KR102090288B1 - Hybrid porous structured material, membrane including the same and method of preparing hybrid porous structure material - Google Patents

Abstract

A hybrid porous structure comprising a matrix comprising a plurality of first pores interconnected in a three-dimensional direction, and a porous material having a second pore filling part or all of each of the plurality of first pores, as a separator Uses and methods of making the hybrid porous structures are provided.

Description

Hybrid porous structure, separation membrane comprising same, and method for manufacturing hybrid porous structure {HYBRID POROUS STRUCTURED MATERIAL, MEMBRANE INCLUDING THE SAME AND METHOD OF PREPARING HYBRID POROUS STRUCTURE MATERIAL}

It relates to a hybrid porous structure, a separator comprising the same, and a method for manufacturing the hybrid porous structure.

A material having a specific size can be separated using a separation membrane including pores, and it can be applied to a water treatment technology by removing contaminants using this property of the separation membrane. The separation membrane that can be used for water treatment may be classified into a microfiltration membrane, an ultrafiltration membrane, a nanofiltration membrane, and a reverse osmosis membrane according to the size of the surface micropores.

The properties of the separator are determined by the properties of the pores formed therein. For example, when the porosity of the separation membrane is high, the driving pressure may be lowered, but the physical strength of the membrane is weakened accordingly, and on the contrary, when the porosity is lowered to increase the physical strength of the membrane, the driving pressure is increased. On the other hand, by narrowing the size distribution of the pores formed in the separation membrane it can be made easier to selectively separate for a specific size target material.

One embodiment of the present invention is to provide a hybrid porous structure having excellent mechanical strength, high pore density per unit area, and nanopores of uniform size.

Another embodiment of the present invention is to provide a separator using the hybrid porous structure.

Another embodiment of the present invention is to provide a method for manufacturing the hybrid porous structure.

According to an embodiment, a hybrid material comprising a matrix including a plurality of first pores interconnected in a three-dimensional direction and a porous material having a second pore filling part or all of each of the plurality of first pores Porous structures are provided.

 The plurality of first pores may be spherical, connected to each other in a three-dimensional direction. The plurality of first pores may have a spherical shape stacked in a closest packing structure in a three-dimensional direction.

The matrix can be made of a non-porous material. For example, the matrix may be made of a non-porous material selected from inorganic oxides, thermoplastic resins, curable resins, and combinations thereof.

The porous material having the second pore may fill 90% or less, for example, 80% or less, for example, 70% or less, for example, 60% or less of the total volume of the plurality of first pores in the matrix. have.

The porous material having the second pores may exist in a form of blocking a portion in which a plurality of first pores in the matrix are interconnected.

The porous material having the second pores may exist in a form of coating the inner walls of the plurality of first pores in the matrix.

The porous material having the second pore may be selected from organic porous materials, inorganic porous materials, organic / inorganic hybrid porous materials, and combinations thereof.

The organic porous material may be selected from self-assembled block copolymers, amphiphilic liquid crystals, metal-containing self-assembled molecules, and combinations of two or more thereof.

The inorganic porous material may be selected from zeolite, metal oxide, mesoporous carbon, and combinations of two or more thereof.

The organic-inorganic hybrid porous material may be selected from metal-organic framework (MOF) and combinations of two or more thereof.

The organic porous material may be derived from a self-assembled block copolymer, and the self-assembled block copolymer may form a self-assembled structure. The self-assembled structure may include nanopores formed by removing some or all of the polymers forming at least one block of the block copolymer.

The self-assembled structure may be a lamellar structure, a cylinder structure, a sphere structure, a gyroid structure, or a combination of one or more of them.

The self-assembled block copolymer is a polystyrene-polymethylmethacrylate block copolymer (PS-b-PMMA), a polystyrene-polybutadiene block copolymer (PS-b-PB), a polystyrene-polyethylene oxide block copolymer (PS -b-PEO), polystyrene-polyvinylpyridine block copolymer (PS-b-PVP), polystyrene-polyethylene-alt-propylene block copolymer (PS-b-PEP), polystyrene-polyisoprene block Copolymers (PS-b-PI), and combinations thereof.

The first pore may have an average diameter of 5nm to 100㎛.

The second pore may have an average diameter of 1nm to 100nm.

The hybrid porous structure may have a shape of a film having two opposite surfaces and a thickness. In the hybrid porous structure having the shape of the membrane, the two surfaces may each occupy 5 to 99% of the total surface area relative to the plurality of first pores, and the wall surface of the membrane in the thickness direction may be the first. It may be in the form that the pores are not exposed.

In the hybrid porous structure having the film shape, the thickness of the film may be 10 nm to 1000 μm.

In another embodiment, a separator comprising a hybrid porous structure according to the above embodiment is provided.

The separation membrane may be in the form of a composite membrane further comprising a support membrane.

