KR102061179B1 - High adsorption capability polymer brush-foam composite and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a high adsorption polymer brush foam composite material excellent in adsorption performance. More specifically, the present invention relates to a polymer composite foam composite material having a high adsorption performance capable of quickly and effectively removing contaminants in water as a foam composite having a polymer brush on a foam substrate having portability and convenience.

Description

High adsorption capability polymer brush-foam composite and manufacturing method

The present invention relates to a high adsorption polymer brush foam composite material excellent in adsorption performance. More specifically, the present invention relates to a polymer composite foam composite material having a high adsorption performance capable of quickly and effectively removing contaminants in water as a foam composite having a polymer brush on a foam substrate having portability and convenience.

Heavy metal ions present in the wastewater flowing into the human body are highly toxic and poorly decomposed, causing serious side effects. The method for removing such heavy metal ions is by using an adsorbent.

On the other hand, the nanoparticles in powder form have a problem that after removing heavy metal ions, complexity and cost increase in the separation process, the adsorption efficiency is lowered when reuse. In addition, if the adsorbent remains in water, it may cause secondary water pollution, and may cause serious adverse effects upon the influx of the human body.

In other words, the removal of contaminants in water using powdered nano-adsorbents is a burden for small businesses or individuals requiring complex processes and high costs.

Therefore, it is necessary to remove the risk of leakage of nanoparticles during use, and to develop an adsorbent having excellent adsorption performance and portability that can be easily used by an individual in a small workplace or an emergency distress situation.

Korean Patent Publication No. 2014-0076598 (2014.06.20)

The present invention has been made to solve the above problems, and an object of the present invention is to provide a highly adsorptive composite that can remove water-soluble contaminants quickly with high adsorption performance and high adsorption rate.

In addition, an object of the present invention is to provide a high adsorption composite that is easy to use individually in a small company or emergency distress, and there is no separate process of separating the adsorbent, there is no fear of secondary contamination due to the loss of the adsorbent.

In order to achieve the above object, the present invention provides a foam substrate, a highly adsorptive foam composite comprising a nanoparticle on the substrate and a polymer brush bonded on the nanoparticle.

In the high adsorption foam composite according to an embodiment of the present invention, the foam base material may be a melamine-based resin foam.

In the highly adsorptive foam composite according to an embodiment of the present invention, the nanoparticles may be dopamine-based or silica-based nanoparticles.

In the highly adsorptive foam composite according to an embodiment of the present invention, the foam substrate may have a hierarchical porous structure including micro pores, meso pores, and macro pores.

In the highly adsorptive foam composite according to an embodiment of the present invention, the polymer brush may include any one selected from cationic polymer electrolytes and anionic polymer electrolytes.

In the highly adsorptive foam composite according to one embodiment of the present invention, the cationic polymer electrolyte is polyallylamine hydrochloride, polyethyleneimine, polydiaryldimethylammonium chloride, polymethacryloxyethyltrialkylammonium halide, polyarylamine Chloride, polyacrylamide, aminoethylated polyacrylamide, polyvinylamine, and polyethyleneamine.

In the highly adsorptive foam composite according to one embodiment of the present invention, the anionic polymer electrolyte is polystyrene sulfonate-co-maleic acid, polyacrylic acid, polystyrene sulfonate, polymethacrylic acid, polyvinyl phosphate and It may include any one or more selected from the group consisting of poly4-ammonium styrene sulfonic acid.

In addition, the present invention

Reacting the foam substrate with the dopamine monomer or the silica precursor compound in a solvent to form the dopamine or silica nanoparticles on the surface of the foam substrate; and

Drying the foam substrate on which the nanoparticles are formed, and then polymerizing it in a polymer electrolyte solution

It provides a method for producing a highly adsorptive foam composite comprising a.

In the method for producing a highly adsorptive foam composite according to an embodiment of the present invention, the polymerization reaction may be carried out by a surface-initiated polymerization method (grafting-from) or a grafting-to method.

In the method for preparing a highly adsorptive foam composite according to an embodiment of the present invention, the solvent may include a mixed solvent in which an alcohol solvent and water are mixed with an ammonia solution.

