KR102339455B1 - Hybrid membrane comprising zeolitic imidazolate framework nanoparticles and method of gas separation using the same - Google Patents

Abstract

The present invention relates to a hybrid membrane in which nanoparticles having a zeolite imidazolate-based structure are mixed and a gas separation method using the same. The hybrid membrane according to the present invention includes nanoparticles including a polymer matrix and a zeolite imidazolate-based structure dispersed in the polymer matrix.

Description

Hybrid membrane containing nanoparticles containing a zeolite imidazolate-based structure and a gas separation method using the same

The present application relates to a hybrid membrane in which zeolitic imidazolate framework (ZIF) nanoparticles having improved compatibility with a polymer are evenly dispersed in a polymer matrix, and a gas separation method using the hybrid membrane.

Metal organic frameworks (MOFs) are relatively new hybrid organic-inorganic materials as microporous crystalline materials composed of metal atoms or metal clusters and organic ligands connecting them by coordination bonds.

The pore size and physical/chemical properties of MOFs can be controlled by selection of appropriate metal atoms and organic ligands.

In addition, through an additional chemical reaction on the MOF, a hybrid-type MOF can be synthesized by substituting a metal atom and an organic ligand, which are components of the MOF, with another metal atom and an organic ligand, and depending on the degree of substitution, the pore size and physical/chemical Further control of the properties is possible. Because of these special properties of MOFs, they have shown potential applications as gas storage and/or absorption, catalysis, and separation membranes.

In particular, zeolitic imidazolate frameworks (ZIF), as a sub-concept of metalorganic frameworks, consist of metal nodes (usually zinc or cobalt) linked to imidazolate (or imidazolate derivative) ligands. .

US 9527872 B2

An object of the present application is to provide a hybrid membrane in which zeolitic imidazolate framework (ZIF) nanoparticles with improved compatibility with a polymer are evenly dispersed in a polymer matrix, and a gas separation method using the hybrid membrane.

However, the problem to be solved by the present application is not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

An object of the present invention is a polymer matrix; And it is achieved by a hybrid membrane comprising nanoparticles comprising a zeolite imidazolate-based structure dispersed in the polymer matrix.

The nanoparticles, metal ions and; and an organic ligand bound to the metal ion, and the organic ligand may include an imidazolate-based organic ligand and an alkylamine-based organic ligand.

In the nanoparticles, at least one of the spacing of the crystal planes, the distribution of the crystal planes, and the bonding strength is controlled according to the ratio of the use ratio of the alkylamine-based organic ligand, and the alkylamine-based organic ligand is directly bonded to the metal ion. can

In the organic ligand, a ratio of the imidazolate-based organic ligand to the alkyl amine-based organic ligand may be 99.9 wt%: 0.1 wt% to 80 wt% to 20 wt%.

When the metal ion is cobalt, the spacing between the (011) crystal planes of the AZIF nanoparticles is 11.9 Å to 12.15 Å, and when the metal ion is zinc, the (011) crystal plane spacing of the AZIF nanoparticles is 12.0 Å to 12.25 Å can be

The nanoparticles may have a size of 100 nm or less, and the pores may be 0.1 nm to 1 nm.

The nanoparticles exhibit a mass reduction of 3% or less within 400° C. in the TGA experiment, and when the metal ion is cobalt, the IR peak of Co-N of the AZIF nanoparticles is 1 to 1 by the alkylamine-based organic ligand. It increases by 3 cm ^-1 , and when the metal ion is zinc, the IR peak of Zn-N of the AZIF nanoparticles may increase ^{by 1.5 to 4 cm -1 by the alkylamine-based organic ligand.}

The content of the nanoparticles in the film may be 15% to 60% by weight.

The content of the nanoparticles in the film may be 30% to 60% by weight.

The thickness of the film may be 50 nm to 100 μm.

The polymer matrix may include any one selected from the group consisting of polyimide, polysulfone (PSF), polyisosulfone (PES), cellulose acetate (CA), polydimethylsiloxane (PDMS), and polyvinyl acetate (PVAc). have.

The film can separate gases having a molecular size difference of 0.1 Å to 5 Å from each other.

The membrane is C ₃ H ₆ /C ₃ H ₈ , C ₂ H ₄ /C ₂ H ₆ , CO ₂ /CH ₄ , CO ₂ /CO, CO ₂ /N ₂ , N ₂ /CH ₄ , and nC ₄ /iC ₄ (n-butane/iso-butane), H ₂ /CH ₄ , H ₂ /C ₃ H ₈ and H ₂ /C ₃ H _{6 It} is possible to separate a mixed gas of a gas set selected from the group consisting of: have.

When the central atom of the nanoparticles is cobalt, _{the transmittance of the nanoparticles to C 3} H ₆ at 35° C. is 200 to 400 Barrer, and the C ₃ H ₆ /C ₃ H ₈ selectivity is 270 to 400, and the nanoparticles When the central atom is zinc, _{the permeability of the nanoparticles to C 3} H ₆ at 35° C. may be 300 to 600 Barrer, and the C ₃ H ₆ /C ₃ H ₈ selectivity may be 140 to 300.

The central atom of the nanoparticles and zinc, at 35 ℃ transmission rate for the film C ₃ H ₆ is 40 to 80 Barrer may be a _{C 3 H 6 / C 3 H} 8 selectivity of 22 to 40.

The central atom of the nanoparticle comprises a cobalt, is from 35 ℃ transmission rate for the film C ₃ H ₆ 40 to 70Barrer may be a _{C 3 H 6 / C 3 H} 8 selectivity of 33 to 60.

A central atom of the nanoparticles includes cobalt, and the C ₃ H ₆ /C ₃ H ₈ energetic selectivity of the film may be 1,000 to 10,000.

The object of the present invention is achieved by a gas separation method comprising the step of separating one or more gases from a mixed gas including two or more gases using the hybrid membrane.

By passing the mixed gas through the membrane, the gases may be separated from each other using a difference in molecular size of the gases included in the mixed gas.

The difference in molecular size of the gases included in the mixed gas may be 0.1 Å to 5 Å.

The hybrid membrane according to the present application has an interface with good compatibility between the polymer and the nanoparticles, so that excellent separation performance can be achieved depending on the target gas to be separated. Accordingly, the hybrid membrane can improve the separation performance of the conventional polymer membrane, in particular H ₂ /CH ₄ , H ₂ /C ₃ H ₆ , H ₂ /C ₃ H _{8 as} well as C ₃ H ₆ /C ₃ H ₈ , C ₂ H ₄ /C ₂ H ₆ , CO ₂ /CH ₄ , CO ₂ /CO, CO ₂ /N ₂ , N ₂ /CH ₄ and n-C4/i-C4 (n-butane/iso- It can effectively separate gas molecules that are difficult to separate, such as butane).

1, in the Example of the present application, the synthesis process of AZIF-67 particles is expressed as a change in reaction temperature with time, and at this time, the color of the solution at each step and the size change of the particles at this time are dynamic light scattering (dynamic light scattering, This is a graph showing the results of analysis by DLS) spectroscopy.
2 is a basic structural formula that can be shown when AZIF-67 nanoparticles are synthesized using various alkylamines.
3 is a diagram showing the structure of rombic octahedron, which is the structure of nanoparticles, and (110) and (200) crystal planes and inter-crystal spacing in the Example of the present application, and the reaction solution when synthesizing AZIF-67 nanoparticles It is an XRD graph of the AZIF-67 nanoparticles obtained according to the amount of Bu3N introduced into the
4 is an XRD graph of AZIF-67 into which various alkylamines synthesized according to the Examples of the present application are introduced.
5 is an XRD graph of AZIF-8 synthesized according to an embodiment of the present application.
6 is a SEM image of ZIF-67 nanoparticles and general ZIF-67 nanoparticles into which various alkylamines synthesized according to the examples of the present application are introduced.
Figure 7, in the embodiment of the present application, AZIF-8-Bu ₃ N5 and general ZIF-8 and AZIF-67-Bu ₃ N5 and general ZIF-67 according to the concentration of each sample dispersed in the NMP solvent according to time A photograph showing the degree of dispersion.
8 is a photograph showing dispersion stability after 3 days after dispersing AZIF-67-Bu ₃ N5 and general ZIF-67 in the NMP solvent for each concentration in the Example of the present application.
9 is a photograph of a hybrid film prepared when AZIF-67 and general ZIF-67 nanoparticles are dispersed in high concentration in 6FDA-DAM polyimide (PI) polymer in Example of the present application.
10 is a photograph of a hybrid membrane prepared by dispersing AZIF-67 and AZIF-8 nanoparticles at high concentrations in various polymers including PSF and PI-based polymers in an example of the present application.
11 is an image analyzed through SEM of a cross-section of a hybrid membrane prepared by dispersing AZIF-67 nanoparticles in various polymer materials in an example of the present application.
12 is a TGA analysis result of AZIF-67 nanoparticles and AZIF-8 introduced with various alkylamines according to an example of the present application.
13 is an image analyzed by a scanning electron microscope (SEM) of a phenomenon in which particles are agglomerated and formed into chunks when an alkylamine group is introduced into the AZIF-67 reaction solution in the Example of the present application.
^{FIG. 14 is 1} H NMR spectra obtained by decomposing AZIF-67 nanoparticles into which butylamines of various amounts and types were introduced, synthesized according to Examples of the present application, with acid.
15 is a photograph of _{AZIF-67-Bu 3} N5 nanoparticles obtained at one time through a large-capacity reaction in an example of the present application.
^{16 is a 1} H NMR spectra obtained by decomposing AZIF-67 nanoparticles with acid according to the amount of tributylamine introduced into the reaction during synthesizing AZIF-67 nanoparticles in an Example of the present application.
^{17 is a 1} H NMR spectra _{obtained by decomposing AZIF-8-Bu 3} N5 nanoparticles with an acid according to an example of the present application.
18 is a BET isothermal graph of AZIF-67 and AZIF-8 nanoparticles according to an example of the present application.
19 is an FT-IR graph analyzing the ionic bond strength between metals and organic ligands of AZIF-8 and AZIF-67 in Examples of the present application.
20 is a graph showing the weight % of AZIF-67 nanoparticles in a hybrid membrane prepared using AZIF-67 nanoparticles synthesized according to an example of the present application through thermogravimetric analysis.
21 is a 6FDA-DAM polyimide (PI) polymer film, a hybrid film in which 20 wt% of ZIF-67 nanoparticles not treated with alkylamine are mixed, and AZIF- into which the synthesized alkylamine group is introduced, according to an example of the present application. _{It is a graph showing the C 3} H ₆ /C ₃ H ₈ single gas separation performance according to the temperature of the hybrid membrane prepared by mixing 20wt% of 67 nanoparticles.

