adsorption isotherm. The most widely used of these adsorption isotherms is the Langmuir isotherm. Langmuir isotherm is applied under the assumption that it can be bound to one molecule or ion at the place of imprinting and that the imprinted molecules are separated from each other so as not to attract each other. Adsorption amount Q according to Langmuir isotherm is calculated according to Equation 5 below.

Q = Q _max bCe / 1 + bCe

In Equation 5, Q represents the amount of adsorbed ions (μmol / g) per unit weight of the porous stamping polymer at the equilibrium concentration,

Ce represents the copper ion concentration (μmol / g) not adsorbed at equilibrium,

b is the Langmuir constant (g / μmol),

Q _max represents the maximum adsorption amount.

The variable can be obtained from the experimental results. Q _max and B values are obtained from the y-axis intercept and the slope of the Langmuir plot.

9 is a graph showing Q _max for the porous stamping polymer prepared in Example 1 using Langmuir adsortion isotherm. As shown in FIG. 9, the maximum adsorption amount of the porous marking polymer was found to be 254 μmol / g, which is similar to the maximum value of 235 μmol / g obtained from the adsorption capacity analysis of the porous marking polymer according to the initial metal ion concentration. It can be seen that the. And since the value of correlation coefficient (correlation coeficient, R ² ) is 0.9654, Langmuir's equation can be applied.

(2) Columnar ( Column type ) Adsorption and Selectivity Experiment

2 g of the porous stamped polymer particles prepared in Example 1 were filled in a column (Alltech, Threaded SS, 4.6 mm id x 250 mm height) using a column filler (Alltech, model1666, USA). Demineralized water was run by five times the column volume. From the back flow by using the demineralized water of 10 ppm of metal ion (Cu ^{+ 2,} Ni ^{+ 2,} Zn ^{+ 2)} and sent to flow through the column at a flow rate of the solution was 2 mL / min. After periodically collecting the solution discharged through the column using a AAS to measure the concentration of each metal ion. pH 6.2 solution was used.

* Results and Analysis

FIG. 10 is a graph illustrating selective adsorption characteristics of copper ions when a mixed solution of Cu (II), Ni (II), and Zn (II) is flowed into a column filled with porous stamping polymer particles prepared in Example 1 . In the case of Ni (II) and Zn (II) ions, the outlet concentration flowing through the column increased rapidly and reached equilibrium concentration within 10 minutes after the injection of the mixed solution. Indicated. The copper ion adsorption characteristics of the copper imprinted polymer were very different from other metal ions. After 40 minutes of solution injection, the effluent concentration began to increase, and after 60 minutes it increased to 70% of the initial concentration and then slowly reached the equilibrium concentration. It can be seen that the porous stamping polymer particles selectively adsorb copper ions more than other ions. It can be seen that the slow adsorption occurred after 60 minutes because the binding force was weakened by filling a large number of the imprinted sites of the porous imprinted polymer particles with copper ions. The adsorbed amount of the porous stamping polymer particles (Cu (II) -MIP) prepared in Example 1 can be obtained by integrating a curve obtained using the relationship between the adsorption amount (μmol / ml) and the outflow amount (ml). The amount of adsorbed copper ions of Cu (II) -MIP for 60 minutes (flow rate 480 ml) was 17.50 μmol / g.

1 is a schematic diagram schematically illustrating a process of forming a metal salt-acid monomer complex by reacting a metal salt solution, an acid monomer and a basic monomer according to an embodiment of the present invention.

2 (a) is a scanning electron microscope photograph taken of the outside of the porous stamping polymer prepared in Example 1, Figure 2 (b) is taken of the inside of the porous stamping polymer prepared in Example 1 Scanning electron micrograph.

3 is an FT-IR spectrogram before and after removal of copper ions from an unmarked porous marking polymer and a porous marking polymer.

Figure 4 is a graph showing the adsorption capacity of the porous stamping polymer with a change in pH (initial concentration 10 ppm).

5 is a graph showing the adsorption capacity of the porous stamping polymer particles according to the particle size.

Figure 6 is a graph measuring the adsorption rate for the metal ion of the porous stamping polymer prepared in Example 1.

7 is a graph showing the adsorption capacity of the porous stamping polymer particles according to the initial metal ion concentration.

8 is a graph comparing the adsorption characteristics of the porous stamping polymer prepared in Example 1 and the commercially available ion exchange resin.

