KR101901372B1 - Hydrophilic metal-organic polyhedra, preparation method thereof and gas separation membrane comprising the same - Google Patents

Abstract

The present invention relates to a hydrophilic metal-organic polyhedra, a method for producing the same, and a gas separation membrane comprising the same, and more particularly, to a hydrophilic metal-organic polyhedron comprising a polyethylene oxide- It can be applied as a gas separation membrane which can exhibit high CO ₂ / N ₂ permeation selectivity by mixing with a polymer

Description

TECHNICAL FIELD The present invention relates to a hydrophilic metal-organic polyhedra, a method for producing the hydrophilic metal-organic polyhedron, and a gas separation membrane comprising the hydrophilic metal-organic polyhedra,

The present invention relates to a hydrophilic metal-organic polyhedra, a method for producing the same, and a gas separation membrane comprising the same, and more particularly, to a hydrophilic metal-organic polyhedron comprising a polyethylene oxide- The present invention relates to a technique for application as a gas separation membrane excellent in gas separation characteristics by mixing with a polymer.

 Many uses of petroleum cause serious problems due to emission of air pollutants and global warming due to greenhouse effect. The Kyoto Protocol was adopted in 1997 to regulate the emission of carbon dioxide, the main cause of global warming. The Kyoto Protocol was officially in effect on February 16, 2005, and Korea will be included in the regulated countries in 2013.

Therefore, efforts to remove carbon dioxide are urgently needed, and it is urgent to develop various technologies for this purpose. One conventional method for separating carbon dioxide is an apparatus and a method for separating water and carbon dioxide from a gas mixture using PSA (Pressure Swing Adsorption) technique using a solid adsorbent material. However, PSA method had the disadvantage tend to be abrasion resistant sorbent is required, and a large amount of the carbon dioxide separation difficult, the reactive gas such as a large SO _X, NO _X adsorbed than carbon dioxide.

One of the other methods for separating carbon dioxide is the separation of carbon dioxide using a polymer membrane. However, existing polymer membranes are not compatible with each other as in the upper bound, which is a graph showing the correlation between the permeability and selectivity reported by Robeson in 2008 Conflicting transmittance and selectivity problems. That is, when the transmittance increases, the selectivity decreases or vice versa.

Therefore, the inventors of the present invention have completed the present invention by focusing on the fact that they can be used as a gas separation membrane having excellent gas separation characteristics by mixing the polymerized poly (ethylene oxide) polymer with crosslinked poly (ethylene oxide) polymer if a hydrophilic metal- .

Patent Document 1. Korean Patent Publication No. 10-1577790 Patent Document 2: Korean Patent Publication No. 10-1650236

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to provide a hydrophilic metal-organic polyhedra, a gas separation membrane including the same, and a method of manufacturing the same.

In order to accomplish the above object, the present invention provides a metal-organic polyhedron represented by the following structural formula 1.

[Structural formula 1]

Wherein M ₁ and M ₂ are the same or different from each other and each independently represents Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Sc ³⁺ , Y ³⁺ , Ti ⁴⁺ , Zr ⁴⁺ , Hf ^{4 +} , V ⁴⁺ , V ³⁺ , V ²⁺ , Nb ³⁺ , Ta ³⁺ , Cr ³⁺ , Mo ³⁺ , W ³⁺ , Mn ³⁺ , Mn ²⁺ , Re ³⁺ , Re ²⁺ , ^{Fe 3+, Fe 2+, Ru 3+} , Ru 2+, Os 3+, Os 2+, Co 3+, Co 2+, Rh 2+, Rh +, Ir 2+, Ir +, Ni 2+, ^{Ni +, Pd 2+, Pd +} , Pt 2+, Pt +, Cu 2+, Cu +, Ag +, Au +, Zn 2+, Cd 2+, Hg 2+, Al 3+, Ga 3+, ^{In 3+, Tl 3+, Si 4+} , Si 2+, Ge 4+, Ge 2+, Sn 4+, Sn 2+, Pb 4+, Pb 2+, As 5+, As 3+, As + , Sb ⁵⁺ , Sb ³⁺ , Sb ⁺ , Bi ⁵⁺ , Bi ³⁺ and Bi ⁺ ;