Hereinafter, with reference to the accompanying drawings, embodiments and examples of the present invention will be described in detail so that those of ordinary skill in the art to which the present invention pertains can easily carry out. However, the present application may be embodied in several different forms and is not limited to the embodiments and examples described herein. And in order to clearly explain the present invention in the drawings, parts irrelevant to the description are omitted, and similar reference numerals are attached to similar parts throughout the specification.

Throughout this specification, when a part is said to be "connected" to another part, it includes not only the case where it is "directly connected" but also the case where it is "indirectly connected" with another member interposed therebetween. do.

Throughout this specification, when a member is said to be located “on” another member, this includes not only a case in which a member is in contact with another member but also a case in which another member is present between the two members.

Throughout this specification, when a part "includes" a certain element, it means that other elements may be further included, rather than excluding other elements, unless otherwise stated.

As used herein, the terms "about," "substantially," and the like are used in a sense at or close to the numerical value when the manufacturing and material tolerances inherent in the stated meaning are presented, and to aid in the understanding of the present application. It is used to prevent an unconscionable infringer from using the mentioned disclosure in an unreasonable way.

As used throughout this specification, the term “step of doing” or “step of” does not mean “step for”.

Throughout this specification, the term "combination(s) of these" included in the expression of the Markush form means one or more mixtures or combinations selected from the group consisting of the components described in the expression of the Markush form, It means to include one or more selected from the group consisting of the above components.

Throughout this specification, reference to “A and/or B” means “A or B, or A and B”.

Throughout this specification, “nanoparticles comprising a zeolite imidazolate-based structure” may be abbreviated as “nanoparticles having a ZIF structure” or “ZIF nanoparticles”. In addition, "Nanoparticles having a controlled crystal structure while simultaneously including an imidazolate-based organic ligand and an alkylamine-based organic ligand that is a heterogeneous non-imidazolate-based structure having a zeolite imidazolate-based structure” means “a nanoparticle having an AZIF structure” may be abbreviated as “nanoparticles”, “AZIF nanoparticles” or, where appropriate, “nanoparticles”.

In the present specification, ZIF-67 and AZIF-67 indicate a case in which the metal ion is cobalt, and ZIF-8 and AZIF-8 indicate a case in which the metal ion is zinc. For example, AZIF-67-Bu3N5 represents AZIF nanoparticles in which the metal ion is cobalt, prepared by adding tertiary butylamine as an alkylamine in a molar ratio 5 times that of the metal ion precursor. In addition, the display of other AZIF nanoparticles can be understood through the example above.

In the following description, a case in which the hybrid membrane is mainly used as a gas separation membrane is exemplified, but the use of the hybrid membrane of the present application is not limited thereto.

Hereinafter, embodiments and examples of the present application will be described in detail with reference to the accompanying drawings. However, the present application is not limited to these embodiments and examples and drawings.

AZIF nanoparticles including an imidazolate-based organic ligand including a zeolite imidazolate-based structure and a heterogeneous non-imidazolate-based alkylamine-based organic ligand according to an exemplary embodiment of the present application include, In the rate-based alkyl amine type, there may be ethyl amine, propyl amine, butyl amine, diethyl amine, dipropyl amine, dibutyl amine, diethyl amine, tripropyl amine, tributyl amine, etc., but is not limited thereto.

In one embodiment of the present application, the alkyl amine includes primary, secondary and/or tertiary amines and includes alkyl chains of various lengths (FIG. 2). For example, methyl, ethyl, propyl, butyl, pentyl, hexyl, eptyl, octyl, nonyl, decyl, undecyl, dodecyl, propadecyl, butadecyl, pentadecyl, hexadecyl, eptadecyl, octadecyl, noda One or more of decyl may be used, but is not limited thereto.

In one embodiment of the present application, the ratio of the imidazolate-based organic ligand to the alkylamine-based organic ligand in the AZIF nanoparticles may be 99.9 wt%: 0.1 wt% to 80 wt%: 20 wt% (Table 1) .

In one embodiment of the present application, the spacing between the crystal planes in the crystal structure of the AZIF nanoparticles is reduced compared to the ZIF nanoparticles. More specifically, in the (011) crystal plane of the AZIF-67 nanoparticles, the (011) interplanar spacing was decreased by about 0.2 Å from (D) 12.30 Å to a maximum of 12.15 Å when compared with ZIF-67 nanoparticles ( 3), the interval can be adjusted according to the degree to which tributylamine is introduced. However, the molar ratio of tributylamine introduced during synthesis was reduced to a maximum at 5 or more, and the spacing between crystal planes did not change any more even if introduced more. The change between the crystal planes can be changed by the chemical bond strength between the metal ion and the organic ligand, the interaction energy between the organic ligand and the gradient change due to the size of the organic ligand, and the mechanical bond strength between the bonding materials, which is a characteristic inherent to a specific material. will be affected When the second organic ligand is introduced, such a change in crystal structure and properties will eventually affect the pore structure of the AZIF nanoparticles. However, the change in the spacing between crystal planes does not directly give a specific tendency to the change in the pore structure of AZIF nanoparticles, and the aforementioned chemical mechanical bond strength between metal ions and organic ligands and the interaction energy and space of organic ligands Under normal conditions, the pore structure and its size may change differently depending on the degree of inclination.

The spacing of the (011) crystal planes of the AZIF nanoparticles in AZIF-67 may be 11.9 Å to 12.15 Å, and the spacing between the (011) crystal planes of the AZIF nanoparticles in AZIF-8 may be 12.0 Å to 12.25 Å.

In one embodiment of the present application, when an excess of tributylamine is introduced during synthesis, (022) and (112) crystal planes grow larger compared to (011) crystal planes (FIG. 3). In addition, when the molar ratio of tributylamine to the metal precursor is 2 to 5, the ratio of each crystal plane is similar, but when the molar ratio is 10, the (022) and (112) crystal planes grow larger compared to the (011) plane (Fig. 3). This phenomenon is due to the fact that when growing on AZIF-67 nanoparticles, the phase of alkylamine in solution becomes as large as methanol, at this time (011), due to maximization of interaction with the crystal plane, the growth of AZIF-67 nanoparticles is (022) and (112) crystal planes may lead to more dominant growth in In this case, when trihexylamine, which has low compatibility with methanol, is used as the second organic ligand in one embodiment, the (022) and (112) planes grow significantly despite using a 5 molar ratio compared to the metal precursor. It can be confirmed by doing (FIG. 4). On the other hand, when triethylamine and tripropylamine, which have good compatibility with a methanol solvent, such as tributylamine, are used, a tendency similar to that when tributylamine is used is shown.

In one embodiment of the present application, the crystal structure of the AZIF-8 nanoparticles showed a change in crystal properties similar to that of the AZIF-67 nanoparticles when compared to the general ZIF-8 nanoparticles (FIG. 5).

In one embodiment of the present application, the size of the nanoparticles may be 100 nm or less, 5 nm to 100 nm or 5 nm to 50 nm ( FIGS. 1 and 6 ), but is not limited thereto. The size of the nanoparticles may vary depending on the type of the metal precursor, but may be 100 nm or less, which is a particle size suitable for manufacturing a mixed matrix membrane (MMM) and exhibiting high gas separation performance. In general, as the particle size decreases, the specific surface area in contact with the polymer increases, contributing to improving compatibility with the polymer. For example, the size of the nanoparticles is about 100 nm or less, about 80 nm or less, about 60 nm or less, about 50 nm or less, about 40 nm or less, about 30 nm or less, about 20 nm or less, about 10 nm or less, about 1 nm to about 100 nm, about 5 nm to about 50 nm, or about 10 nm to about 30 nm, but is not limited thereto.

In one embodiment of the present application, the nanoparticles may have improved dispersibility in an organic solvent, particularly an amphiphilic solvent (FIG. 7). The organic solvent may be an amphiphilic solvent such as N-methyl pyrrolidone (NMP) or dimethylformamide (DMF), but is not limited thereto.

In one embodiment of the present application, AZIF-67 and AZIF-8 nanoparticles may be dispersed to a concentration of about 110 mg/mL with respect to the organic solvent ( FIG. 7 ), but is not limited thereto. For example, the dispersion concentration of the nanoparticles in the organic solvent is about 10 mg/mL to about 110 mg/mL, about 10 mg/mL to about 90 mg/mL, about 10 mg/mL to about 70 mg/mL mL, about 10 mg/mL to about 50 mg/mL, about 10 mg/mL to about 30 mg/mL, about 10 mg/mL to about 20 mg/mL, about 20 mg/mL to about 100 mg/mL, about 20 mg/mL to about 80 mg/mL, about 20 mg/mL to about 60 mg/mL, about 20 mg/mL to about 40 mg/mL, about 30 mg/mL to about 100 mg/mL, about 30 mg/mL to about 80 mg/mL, about 30 mg/mL to about 60 mg/mL, or It may be about 30 mg/mL to about 40 mg/mL, but is not limited thereto. The dispersion concentration may be about 110 mg/mL or more, but agglomeration may occur.

In one embodiment of the present application, when dispersed in NMP through sonication, in the case of AZIF-67-Bu ₃ N5 particles or AZIF-8-Bu ₃ N5 particles, even at a high concentration of 110 mg/mL, water bath sonication in less than 1 minute Dispersion is possible even in treatment, and preferably, high concentration dispersion is possible even in 30 seconds or less, and at a low concentration of 10 mg/mL, dispersion is possible even in a time of 10 seconds or less. On the other hand, in the case of ZIF-67 and ZIF-8, it was confirmed that particles were not dispersed when water bath sonication was treated for the same time as AZIF-67 particles and AZIF-8 particles, and complete dispersion despite the low concentration of 10 mg/mL This was not done, and it was confirmed that the sonication was stopped and a sediment was formed on the floor at the same time (FIG. 7). 7 shows the concentration and sonication time of each sample.