In the method for producing a highly adsorptive foam composite according to an embodiment of the present invention, the polymer electrolyte may include any one selected from a cationic polymer electrolyte and an anionic polymer electrolyte.

In addition, the present invention provides a compact portable molded article comprising the above-mentioned highly adsorptive foam composite.

Highly adsorbent foam composite according to the present invention has the advantage that can significantly increase the adsorption performance. In particular, by greatly improving the adsorption rate can be quickly removed contaminants in the water, there is an advantage that can improve the heavy metal removal efficiency.

In addition, it can be easily used in small businesses or can be used individually in an emergency distress, there is an advantage that can provide a high adsorption composite without the burden of secondary pollution due to the loss of adsorbent without a separate separation process.

Figure 1 shows the results of measuring the synthesis process of the foamed composite according to an embodiment of the present invention by a scanning electron microscope.
Figure 2 shows the XPS spectrum of the foamed composite according to an embodiment of the present invention.
Figure 3 is a graph showing the adsorption efficiency according to the copper ion pH concentration of the foamed composite according to an embodiment of the present invention (a) polyacrylamide foamed composite, b) polyacrylic acid foamed composite, c) polyethyleneimine foamed composite. d) the maximum adsorption capacity for copper of the three types of polymer brush-foaming composites according to pH).
Figure 4 is a graph showing the ln q of the copper ions over time of the foamed composite according to an embodiment of the present invention (black line: polyacrylamide foamed composite, blue line: polyacrylic acid foamed composite, red line: polyethyleneimine Foamed composites). b) Table containing rate constants for three types of polymer brush-foaming composites. c) Table showing the maximum adsorption capacities of 10 mg / L copper and lead using three foamed composites. d) Graph showing the maximum adsorption capacities of copper and lead at 10 mg / L and 50 mg / L concentrations using three different foam composites.
Figure 5 shows the illustration and the possibility and stability for real life application of the polyethyleneimine foam composite according to an embodiment of the present invention.
Figure 6 shows the maximum adsorption capacity and adsorption isotherm according to the lead concentration of the foamed composite according to Examples 1 to 4 of the present invention.
Figure 7 shows the cytotoxicity test results of the foamed composite according to Examples 1 to 4 of the present invention.

Hereinafter, with reference to the accompanying drawings and embodiments will be described in detail with respect to a highly adsorptive composite and a method for producing the same. However, the following specific examples or examples are only one reference for describing the present invention in detail, but the present invention is not limited thereto and may be implemented in various forms.

Also, unless defined otherwise, all technical and scientific terms have the same meanings as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description herein is for the purpose of effectively describing particular embodiments only and is not intended to be limiting of the invention.

In addition, the drawings introduced below are provided as examples to sufficiently convey the spirit of the present invention to those skilled in the art. Therefore, the present invention is not limited to the drawings presented below and may be embodied in other forms, and the drawings presented below may be exaggerated to clarify the spirit of the present invention.

Also, the singular forms used in the specification and the appended claims may be intended to include the plural forms as well, unless the context clearly indicates otherwise.

Throughout the specification, when a part is said to "include" a certain component, it means that it may further include other components, without excluding the other components unless otherwise stated.

The highly adsorptive composite according to the present invention includes a foam substrate, nanoparticles on the substrate, and a polymer brush bonded on the nanoparticles.

The foam base material is preferably a melamine resin foam. More preferably, it may be a melamine formaldehyde foam.

The melamine formaldehyde foam is not particularly limited, but may be prepared by foaming in a solvent using a blowing agent using a melamine formaldehyde precondensate.

Such foam substrates are not significantly limited in shape, may have a form of cloth or cloth, and may be in the form of a sponge. It can be adjusted with size depending on the application.

In addition, the foam substrate may have various pore sizes without limiting the size of the pores. Preferably the foam substrate has a hierarchical porous structure comprising micropores, mesopores and macropores. In this case, the micro-pores, meso-pores and macro-pores in the present invention are classified according to the classification of IUPAC, micro-pores less than 2nm (Micro-pores), mesopores (Meso-pores), the size of less than 50nm 2nm, And pores larger than 50 nm are assumed to be macropores. The foam base material having the hierarchical porous structure can improve the adsorption rate at the same time as the adsorption at high speed by the cascade effect.