S ₁ and S ₂ are the same or different and are each independently selected from the group consisting of N, N-Dimethyl Formamide (DMF), Methyl ethyl ketone (MEK), formaldehyde Dimethylformamide (DEF), dimethylacetamide (DMA), methanol (MeOH), ethanol (EtOH), tetrahydrofuran (THF) H ₂ O), 1-methyl-2-pyrrolidinone (NMP), dimethyl sulfoxide (DMSO), and diethyl ether Or two or more organic solvents;

N is an integer from 3 to 100;

L ₁ , L ₂ , L ₃ and L ₄ are the same or different and each independently an organic ligand represented by the following structural formula 2:

[Structural formula 2]

Wherein R ₁ , R ₂ and R ₃ are the same or different and each independently represents a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms A substituted or unsubstituted C1-C20 alkylamine group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6- A substituted or unsubstituted arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, Or an unsubstituted heteroaryloxy group having 2 to 30 carbon atoms;

And x is an integer of 1 to 20.

The M ₁ and M ₂ may be Cu ²⁺ .

L ₁ , L ₂ , L ₃ and L ₄ may be organic ligands represented by the following structural formula 3:

[Structural Formula 3]

L ₁ , L ₂ , L ₃ and L ₄ may be an organic ligand represented by the following structural formula 4.

[Structural Formula 4]

The metal-organic polyhedron may have a pore inlet of 5 to 8 angstroms and an inner pore of 10 to 15 angstroms.

The present invention also provides a gas separation membrane comprising the metal-organic polyhedrons according to the present invention.

The gas separation membrane may further include a cross-linked polyethylene oxide polymer.

The thickness of the gas separation membrane may be 10 to 800 m.

The gas may be carbon dioxide.

The present invention also relates to a process for producing a metal-organic polyhedron represented by the following structural formula 1, comprising the steps of: (a) reacting a metal precursor, a first solvent and a solution containing an organic ligand represented by the following structural formula 2 to provide.

[Structural formula 1]

Wherein M ₁ and M ₂ are the same or different from each other and each independently represents Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Sc ³⁺ , Y ³⁺ , Ti ⁴⁺ , Zr ⁴⁺ , Hf ^{4 +} , V ⁴⁺ , V ³⁺ , V ²⁺ , Nb ³⁺ , Ta ³⁺ , Cr ³⁺ , Mo ³⁺ , W ³⁺ , Mn ³⁺ , Mn ²⁺ , Re ³⁺ , Re ²⁺ , ^{Fe 3+, Fe 2+, Ru 3+} , Ru 2+, Os 3+, Os 2+, Co 3+, Co 2+, Rh 2+, Rh +, Ir 2+, Ir +, Ni 2+, ^{Ni +, Pd 2+, Pd +} , Pt 2+, Pt +, Cu 2+, Cu +, Ag +, Au +, Zn 2+, Cd 2+, Hg 2+, Al 3+, Ga 3+, ^{In 3+, Tl 3+, Si 4+} , Si 2+, Ge 4+, Ge 2+, Sn 4+, Sn 2+, Pb 4+, Pb 2+, As 5+, As 3+, As + , Sb ⁵⁺ , Sb ³⁺ , Sb ⁺ , Bi ⁵⁺ , Bi ³⁺ and Bi ⁺ ;

S ₁ and S ₂ are the same or different and are each independently selected from the group consisting of N, N-Dimethyl Formamide (DMF), Methyl ethyl ketone (MEK), formaldehyde Dimethylformamide (DEF), dimethylacetamide (DMA), methanol (MeOH), ethanol (EtOH), tetrahydrofuran (THF) H ₂ O), 1-methyl-2-pyrrolidinone (NMP), dimethyl sulfoxide (DMSO), and diethyl ether Or two or more organic solvents;

N is an integer from 3 to 100;

L ₁ , L ₂ , L ₃ and L ₄ are the same or different and each independently an organic ligand represented by the following structural formula 2:

[Structural formula 2]

Wherein R ₁ , R ₂ and R ₃ are the same or different and each independently represents a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms A substituted or unsubstituted C1-C20 alkylamine group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6- A substituted or unsubstituted arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, Or an unsubstituted heteroaryloxy group having 2 to 30 carbon atoms.