In one embodiment of the present application, the AZIF-67-Bu ₃ N5 and AZIF-8-Bu ₃ N5 nanoparticles show long-term dispersion stability in the organic solvent and the period may be 3 days or 7 days (Fig. 8), but is not limited thereto. 8 is a photograph of a state in which the experimental sample of FIG. 7 was left for 3 days. More specifically, in the case of AZIF-67-Bu ₃ N5 and AZIF-8-Bu ₃ N5 nanoparticles, their dispersibility was maintained even after 3 days despite high concentration dispersion of 110 mg/mL after 40 seconds of water bath sonication treatment. On the other hand, in the case of ZIF-67 and ZIF-8, almost all particles were found to be precipitated even at a low concentration of 10 mg/mL 3 days after the 20-minute water bath sonication treatment. Through this, it was possible to confirm the long-term dispersion stability of the developed AZIF-67 and AZIF-8 nanoparticles (FIG. 8).

In one embodiment of the present application, the pore size of the AZIF nanoparticles may be about 1 nm or less or less. For example, the pore size of the nanoparticles including the zeolite imidazolate-based structure is about 0.1 nm to about 1 nm, about 0.1 nm to about 0.9 nm, about 0.1 nm to about 0.8 nm, about 0.1 nm to about 0.7 nm, about 0.1 nm to about 0.6 nm, about 0.1 nm to about 0.5 nm, about 0.2 nm to about 1 nm, about 0.2 nm to about 0.9 nm, about 0.2 nm to about 0.8 nm, about 0.2 nm to about 0.7 nm, It may be about 0.2 nm to about 0.6 nm, or about 0.2 nm to about 0.5 nm, but is not limited thereto.

Based on XRD analysis, it is known that ZIF-7 has a pore size of 0.29 nm, ZIF-67 has a pore size of 0.33 nm, and ZIF-8 has a pore size of 0.34 nm. Various pore sizes can be adjusted.

In one embodiment of the present application, a hybrid membrane (composite film, composite membrane, hybrid film, separator) in which AZIF-67 and/or AZIF-8 nanoparticles are dispersed in a high concentration in a polymer matrix is provided. (FIGS. 9 and FIG. 10).

In one embodiment of the present application, the content of AZIF nanoparticles dispersed in the polymer matrix in the hybrid membrane may be about 15% by weight, about 20% by weight, or 30% by weight or more based on the total weight of the separator ( Fig. 9). For example, the content of the AZIF nanoparticles may be 15% by weight, 20% by weight, 30% by weight, 40% by weight, or 50% by weight or more based on the total weight of the separator. The upper limit of the content may be, but is not limited to, 60% by weight, 70% by weight or 80% by weight. On the other hand, in the case of ZIF-67 and ZIF-8, a non-uniform film was produced even when 30 wt% was introduced, and a hybrid film was not formed at 40 wt% or more.

In one embodiment of the present application, the hybrid membrane has flexible properties (FIG. 9). For example, a hybrid membrane containing 40% by weight of AZIF-67 exhibits folding properties without deformation to its original shape. On the other hand, in the case of ZIF-67, in the case of a hybrid membrane containing 40 wt%, it was easily broken.

In one embodiment of the present application, in the case of AZIF-67 and AZIF-8 introduced in the hybrid membrane, the nanoparticles are a hybrid membrane in which AZIF nanoparticles are introduced at a high concentration not only in a polyimide-based polymer matrix but also in various engineering polymer materials. painting is possible (FIG. 10). For example, in the case of polysulfone polymer material, when 40 wt% of AZIF nanoparticles were introduced, a hybrid membrane could be prepared, which also showed flexible properties (FIG. 10).

As the polymer used in the hybrid membrane of the present application, a general glassy or rubbery material may be used. Specifically, at least one of polyimide, polysulfone (PSF), polyisosulfone (PES), cellulose acetate (CA), polydimethylsiloxane (PDMS), and polyvinyl acetate (PVAc) may be used, but is not limited thereto. Polymers may also use a polymer of intrinsic microporosity.

In one embodiment of the present application, the AZIF nanoparticles introduced into the hybrid membrane can be uniformly dispersed in the polymer even at a high concentration. For example, even in the case of a hybrid membrane in which 40 wt% of AZIF nanoparticles are introduced, it has a uniform surface without phase separation on the film surface ( FIGS. 9 and 10 ). It becomes uniformly dispersed (FIG. 11). On the other hand, in the case of general ZIF-67 nanoparticles, when 30 wt% was introduced, it was found that the particles agglomerate.

In one embodiment of the present application, the AZIF nanoparticles introduced into the hybrid membrane have high interfacial adhesion (or compatibility) with various engineering polymer materials including polyimide-based polymer materials ( FIG. 11 ). For example, 6FDA-DAM, Ultem ^® , Matrimid 5218 ^® , and shows good interfacial adhesion with polymer materials such as PSF, but is not limited thereto. On the other hand, in the case of ZIF nanoparticles, it was found that clusters were formed due to aggregation of particles and voids were formed at the interface with the polymer (FIG. 11).

In one embodiment herein, the thickness of the hybrid film prepared by dispersing AZIF nanoparticles in a high concentration in a polymer matrix may be 50 nm or more, or 100 nm or more. The upper limit of the thickness is not limited thereto, but may be 10 μm, 50 μm, 100 μm, 200 μm, or 500 μm. In the case of a composite film pre-standing film, it may be 10 μm or less, but is not limited thereto.

In one embodiment of the present application, the hybrid membrane may be used as a separation membrane to separate one or more gases from a mixed gas including two or more gases. For example, by passing the mixed gas through the hybrid membrane, the gases may be separated from each other using a difference in molecular size of gases included in the mixed gas.

In one embodiment of the present application, the hybrid film may be formed using only AZIF nanoparticles as nanoparticles, but is not limited thereto. For example, AZIF nanoparticles and ZIF nanoparticles may be mixed and used, and two or more types of AZIF nanoparticles may be used.

In one embodiment of the present application, the difference in molecular size of the gases included in the mixed gas may be about 0.1 Å to about 5 Å, but is not limited thereto.

In one embodiment of the present application, the mixed gas is H ₂ /CH ₄ , H ₂ /C ₃ H ₆ , H ₂ /C ₃ H _{8 as} well as C ₃ H ₆ /C ₃ H ₈ , C ₂ H ₄ of the gas set consisting of /C ₂ H ₆ , CO ₂ /CH ₄ , CO ₂ /CO, CO ₂ /N ₂ , N ₂ /CH ₄ and n-C4/i-C4 (n-butane/iso-butane). It may include a gas set selected from the group, but is not limited thereto.

In one embodiment of the present application, the AZIF nanoparticles included in the hybrid membrane are H ₂ /CH ₄ , H ₂ /C ₃ H ₆ , H ₂ /C ₃ H _{8 as} well as C ₃ H ₆ /C ₃ H ₈ , C ₂ H ₄ /C ₂ H ₆ , CO ₂ /CH ₄ , CO ₂ /CO, CO ₂ /N ₂ , N ₂ /CH ₄ and n-C4/i-C4 (n-butane/iso-butane ) has improved separation selectivity within the gas set of

In one embodiment of the present application, the AZIF nanoparticles may have improved C ₃ H ₆ permeability and C ₃ H ₆ /C ₃ H _{8 selectivity for C 3} H ₆ /C ₃ H ₈ gas, but limited thereto it is not going to be

In one embodiment of the present application, the hybrid membrane may have a transmittance of about 1 Barrer or more to _{the C 3} H _{6 gas, but is not limited thereto.} For example, the hybrid membrane may have a permeability of about 1 Barrer or more, about 10 Barrer or more, about 20 Barrer or more, about 30 Barrer or more, about 40 Barrer or more, or about 50 Barrer or more, for _{the C 3} H _{6 gas,} However, the present invention is not limited thereto.

In another embodiment of the present application, the hybrid membrane may have a permeability of about 10 Barrer to about 100 Barrer for _{the C 3} H _{6 gas, but is not limited thereto.} For example, the hybrid membrane is the C ₃ H ₆ The gas permeability is about 10 Barrer to about 100 Barrer, about 10 Barrer to about 80 Barrer, about 10 Barrer to about 60 Barrer, about 10 Barrer to about 40 Barrer, about 10 Barrer to about 20 Barrer, about 30 Barrer to about 100 Barrer, about 50 Barrer to about 100 Barrer, about 70 Barrer to about 100 Barrer, or about 90 Barrer to about 100 Barrer, but is not limited thereto.

In one embodiment of the present application, the hybrid film may have a selectivity of about 1 or more to the _{C 3} H ₆ /C ₃ H _{8 gas, but is not limited thereto.} For example, the hybrid membrane _{may have a selectivity for C 3} H ₆ /C ₃ H ₈ gas of about 1 or more, about 10 or more, about 20 or more, about 30 or more, about 40 or more, or about 50 or more, It is not limited.

In another embodiment of the present application, the hybrid membrane _{may have a separation selectivity for C 3} H ₆ /C ₃ H ₈ gas of about 10 to about 100, but is not limited thereto. For example, the hybrid membrane _{may have a separation selectivity for C 3} H ₆ /C ₃ H ₈ gas of about 10 to about 100, about 10 to about 80, about 10 to about 60, about 10 to about 40, about 10 to about 20, about 30 to about 100, about 50 to about 100, about 70 to about 100, or about 90 to about 100, but is not limited thereto.

AZIF-67 nanoparticles may have a transmittance of 200 to 400 Barrer for _{C 3} H _{8 at 35° C., and a selectivity of C 3} H ₆ /C ₃ H ₈ of 270 to 400. AZIF-8 nanoparticles may have a transmittance of 300 to 600 Barrer for _{C 3} H _{8 at 35° C., and a selectivity of C 3} H ₆ /C ₃ H ₈ of 140 to 300.

The hybrid membrane containing AZIF-8 nanoparticles has a transmittance of 40 to 50, 40 to 80, or 70 to 80 Barrer for _{C 3} H _{8 at 35° C. and a selectivity of C 3} H ₆ /C ₃ H ₈ of 22 to 30, 22 to 40 or 30 to 40. In particular, when 40 wt% or more of AZIF-8 nanoparticles are included _{, the transmittance for C 3} H ₈ is 70 to 80 Barrer, and C ₃ H ₆ /C ₃ H ₈ The selectivity may be between 30 and 40.