The foam substrate forms nanoparticles on its surface. The nanoparticles are not particularly limited, but are preferably dopamine or silica nanoparticles that can impart high adsorption performance through the formation of a polymer brush while binding is well performed on a substrate.

The dopamine nanoparticles may be a dopamine-based polymer, which is formed by surface polymerization on a foam substrate.

The dopamine-based polymer may include a dopamine-based monomer, preferably a compound represented by the following Chemical Formula 1 with a high molecular compound.

[Formula 1]

In addition, the dopamine-based monomer may include a compound having a catechol group or a derivative thereof. As a specific example, the dopamine-based monomer may include a compound represented by the following formula (2).

[Formula 2]

In Formula 2, R ₁₁ and R ₁₂ may each independently be hydrogen or C1-C5 alkyl.

As the silica nanoparticles, silicon-containing alkoxide compounds may be used. For example, tetraethylorthosilicate (TEOS) and monomethyl-triethoxysilane (MTES) may be used, but is not limited thereto.

The nanoparticles are preferably contained 10 to 30 wt% on the foam substrate. When the above range is satisfied, the polymer brush is well formed, and thus the adsorption performance can be improved.

The highly adsorptive foam composite according to the present invention includes nanoparticles on a foam substrate, and furthermore, a polymer brush is formed on the nanoparticles.

The polymer brush is an aggregate of polymer chains in which one end of the chain is chemically or physically bound on the nanoparticle. The conformation of the polymer brush can be controlled by the density (grafting density) and molecular weight on the surface, it can be formed by grafting the polymer chain on the surface of the nanoparticles (grafting). In addition, it may be formed by bonding to the surface of the foam substrate or the interface of the foam substrate and nanoparticles.

The polymer nanobrush can be used without limitation as long as it is a material capable of adsorption of ions that are impurities in the water, such as heavy metal ions, but preferably using a polymer electrolyte can increase the adsorption rate and further improve the adsorption rate. Even better.

The polymer brush may preferably include any one selected from cationic polymer electrolytes and anionic polymer electrolytes.

The cationic polymer electrolyte may be used without any limitation as long as it is a cationic polymer electrolyte, but is preferably polyallylamine hydrochloride (PAH), polyethylenimine (PEI), or polydiaryldimethylammonium chloride. (polydiallyldimethylammonium chloride, PDDA), polymethacryloxyethyltrialkyl ammonium halide, polyallylamine chloride, polyacrylamide, aminoethylated polyacrylamide, Any one or more selected from the group consisting of polyvinylamine, Hofman-degradated polyacrylamide, polyethyleamine, cationized starch and chitosan can be used. have. More preferably, the use of polyethyleneimine or polyacrylamide is excellent in adsorption performance and various in terms of biocompatibility even under various aquatic conditions.

The anionic polymer electrolyte is not particularly limited as long as it is an anionic polymer electrolyte, but is preferably polystyrene sulfonic acid co-maleic acid, polyacrylic acid, polystyrene sulfonic Any one or more selected from the group consisting of polystyrenesulfonicacid, polymetacrylicacid, polyvinylphosphate, and poly4-ammoniumstyrenesulfonicacid may be used, but is not limited thereto. It doesn't happen. Preferably, polyacrylic acid is better in terms of adsorption performance.

The polymer electrolyte is not particularly limited in its molecular weight, but is preferably in the range of 10,000 to 1,000,000 daltons. When the molecular weight of the polymer electrolyte is less than the above range, the formation of the polymer brush may not be performed well, and when it exceeds the above range, the adsorption efficiency may decrease.

The present invention comprises the step of forming the dopamine or silica nanoparticles on the surface of the foam substrate by reacting the foam substrate with the dopamine monomer or silica precursor compound in a solvent and drying the foam substrate on which the nanoparticles are formed and then put in a polymer electrolyte solution It provides a method for producing a highly adsorptive foam composite comprising the step of polymerization.