In another embodiment,

Stacking a plurality of spherical particles for forming the first pores to contact each other in a three-dimensional direction;

Filling a gap between the stacked spherical particles and injecting a liquid non-porous material to coat the outer surfaces of the spherical particles, followed by curing;

Dissolving and removing the plurality of spherical particles for forming the first pores in the cured non-porous material, thereby forming a matrix comprising a plurality of first pores that are connected in a three-dimensional direction;

Forming a hybrid structure by injecting a self-assembled block copolymer in which at least two or more polymers are covalently linked into a plurality of first pores in the matrix; And

Forming a porous material having second pores by partially or completely eluting a polymer forming at least one block in the self-assembled block copolymer among the hybrid structures.

Containing,

A porous material having a second pore is provided in a method of manufacturing a hybrid porous structure filling part or all of each of the plurality of first pores.

The step of forming a stacked body in which the plurality of spherical body particles for forming the first pores are brought into contact with each other in a three-dimensional direction includes forming a stacked body in which the spherical body particles are stacked in the closest stacked structure.

The plurality of spherical particles for forming the first pores may be colloidal particles.

The step of injecting the self-assembled block copolymer into a plurality of first pores in the matrix to form a hybrid structure includes adjusting and injecting the concentration of the self-assembled block copolymer.

By adjusting and injecting the concentration of the self-assembled block copolymer, a position in the first pore of the porous material having the resulting second pores can be adjusted. For example, by adjusting the concentration of the self-assembled block copolymer, the porous material having the second pores is connected to the entire inner wall of the first pores or the first pores adjacent to each other in each of the plurality of first pores It can be adjusted to exist only in the part where it is.

The size of the second pores of the porous material having the second pores can be adjusted by adjusting the relative proportions of the at least two polymers of the self-assembled block copolymer.

The hybrid porous structure has excellent mechanical strength while increasing the pore density per unit area, and also includes a porous material having a second pore having a uniform size of nano pores, so that it can be used as a separator material for nanofiltration membranes or ultrafiltration membranes. Do. In addition, the structure can be effectively applied to a biofilter for water treatment, in particular, that can selectively separate only particles of a specific size, and such a water filter biofilter can significantly improve water permeation.

1 is a schematic diagram of a hybrid porous structure 10 according to an embodiment.
FIG. 2 shows that when the entire interior of the first pore 1 of the hybrid porous structure is filled with the porous material 3 having the second pore ((a)), and the first pore 1 of the hybrid porous structure is partially A schematic diagram showing the cross section of the form ((b)) in which the porous material 3 having the second pores is partially filled, and the other part of the first pores 1 is partially filled with the porous material 3 having the second pores As shown.
3 is a schematic cross-sectional view schematically showing a form in which a porous material 3 having a second pore exists only at a specific position of the first pores 1 of the hybrid porous structure.
4 is a schematic view showing the porous structure of FIG. 3 in three dimensions, and FIG. 4 (b) is an enlarged view of a portion of FIG. 4 (a).
5 is a schematic view schematically showing a cross section of a hybrid porous structure according to an embodiment, and shows that a porous material 3 having a second pore is coated on an inner wall of a plurality of first pores 1 in the structure .
FIG. 6 is a schematic view showing FIG. 5 in three dimensions, and shows that a porous material having a second pore is coated on an inner wall of the first pore.
7 is a schematic diagram showing each step of the method for manufacturing a hybrid porous structure according to an embodiment of the present invention.
FIG. 8 is a scanning electron micrograph (SEM) photograph of a cross section of a hybrid porous structure in which porous materials having second pores are formed in a form in which the first pores are adjacent to each other and are manufactured according to Example 1;
9 is a scanning electron microscope (SEM) photograph of a cross section of a hybrid porous structure coated with a porous material having second pores on the entire inner wall of the first pore, prepared according to Example 2.
10 is a graph showing a change in permeability according to a pressure change of the separator comprising the hybrid porous structures according to Examples 1 to 3.

Hereinafter, one embodiment will be described in detail so that those skilled in the art to which the present invention pertains can easily practice. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein.

The present invention can be implemented in a number of different forms and is described with reference to the drawings as needed and is not limited to the embodiments described herein. The size and thickness of each component shown in the drawings of the present specification are arbitrarily shown for convenience of description, and thus the present invention is not necessarily limited to what is illustrated. In addition, since the size and thickness of each component shown in the drawings are arbitrarily exaggerated for convenience of description, the present invention is not necessarily limited to what is illustrated. In addition, the same code | symbol in each figure represents the same element.

The hybrid porous structure according to an embodiment of the present invention includes a matrix including a plurality of first pores interconnected in a three-dimensional direction, and a second pore filling part or all of each of the plurality of first pores It provides a hybrid porous structure comprising a porous material having.

As an example, the plurality of first pores may be spheres connected to each other in a three-dimensional direction, for example, spherical shapes stacked in a closest packing structure in a three-dimensional direction.

Therefore, the form in which the first pores are stacked may form, for example, an opal structure. The opal structure refers to a structure in which a spherical body having a certain size is stacked in a closest packing structure. The densest stacking structures include, for example, hexagonal close-packing (hcp) and face-centered cubic (fcc).