The hybrid membrane containing AZIF-67 nanoparticles has a transmittance of 40 to 50, 40 to 70, or 60 to 80 Barrer for _{C 3} H _{8 at 35° C., and C 3} H ₆ /C ₃ H ₈ The selectivity may be from 33 to 40, from 33 to 60 or from 50 to 60. In particular, the selectivity of AZIF-67 nanoparticles by 40 weight C ₃ H ₆ /C ₃ H ₈ may be 50 to 60.

_{The C 3} H ₆ /C ₃ H ₈ energetic selectivity of the hybrid membrane including the AZIF-67 nanoparticles may be 1,000 to 5,000 or 1,000 to 10,000.

In one embodiment of the present application, the AZIF nanoparticles have a characteristic of high purity. The purity may be 99% or more or 99.5% or more, but is not limited thereto. For example, in the case of an unreacted organic ligand that may be an impurity, it is decomposed at a low temperature, whereas AZIF nanoparticles are thermally stable up to about 400°C (FIG. 12). Comparing the TGA graphs of AZIF nanoparticles and ZIF nanoparticles, AZIF does not show any weight change at high temperatures over 400℃, but in general ZIF-67 and ZIF-8, the weight changes from below 300℃, especially for ZIF-8. In the case of AZIF-67 and AZIF-8, it was confirmed that the developed AZIF-67 and AZIF-8 had relatively high purity through the change in weight from about 180°C, which is the decomposition temperature of the organic ligand (FIG. 12).

AZIF nanoparticles may exhibit a mass reduction of 3% or less at 400° C. under the TGA experimental conditions of the present application, specifically, a mass reduction of 0.01% to 3%, 0.01% to 2%, or 0.1% to 2%.

A second aspect of the present application is a method for producing AZIF nanoparticles, wherein a precursor solution including a metal precursor, an imidazole-based ligand compound and a first polar solvent is heated under stirring, and an organic base solution is added to the precursor solution heated under stirring was added to obtain a suspension containing micro-sized chunks containing a zeolite imidazolate-based structure whose crystal structure was controlled, and a second polar solvent was added to the suspension heated under stirring to prepare the suspension. It provides a method for producing AZIF nanoparticles, comprising diluting and filtering the diluted suspension to obtain nanoparticles comprising the zeolite imidazolate-based structure.

In order to prepare AZIF nanoparticles according to an embodiment of the present application, first, a precursor solution including a metal precursor, an imidazole-based ligand compound, and a first polar solvent is heated under stirring.

In the method for producing AZIF nanoparticles according to an embodiment of the present application, unlike the ZIF particle synthesis method, the metal precursor and the imidazole-based ligand compound are simultaneously put and dissolved together, or the metal precursor and the imidazole-based ligand compound are separately prepared. It involves mixing after dissolving.

In one embodiment of the present application, the metal precursor may include an acetate-based metal salt, but is not limited thereto. For example, the metal precursor may include, but is not limited to, cobalt (Co) acetate tetrahydrate metal salt, zinc (Zn) acetate dihydrate metal salt, and the like.

In one embodiment of the present application, the metal precursor is Co, Zn, Sc, Ti, V, Cr, Mn, Fe, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd , Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Lr, Rf, Db, Sg, Bh, Hs, Mt, Ds, Rg and at least one metal selected from the group consisting of Uub It may include an acetate salt, but is not limited thereto.

In one embodiment of the present application, the imidazole-based ligand compound may include one or more selected from imidazole-based compounds represented by the following Chemical Formula 1 or Chemical Formula 2, but is not limited thereto:

[Formula 1]

;

;

[Formula 2]

;

;

In each of Formula 1 and Formula 2,

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently H, a C1 to C10 linear or branched alkyl group, halogen, hydroxy, cyano, nitro or aldehyde group ego,

A ¹ , A ² , A ³ , and A ⁴ are each independently C or N, provided that R ⁵ , R ⁶ , R ⁷ , and R ⁸ are present only when ^{A 1} and A ^{4 are C} .

In one embodiment of the present application, the molar ratio of the metal precursor and the imidazole-based ligand compound may be from about 1:1 to about 1:10, and may be 1:2, but is not limited thereto. For example, the molar ratio of the metal precursor and the imidazole-based ligand compound is about 1:1 to about 1:10, about 1:1 to about 1:8, about 1:1 to about 1:6, about 1: 1 to about 1:4, about 1:1 to about 1:2, about 1:2 to about 1:10, about 1:2 to about 1:8, about 1:2 to about 1:6, about 1: 2 to about 1:4, or about 1:1 to about 1:2, but is not limited thereto.

In one embodiment of the present application, the first polar solvent comprises at least one selected from the group consisting of alcohol, ethylene glycol, water, dimethylformamide, dimethyl sulfoxide, acetonitrile and dimethylacetamide. may be, but is not limited thereto. However, as the first polar solvent, a solvent capable of causing a dehydrogenation reaction to the ligand used due to its high basicity cannot be used.

In one embodiment of the present application, the concentration of the metal precursor in the precursor solution may be about 0.01 M to about 0.4 M, but is not limited thereto. For example, the concentration of the metal precursor in the precursor solution is from about 0.01 M to about 0.4 M, from about 0.01 M to about 0.3 M, from about 0.01 M to about 0.2 M, from about 0.01 M to about 0.1 M, from about 0.01 M to about 0.05 M, about 0.05 M to about 0.4 M, about 0.08 M to about 0.4 M, about 0.08 M to about 0.3 M, about 0.08 M to about 0.2 M, about 0.1 M to about 0.4 M, about 0.1 M to about 0.3 M, or about 0.1 M to about 0.2 M, but is not limited thereto.

In one embodiment of the present application, the heating temperature of the precursor solution may be in the range of about 30 °C to about 90 °C, but is not limited thereto. For example, the heating temperature of the precursor solution may be from about 30°C to about 80°C, from about 30°C to about 70°C, from about 30°C to about 65°C, from about 30°C to about 60°C, or from about 30°C to about 50°C. ℃ may be, but is not limited thereto.

In one embodiment of the present application, the heating temperature of the precursor solution may be maintained isothermal, but is not limited thereto. The precursor solution is a solution in a transparent state, and may be in a state in which crystalline ZIF particles are not formed. In this case, one of the metal (M) salts of the metal precursor and the ligand (L) of the imidazole-based ligand compound are present in a bonded state, and have a structure as shown in Chemical Formula 4 below. As shown in Chemical Formula 4 below, the basic structure is L-M-L, and the amine of the ligand is in a state in which dehydrogenation is hardly progressed, and binding to one or more metal ions is difficult. However, even if the amine of the imidazole-based ligand compound is dehydrogenated to form ZIF nanoparticles, it is a precursor aggregate whose size is so small that it cannot be defined as a crystalline material. If the heating temperature is not isothermal, there is a difference in the components of the obtained ZIF particles, and the uniformity of the particle size is lowered, and accordingly, precipitates are found in the precursor solution or become opaque, which causes reduced metals to be generated Or, as ZIF particles have already been generated, there will be differences in the size and composition of the AZIF nanoparticles obtained in the final step.

[Formula 4]

1 is data according to Example 1 of the present invention. In the synthesis of AZIF-67-Bu ₃ N ₅ particles, the change according to the time-dependent reaction temperature change was divided into a total of 4 steps from S1 to S4, and the color of the solution and each solution were diluted with NMP to obtain dynamic light scattering (dynamic light scattering). , DLS) are the results analyzed by spectroscopy. According to the results of DLS analysis, no particles were detected in S1 and S2.

Referring to FIG. 1 , the initial color of the solution is transparent pink until the organic base solution is added, and the color changes to purple after the organic base solution is added.

According to the results of DLS analysis of the solutions obtained in the above 4 steps, AZIF-67 particles are not synthesized in steps S1 and S2 having a pink solution, but particles are synthesized from step S3, in which an organic base solution is added.

As shown in Chemical Formula 5, the basic structure of the synthesized particles is LML, and the amine of the ligand is in a state in which dehydrogenation is in progress and is in a state capable of binding to other metal precursors, and additionally, an alkylamine is a second organic ligand It may have a structure included as (Formula 5).

[Formula 5]

The ZIF-67 particles synthesized in step S3 have two types of particle size groups: ~30nm and ~2μm.

6 and 11 are SEM images taken after simple sonication before purification of the sample corresponding to S4 in FIG. 1 and SEM images taken after being well dispersed in NMP after purification. 6 and 11 , the initially synthesized AZIF-67 particles exist in the form of micro-sized chunks, and when they are purified and dispersed in NMP, they can be dispersed into nano-sized particles.

In one embodiment of the present application, the stirring time of the organic precursor solution may be about 10 minutes to about 36 hours, but is not limited thereto. For example, the stirring time of the organic precursor solution is about 10 minutes to about 36 hours, about 10 minutes to about 24 hours, about 10 minutes to about 12 hours, about 10 minutes to about 6 hours, about 10 minutes to about 1 hours, from about 10 minutes to about 30 minutes, from about 30 minutes to about 36 hours, from about 1 hour to about 36 hours, from about 12 hours to about 36 hours, or from about 24 hours to about 36 hours, but is not limited thereto no. When the stirring time exceeds about 36 hours, the metal salt is reduced to produce AZIF nanoparticles containing a reduced metal, and when the stirring time is out of a suitable temperature range, the stirring time may be reduced or increased.

Then, an organic base solution is added to the precursor solution heated under the stirring to obtain a suspension including micro-sized chunks.

The organic base solution may be added between 5 seconds and 5 minutes, and may be added within 30 seconds. If the addition time of the organic base solution exceeds about 5 minutes, the composition and performance of the final product may be affected, and the yield of AZIF nanoparticles will be reduced. In addition, it is preferable to continuously add a certain amount if possible in terms of the addition rate.