And x is an integer of 1 to 20.

The metal precursor may be Cu.

L ₁ , L ₂ , L ₃ and L ₄ may be organic ligands represented by the following structural formula 3:

[Structural Formula 3]

L ₁ , L ₂ , L ₃ and L ₄ may be an organic ligand represented by the following structural formula 4.

[Structural Formula 4]

The organic ligand represented by Formula 2 may be prepared by reacting a solution containing (a-I) dimethyl-5-hydroxyisophthalate, a second solvent and a monomer represented by the following Formula 5 in the presence of a catalyst to form a first reaction solution ; (a-II) reacting a solution containing the first reaction solution, a third solvent and a hydroxide to obtain a second reaction solution; And (a-III) adding an acid to the second reaction solution to obtain a precipitate.

[Structural Formula 5]

Y is an integer of 1 to 20;

The first, second and third solvents may be the same or different from each other and each independently selected from the group consisting of N, N-Dimethyl Formamide (DMF), Methyl ethyl ketone (MEK), formaldehyde Dimethylformamide (DEF), dimethylacetamide (DMA), methanol (MeOH), ethanol (EtOH), tetrahydrofuran (THF) ), Water (H ₂ O), 1-methyl-2-pyrrolidinone (NMP), dimethyl sulfoxide (DMSO), diethyl ether ), And mixtures thereof.

The present invention also relates to a process for the preparation of (A) a process for the production of (A) a process for polymerizing a solution comprising polyethylene glycol diacrylate (PEGDA), polyethylene glycol methyl ether acrylate (PEGMEA) and the metal- The present invention also provides a method for producing a gas separation membrane.

The polymerization may be carried out by irradiation with ultraviolet light of 70 to 200 mW / cm ² .

According to the present invention, it is possible to provide a gas separation membrane capable of producing a hydrophilic metal-organic polyhedron and exhibiting high CO ₂ / N ₂ permeation selectivity by mixing it with a crosslinked polyethylene oxide polymer.

1 is a schematic diagram showing a process of synthesizing PEO ₃ -Tos according to Production Example 1 of the present invention.
2 is a ¹ H-NMR spectrum of PEO ₃ -Tos prepared from Production Example 1 of the present invention.
3 is a schematic view showing a process of synthesizing PEO ₃ -BDC according to Production Example 2 of the present invention.
4 is a ¹ H-NMR spectrum of PEO ₃ -BDC prepared in Production Example 2 of the present invention.
5 is a schematic view showing a process of synthesizing PEO ₆ -Tos according to Production Example 3 of the present invention.
6 is a ¹ H-NMR spectrum of PEO ₆ -Tos prepared from Production Example 3 of the present invention.
7 is a schematic view showing a process of synthesizing PEO ₆ -BDC according to Production Example 4 of the present invention.
8 is a ¹ H-NMR spectrum of the PEO ₆ -BDC prepared in Production Example 4 of the present invention
9 is an image showing the X-ray single crystal structure of the hydrophilic metal-organic polyhedron (PEO _x -MOP) prepared in Example 1 of the present invention.
10 is a schematic view illustrating a process of synthesizing a PEO _x -MOP @ XLPEO gas separation membrane according to a second embodiment of the present invention.
11 is an image of a PEO _x -MOP @ XLPEO gas separation membrane produced from Example 2 of the present invention.

In the following, various aspects and various embodiments of the present invention will be described in more detail.

The present invention provides a metal-organic polyhedron represented by the following structural formula (1).

[Structural formula 1]

Wherein M ₁ and M ₂ are the same or different from each other and each independently represents Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Sc ³⁺ , Y ³⁺ , Ti ⁴⁺ , Zr ⁴⁺ , Hf ^{4 +} , V ⁴⁺ , V ³⁺ , V ²⁺ , Nb ³⁺ , Ta ³⁺ , Cr ³⁺ , Mo ³⁺ , W ³⁺ , Mn ³⁺ , Mn ²⁺ , Re ³⁺ , Re ²⁺ , ^{Fe 3+, Fe 2+, Ru 3+} , Ru 2+, Os 3+, Os 2+, Co 3+, Co 2+, Rh 2+, Rh +, Ir 2+, Ir +, Ni 2+, ^{Ni +, Pd 2+, Pd +} , Pt 2+, Pt +, Cu 2+, Cu +, Ag +, Au +, Zn 2+, Cd 2+, Hg 2+, Al 3+, Ga 3+, ^{In 3+, Tl 3+, Si 4+} , Si 2+, Ge 4+, Ge 2+, Sn 4+, Sn 2+, Pb 4+, Pb 2+, As 5+, As 3+, As + , Sb ⁵⁺ , Sb ³⁺ , Sb ⁺ , Bi ⁵⁺ , Bi ³⁺ and Bi ⁺ ;