In this case, the solvent may preferably use a hydrophilic organic solvent so that the nanoparticles can be well formed on the foam substrate. The hydrophilic organic solvent is an organic compound having a hydrophilic group, and may be used without limitation as long as it is an organic solvent having a hydroxy group, an amine group, a carboxyl group, or the like. Preferably alcoholic solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, methoxy methanol, ethoxy methanol, methoxy propanol, ethoxy propanol and diacetone alcohol It is possible to use a single substance or a mixture consisting of two or more selected.

More preferably, the solvent may be a mixed solvent in which an alcohol solvent and water are mixed with an aqueous ammonia solution.

The nanoparticles may be dopamine or silica nanoparticles.

The dopamine nanoparticles may be a dopamine-based polymer formed using a dopamine-based monomer, which is formed by surface polymerization on a foam substrate.

Preferably, the polymer may include a polymer compound including a monomer represented by Formula 1 below.

[Formula 1]

The dopamine-based monomer may include a compound having a catechol group or a derivative thereof. As a specific example, the dopamine-based monomer may include a compound represented by the following formula (2).

[Formula 2]

In Formula 2, R ₁₁ and R ₁₂ may each independently be hydrogen or C1-C5 alkyl.

As the silica nanoparticles, silicon-containing alkoxide compounds may be used. For example, tetraethylorthosilicate (TEOS) and monomethyl-triethoxy silane (MTES) may be used, but is not limited thereto.

The dopamine monomer or silica precursor compound is preferably contained in the solvent in the range of 0.001 to 10% by weight to react. If the above range is satisfied, the nanoparticles may be formed evenly distributed on the foam substrate.

The foam substrate on which the nanoparticles are formed may be dried and then immersed in a polymer electrolyte solution to form a polymer brush on the nanoparticles by performing a polymerization reaction.

In this case, the polymer electrolyte may include any one selected from a cationic polymer electrolyte and an anionic polymer electrolyte as described above.

The polymerization reaction is not particularly limited, but may be carried out by a surface-initiated polymerization method (grafting-from) or a grafting-to method using an initiator.

The present invention provides a compact portable molded body comprising the above-mentioned highly adsorptive foam composite. In this case, the small portable molded body may be in the form of a tea bag, and the present invention is not limited thereto and may have various forms. Preferably, the form can be changed without limitation as long as it is easy to apply in daily life or small business and can be easily applied by individual users in case of emergency distress.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following Examples and Comparative Examples are only examples for describing the present invention in detail, and the present invention is not limited by the following Examples and Comparative Examples.

(Example 1)

0.9 mL of ammonia solution was added to a mixed solution of 30 mL of 2-propanol and 5.4 mL of distilled water, followed by stirring at 25 ° C. for 1 minute. Next, 0.9 mL of a tetraethylorthosilicate (TEOS) solution and a melamine / formaldehyde foam (Basotect®, Basf) (1 × 1 × 2 cm 3) substrate are added to the mixed solution and reacted for 4 hours. Thereafter, the foam substrate was taken out, washed with distilled water, and dried in an oven (50 ° C.) for 12 hours. After drying, the mixture was refluxed in 30 mL of ethanol and 0.25 mL MPS (3- (trimethoxysilyl) propylmethacrylate) solution at 80 ° C for 10 hours, washed with distilled water, and then washed with 0.1 g acrylamide and 2.5 mg AIBN. (α, α′-azobis (isobutyronitrile)) was dissolved in 30 mL acetonitrile and refluxed at 80 ° C. for 10 hours, washed with distilled water, and dried in an oven (50 ° C.) for 12 hours to obtain polyacrylamide- Foam composites were prepared.

(Example 2)

0.9 mL of ammonia solution was added to a mixed solution of 30 mL of 2-propanol and 5.4 mL of distilled water, followed by stirring at 25 ° C. for 1 minute. Next, 0.9 mL of a tetraethylorthosilicate (TEOS) solution and a melamine / formaldehyde foam (Basotect®, Basf) (1 × 1 × 2 cm 3) substrate are added to the mixed solution and reacted for 4 hours. Thereafter, the foam substrate was taken out, washed with distilled water, and dried in an oven (50 ° C.) for 12 hours. After drying, the mixture was poured into 30 mL of ethanol and 0.25 mL MPS (3- (trimethoxysilyl) propylmethacrylate) mixture, refluxed at 80 ° C. for 10 hours, washed with distilled water, and then washed with 0.1 g acrylic acid and 2.5 mg AIBN. (α, α′-azobis (isobutyronitrile)) was dissolved in 30 mL of acetonitrile, refluxed at 80 ° C. for 10 hours, washed with distilled water, dried in an oven (50 ° C.) for 12 hours, and then polyacrylic acid-foamed. The complex was prepared.