In the hybrid porous structure, the matrix including the plurality of first pores may be made of a non-porous material, for example, a non-porous material selected from inorganic oxides, thermoplastic resins, curable resins, and combinations thereof.

The hybrid porous structure includes a plurality of first pores, and a porous material having the second pores in the plurality of first pores, while maintaining excellent mechanical strength by including a matrix of a non-porous material. By doing so, it is possible to secure a high porosity ratio on the entire side of the structure, including the porous region in a high volume ratio.

In addition, the porous structure can easily and freely control the physical properties of the entire hybrid porous structure by freely adjusting the size and porosity of the first and second pores.

1 is a schematic diagram of the hybrid porous structure 10 according to an embodiment.

In FIG. 1, a plurality of first pores 1 in the matrix 2 are connected to each other in a three-dimensional direction, and in each first pore 1, a porous material having second pores represented by small dots ( 3) is included. In FIG. 1, the porous material having the second pores fills the entirety of the plurality of first pores.

In each drawing, the plurality of first pores means a pupil portion that is actually partitioned by spherical wall surfaces of the matrix 2, but for convenience of description, in some drawings, a matrix for partitioning the first pores The portion of the round wall in (2) was denoted as the first pore (1).

According to another embodiment of the present invention, the porous material having the second pores may not only fill all of the plurality of first pores, but also a part of the first pores may be entirely filled with the porous material having the second pores. In addition, some of the porous materials having the second pores may be partially filled, or the porous materials having the second pores may not be filled at all.

When the first pores 1 having a spherical shape are present in the matrix 2, and the porous material 3 having the second pores is completely filled therein, and a part of the first pores is porous with the second pores Fig. 2 (a) and (b) respectively show schematic cross-sectional views of a form in which the porous material 3 having the second pores is partially filled with the material, and the other part is completely filled.

Meanwhile, the porous material 3 having the second pores may be filled to exist only in a specific position of the plurality of first pores 1. 3 schematically shows this.

Referring to FIG. 3, the spherical first pores 1 are present in the matrix 2, and the porous material 3 having the second pores is present only in a portion where the first pores 1 are in contact with each other. It shows. 4 (a) and (b) of FIG.

Referring to (a) of FIG. 4, it can be seen that spherical first pores are stacked, and porous materials having second pores exist only in portions where the first pores are connected to each other. FIG. 4 (b) is an enlarged view of a portion of FIG. 4 (a). In (b) of FIG. 4, it is shown that a porous material having a second pore exists only in a specific portion of the first pore, that is, a portion where the first pore is connected to another first pore.

5 schematically shows that a porous material 3 having a second pore is coated on an inner wall of a plurality of first pores 1 in the matrix 2 in the hybrid porous structure. 6 is a schematic diagram showing FIG. 5 in three dimensions. Referring to FIG. 6, unlike FIG. 4, it shows that a porous material having a second pore is coated on the entire inner wall of the first pore.

On the other hand, the porous material having the second pore, by adjusting the concentration or content of the raw material forming the porous material, as described in more detail in the embodiment of the method for producing the hybrid porous structure to be described later, the The thickness coated on the inner walls of the plurality of first pores may vary, and thus, when the porous material having the second pores is sufficiently present at a high concentration, the inside of the plurality of first pores may be entirely filled. Alternatively, even if the porous material having the second pores does not completely fill the insides of the plurality of first pores, the insides of the plurality of first pores may be filled with a predetermined volume ratio or more. For example, the porous material including the second pore is 90% or less, for example, 80% or less, for example, 70% or less, for example, 60%, for the total volume of the plurality of first pores in the matrix You can fill in below. In this case, the plurality of first pores may be equally or equally filled to 90% or less, for example, 80% or less, for example, 70% or less, or for example, 60% or less, or Some of the pores are 100% filled with the porous material, while others can be filled with about 90%, while others are filled with only about 30%, or the first pore in an empty form without containing the porous material at all Can also exist.

The porous material having the second pore is a material known as porosity and can be made without limitation. For example, it may be made of at least one selected from organic porous materials, inorganic porous materials, organic-inorganic hybrid porous materials, and combinations thereof.

Examples of the inorganic porous material include metal oxides such as zeolite and silica, mesoporous carbon, etc., and examples of the organic-inorganic hybrid porous material include a metal-organic framework (MOF), As described above, a material having nanopores formed in the particles can be used as a material in the porous region. The size of the nano pores may be on average about 1 nm to about 1,000 nm, for example, about 5 nm to 500 nm, and for example, about 10 nm to 100 nm.