S ₁ and S ₂ are the same or different and are each independently selected from the group consisting of N, N-Dimethyl Formamide (DMF), Methyl ethyl ketone (MEK), formaldehyde Dimethylformamide (DEF), dimethylacetamide (DMA), methanol (MeOH), ethanol (EtOH), tetrahydrofuran (THF) H ₂ O), 1-methyl-2-pyrrolidinone (NMP), dimethyl sulfoxide (DMSO), and diethyl ether Or two or more organic solvents;

N is an integer from 3 to 100;

L ₁ , L ₂ , L ₃ and L ₄ are the same or different and each independently an organic ligand represented by the following structural formula 2:

[Structural formula 2]

Wherein R ₁ , R ₂ and R ₃ are the same or different and each independently represents a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms A substituted or unsubstituted C1-C20 alkylamine group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6- A substituted or unsubstituted arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, Or an unsubstituted heteroaryloxy group having 2 to 30 carbon atoms;

And x is an integer of 1 to 20.

The M ₁ and M ₂ may be Cu ²⁺ .

L ₁ , L ₂ , L ₃ and L ₄ may be organic ligands represented by the following structural formula 3:

[Structural Formula 3]

L ₁ , L ₂ , L ₃ and L ₄ may be an organic ligand represented by the following structural formula 4.

[Structural Formula 4]

Particularly, when the center metal ion M is Cu ²⁺ and the organic ligands L ₁ , L ₂ , L ₃ and L ₄ are organic ligands represented by the structural formula 3 or 4, they include other kinds of central metal ions and organic ligands It was confirmed that the gas separation characteristics were much better than those in the case where the gas separation was performed.

The metal-organic polyhedron may have pore openings of 5 to 8 angstroms, preferably 6 to 7 angstroms, and internal pores of 10 to 15 angstroms, preferably 13 to 14 angstroms.

The present invention also provides a gas separation membrane comprising the metal-organic polyhedrons according to the present invention.

The gas separation membrane may further include a cross-linked polyethylene oxide polymer. It has been reported that the polarity of polyethylene oxide shows strong affinity with carbon dioxide, and accordingly, researches on separators based on polyethylene oxide are actively underway. Particularly, when the gas separation membrane further comprises a crosslinked polyethylene oxide polymer, the gas separation membrane can be made of a mixed gas of carbon dioxide and nitrogen as well as CO ₂ / CH ₄ , CO ₂ / H _It was confirmed that the separation characteristics of carbon dioxide, which is regarded as an impurity, are remarkably excellent even in a mixed gas of _two or more.

The thickness of the gas separation membrane may be 10 to 800 탆, preferably 100 to 400 탆. When the thickness is 10 μm or less, the gas selectivity is low, and when the thickness is 800 μm or more, the gas permeability may be deteriorated.

The gas is H ₂ O, SF _4, H _2, CH _4,, propane, propene, ethylene, acetylene NO _2, H ₂ S, SO _2, O _2, CO, Ar, He, N _2, CO _2, Kr, Ne, CFCs, and O ₃ , but is not limited thereto. Particularly, it was confirmed that the separation characteristics for carbon dioxide (CO ₂ ) were excellent.

The present invention also relates to a process for producing a metal-organic polyhedron represented by the following structural formula 1, comprising the steps of: (a) reacting a metal precursor, a first solvent and a solution containing an organic ligand represented by the following structural formula 2 to provide.