(Example 3)

80 μl of ammonia solution was added to a mixed solution of 8 mL of ethanol and 18 mL of distilled water, followed by stirring at 25 ° C. for 30 minutes. Next, 0.1 g / 2 mL of dopamine hydrochloride solution and melamine / formaldehyde foam (Basotect®, Basf) (1 × 1 × 2 cm 3) substrate are added to the mixed solution and reacted for 6 hours. Thereafter, the foam substrate was taken out, washed with distilled water, and dried in an oven (50 ° C.) for 12 hours. When drying is complete, 30 mL polyethyleneimine (weight average molecular weight: 25,000 g / mol) made in a tris-C HCl (tris (C ₄ H ₁₁ NO ₃ ) -HCl solution, 10 mM, pH = 8.5) solution at a concentration of 0.3 mg / mL. ) Was refluxed at 60 ° C. for 3 hours and then stirred at 25 ° C. for 16 hours. When the reaction was completed, washed with distilled water, and then dried in an oven (50 ℃) for 12 hours to prepare a polyethyleneimine-foaming complex.

(Example 4)

Instead of using a polyethyleneimine having a weight average molecular weight of 25,000g / mol, it was carried out in the same manner as in Example 3 except that polyethyleneimine having a weight average molecular weight of 75,000g / mol was used.

(Heavy metal ion adsorption test)

Pb (NO ₃ ) ₂ and Cu (NO ₃ ) ₂ are dispersed in water to prepare a heavy metal solution containing lead (II) ions and copper (II) ions, respectively. Initial concentrations of the respective heavy metal solutions were specified, and the pH concentrations of the solutions were adjusted to 3, 6, and 8 using sodium hydroxide and hydrochloric acid, respectively. The polymer brush-foaming composite prepared in Example was added to 60 mL of each heavy metal ion solution and reacted by stirring, and then 10 mL of the heavy metal ion solution was separated from the polymer brush-foaming complex at a specified time, and ICP (Inductively Through the coupled plasma mass spectroscopy analysis, the concentrations of adsorbed lead and copper ions and remaining ions were calculated using the following equation.

(Equation 1) qe = (Co-Ce) V / m

In Equation 1, qe is the maximum adsorption capacity of heavy metal ions (mg / g), Co is the initial concentration of the heavy metal ion solution (mg / L), Ce is the concentration of heavy metal ions (mg / L) at equilibrium, m is The mass (g) of the adsorbent, V is the volume (L) of heavy metal ions.

(Cytotoxicity test)

Lactate dehydrogenase (LD) was assessed for cytotoxicity of the foamed complexes prepared in the Examples through supernatant media analysis using osteoblastic MC3TC-E1 cell line and medium (MEM + 2 mM glutamine + 10% fetal bovine serum). The cytotoxicity detection kit of Takara Bio Co. was used, and each foamed complex was prepared for the cytotoxicity test according to a standard protocol provided by the manufacturer. Cells were incubated with each foamed complex. After incubation at 37 ° C. for 48 hours at 5% CO ₂ conditions, the mixture was centrifuged to collect the supernatant. LD activity was determined by measuring absorbance at 490 nm using a microplate reader.

Instrument analysis

SEM images were measured using Hitachi S-4800. XPS analysis was performed by Kratos analytical Axis NOVA spectrometer using aluminum cathode at 600W. ICP-MS analysis was performed using the Optima 8300DV model from PerkinElmer. UV-vis spectra were used by Sinco Sinco Evloution201.