Meanwhile, as the organic porous material, for example, a self-assembled block copolymer may be used. Self-assembled block copolymers are two or more polymer blocks having different physical properties and chemical properties, and are linked through covalent bonds, resulting in microphase separation due to incompatibilities between the blocks, and thermodynamically stable nanostructures For example, it is widely known as a material that induces a self-assembled structure in a form in which spheres, cylinders, and lamellas are periodically arranged. In order to prepare a porous material having second pores in a hybrid porous structure according to an embodiment of the present invention, nanopores formed by removing some or all of the polymers forming at least one block of the self-assembled block copolymer It can form a self-assembled structure including. The generated pores may have a complicated structure such as a tubular shape, not a spherical shape, and the diameter of the tubular nanopores may be, for example, about 1 nm to about 100 nm on average. These pores can be prepared using a solvent that selectively dissolves only certain polymers contained in self-assembled block copolymers.

In the self-assembled block copolymer for producing a porous material having the second pores of the hybrid porous structure according to the embodiment of the present invention, the block copolymer known to be capable of forming the above-described fine nanostructure can be used without limitation. You can. For example, a block copolymer in which a polystyrene block and a polymer block other than polystyrene are covalently bonded may be used. Specifically, polystyrene-polymethyl methacrylate block copolymer (PS-b-PMMA), polystyrene-polybutadiene block copolymer (PS-b-PB), polystyrene-polyethylene oxide block copolymer (PS-b-PEO) , Polystyrene-polyvinylpyridine block copolymer (PS-b-PVP), polystyrene-polyethylene-alt-propylene block copolymer (PS-b-PEP), polystyrene-polyisoprene block copolymer (PS- b-PI), or a block copolymer made of a combination of two or more thereof, and the like, but are not limited thereto.

Other examples of the organic porous material capable of forming the porous material include a hybridized single-molecule or low-molecular organic material capable of self-assembly. Specifically, a liquid crystal (liquid crystal) as a small molecule having amphiphilicity, and a metal-containing single molecule or a low molecular substance such as metallocene. In addition, hydrogen bonding, metal coordination, hydrophobic force, van der Waals force, pi-pi interaction, and electrostatic effects It is possible to use a self-assembled mono- or low-molecular substance. After forming a nanostructure through the self-assembled hybridized material, a portion of the hybridized material may be removed to form a porous material forming the second pore structure.

Since the hybrid porous structure according to the embodiment of the present invention includes the nanostructured porous material as described above, it is possible to selectively separate only particles of a specific size, as well as utilization as a separator material for a nanofiltration membrane or an ultrafiltration membrane, In particular, it can be effectively applied to biofiltration for water treatment.

In order to apply the hybrid porous structure to a separator or the like, it is necessary to adjust its physical properties, and it is easy to control its physical properties when the pore size and structure of the porous material are constant. The self-assembled structure described above is easily controlled by the molecular weight of the self-assembled block copolymer, the content ratio between polymers forming each block, and the like, and can be designed to have a uniform nanostructure of a desired size. Therefore, in the self-assembled structure designed as described above, by removing at least a part of at least one block to form pores, a porous material having uniform nanostructured pores can be easily formed. As described above, the self-assembled block copolymer can be easily formed of a porous material having a uniform nanostructure, and its manufacturing process is also very easy to form a porous material having a second pore of the hybrid porous structure. Very useful as a substance.

In order for the hybrid porous structure to be usefully applied as a separator, not only a uniform nano-porous structure, but also a high pore density per unit area of the entire hybrid porous structure must be high. This is because an effective function of the separator can be expected even at a low applied pressure when the pore density per unit area of the entire hybrid porous structure is high. As described above, a self-assembled block copolymer can be used to form a uniform nanostructured porous structure, and a plurality of porous materials including such porous structures are stacked so that a plurality of spherical bodies contact each other in a three-dimensional direction. By being present in the first pore of, it is possible to increase the pore density per unit area of the entire hybrid porous structure.

The plurality of first pores in the hybrid porous structure may have a narrower or substantially uniform spherical shape, while maintaining the mechanical strength of the hybrid porous structure, and increase the pore density per unit area of the entire hybrid porous structure. However, the hybrid porous structure may vary the size of the first pore according to the intended application. For example, the size of the first pore may be formed to become smaller or larger as it goes from one side to the other.

The hybrid porous structure may control the maximum pore density per unit area of the entire hybrid porous structure by controlling the size of one first pore constituting the laminate in a stacked shape in which a plurality of first pores are in contact with each other. have. For example, one first pore constituting the laminate may have an average diameter of about 1 nm to about 100 μm, and another example, an average diameter of about 10 nm to about 10 μm. As another example, it may have an average diameter of about 100 nm to about 1 μm. The hybrid porous structure includes a plurality of first pores having a size in the above range, and thus can be used as a separator having a high pore density per unit area.

The first pores of the hybrid porous structure contact each other in a three-dimensional direction to form a stacked shape of a plurality of spherical bodies interconnected, so that each of the pores can be connected in three dimensions. Due to the characteristics of the three-dimensional connection structure, defects are automatically compensated, and the hybrid porous structure can exhibit a very good effect in separating a target material of a specific size when applied to a separator.