[Structural formula 1]

Wherein M ₁ and M ₂ are the same or different from each other and each independently represents Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Sc ³⁺ , Y ³⁺ , Ti ⁴⁺ , Zr ⁴⁺ , Hf ^{4 +} , V ⁴⁺ , V ³⁺ , V ²⁺ , Nb ³⁺ , Ta ³⁺ , Cr ³⁺ , Mo ³⁺ , W ³⁺ , Mn ³⁺ , Mn ²⁺ , Re ³⁺ , Re ²⁺ , ^{Fe 3+, Fe 2+, Ru 3+} , Ru 2+, Os 3+, Os 2+, Co 3+, Co 2+, Rh 2+, Rh +, Ir 2+, Ir +, Ni 2+, ^{Ni +, Pd 2+, Pd +} , Pt 2+, Pt +, Cu 2+, Cu +, Ag +, Au +, Zn 2+, Cd 2+, Hg 2+, Al 3+, Ga 3+, ^{In 3+, Tl 3+, Si 4+} , Si 2+, Ge 4+, Ge 2+, Sn 4+, Sn 2+, Pb 4+, Pb 2+, As 5+, As 3+, As + , Sb ⁵⁺ , Sb ³⁺ , Sb ⁺ , Bi ⁵⁺ , Bi ³⁺ and Bi ⁺ ;

S ₁ and S ₂ are the same or different and are each independently selected from the group consisting of N, N-Dimethyl Formamide (DMF), Methyl ethyl ketone (MEK), formaldehyde Dimethylformamide (DEF), dimethylacetamide (DMA), methanol (MeOH), ethanol (EtOH), tetrahydrofuran (THF) H ₂ O), 1-methyl-2-pyrrolidinone (NMP), dimethyl sulfoxide (DMSO), and diethyl ether Or two or more organic solvents;

N is an integer from 3 to 100;

L ₁ , L ₂ , L ₃ and L ₄ are the same or different and each independently an organic ligand represented by the following structural formula 2:

[Structural formula 2]

Wherein R ₁ , R ₂ and R ₃ are the same or different and each independently represents a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms A substituted or unsubstituted C1-C20 alkylamine group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6- A substituted or unsubstituted arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, Or an unsubstituted heteroaryloxy group having 2 to 30 carbon atoms.

As a specific example, the step (a) may be carried out in a Teflon reactor at 60 to 150 ° C, preferably 70 to 90 ° C.

And x is an integer of 1 to 20.

The metal precursor may be Cu and the metal precursor may be selected from the group consisting of pure metal nano powder, chloride, bromide, iodide, nitrate, nitrite, sulfate, But is not limited to, one or more types selected from acetate, sulfite, acetylacetoate and hydroxide. Specifically, it may be an acetic acid salt.

L ₁ , L ₂ , L ₃ and L ₄ may be organic ligands represented by the following structural formula 3:

[Structural Formula 3]

L ₁ , L ₂ , L ₃ and L ₄ may be an organic ligand represented by the following structural formula 4.

[Structural Formula 4]

The organic ligand represented by Formula 2 may be prepared by reacting a solution containing (a-I) dimethyl-5-hydroxyisophthalate, a second solvent and a monomer represented by the following Formula 5 in the presence of a catalyst to form a first reaction solution ; (a-II) reacting a solution containing the first reaction solution, a third solvent and a hydroxide to obtain a second reaction solution; And (a-III) adding an acid to the second reaction solution to obtain a precipitate.

[Structural Formula 5]

Y is an integer of 1 to 20;

As a specific example, the step (a-I) may be carried out by a reflux reaction at 80 to 200 ° C, preferably 100 to 120 ° C for 5 to 30 hours, preferably 22 to 26 hours (A-II) may be carried out by a reflux reaction at 50 to 150 ° C, preferably 70 to 90 ° C for 5 to 30 hours, preferably 22 to 26 hours, Preferably potassium carbonate, and the hydroxide is preferably sodium hydroxide, and the acid is preferably hydrochloric acid.

Further, the precipitate obtained after the step (a-III) may be washed with water and filtered to vacuum-dry the resulting product.