Figure 1 shows a scanning electron micrograph of the melamine formaldehyde foam substrate according to Examples 1 to 3. Figure a) shows that the melamine formaldehyde foam is a network structure consisting of interconnected skeleton before synthesis with the polymer brush, it can be seen that the surface is smooth. Figures b) and e) show the surface modification for synthesizing melamine formaldehyde foam and polymer brush. It can be seen that silica (b) and polydopamine (e) particles are distributed on the surface of the foam, respectively. Subsequently, when the polymer brush is synthesized in the foam, the surface is covered with particles having an irregular shape and size as a whole. Figures c), d) and f) show polyacrylamide, polyacrylic acid and polyethyleneimine, respectively. To show.

Figure 2 shows the X-ray photoelectron spectroscopy spectrum showing the compositional changes before and after the synthesis of the polymer brush in the melamine formaldehyde foam. Figure a) shows the C 1s deconvolution signal of polyacrylamide, pp * (291.8 eV) binding according to melamine formaldehyde foam, NC = O (288.8 eV) binding confirms the presence of polyacrylamide It can be. Figure b) shows the C 1s deconvolution signal for polyacrylic acid, showing four bonds: CC (284.6 eV), CO (286.9 eV), C = O (289.2 eV), pp * (291.2 eV), and C ═O bond is one that can confirm the presence of polyacrylic acid. Figures c) and d) show N 1s deconvolution signals before and after the synthesis of polyethylenimine, -N = (398 eV), -NH- (398.9 eV), -NH ₂ (399.9eV), -NC- (401eV) shows four bonds, and after addition of polyethyleneimine, the Michael addition reaction between the catechol group of polydopamine and the primary amine group of polyethylenimine, through different bonds and the difference in signal strength of the secondary amine (-NH-) It was confirmed that there is a synthesis by.

Figure 3 shows the test results of removing the copper by using the high adsorption foam composite according to Examples 1 to 3 of the present invention at various pH conditions, all showed similar behavior. Specifically, at low pH (pH = 3), the removal efficiency decreased due to the decrease in adsorption position and the electrostatic repulsion caused by the proton addition reaction of the amine group of polyacrylamide and polyethyleneimine and the carboxyl group of polyacrylic acid. As the deprotonation occurred, the removal efficiency was excellent. When the pH was 8, metal hydroxides were formed by hydrolysis of copper ions, and the removal efficiency was slightly decreased.

Figure 4 shows the results of measuring the rate constant and efficiency in the heavy metal ion removal test using a highly adsorptive foam composite according to Examples 1 to 3 of the present invention. Figures a) and b) show the ln q values and rate constants over time for copper removal. When the pH is 6, the rate constants of the highly adsorptive foam composites according to Examples 1 to 3 were calculated as 7.3 × 10 ⁻² , 8.4 × 10 ⁻² , and 54.3 × 10 ⁻² , respectively, and polyethyleneimine according to Example 3 It was confirmed that the foamed composite reacted more rapidly than the other two foamed composites. Figure c) shows the results of the lead removal test. The efficiency of the polyethyleneimine foam composite according to Example 3 was the best, but the maximum adsorption capacity (0.67 mmol / g) of lead was higher than that of copper (3.74 mmol / g). Appeared low. Figure d) shows the results of copper and lead removal according to the concentration. The maximum adsorption capacity was large at the initial concentration of heavy metal ions. This is because the initial concentration of high heavy metal ions provided an important driving force to overcome the mass transfer resistance of the metal ions between the aqueous solution and the solid phase.

FIG. 5 shows examples, possibilities, and stability for real-life application of the polyethyleneimine foam composite according to Examples 3 and 4, and FIG. A) shows a size of 2 × 2 × 1 cm 3 in 300 mL of a solution containing heavy metal ions. Soaked polyethyleneimine foam composite. Figure b) shows the effect of polyethyleneimine molecular weight on the heavy metal removal test and heavy metal removal test results at low concentrations, polyethyleneimine foam composite according to Example 3 (MW: 25,000g / mol) and according to Example 4 In the case of polyethyleneimine foam composite (MW: 75,000g / mol) ethylene imine), heavy metal ions were rapidly removed by preparing low concentrations of copper and lead at 0.368 mg / L and 0.25 mg / L, respectively. It can be confirmed that it is removed and lowered to the drinking water standard (lead: 7.2 μg / L) within 2 hours. In particular, in the case of the foamed composite according to Example 3, it fell below the drinking water reference value within 3 minutes. Figure c) is a graph showing the chemical stability of the foamed composites in the pH range 2-8, all of which were not measured in the UV-vis spectrum measured in the range 230-800 nm.