On the other hand, in the case of the hybrid porous structure according to an embodiment of the present invention, even if the pore density per unit area is not the maximum, it was confirmed that it shows an excellent removal rate. Specifically, as can be seen from the examples described below, in the case of the hybrid porous structure according to Example 1 of the present invention, the porous material having the second pore does not completely fill the interior of the first pore, and the first pore A hybrid porous structure was prepared in such a way that a porous material having the second pores was formed only at a portion connected to adjacent first pores. In the case of the hybrid porous structure according to Example 1, Examples 2 and 3 It has been confirmed that the pore density per unit area is not high compared to the hybrid porous structure, and has a sufficient impurity removal rate, and shows a significantly higher water permeability than Examples 2 and 3. That is, as a result of evaluating the removal rate of gold (Au) particles having a size of 5, 10, 20, and 30 nm as a separation membrane containing the hybrid porous structure according to Example 1, the size of the second pores was adjusted to 16 nm The removal rate of the gold particles of the separator including the hybrid porous structure of Example 1 and the hybrid porous structure of Example 4 in which the size of the second pore was adjusted to 22 nm, in the case of Example 1, the 20 nm gold particle It was confirmed to remove 100% level, in the case of Example 4 it was confirmed to remove 89%. That is, in the case of a hybrid porous structure prepared by forming a porous material having a second pore only in a region where the first pores are connected to each other without filling the first pores, impurities larger than the size of the second pores are 100% removed. You can see that This is, in the hybrid porous structure prepared in Examples 1 and 4, the porous material having a second pore present only in the connection portion of the adjacent first pores of the first pores, in the hybrid porous structure, the second It acts as a fine microscopic (sieving) filter impurities particles larger than the pores, indicating that the impurities can be effectively prevented from moving from one first pore to another first pore. That is, since the porous materials having the second pores effectively block the connecting portions of the first pores in the hybrid porous structure, only a material smaller than the second pores of the porous material having the second pores passes through the porous material, and one It can move from the first pore to another second pore. Accordingly, it can be seen that, in the case of the hybrid porous structure according to the above embodiment, even if the pore density per unit area is not maximized, it has excellent impurity removal capability.

On the other hand, it can be expected to some extent that the permeability of the separator comprising the hybrid porous structures according to Examples 1 and 4 above will be somewhat higher than that of the hybrid porous structures of Example 2 or Example 3. However, as can be seen from Experimental Example 1 to be described later, in the case of a separation membrane including the hybrid porous structure according to Example 1, the water permeation amount is about 2,000 LMH or more at a pressure of 1.0 bar, which indicates the hybrid porous structure according to Example 3. It exhibits a permeability of about 20 times higher than the permeability of the separator, and is about 3 times higher than the separator comprising the hybrid porous structure according to Example 2. This increase in permeability represents a surprisingly unexpected improvement in permeability, which is remarkably high even considering that the permeability of a commercial ultrafiltration membrane is about 1,000 LMH. On the other hand, as described above, the separation membrane according to Example 1, despite having such a high permeability, the surprising removal effect that the impurity removal rate can also remove impurities having a particle diameter larger than the second pore to 100% level Have

Meanwhile, the matrix including the first pores is made of a non-porous material, thereby improving the mechanical properties of the hybrid porous structure. For example, in the separation membrane for water treatment, the matrix may have an average pore size in the range of 1 to 30 mm 2. However, when used as a selective separation membrane of a gas such as CO ₂ , it is possible to enhance the non-porous properties of the matrix to have a smaller pore size range. That is, the pore size of the matrix material that realizes the non-porous properties of the hybrid porous structure may be changed according to the use as a separator. As described above, the hybrid porous structure simultaneously includes a matrix made of a non-porous material including a plurality of first pores connected to contact each other in a three-dimensional direction, thereby hierarchically forming a pore structure made of the first pores. It is formed as a hybrid structure containing.

The material constituting the non-porous region can be used without limitation as long as it can maintain the mechanical strength of the hybrid porous structure to a desired level and can be applied to a manufacturing method described below. According to the method for producing a hybrid porous structure described below, after preparing a three-dimensional laminate structure with colloidal particles, forming a non-porous region to fill the gap, and then removing the laminate of colloidal particles therein , A matrix formed of a non-porous material including a plurality of first pores connected to each other in a three-dimensional direction is formed. The non-porous region should not be removed when performing the process of removing the stack of colloidal particles therein, and also the process for forming the second pores of the porous material having the second pores present in the first pore It must be able to be removed even when performed. Any material that satisfies these conditions in the manufacturing process and has a non-porous property suitable for the application and has a predetermined mechanical strength may be used as the matrix material without limitation to its type. For example, the non-porous material forming the matrix may be an inorganic oxide, a thermoplastic resin, or a curable resin.

Specific examples of the inorganic oxide that can be used as the non-porous material are titanium oxide, tin oxide, lead oxide, zirconium oxide, nickel oxide, copper oxide, yttrium (Y) oxide, magnesium oxide, calcium oxide, aluminum oxide, boron oxide, Silicon oxide, zeolite, and the like, and a solution containing these precursors is injected to fill a gap between a plurality of spherical bodies forming the laminate, and then cured by a sol-gel reaction to form a matrix of the hybrid porous structure. Can form.