In one embodiment of the present application, the micro-sized chunk including the zeolite imidazolate-based structure may have a size of about 1 μm to about 10 μm, but is not limited thereto. For example, the size of the micro-sized chunks comprising the zeolite imidazolate-based structure is from about 1 μm to about 10 μm, from about 1 μm to about 9 μm, from about 1 μm to about 8 μm, from about 1 μm to about 7 μm, about 1 μm to about 6 μm, about 1 μm to about 5 μm, about 1 μm to about 4 μm, about 1 μm to about 3 μm, about 1 μm to about 2 μm, about 2 μm to about 10 μm , about 3 μm to about 10 μm, about 4 μm to about 10 μm, about 5 μm to about 10 μm, about 6 μm to about 10 μm, about 7 μm to about 10 μm, about 8 μm to about 10 μm, about 9 μm to about 10 μm, about 2 μm to about 9 μm, about 3 μm to about 8 μm, about 4 μm to about 7 μm, or about 5 μm to about 6 μm.

In one embodiment of the present application, the organic base solution may include one or more organic bases selected from the group consisting of a primary amine, a secondary amine, and a tertiary amine.

In one embodiment of the present application, the primary amine, the secondary amine and the tertiary amine may each independently be an amine compound represented by the following Chemical Formula 3:

[Formula 3]

In Formula 3,

R ⁹ , R ¹⁰ and R ¹¹ are each independently H or a C1 to C18 linear or branched alkyl group.

In one embodiment of the present application, the pKa of the organic base solution may be greater than about 7. For example, the pKa value of the organic base solution is greater than about 7, greater than about 7.5, greater than 7.8, greater than about 8, greater than about 9, greater than about 10, greater than about 11, greater than about 12, greater than about 13, or greater than about 14 days. can Also for example, pKa may be 7 to 10, 7 to 12, or 7 to 14. If the pKa value is less than 7, crystalline AZIF particles cannot be formed or the yield of crystalline AZIF particles is greatly reduced.

Further, the suspension is diluted by adding a second polar solvent to the suspension heated under stirring.

In one embodiment of the present application, the second polar solvent is preferably a solvent having a pH exceeding 5 and good solubility in the metal salt and ligand used in the reaction. The pH of the second polar solvent may be 5 to 7, 5 to 9, or 5 to 11. For example, it may include one or more selected from the group consisting of alcohol, methanol, ethanol, propanol, ethylene glycol, water, dimethylformamide, dimethyl sulfoxide, acetonitrile and dimethylacetamide. However, the present invention is not limited thereto. When the pH of the second polar solvent is 5 or less, the zeolite imidazolate-based structure of the nanoparticles to be synthesized may be damaged. In addition, the second polar solvent preferably has good solubility for unreacted reactants, that is, a metal precursor and a ligand.

In addition, the additional stirring time after diluting the suspension may be from about 1 minute to about 10 minutes, and if it exceeds 10 minutes, the size of the micro-sized chunks decreases, making it difficult to apply to purification through a filter or the yield may be greatly reduced. However, the present invention is not limited thereto. Finally, the diluted suspension is filtered to obtain AZIF nanoparticles.

In one embodiment of the present application, the filter may use a vacuum filter during filtering, and the type of the filter may be paper, metal, glass, plastic, ceramic, etc., but is not limited thereto. However, when water is used as a solvent, it is not suitable to use paper or Teflon-based filter paper, and when a solvent capable of dissolving plastic is used, plastic cannot be used either.

In one embodiment of the present application, the pore size of the filter may be about 1 μm to about 8 μm. For example, the pore size of the filter may be between about 1 μm and about 8 μm, between about 1 μm and about 7 μm, between about 1 μm and about 6 μm, between about 1 μm and about 5 μm, between about 1 μm and about 4 μm in size. , may be from about 1 μm to about 3 μm, from about 1 μm to about 2 μm, but is not limited thereto. If the pore size of the filter is smaller than about 1 μm, the time required for filtering may be considerably longer, and if the pore size is about 8 μm or more, filtering may not be possible or the yield may be significantly reduced.

In one embodiment of the present application, the method may further include stirring the diluted suspension for about 10 minutes or less before the filtering or stopping without stirring, but is not limited thereto.

The manufacturing method according to an embodiment of the present application may further include drying the obtained AZIF nanoparticles.

In one embodiment of the present application, the drying may be performed at a temperature of about 30° C. to about 110° C., and the drying temperature is most preferably about 80° C., but is not limited thereto. For example, the drying temperature may be from about 30°C to about 110°C, from about 40°C to about 100°C, from about 50°C to about 90°C, from about 60°C to about 80°C, from about 70°C to about 80°C, about 80 ℃ to about 90 ℃, or about 70 ℃ to about 90 ℃ may be, but is not limited thereto.

The method for preparing AZIF nanoparticles according to an embodiment of the present application exhibits a high yield and enables mass synthesis. Here, the high yield means that the weight ratio of the AZIF nanoparticles obtained based on the weight of the metal and ligand precursor included in the AZIF structure is higher than about 80%. The nanoparticles comprising the ZIF structure may be obtained in a ratio of about 30% to about 97% depending on the addition ratio of the organic base solution, but the yield of the obtained AZIF nanoparticles is about 85% to about 95% It is preferred, but not limited thereto.

Hereinafter, the present application will be described in more detail with reference to Examples, but the present application is not limited thereto. The experimental data described above were obtained by experimenting with the samples obtained in Examples below.

[Example 1]

2-methylimidazole (39.55 g) and Cobalt(II) acetate tetrahydrate (60 g) were placed in a 3 L RB flask, 1416.8 mL of methanol was added, and dissolved well through stirring for 10 minutes. Stirring was rotated for 10 minutes while maintaining isothermal temperature at 60°C using a heating mantle. After that, tributylamine (Bu ₃ N, 286.2 mL) was quickly added under strong stirring and stirring was maintained for 1 minute. After that, 1 L methanol was additionally added, stirring was continued for 1 minute, and stirring was stopped. Filtering was carried out using cellulose filter paper, and the filtered solid material was purified using an additional 1.5 L of methanol. The solid material obtained after the purification process was placed in a vacuum oven at 80° C. and dried for 24 hours. The weight of the obtained ZIF-67-Bu ₃ N-5 was 51.5 g, which corresponds to about 95.7% of the weight (53.8 g) introduced in the synthesis ^{of Co 2 + and 2-methylimidazole, which are components of ZIF-67.} yield was shown.

[Example 2]

ZIF-67 particles containing _{Bu 2} N using the same method and molar ratio as in Example 1 (Metal: Ligand: Base = 1: 2: 5), but using a different organic base, dibutylamine (Bu ₂ N). (AZIF-67-Bu ₂ N5) was obtained.

[Example 3]

ZIF-67 particles containing _{Bu 1} N using the same method and molar ratio as in Example 1 (Metal: Ligand: Base = 1: 2: 5), but using a different organic base, butylamine (Bu ₁ N). (AZIF-67-Bu ₁ N5) was obtained.

In addition, various AZIF-67 and AZIF-8 nanoparticles were obtained while changing the type and amount of alkylamine in the same manner as in the above example.

^{14 is a 1} H NMR analysis result obtained after synthesizing the AZIF nanoparticles prepared in Example and then disintegrating the crystal structure using an acid. 14 shows the structures of the components 2-methylimidazole and the organic base along with ^{the analyzed 1 H NMR spectrum.} In addition, the same mark was placed on the chemical structure corresponding to each peak. ^{Through 1} H NMR analysis, it was confirmed that the organic base was included in the AZIF-67 structure, and the amount of organic base introduced was controlled through the phenomenon that the size of the observed peak of the organic base increased with the increase in the amount applied during synthesis. I was able to confirm that this is possible.

Table 1 below summarizes the molar ratios of the reactants introduced during the synthesis of the AZIF-67 nanoparticles synthesized in the above Examples and the ratios of the ligand and the organic base in the obtained particles. Confirming that the particular Bu ₃ N is the molar ratio of the introduced in AZIF-67 introduced Bu ₃ N is improved greatly from 5 to 10 compared to the cobalt precursor probes even though the ratio of the introduced Bu ₃ N applied does not significantly different .

Co: 2 mim: Bu ₁ N 2mm/ Bu ₁ N
(wt%) AZIF-67-Bu ₁ N1 1: 2: 1 98.9/1.1 AZIF-67-Bu ₁ N2 1: 2: 2 97.9/2.1 AZIF-67-Bu ₁ N3 1: 2: 3 97.0/3.0 AZIF-67-Bu ₁ N5 1: 2: 5 95.6/4.4 _{Co: 2} mim: Bu 2 N 2mm/ Bu ₂ N
(wt%) AZIF-67-Bu ₂ N1 1: 2: 1 98.8/1.2 AZIF-67-Bu ₂ N2 1: 2: 2 97.2/2.8 AZIF-67-Bu ₂ N3 1: 2: 3 95.2/4.8 AZIF-67-Bu ₂ N5 1: 2: 5 93.5/6.5 Co: 2 mim: Bu ₃ N 2mm/ Bu ₃ N
(wt%) AZIF-67-Bu ₃ N1 1: 2: 1 91.6/8.4 AZIF-67-Bu ₃ N2 1: 2: 2 85.8/14.2 AZIF-67-Bu ₃ N3 1: 2: 3 84.7/15.3 AZIF-67-Bu ₃ N5 1: 2: 5 81.6/18.4 AZIF-67-Bu ₃ N5 (Scale-up) 1: 2: 5 81.6/18.4 AZIF-67-Bu ₃ N10 1: 2: 10 80.3/19.7

[Example 4]

Using the same method and molar ratio as in Example 1 (Metal: Ligand: Base = 1: 2: 5), but using 180 g of applied Cobalt(II) acetate tetrahydrate, ZIF-67 nanoparticles containing _{Bu 3 N5 (} AZIF-67-Bu ₃ N5) was obtained. The amount of nanoparticles finally obtained was 155 g, which showed a yield of 96.2% compared to 161.1 g, which is the weight of 100% of cobalite ions and 2-methylimidazole applied (FIG. 15).

In addition, it was confirmed that the reproducibility was high as the weight ratio of 2 mim/Bu ₃ N shown in Table 1 was 81.6/18.4, which was _{approximately the same as that of AZIF-67-Bu 3 N nanoparticles synthesized on a low scale.} (Table 1).

[Example 5]

Using the same method as in Example 1, but using another organic base, triethylamine (Et ₃ N), ZIF-67 nanoparticles containing _{Et 3} N were synthesized by changing the molar ratio of _{Et 3 N from 1 to 9.} Particles (AZIF-67-Et ₃ NX, X = 1, 3, 5, 7, 9) were obtained.