Figure 6 shows the maximum adsorption capacity and adsorption isotherm according to the lead concentration of the foamed composite according to Examples 1 to 4 of the present invention, Figure a) shows that the maximum adsorption capacity increases as the concentration of lead, Figure b ) Shows constants calculated using Langmuir isotherm equation (1) and Freundlich isotherm equation (2). This is in close proximity to the Langmuir mode and indicates that lead is made up of monolayer adsorption on the foamed composite.

Ce / qe = 1 / KLqm + Ce / qm (1)

ln qe = lnKf + 1 / n (lnCe) (2)

Ce and qe are equilibrium concentrations (mg / L) and heavy metal adsorption capacity (mg / g), respectively, and KL and Kf are constants of the equations.

Figure 7 shows the cytotoxicity test results of the foamed composite according to Examples 1 to 4 of the present invention, the cell viability of the polyacrylic acid foamed composite of Example 2 and the polyethyleneimine foamed composite of Examples 3 and 4 is 98% The polyacrylamide foam composite of Example 1 was found to be 92.4%.

As described above, the highly adsorptive foam composite according to the present invention has a stable structure, it is possible to remove the heavy metal in various conditions, it was confirmed that it can be applied to a wide range including the real life.

As described above in the present invention has been described by a limited embodiment, which is provided only to help a more general understanding of the present invention, the present invention is not limited to the above embodiments, it is to be understood that the general knowledge in the field Those having a variety of modifications and variations are possible from these descriptions. Therefore, the spirit of the present invention should not be limited to the embodiments described, and all of the equivalents and equivalents of the claims as well as the claims to be described later belong to the scope of the present invention. .

Claims (12)

Foam substrates;
Dopamine polymer nanoparticles formed on the foam substrate; And
Highly adsorbent foam composite for removing contaminants including; a polymer brush bonded on the nanoparticles. The method of claim 1,
The foam base material is a super absorbent foam composite for removing contaminants which is a melamine-based resin foam. delete The method of claim 1,
The foam substrate is a highly adsorptive foam composite for removing contaminants having a hierarchical porous structure including micro pores, meso pores and macro pores. The method of claim 1,
The polymer brush is a highly adsorptive foam composite for removing contaminants including any one selected from cationic polymer electrolyte and anionic polymer electrolyte. The method of claim 5,
The cationic polymer electrolyte is polyallylamine hydrochloride, polyethyleneimine, polydiaryldimethylammonium chloride, polymethacryloxyethyltrialkylammonium halide, polyarylamine chloride, polyacrylamide, aminoethylated polyacrylamide, poly Highly adsorbent foam composite for removing contaminants comprising at least one selected from the group consisting of vinylamine and polyethyleneamine. The method of claim 5,
The anionic polymer electrolyte is any one selected from the group consisting of polystyrenesulphonic acid-co-maleic acid, polyacrylic acid, polystyrenesulphonic acid, polymethacrylic acid, polyvinylphosphate and poly4-ammonium styrenesulphonic acid. Highly adsorbent foam composite for removing contaminants comprising one or more. Forming a dopamine polymer nanoparticle on the surface of the foam substrate by reacting the foam substrate with the dopamine monomer in a solvent, and
Method of producing a highly adsorptive foam composite for removing contaminants comprising the step of drying the foam substrate on which the nanoparticles are formed and then polymerized in a polymer electrolyte solution. The method of claim 8,
The polymerization reaction is a method for producing a highly adsorbent foam composite for removing contaminants is carried out by a surface-initiated polymerization method (grafting-from) or a grafting-to method. The method of claim 8,
The solvent is a method for producing a highly adsorptive foam composite for removing contaminants, including a mixed solvent in which an alcohol solvent and water are mixed with an ammonia solution. The method of claim 8,
The polymer electrolyte is a method for producing a highly adsorptive foam composite for removing contaminants including any one selected from cationic polymer electrolyte and anionic polymer electrolyte. Small portable molded article prepared by the method for producing a highly adsorbent foam composite for removing contaminants according to any one of claims 1, 2 and 4.

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