The first, second and third solvents may be the same or different from each other and each independently selected from the group consisting of N, N-Dimethyl Formamide (DMF), Methyl ethyl ketone (MEK), formaldehyde Dimethylformamide (DEF), dimethylacetamide (DMA), methanol (MeOH), ethanol (EtOH), tetrahydrofuran (THF) ), Water (H ₂ O), 1-methyl-2-pyrrolidinone (NMP), dimethyl sulfoxide (DMSO), diethyl ether ), And mixtures thereof, but is not limited thereto. Preferably, the first solvent is dimethylformamide, the second solvent is methylethylketone, and the third solvent is ethanol.

The present invention also relates to a process for the preparation of (A) a process for the production of (A) a process for polymerizing a solution comprising polyethylene glycol diacrylate (PEGDA), polyethylene glycol methyl ether acrylate (PEGMEA) and the metal- The present invention also provides a method for producing a gas separation membrane.

The radical polymerization initiator may be at least one selected from the group consisting of a photopolymerization initiator and a thermal polymerization initiator. Examples of the photopolymerization initiator include, but are not limited to, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4- (2- hydroxyethoxy) 2-hydroxy-2-propyl ketone, 1-hydroxycyclohexyl phenyl ketone, and other acetophenone derivatives; Benzoin alkyl ether compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; methyl benzoyl benzoate, 4-phenyl benzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, (4-benzoylbenzyl) trimethylammonium chloride; Thioxanthone-based compounds; Acylphosphine oxide derivatives such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide; Or an azo group such as 2-hydroxymethylpropionitrile, 2,2 '- (azobis (2-methyl-N- (1,1'-bis (hydroxymethyl) -2- hydroxyethyl) propionamide) And the like can be used alone or in combination of two or more, but the present invention is not limited thereto.

The thermal polymerization initiator is not particularly limited. For example, azo (azo) initiator, peroxide initiator, redox initiator or organic halide initiator may be used alone or in combination of two or more thereof . The thermal polymerization initiator may include, but is not limited to, sodium persulfate (Na ₂ S ₂ O ₈ ) or potassium persulfate (K ₂ S ₂ O ₈ ).

The content of the photopolymerization initiator and / or the thermal polymerization initiator can be selected as long as it can exhibit polymerization initiating effect. In a non-limiting example, the photopolymerization initiator may be contained in an amount within a range of 0.005 to 0.5 parts by weight based on 100 parts by weight of the hydrophilic monomer , and the thermal polymerization initiator may be included within a range of 0.01 to 0.5 parts by weight with respect to 100 parts by weight of the hydrophilic monomer have.

In a nonlimiting example, the polymerization initiator can be a photopolymerization initiator and a thermal polymerization initiator. In this case, the photopolymerization initiator is introduced into the neutralizing agent aqueous solution together with the hydrophilic monomer and the crosslinking agent, The aqueous solution of the neutralizing agent. In the present invention, 1-hydroxycyclohexyl phenylketone (HCPK) can be preferably used as the photoinitiator.

The polymerization may be carried out for 10 to 60 minutes, preferably 20 to 40 minutes, by ultraviolet irradiation at 70 to 200 mW / cm ² , preferably 90 to 110 mW / cm ² .

Hereinafter, production examples and embodiments according to the present invention will be described in detail with reference to the accompanying drawings.

Production Example 1: PEO ₃ Synthesis of -Tos

To a 200 mL beaker was added 15 mL (91.72 mmol) of triethylene glycol monomethylether, 20.2841 g (106.2 mmol) of p-toluenesulphonyl chloride and 70 mL of tetrahydrofuran (THF) 70 mL solution of sodium hydroxide (5.634 g) dissolved in 10 mL of distilled water was slowly poured into the solution and stirred for 6 hours. 35% hydrochloric acid (HCl) was diluted 10-fold and slowly added to the stirred solution for 6 hours. After confirming that the pH was 1 to 2 by using a pH paper, chloroform and distilled water were used. (yield = 100%) of PEO ₃ -Tos (2- (2-methoxyethoxy) ethoxy) ethyl 4-methylbenzenesulfonate was synthesized by extracting the oily product (FIG. 1).