It was confirmed that the synthesized AZIF-67-Et _{3 NX nanoparticles contained Et 3} ^{N through 1} H NMR analysis in FIG. 16 . And the more the ratio of the Et ₃ N is applied to synthesizing increase could be confirmed that the introduced amount of Et ₃ N increases Et ₃ N ¹ through an increase in the H NMR peak. In addition, XRD analysis was performed to confirm the crystal structure of AZIF-67-Et ₃ N5, and the results are shown in FIG. 4 . Compared with general ZIF-67 nanoparticles, the crystal structure change was shown in a similar trend to that _{of AZIF-67-Bu 3 N5 synthesized in Example 1.}

[Example 6]

AZIF-8 nanoparticles were obtained using the same method and molar ratio as in Example 1 (Metal: Ligand: Base = 1: 2: 5), but using another metal precursor, Zinc(II) acetate dihydrate.

It was confirmed that the synthesized AZIF-8-Bu ₃ N5 nanoparticles contained Bu3N in AZIF-8-Bu ₃ ^{N5 nanoparticles through the analysis of each XRD and 1} H NMR result in FIGS. 5 and 17 , and it was confirmed that the general ZIF-8 It was confirmed that the crystal structure change similar to the change in _{the AZIF-67-Bu 3} N5 crystal structure obtained in Example 1 was compared with the crystal structure of .

[Membrane-Example 1]

Different AZIF-67 Nano AZIF-67-Bu in a glass bottle to prepare a hybrid film having a particle content of ₃ N ₅ nm 30 minutes AZIF-67-Bu ₃ N ₅ nanoparticles solvent through sonicator mixing the particles with NMP uniformly dispersed in it. _{AZIF-67-Bu 3} N ₅ nanoparticles were uniformly dispersed in the solvent using a cone-shaped ultrasonicator for 2 minutes. After mixing the 6FDA-DAM polymer in a solvent in which AZIF-67-Bu ₃ N ₅ nanoparticles are uniformly dispersed and stirring it through a roller for 12 hours, a glass bottle containing the uniformly dissolved polymer solution is placed in a sonicator for 30 minutes. After removing the microbubbles in the solution, the polymer solution was spread in a thin layer of 150 μm using a casting knife on a glass plate and dried under vacuum conditions at 120° C. for 12 hours. After 12 hours, the vitrified hybrid membrane was dried again under vacuum conditions at 120° C. for 12 hours to remove residual solvent. The hybrid membrane obtained at this time is shown in FIGS. 9 and 10, and showed ^{uniformity and flexibility even when various types of polymers such as Polysulfone (PSF) and Matrimid 5215 ®} were applied and high concentration of AZIF-67 was applied (FIG. 10). The amount of NMP used in the hybrid membrane manufacturing process was 9 times the mass of NMP of the hybrid membrane. Hybrid membranes having various AZIF-67 contents were prepared in this way.

[Membrane-Example 2]

The membrane-a hybrid membrane was prepared using the same method and weight ratio as in Example 1, but using different nanoparticles (AZIF-8-Bu ₃ N5) ( FIG. 10 ). Polyetherimide (Ultem ^® ), a PI-based polymer, was used as the polymer used, and it was confirmed that the film-like the hybrid film obtained in Example 1 showed uniformity and flexibility ( FIG. 10 ).

[Membrane-Comparative Example 1]

Membrane-Comparative Example 1 is a single polymer membrane containing no AZIF nanoparticles and no ZIF nanoparticles. After mixing 10% by weight of 6FDA-DAM polymer and 90% by weight of NMP in a glass bottle and stirring through a roller for 12 hours, a glass bottle containing a uniformly dissolved polymer solution is placed in an ultrasonic grinder for 30 minutes to remove microbubbles in the solution. Then, the polymer solution was spread in a thin layer with a thickness of 150 μm using a casting knife on a glass plate and dried under vacuum conditions at 120° C. for 12 hours. After 12 hours, the vitrified membrane was dried again under vacuum conditions at 120° C. for 12 hours to remove residual solvent.

[Membrane-Comparative Example 2]

AZIF-67 nanoparticles were replaced with ZIF-67 nanoparticles, and a hybrid membrane was prepared in the same manner as in Membrane-Example 1.

[Membrane-Comparative Example 3]

A hybrid membrane was prepared in the same manner as in Example 1, replacing AZIF-8 particles with ZIF-8 particles.

[Comparative Example 1: Preparation of ZIF-67]

Under room temperature conditions, 2-methylimidazole (22.70 g) and distilled water (80 g) were mixed in a 100 mL glass vial and well dissolved by stirring at a speed of 300 rpm for 5 minutes. Cobalt(II) nitrate hexahydrate (1.17 g) and distilled water (8 g) were mixed in a 100 mL glass vial and well dissolved through stirring at a speed of 300 rpm for 5 minutes. Then, the two solutions were mixed in a 400 mL flask and the precipitate was captured for 12 hours at room temperature. A total of 6 plastic containers were prepared by putting the precipitation solution in a plastic container for a 50mL centrifuge at 18mL each, and centrifugation was performed at a speed of 8000 rpm for 30 minutes. For purification of the ZIF-67 particles obtained after centrifugation, filtering was performed using cellulose filter paper, and the filtered solid material was purified three times using 500 mL of methanol. The purified ZIF-67 particles were dried at 100° C. under vacuum conditions for 12 hours. The weight of the obtained ZIF-67 particles was about 0.6 g.

[Comparative Example 2: Preparation of ZIF-8]

Under room temperature conditions, 2-methylimidazole (22.70 g) and distilled water (80 g) were mixed in a 100 mL glass vial and well dissolved by stirring at a speed of 300 rpm for 5 minutes. Zinc(II) nitrate hexahydrate (1.90 g) and distilled water (8 g) were mixed in a 100 mL glass vial and well dissolved through stirring at a speed of 300 rpm for 5 minutes. The subsequent synthesis method was carried out in the same manner as the ZIF-67 synthesis method, and the weight of the obtained ZIF-8 particles was about 0.8 g.

[Experimental Example 1]

For the crystal structure analysis of AZIF-67 nanoparticles, X-ray diffraction analysis (X-ray Diffraction, XRD) was used and compared with general ZIF-67 particles. Measurements were made at intervals of 0.01° from 5° to 30° based on 2θ under CuKα λ = 1.5406 A° at room temperature using a Rigaku Dmax2500 diffractometer.

3 to 5, in the case of AZIF-8 and AZIF-67 nanoparticles, their crystal structures showed a relatively reduced interplanar spacing compared to general ZIF-8 and ZIF-67 particles, and Bu ₃ N was When a molar ratio of 10 to the precursor was used, the (002) and (112) crystal planes grew significantly, and in the case of Hx3N, the same trend was observed even when only the molar ratio of 5 was used. Through this, it was confirmed that the sodalite (SOD) structure, which is the basic ZIF-67 and ZIF-8 structure, was maintained except for changes in the spacing of the crystal planes and the growth of specific crystal planes ( FIGS. 3 and 4 ). In addition, in the case of AZIF-8 nanoparticles, it was confirmed that there was a change similar to the crystal structure change of AZIF-67 nanoparticles (FIG. 5).

[Experimental Example 2]

Thermogravimetric Analysis (TGA) was performed to evaluate the thermal stability of the AZIF-67 and AZIF-8 particles introduced with various alkylamine groups. The measurement was performed using Mettler Toledo TGA1 equipment at _{a flow rate of 50 cc/min under N 2} gas condition, and the change in weight of each particle according to temperature change was recorded from 25°C to 800°C at a temperature increase rate of 5°C/min.

As shown in FIG. 12 , in the case of ZIF-67 particles, the weight of the particles started to decrease from around 250° C., and it was confirmed that the particle weight decreased by about 15 wt% at around 500° C.

[Experimental Example 3]

For surface area analysis of AZIF-67 and AZIF-8 nanoparticles introduced with alkylamine groups, Brunauer-Emmett-Teller (BET) was used and compared with ZIF-67 and ZIF-8 nanoparticles. _{The measurement was carried out under N 2} 77K conditions using Micromeritics ASAP 2020, and the particles were used after pretreatment for 3 hours under vacuum conditions at 120° C. before BET measurement.

As shown in FIG. 18, when comparing general ZIF-67 and AZIF-8 in the isothermal analysis graph according to the pressure change of AZIF-67 and AZIF-8 nanoparticles introduced with an alkylamine group, a similar trend was shown, but When a molar ratio of 10 to that of the metal precursor was used, the N ₂ adsorption curve decreased.

[Experimental Example 4]

Changes in mechanical bond strength between organic ligands and metals (metal ions) in AZIF-67 and AZIF-8 nanoparticles were analyzed using Fourier transform infrared spectroscopy (FT-IR) (FIG. 19). Measurements were carried out at room temperature by Thermo Fisher Scientific Inc. ^{The wave number range from 400 cm -1} to 4000 cm ^-1 was scanned at a speed of 1.9285 cm/sec using Nicolet iS50 of . Each measurement sample was prepared by mixing particles and KBr in a ratio of 1:100 by weight using potassium bromide (KBr, ≥99% FT-IR grade) purchased from Sigma Aldrich, and then pressing into circular pellets with a diameter of 1 cm. .

As shown in FIG. 19 , in the case of the AZIF nanoparticles, a phenomenon in which the pick moves at a relatively high wavenumber compared to the ZIF nanoparticles was confirmed. Through this, it was confirmed that the bond strength between the metal and the organic ligand was relatively higher due to the introduction of alkylamine, and it was confirmed that the change occurred more significantly in AZIF-8.

More specifically, in the case of general ZIF-67, a pick related to the binding (N-Co) between the amine and metal ion of the organic linkage at ^{424.4 cm -1} _{appears. In the case of AZIF-67-Bu 3} N ₅ , the pick is It moves to 426.2 cm ^-1 and shows a difference of about 1.8 cm ^-1 . In the case of ZIF-8 ^{, an N-Zn related pick comes out at 419.1 cm -1} , and in the case of AZIF-8-Bu ₃ N ₅ , 421.6 cm. ^The pick appears at ^-1 , and the difference is about 2.5cm -1. In addition, in the case of AZIF, it seems that the degree of amine bonding between the metal ion and the ligand became more constant through the narrower dispersion. For example, in the case of ZIF nanoparticles, there are parts such as metal vacancy, dangling linker, or linker vacancy, which are a type of defect. can, but In the case of AZIF, alkylamine promotes dehydrogenation of organic binders to promote crystallinity, and alkylamines can be bound in places such as linker vacancy, so it seems to have more uniform MN bond strength. Through this, it was confirmed that the alkylamine had a direct bond with the metal.