Specific examples of the thermoplastic resin that can be used as the non-porous material are polyamide, polyethylene, polyester, polyisobutylene, polytetrafluoroethylene, polypropylene, polyacrylonitrile, polysulfone, polyethersulfone, polycarbonate , Polyethylene terephthalate, polyimide, polyvinylene fluoride, polyvinyl chloride, cellulose acetate, cellulose diacetate, cellulose triacetate, and the like.

Examples of the curable resin that can be used as the non-porous material include materials selected from the group consisting of thermosetting resins, photocurable resins, and combinations thereof. Each of the thermosetting resin and the photocurable resin can be used without limitation, a resin known as a thermosetting resin or a photocurable resin. Specifically, a thermosetting resin such as polydimethylsiloxane (PDMS) or a photocurable resin that can be cured by electromagnetic waves such as UV curable resin may be used. As specific examples of the UV curable resin, polyurethane-based, polyacrylate-based, polyepoxy-based, polyurethane-acrylate-based, polyester-acrylate-based, polyepoxyacrylate-based, silicone-based UV-curable resins, and the like can be exemplified.

A thermoplastic resin mixed with a solvent or a curable resin mixed with a solvent; Alternatively, a non-porous matrix may be prepared by injecting a liquid thermoplastic resin or a liquid curable resin in a molten state so as to fill a gap between a plurality of first pore forming spherical bodies forming the laminate, and then drying, cooling, or curing the liquid. .

The hybrid porous structure is formed of materials constituting a hybrid porous layer structure as described above, and thus effectively acts even at a low driving pressure and has excellent mechanical stability, and thus can be usefully used as a material for the next generation water treatment separation membrane. have. In addition, selective separation of microbial and environmental substances may be possible, and thus, it can be applied to applications such as sewage / wastewater treatment, food processing, and oil separation.

In order to be used as a separator, the hybrid porous structure has a membrane shape having two opposing surfaces and a thickness, wherein the two surfaces each have a relative area occupied by the first pores of about 5 to about 99% of the total surface area. Preferably, the first pores may be present in an exposed form, and the wall surface of the film in the thickness direction may be formed so that the first pores are not exposed. For example, each of the two surfaces may have a relative area occupied by the first pores of about 25 to about 90% of the total surface area, for example, about 50 to about 80%.

The hybrid porous structure may be formed of a film having a thickness of about 10nm to about 1000㎛. When the thickness of the film is thick, mechanical strength may be increased, but relatively high applied pressure may be required. In this way, the thickness of the membrane may be adjusted to have desired characteristics according to the purpose of the separation membrane. For example, the thickness of the film may be about 100 nm to about 500 μm. In another example, the thickness of the film may be about 1000nm to about 250㎛.

Accordingly, according to another embodiment of the present invention, there is provided a separator comprising a membrane formed of a hybrid porous structure according to the embodiment.

The separation membrane is a microfiltration membrane (MF), ultrafiltration membrane (UF), ultrafiltration membrane (NF), nanofiltration membrane (NF), reverse osmosis membrane (RO) by controlling the nanoporous structure of the porous region according to the application. ), Forward osmosis (FO).

The separator may be made of a single membrane or a composite membrane further comprising a heterogeneous membrane. For example, the separation membrane may be a single membrane of a membrane formed from the hybrid porous structure (hereinafter referred to as a 'hybrid porous structure membrane'). When the separation membrane is a composite membrane, for example, it may be a composite membrane in which a support membrane is bonded to the hybrid porous structure membrane. The support film is not limited in form and type, and a film formed by a known method can be used.

When the separation membrane is a composite membrane, the thickness of the hybrid porous membrane is as described above, and the thickness of the support membrane is about 200 µm to about 500 µm, for example, about 100 µm to about 250 µm, another for example about It may be 50㎛ to about 125㎛.

The support membrane is also a microfiltration membrane (MF), ultrafiltration membrane (UF), ultrafiltration membrane (NF), nanofiltration membrane (NF), reverse osmosis (RO) or forward osmosis membrane (FO) forward osmosis).

The support membrane is, for example, a polyacrylate-based compound, a polymethacrylate-based compound, a polystyrene-based compound, a polycarbonate-based compound, a polyethylene terephthalate-based compound, a polyimide-based compound, a polybenzimidazole-based compound, poly Benzthiazole-based compounds, polybenzoxazole-based compounds, poly-epoxy-based resin compounds, polyolefin-based compounds, polyphenylenevinylene compounds, polyamide-based compounds, polyacrylonitrile-based compounds, polysulfone-based compounds, cellulose-based compounds, poly And vinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinylchloride (PVC) compounds, and combinations thereof.

Hereinafter, a method of manufacturing the hybrid porous structure will be described.