Production Example 2: PEO ₃ Synthesis of BDC

10 g of PEO ₃ -Tos, 5 g of dimethyl-5-hydroxy isophthalate (DHI, 23.79 mmol) and potassium carbonate (K ₂ CO ₃ , 16.43 g) synthesized in Preparation Example 1, Was mixed with methyl ethyl ketone (MEK, 300 mL) and subjected to a reflux reaction at 110 ° C for one day. After cooling the mixed solution, the solvent was removed using a rotary evaporator, and oily product in chloroform layer 3 was extracted with chloroform and distilled water. After 200 mL of ethanol was added to the product solution, the solution was slowly poured into 100 mL of distilled water and sodium hydroxide (NaOH, 23.324 g) was slowly poured into the solution. After cooling the mixed solution, 150 ~ 200 mL of solvent was removed with a rotary evaporator and the solvent was removed. Then, 35% hydrochloric acid was slowly added to the remaining solution to obtain a precipitate. The resulting precipitate was filtered while washing with a small amount of water to obtain a product in the form of a white powder, and vacuum dried (PEO ₃ -BDC, yield = 82%) [Fig.

Production Example 3: PEO ₆ Synthesis of -Tos

To a 200 mL beaker, add 9 mL (34.22 mmol) of hexaethylene glycol monomethyl ether, 13 g (68.2 mmol) of p-toluenesulphonyl chloride and 70 mL of tetrahydrofuran (THF) To the mixed solution, a solution prepared by dissolving 5.634 g of sodium hydroxide in 10 mL of distilled water was poured slowly, followed by stirring for 6 hours. 35% hydrochloric acid (HCl) was diluted 10-fold and slowly added to the stirred solution for 6 hours. After confirming that the pH was 1 to 2 by using a pH paper, chloroform and distilled water were used. (oily) by extracting the product, was synthesized from _{PEO 6 -Tos (2- (2- (} 2- (2- (2- (2-methoxyethoxy) ethoxy) ethoxy) ethoxy) ethoxy) ethyl 4-methylbenzenesulfonate) ( yield: = ~ 90%) [Fig. 5].

Production Example 4: PEO ₆ Synthesis of BDC

20 g of PEO ₆ -Tos, 5 g of dimethyl-5-hydroxy isophthalate (DHI, 23.79 mmol) and potassium carbonate (K ₂ CO ₃ , 16.43 g) synthesized in Preparation Example 3, Was mixed with methyl ethyl ketone (MEK, 300 mL) and subjected to a reflux reaction at 110 ° C for one day. After cooling the mixed solution, the solvent was removed using a rotary evaporator, and oily product in chloroform layer 3 was extracted with chloroform and distilled water. 200 mL of ethanol was added to the resulting product solution, and the solution was slowly poured into 100 mL of distilled water and sodium hydroxide (NaOH, 10.35 g) was slowly poured into the solution. After cooling the mixed solution, 150 ~ 200 mL of solvent was removed with a rotary evaporator and the solvent was removed. Then, 35% hydrochloric acid was slowly added to the remaining solution to obtain a precipitate. The resulting precipitate was filtered while washing with a small amount of water to obtain a brown powdery product, and vacuum dried (PEO ₆ -BDC, yield = 82%) (FIG. 7).

Example 1: Hydrophilic metal-organic polyhedra (PEO _x -MOP)

A mixture of a PEO _x -BDC (1.5g), dimethylformamide (DMF, 50 mL), Cu (CH 3 CO 2) 2 · H 2 O (0.86g, 4.73mmol) prepared from Preparative Example 2 or 4, Lt; / RTI > The dissolved blue solution was reacted in a Teflon reactor at 80 ° C for one day to synthesize PEO _x -MOP.

Example 2: PEO _x -MOP @ XLPEO gas separation membrane synthesis

8 g of polyethylene glycol diacrylate (PEDGA) and 2 g of poly (ethylene oxide) methyl ether acrylate (PEDMEA) were placed in a vial and mixed for 10 minutes, PEO ₃ -MOP (250 mg) synthesized from 1 was added thereto and dissolved by stirring for 2 hours. 100 mg (0.49 mmol) of 1-hydroxycyclohexyl phenylketone (HCPK) as an initiator of the radical polymerization was added to the dissolved solution and stirred for 1 hour. After stirring, 1.5 mL of the blue transparent solution was poured into a quartz plate, spread evenly, covered with a glass plate, and then subjected to radical polymerization through a UV device. At this time, the UV intensity was 100 mW / cm < 2 > and reacted for 30 minutes (Fig. 10).