The IR peak of Co-N of AZIF-67 nanoparticles can be increased ^{by 1 to 3 cm -1 by an organic ligand of an alkylamine series.} That is, the IR peak of Co-N is increased by ^{1 to 3 cm -1 compared to the ZIF-67 nanoparticles.} Similarly, the IR peak of Zn-N of AZIF-8 nanoparticles can be increased ^{by 1.5 to 4 cm -1 by an organic ligand of an alkylamine series.}

[Experimental Example 5]

Cross-sections of AZIF-67 nanoparticles and hybrid membranes were photographed using a scanning electron microscope (SEM). Filming was performed using Inspect F FEG-SEM equipment at room temperature and under vacuum conditions.

As shown in FIG. 6 , the size of the AZIF-67 particles was confirmed to be about 50 nm, but when combined with the DLS result of FIG. 1 , the size is not limited to 50 nm and may be smaller. As shown in FIG. 11 , in the case of the AZIF-67-based hybrid membrane of Example 7, it was confirmed that the nanoparticles were evenly dispersed in the polymer matrix without agglomeration even when nanoparticles were introduced at a high concentration. In addition, it was confirmed that the compatibility between the polymer and the particles was very good.

[Experimental Example 6]

Membrane - Thermogravimetric analysis (TGA) was performed to confirm the weight % of AZIF-67 particles in the hybrid membrane prepared in Example 1. The measurement was carried out by injecting a flow rate of ^{50 cm 3} /sec in the air condition at a heating rate of 5 °C/min from 25 °C to 800 °C using the METTLER TOLED TGA1 equipment.

As shown in FIG. 20, the weight of 6FDA-DAM polymer was reduced from 100% by weight to 0% by weight after TGA analysis up to 800°C, and AZIF-67 nanoparticles after TGA analysis up to 800°C, the weight decreased from 100% by weight. decreased to 35.5 wt%. The hybrid membrane containing 20% by weight of AZIF-67 nanoparticles decreased from 100% by weight to 7.0% by weight, and the hybrid membrane containing 30% by weight of AZIF-67 nanoparticles decreased from 100% by weight to 10.8% by weight. Finally, the hybrid membrane containing 40 wt% of AZIF-67 nanoparticles was reduced from 100 wt% to 15.9 wt%. All residues remaining after TGA analysis of AZIF-67 nanoparticles and hybrid membranes containing them refer to cobalt oxide (CoO), and the weight percent of pure Co can be calculated using the molecular weight ratio between Co and O in CoO. Therefore, if the weight% of Co of the hybrid membrane representing different weight% is all divided by the weight% of Co of AZIF-67, the actual weight% of AZIF-67 nanoparticles in the hybrid membrane can be calculated, and as a result, the membrane-prepared in Example 1 It was confirmed that the actual weight % of AZIF-67 nanoparticles in one hybrid membrane was almost equal to the theoretical weight %, which is shown in Table 2.

CoO wt% Co wt% Actual ZIF-67-Bu ₃ N5 wt% ZIF-67-Bu ₃ N5 35.5 27.9 - Membrane-Example 1
(20% by weight) 7.0 5.5 19.7 Membrane-Example 1
(30% by weight) 10.8 8.5 30.5 Membrane-Example 1
(40% by weight) 15.9 12.5 45.5

[Experimental Example 7]

_{Single C 3} H ₆ and C ₃ H ₈ permeability and C ₃ H ₆ /C ₃ H ₈ selectivity of the hybrid membranes or membranes prepared in Membrane-Example and Membrane-Comparative Example were measured. Specifically, the permeability and selectivity of each gas were measured using a permeability device having a constant volume at 2 atm and 35°C conditions. Each hybrid membrane was placed in a permeability device and maintained in a vacuum state for at least 24 hours, and then the permeability and selectivity were measured through a leak test before measurement. The steady-state permeation rate and leak rate of the gas passing through the hybrid membrane were used to calculate the permeability and selectivity. Selectivity was calculated using the ratio of _{C 3} H ₆ permeability to C ₃ H ₈ permeability of each hybrid membrane.

As shown in Table 3, the hybrid membrane prepared including the AZIF-67 particles (membrane-Example 1) showed C ₃ H ₆ permeability and C compared to the hybrid membrane including the same amount of ZIF-67 particles of Comparative Example 2 _It was confirmed that all 3 H ₆ /C ₃ H _{8 selectivities were increased.} In the case of the 20 wt% hybrid membrane of particles of Membrane-Example 1, higher C ₃ H ₆ permeability and C ₃ H ₆ /C ₃ H ₈ selection despite having the same nanoparticle content as the hybrid membrane of Membrane-Comparative Example 2 shown in the figure. In addition, unlike the hybrid membrane containing 30% by weight of AZIF-67 particles (membrane-Example 1), ZIF-67 particles contain 30% by weight or more in the 6FDA-DAM polymer due to the high particle content inside. Agglomeration was observed, and it was impossible to measure the transmittance due to the low mechanical properties of the hybrid membrane.

Sample C ₃ H ₆ Permeability
(Barrer) C ₃ H ₈ permeability
(Barrer) C ₃ H ₆ /C ₃ H ₈ Selectivity (-) Membrane-Comparative Example 1 6FDA-DAM 16.63 1.47 11.3 Membrane-Comparative Example 2
(20% by weight) 34.14 1.14 29.9 Membrane-Example 1
(20% by weight) 41.80 1.15 36.5 Membrane-Example 2
(30% by weight) 49.78 1.06 47.0 Membrane-Example 3
(40% by weight) 62.08 1.07 58.2

In the case of AZIF-67 particles, it was possible to prepare a hybrid membrane containing 40% by weight of particles without particle agglomeration, and high C ₃ H ₆ permeability of 62 Barrer and high C ₃ H ₆ /C _{3 of 58.2.} It _{was confirmed that H 8} selectivity is possible.

As shown in Table 4, in the _{case of the hybrid membrane containing 20% by weight of the AZIF-8-Bu 3} N5 particles prepared in Membrane-Example 2, the hybrid membrane formed using the same amount of ZIF-8 particles of Comparative Example 3 was higher than that of the hybrid membrane. _{High C 3} H ₆ permeability and C ₃ H ₆ /C ₃ H ₈ selectivity at 35° C. were confirmed.

Sample C ₃ H ₆ Permeability
(Barrer) C ₃ H ₈ permeability
(Barrer) C ₃ H ₆ /C ₃ H ₈ Selectivity (-) Membrane-Comparative Example 1 16.63 1.47 11.3 Membrane-Comparative Example 3
(20% by weight) 37.73 1.82 20.7 Membrane-Example 2
(20% by weight) 41.05 1.64 25.0

Sample measurement temperature
( ^o C) C ₃ H ₆ Permeability
(Barrer) C ₃ H ₈ permeability
(Barrer) C ₃ H ₆ /C ₃ H ₈ Selectivity (-) Membrane-Comparative Example 1 35 16.63 1.47 11.3 50 19.40 1.92 10.1 70 22.31 2.45 9.1 Membrane-Comparative Example 2
(20% by weight) 35 34.14 1.14 29.9 50 37.16 1.58 23.6 70 40.82 2.23 18.3 Membrane-Example 1
(20% by weight) 35 41.80 1.15 36.5 50 43.74 1.35 27.2 70 46.97 1.56 20.5

_{Using the same measurement method as in the above experiment, the C 3} H ₆ /C ₃ H ₆ single gas separation performance of the hybrid membrane containing various particles and concentrations at the measurement temperature change of 35℃, 50℃ and 70℃ at 2 atm was confirmed. did As it is shown in Figure 21 and Table 5, as the all the produced hybrid film or film measured temperature increase permeability of the C ₃ H ₆ is increased, and _{C 3 H 6 / C 3 H} 8 selectivity showed a tendency to decrease , AZIF-67 particles (ie, ZIF-67-Bu 3 N5) hybrid membrane separation performance is higher at all under the same conditions than the hybrid membranes separating efficiency containing a ZIF-67 particles C containing ₃ H ₆ permeability and C ₃ H ₆ /C ₃ H _{8 It} showed selectivity.

Sample Gas D ^a S ^b P
(Barrer) C ₃ H ₆ /C ₃ H ₈ (-)

Membrane-Comparative Example 1
C ₃ H ₆ 5.29E-09 3.17E-01 16.63 10.4 1.1 11.3 C ₃ H ₈ 5.16E-10 2.78E-01 1.47 Membrane-Comparative Example 1
50 ^o C C ₃ H ₆ 7.99E-09 2.43E-01 19.40 9.5 1.1 10.1 C ₃ H ₈ 8.44E-10 2.28E-01 1.92 Membrane-Comparative Example 1
70 ^o C C ₃ H ₆ 1.17E-08 1.90E-01 22.31 8.6 1.1 9.1 C ₃ H ₈ 1.37E-09 1.79E-01 2.45 Membrane-Comparative Example 2
20wt%_35 ^o C C ₃ H ₆ 7.72E-09 4.40E-01 34.14 24.8 1.2 29.9 C ₃ H ₈ 3.11E-10 3.70E-01 1.14 Membrane-Comparative Example 2
20wt%_50 ^o C C ₃ H ₆ 1.08E-08 3.35E-01 37.16 20.4 1.1 23.6 C ₃ H ₈ 5.29E-10 2.92E-01 1.58 Membrane-Comparative Example 2
20wt%_70 ^o C C ₃ H ₆ 1.52E-08 2.66E-01 40.82 16.5 1.1 18.3 C ₃ H ₈ 9.20E-10 2.41E-01 2.23 Membrane-Example 1
20wt%_35 ^o C C ₃ H ₆ 1.20E-08 3.48E-01 41.80 36.1 1.0 36.5 C ₃ H ₈ 3.32E-10 3.45E-01 1.15 Membrane-Example 1
20wt%_50 ^o C C ₃ H ₆ 1.63E-08 2.69E-01 43.74 27.1 1.0 27.2 C ₃ H ₈ 6.01E-10 2.68E-01 1.35 Membrane-Example 1
20wt%_70 ^o C C ₃ H ₆ 2.28E-08 2.06E-01 46.97 20.4 1.0 20.5 C ₃ H ₈ 1.12E-09 2.05E-01 1.56