9 is a graph showing Q _max for the porous stamping polymer prepared in Example 1 using Langmuir adsortion isotherm.

10 is a graph measuring selective adsorption characteristics for copper ions when a mixed solution of Cu (II), Ni (II), and Zn (II) is flowed into a column filled with porous stamping polymer particles prepared in Example 1 to be.

Claims (17)

As a method of producing porous stamping polymer particles for selectively separating heavy metal ions, (S1) reacting the metal salt solution, the acidic monomer, and the basic monomer to prepare a metal salt-acidic monomer complex solution; (S2) preparing a stabilizer aqueous solution; (S3) mixing the metal salt-acid monomer complex solution obtained in step (S1) and the stabilizer aqueous solution obtained in step (S2), and then mixing a porous solvent solution with the mixed solution; (S4) polymerizing the mixed solution mixed in the step (S3) with a crosslinking agent and an initiator to obtain a polymer containing a metal ion; And (S5) removing metal ions from the polymer obtained in step (S4) Including, The metal salt in the step (S1) is a salt selected from the group consisting of Cu, Pb, Cd, Li, Na, Mg, Ca, Zn, Hg and Fe, Porous solvent (porogenic solvent) used in the step (S3) is toluene, benzene and xylene method for producing a porous marking polymer particles that can separate heavy metal ions, characterized in that selected from the group consisting of. The method of claim 1, The metal salt solution in the step (S1) is a metal salt; And water, a C ₁ to C ₆ alcohol, and a solvent selected from the group consisting of C ₁ to C ₆ hydrocarbons. delete The method of claim 1, The metal salt is a method of producing a porous stamping polymer particles, characterized in that CuSO ₄ . The method of claim 1, The acid monomer is a method for producing a porous stamping polymer particles, characterized in that the carboxyl group-containing acrylate monomer, styrene monomer or silane-based monomer. The method of claim 5, The acidic monomer is a method of producing a porous stamping polymer particles, characterized in that selected from the group consisting of acrylic acid, methacrylic acid, ethacrylic acid, vinyl benzoic acid, divinyl benzoic acid and ethylene glycol dimethyl methacrylate. The method of claim 1, The basic monomer is a method for producing a porous stamping polymer particles, characterized in that the vinylpyridine monomer. The method of claim 7, wherein The vinylpyridine-based monomer is a method for producing porous marking polymer particles, characterized in that selected from the group consisting of 4-vinylpyridine and 2-vinylpyridine. The method of claim 1, The ratio of the basic monomers to the acidic monomers in the step (S1) is a method for producing porous marking polymer particles, characterized in that 0.01 to 100. delete The method of claim 1, The crosslinking agent is a method for producing a porous stamping polymer particles, characterized in that the acrylate monomer, styrene monomer or silane-based monomer. The method of claim 11, The crosslinking agent is a method of producing a porous stamping polymer particles, characterized in that ethylene glycol dimethacrylate. The method of claim 1, The initiator is a redox-based initiator or peroxide-based initiator, characterized in that for producing porous marking polymer particles. The method of claim 13, The initiator is azodiisobutyronitrile (azodiisobutyronitrile) characterized in that the method for producing a porous stamping polymer particles. The method of claim 1, The stabilizer is a porous stamping polymer particles, characterized in that selected from the group consisting of hydroxy ethyl cellulose, modified hydroxy ethyl cellulose, poly (vinyl alcohol), poly (ethylene oxide), polyvinyl methyl ether and polymethacrylic acid Manufacturing method. delete As a method of producing porous stamping polymer particles for selectively separating copper ions, (a) reacting a copper sulfate solution, a methacrylate monomer and 4-vinylpyridine to prepare a metal salt-acid monomer complex solution; (b) preparing a stabilizer aqueous solution using hydroxy ethylcellulose; (c) after mixing the metal salt-acid monomer complex solution obtained in step (a) and the stabilizer aqueous solution obtained in step (b), toluene, azodiisobutyronitrile and ethylene glycol dimethacrylate are added to the mixed solution. Mixing; (d) polymerizing the mixed solution mixed in step (c) to obtain a polymer containing copper ions; And (e) removing copper ions from the polymer obtained in step (d) Method of producing a porous stamping polymer particles capable of separating the copper ions comprising a.

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