On the other hand, Crosslinked polyethylene oxide (XLPEO) film ( Science 2006 , 311 , 639) was used as Comparative Example 1 with reference to the contents disclosed in the prior art.

FIGS. 2, 4, 6 and 8 show the ¹ H-NMR spectra of the materials prepared from Production Examples 1, 2, 3 and 4 of the present invention, respectively. Referring to the above figures, it can be seen that the synthesis of the material has been successful from each production example.

9 is an image showing the X-ray single crystal structure of the hydrophilic metal-organic polyhedron (PEO _x -MOP) prepared in Example 1 of the present invention. the results are as follow. X- ray crystal structure: Cubic, Pa -3, a = 39.547 (5), V = 61849 (12) Å 3, Z = 48, T = 100 K, ρ c a lc = 0.882 g / cm 3, R 1 _{= 0.1093, wR 2 = 0.3312,} GOF = 1.222.

11 is an image of a PEO _x -MOP @ XLPEO gas separation membrane produced from Example 2 of the present invention. Referring to FIG. 11, it can be confirmed that the gas separation membrane is blue due to the copper precursor contained in the metal-organic polyhedron.

Table 1 shows the gas separation characteristics of the gas separation membranes prepared in Example 2 of the present invention and the crosslinked polyethylene oxide membranes of Comparative Example 1 in a mixed gas of carbon dioxide and nitrogen.

Referring to Table 1, it can be seen that the gas separation membrane prepared from Example 2 of the present invention is much superior in CO ₂ / N ₂ selectivity to the crosslinked polyethylene oxide membrane of Comparative Example 1 that has been reported.

Membrane thickness N ₂ transmittance
(barrers) CO ₂ transmittance
(barrers) CO ₂ / N ₂ selectivity Comparative Example 1 480 ± 10 5.63 108.70 19.3 Example 1 350 ± 20 3.46 88.64 25.7

Therefore, according to the present invention, hydrophilic metal-organic polyhedra are prepared and mixed with the crosslinked polyethylene oxide polymer, so that it can be applied as a gas separation membrane having excellent CO ₂ / N ₂ selectivity.

Claims (17)

delete delete delete delete delete delete delete delete delete (a) reacting a metal precursor, a first solvent and a solution containing an organic ligand represented by the following structural formula 3 or 4, wherein the metal-organic polyhedron is represented by the following structural formula 1,
Wherein the metal precursor is a Cu precursor, the first solvent is dimethylformamide,
The organic ligand represented by the above structural formula 3 or 4 is
(a-I) reacting a solution containing dimethyl-5-hydroxyisophthalate, a second solvent and a monomer represented by the following structural formula 5 in the presence of a catalyst to obtain a first reaction solution;
(a-II) reacting a solution containing the first reaction solution, a third solvent and a hydroxide to obtain a second reaction solution; and
(a-III) adding an acid to the second reaction solution to obtain a precipitate. The method of producing a metal-organic polyhedron,
[Structural formula 1]

M < ₁ > and M < ₂ > are the same or different from each other and are respectively Cu2 ⁺ or Cu ⁺
Wherein S ₁ and S ₂ are each N, N-Dimethyl Formamide (DMF)
N is an integer from 3 to 100;
Wherein L ₁ , L ₂ , L ₃ and L ₄ are the same or different and each independently an organic ligand represented by the following structural formula 3 or 4,
[Structural Formula 3]

[Structural Formula 4]

[Structural Formula 5]

Y is an integer of 1 to 20; delete delete delete delete 11. The method of claim 10,
The second solvent and the third solvent may be the same or different from each other and may be independently selected from the group consisting of N, N-Dimethyl Formamide (DMF), Methyl ethyl ketone (MEK), formaldehyde (FA) N-diethyl formamide (DEF), dimethylacetamide (DMA), methanol, MeOH, ethanol, EtOH, Tetrahydrofuran, THF, water, H ₂ O), 1-methyl-2-pyrrolidinone (NMP), dimethyl sulfoxide (DMSO), diethyl ether And mixtures thereof. ≪ RTI ID = 0.0 > 11. < / RTI > delete delete

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