*a: Diffusivity (diffusivity, D , cm ² /sec)

*b: Solubility (solubility, S , cc (STP)/cc Poly/cmHg)

_{Table 6 shows C 3} H ₆ /C ₃ H ₈ single gas separation performance diffusivity, solubility, diffusivity selectivity, and solubility selectivity according to the temperature of the hybrid membrane prepared using AZIF-67 nanoparticles according to the example of the present application is a diagram showing The numbers shown in Table 6, using the Arrhenius equation based on the gas-specific transmission rate of each of the hybrid film activation energy (E _P), diffusivity activation energy (E _D), and the heat of sorption table it was calculated on the (H _S) value of 8 shown in

Sample Gas E _P (kJ/mol) E _D (kJ/mol) H _S (kJ/mol) Membrane-Comparative Example 1 C ₃ H ₆ 7.3 20.4 -13.1 C ₃ H ₈ 12.2 24.4 -12.2 Membrane-Comparative Example 2 20wt% C ₃ H ₆ 4.9 16.8 -11.9 C ₃ H ₈ 16.7 31.6 -14.6 Membrane-Example 1 20wt% C ₃ H ₆ 2.9 16.1 -13.2 C ₃ H ₈ 17.3 34.2 -16.9

As shown in Table _{7, C 3 H 6 6FDA-} DAM may be confirmed that the polymer film is a lower hybrid film E _P value containing a ZIF-67 particles and AZI-67F nanoparticles compared to E _P value, especially AZIF for It can be seen that the E _P value of the hybrid membrane containing -67 nanoparticles is the lowest (ie, 2.9). On the other hand, it can be seen that the E _P value of the 6FDA-DAM polymer membrane for _{C 3} H ₈ increased compared to the E _P value of the hybrid membrane containing ZIF-67 particles and AZIF-67 nanoparticles. It can be seen that one hybrid membrane had the highest E _P value (ie, 17.3). This is ZIF-67 nanoparticles and AZIF-67 nanoparticles, C ₃ H ₆ / C ₃ H ₈ can be seen to be effective in the gas separation, in the case of AZIF-67 nano particles more effectively as compared to ZIF-67 particles C ₃ through It can be seen that H ₆ /C ₃ H _{8 shows separation performance.}

Sample Energetic selectivity
(-) Entropic selectivity
(-) diffusivity selectivity
(-) Membrane-Comparative Example 1 4.8 2.1 10.1 Membrane-Comparative Example 2
20 wt% 322.7 0.08 24.8 Membrane-Example 1
20 wt% 1170.2 0.03 36.1

In general, _{selectivity in C 3} H ₆ /C ₃ H ₈ gas separation is determined by diffusivity selectivity. The diffusivity selectivity can be expressed as the product of the energetic selectivity related to the size of gas molecules or membrane passing through the membrane pores and the entropic selectivity related to the shape or membrane pore structure of the gas molecules passing through the membrane pores. Table 9 shows the energetic selectivity and entropic selectivity of each of the 6FDA-DAM polymer membrane, the ZIF-67 particle, and _{the hybrid membrane containing 20% by weight of the AZIF-67-Bu 3 N5 particle according to the example.}

As shown in Table 8, _{the energetic selectivity of C 3} H ₆ /C ₃ H ₈ was higher than that of the 6FDA-DAM polymer film containing ZIF-67 or AZIF-67 particles (ie, ZIF-67-Bu ₃ N5). It can be seen that the hybrid membrane significantly increased. In particular, it was confirmed that the hybrid membrane containing AZIF-67-Bu ₃ N5 particles exhibited improved energetic selectivity compared to the hybrid membrane containing ZIF-67 particles (ie, 1170.2). On the other hand _{, in the case of the entropic selectivity of C 3} H ₆ /C ₃ H ₈ , the hybrid membrane containing ZIF-67 or AZIF-67 particles (ie, AZIF-67-Bu ₃ N5) was significantly higher than that of the 6FDA-DAM polymer membrane. It can be seen that a decrease In particular, it was confirmed that the hybrid membrane containing AZIF-67-Bu3N5 particles exhibited very low energetic selectivity compared to the hybrid membrane containing ZIF-67 particles (ie, 0.03).

These results show that ZIF-67 particles _{can effectively separate C 3} H ₆ and C ₃ H ₈ gases according to their size, while AZIF-67-Bu ₃ N5 particles are superior to ZIF-67 particles in the hybrid membrane. This indicates that C ₃ H ₆ and C ₃ H ₈ gases can be separated more effectively according to size. As can be seen in FIG. 19 showing the FT-IR results of ZIF-67-Bu ₃ N5 particles, the sieving function for _{C 3} H ₆ /C ₃ H _{8 separation is significantly improved as the ionic bond between Co-N is strengthened.} It can be interpreted as a result of the increase.

According to these results, when AZIF-67 particles and AZIF-8 particles are used in manufacturing _{a C 3} H ₆ /C ₃ H _{8 gas separation membrane, C 3} H ₆ /C _{3 is superior to ZIF-67 particles and ZIF-8 particles.} It was confirmed that it is possible to prepare a hybrid membrane having _{H 8 separation performance.}

The above description of the present application is for illustration, and those of ordinary skill in the art to which the present application pertains will understand that it can be easily modified into other specific forms without changing the technical spirit or essential features of the present application.

Claims (20)

polymer matrix; and
It contains nanoparticles comprising a zeolite imidazolate-based structure dispersed in the polymer matrix,
The nanoparticles are
metal ions;
It contains an organic ligand bound to the metal ion,
The organic ligand includes an imidazolate-based organic ligand and an alkylamine-based organic ligand,
In the organic ligand, a ratio of the imidazolate-based organic ligand to the alkyl amine-based organic ligand is 99.9% by weight: 0.1% by weight to 80% by weight:20% by weight. delete According to claim 1,
The nanoparticles are
At least one of the spacing of the crystal planes, the distribution of the crystal planes, and the bonding strength is controlled according to the ratio of the alkylamine-based organic ligands used,
wherein the alkylamine-based organic ligand is directly bonded to the metal ion. delete According to claim 1,
When the metal ion is cobalt, the spacing between the (011) crystal planes of the nanoparticles is 11.9 Å to 12.15 Å,
When the metal ion is zinc, the spacing between the (011) crystal planes of the nanoparticles is 12.0 Å to 12.25 Å. According to claim 1,
The nanoparticles have a size of 100 nm or less, and the pores are 0.1 nm to 1 nm. According to claim 1,
The nanoparticles show a mass reduction of 3% or less within 400 ° C in the TGA experiment,
When the metal ion is cobalt, the IR peak of Co-N of the nanoparticles increases ^{by 1-3 cm -1 by the organic ligand of the alkylamine series,}
When the metal ion is zinc, the IR peak of Zn-N of the nanoparticles increases ^{by 1.5 to 4 cm -1 by the alkylamine-based organic ligand.} According to claim 1,
The hybrid membrane wherein the content of the nanoparticles in the membrane is 15% to 60% by weight. According to claim 1,
The hybrid membrane wherein the content of the nanoparticles in the membrane is 30% to 60% by weight. According to claim 1,
A hybrid film having a thickness of 50 nm to 100 µm. According to claim 1,
The polymer matrix is a hybrid comprising any one selected from the group consisting of polyimide, polysulfone (PSF), polyisosulfone (PES), cellulose acetate (CA), polydimethylsiloxane (PDMS), and polyvinyl acetate (PVAc). membrane. According to claim 1,
The membrane is a hybrid membrane that separates gases having a molecular size difference of 0.1 Å to 5 Å from each other. According to claim 1,
The membrane is C ₃ H ₆ /C ₃ H ₈ , C ₂ H ₄ /C ₂ H ₆ , CO ₂ /CH ₄ , CO ₂ /CO, CO ₂ /N ₂ , N ₂ /CH ₄ , nC ₄ /iC ₄ (n-butane/iso-butane), H ₂ /CH ₄ , H ₂ /C ₃ H _{8 ,} and H ₂ /C ₃ H ₆ A hybrid membrane for separating a mixed gas of a gas set selected from the group consisting of According to claim 1,
When the central atom of the nanoparticles is cobalt,
And at 35 ℃ permeability for C ₃ H ₆ of the nanoparticles 200 to _{400Barrer, C 3 H 6 / C} 3 H 8 selectivity of 270 to 400,
When the central atom of the nanoparticles is zinc,
The permeability of the nanoparticles to C ₃ H ₆ at 35° C. is 300 to 600 Barrer, and the C ₃ H ₆ /C ₃ H ₈ selectivity is 140 to 300 hybrid membrane. According to claim 1,
The central atom of the nanoparticles contains zinc,
A hybrid membrane wherein the membrane has a C ₃ H ₆ permeability of 40 to 80 Barrer and a C ₃ H ₆ /C ₃ H ₈ selectivity of 22 to 40 at 35°C. According to claim 1,
The central atom of the nanoparticles contains cobalt,
A hybrid membrane wherein the membrane has a C ₃ H ₆ permeability of 40 to 70 Barrer and a C ₃ H ₆ /C ₃ H ₈ selectivity of 33 to 60 at 35°C. According to claim 1,
The central atom of the nanoparticles contains cobalt,
Hybrid membrane, characterized in that the _{C 3} H ₆ /C ₃ H ₈ energetic selectivity of the membrane is 1,000 to 10,000. 18. A gas separation method comprising the step of separating one or more gases from a mixed gas comprising two or more gases using the hybrid membrane according to any one of claims 1, 3 and 5 to 17. 19. The method of claim 18,
A gas separation method for separating the gases from each other by passing the mixed gas through the membrane, using a difference in molecular size of the gases included in the mixed gas. 19. The method of claim 18,
The difference in molecular size of the gases included in the mixed gas is 0.1 Å to 5 Å.

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