Method of manufacturing a hybrid porous structure according to an embodiment of the present invention,

Stacking a plurality of spherical particles for forming the first pores to contact each other in a three-dimensional direction;

Filling a gap between the stacked spherical particles and injecting a liquid non-porous material to coat the outer surfaces of the spherical particles, followed by curing;

Dissolving and removing the plurality of spherical particles for forming the first pores in the cured non-porous material to form a matrix comprising a plurality of spherical first pores interconnected in a three-dimensional direction;

Forming a hybrid structure by injecting a self-assembled block copolymer in which at least two or more polymers are covalently linked into a plurality of first pores in the matrix; And

Step of partially or completely eluting and removing the polymer forming at least one kind of block in the self-assembled block copolymer among the hybrid structures.

A method of manufacturing a hybrid porous structure in which a porous material having a second pore fills part or all of each of the plurality of first pores is provided.

The step of forming a stacked body in which the plurality of spherical body particles for forming the first pores are brought into contact with each other in a three-dimensional direction includes forming a stacked body in which the spherical body particles are stacked in the closest stacked structure.

7 is a schematic diagram showing each step of the method for manufacturing the hybrid porous structure.

First, a plurality of first pore-forming spherical particles 4 are stacked so as to contact each other in a three-dimensional direction to form a laminate. Figure 7 (a) is a plurality of first pores for forming spherical particles (4) is formed of a stack of opal structures. As described above, in one embodiment, the size of the spherical particles 4 may be determined according to the pore density per unit area of the hybrid porous structure to be finally obtained. For example, the average diameter of the spherical particles 4 may be about 1 nm to about 100 μm, for example about 10 nm to about 10 μm, and for example about 100 nm to about 1 μm. As far as the shape of the spherical particles 4 and the laminate are concerned, it is the same as the description of the spherical and laminated bodies described to describe the shape of the first pores of the hybrid porous structure. For example, the spherical particles 4 may form an opal structure while having a size in the above range.

The plurality of spherical particles 4 for forming the first pores may be used without limitation as long as they are materials that can be selectively removed by etching after formation of the non-porous matrix 2. For example, in order to form a small size deviation between the spherical particles 4, colloidal particles may be used as the spherical particles 4. For example, spin coating, dip coating, sedimentation, spraying method using inorganic colloidal particles such as SiO ₂ or organic colloidal particles such as polystyrene (PS) and polymethyl methacrylate (PMMA), An opal structure of colloidal particles having a crystal lattice may be formed by using a coating method using a lamination method using an external stimulus such as an electrophoresis method, a LB (Langmuir-Blodgett) method, a mold-guide method, or the like.

A structure is formed by injecting a liquid non-porous matrix forming material 2 'so that the gaps between the spherical particles 4 of the laminate formed as described above are filled (Fig. 7 (b)). The liquid non-porous matrix forming material may be a thermoplastic resin, a curable resin, or an inorganic oxide precursor solution, and the detailed description is as described for the non-porous material constituting the matrix included in the hybrid porous structure. The method of injecting the liquid non-porous matrix forming material 2 'may be by a rotation coating method, a capillary filling method, a immersion coating, a spray method, or the like, but is not limited thereto.

To produce a free-standing thin-film hybrid porous structure 10 with both sides of the thin film open, in order to manufacture a plurality of first pores 1 on both sides of the thin film, the above Before curing the matrix forming material 2 'to form the matrix 2, some of the matrix forming material 2' is partially removed so that the spherical particles 4 are exposed on the surface (Fig. 7 (c). )). Subsequently, the matrix forming material 2 'is cured to form a matrix 2 (FIG. 7 (d)). By controlling the degree to which the spherical particles 4 are exposed, the relative area occupied by the plurality of first pore regions 1 on one surface of the thin film that is finally manufactured is about 5 to about 99% of the total surface area, for example For example, it may be about 25 to about 90%, and for example, about 50 to about 80%.

Subsequently, only the spherical particles 4 are removed using a solvent capable of selectively dissolving and removing only the spherical particles 4, thereby forming a spherical laminate shape connected in three-dimensional directions in the matrix 2 A plurality of first pores 1 are formed (Fig. 7 (e)). The small dots indicated on the first pore 1 in FIG. 7 (e) indicate that the first pores are interconnected with adjacent first pores.

Removal of the spherical particles 4 can be removed using hydrofluoric acid (HF) if the spherical particles 4 are inorganic oxide colloidal particles such as SiO _2, and the spherical particles 4 are polystyrene and The same organic colloidal particles can be removed using an organic solvent such as toluene. Depending on the type and size of the colloidal particles used as the spherical particles 4, it is possible to control the size of the lattice structure of the first pores of the laminate structure and the size of the pores at the inter-lattice connection sites.

A self-assembled structure is formed by injecting a self-assembled block copolymer into the plurality of first pores 1 in the first pore-containing matrix 2 (FIG. 7 (f)). Subsequently, a part or all of the polymer forming the at least one block in the self-assembled block copolymer is eluted and removed to form porous materials 3 having second pores, thereby forming a hybrid porous structure having a hierarchical pore structure. (10) can be obtained (Fig. 7 (g)).

The method for injecting the self-assembled block copolymer into the first pores 1 in the first pore-containing matrix 2 includes filling a melt or dilution solution of the self-assembled block copolymer, for example, a capillary tube. It can be performed by infiltrating into macropores 5 such as capillary filling, spin coating, deposition coating, or the like. Subsequently, a self-assembled block copolymer having a self-assembled structure formed on the surface inside the first pore 1 by solidifying the melt or dilution solution of the self-assembled block copolymer (in this case, forming a self-assembled structure) Can be coated. Depending on the injection method of the self-assembled block copolymer, a melt or diluent of the self-assembled block copolymer can be appropriately used.

Subsequently, a solvent that selectively dissolves only a polymer forming a block of at least one type of the self-assembled block copolymer is used in order to elute and remove some or all of the polymers forming a block of the self-assembled block copolymer. By doing so, the block copolymer can be etched. In this way, by forming a porous material (3) comprising a second pore smaller than the first pore into the plurality of first pores (1) in the non-porous matrix (2), the first in the non-porous matrix (2) It is possible to obtain a hybrid porous structure 10 comprising a porous material 3 having one pore 1 and a smaller second pore in the first pore.

As described above, the method for manufacturing the hybrid porous structure 10 is first to form a plurality of first pore-containing non-porous matrix 2, and then porous material having a second pore into the first pore 1 Since the porous material having the second pores can be formed by injecting the material forming 3), it can be easily applied to large area processing and industrial processing of several tens of micrometers thick.

On the other hand, in preparing a porous material (3) having a second pore by injecting the self-assembled block copolymer into a plurality of first pores (1) in the matrix (2), the self-assembled block copolymer of By adjusting the concentration, the ratio of the porous material having the second pore to the total volume ratio of the plurality of first pores, or the position of the porous material having the second pore in the first pore may be adjusted.

Specifically, as can be seen from the examples described below, the polystyrene-polymethyl methacrylate block copolymer having a content of about 20 to 30% of polymethyl methacrylate (PMMA) as the self-assembled block copolymer ( When using PS-b-PMMA), a solution containing 7% by weight of the block copolymer is injected into a matrix containing the first pores to form a porous material having a second pore, and In the case of using a solution containing a concentration of 10% by weight of the coalescence, and when using a solution containing the block copolymer in a concentration of 14% by weight, in the first pore of the porous material having a second pore formed from each The presence position and content of in are different. For example, when a porous material containing a second pore is formed by using a solution containing the block copolymer at a concentration of 7% by weight (Example 1), the porous material containing the second pores is in a plurality of first pores. In, the first pores are connected to adjacent first pores, that is, on the region where the partition walls of each pore forming one first pore and another another first pore do not exist, covering the region The second pore-containing porous material was formed into a shape. 3 is a simplified cross-sectional view of this, and FIG. 4 is a representation of FIG. 3 in a three-dimensional form. As can be seen from Figure 4 (a) and Figure 4 (b), a porous material containing a pore structure much smaller than the size of the first pores, inside a plurality of first pores formed in the form of a spherical laminate This, it can be seen that the first pores are present only in the connected region. 8 is a scanning electron for a cross-section of a hybrid porous structure prepared according to Example 1, showing a form in which the porous material having the second pores exists only in the first pores and on the connecting portions between the first pores. This is a micrograph (SEM).

On the other hand, Figure 9, prepared according to Example 2, using a solution containing the concentration of the block copolymer in 10% by weight of the scanning electrons for the cross section of the hybrid porous structure comprising a porous material having a second pore This is a micrograph (SEM). From FIG. 9, it can be seen that on the inner walls of the plurality of first pores, a porous material including smaller pores is coated as a whole.

Meanwhile, the size of the second pores of the porous material having the second pores can be adjusted by adjusting the relative proportions of the at least two polymer types or two or more polymers of the self-assembled block copolymer.

For example, as in Example 1 and Example 4 described later, when the volume ratio of PMMA in the polystyrene-polymethylmethacrylate block copolymer (PS-b-PMMA) is 20% (Example 1) ), While the diameter of the second pore can be adjusted to about 16 nm, when the molar ratio of the PMMA is about 28% (Example 4), the diameter of the second pore is adjusted to about 22 nm.

By adjusting the content of the polymer forming each block in the block copolymer, it is possible to easily and uniformly adjust the size of the second pores of the porous material prepared from the block copolymer. In the hybrid porous structure in which the size of the second pores is adjusted as described above, the size of the removable impurity particles according to the size of the second pores can be selected. For example, in the case of a hybrid porous structure in which the second pores having a diameter size of 16 nm are formed, gold (Au) particles having a size of about 20 nm can be removed with almost 100% efficiency, while having a size of 22 nm. In the case of the hybrid porous structure in which the second pores were formed, the removal rate of gold particles having a size of 20 nm was about 89%.

As described above, the method of manufacturing the hybrid porous structure according to the embodiment of the present invention is provided as a bypass of the feed solution containing impurities by controlling the size of the spherical particles forming the first pores. While the size of the plurality of first pores in the matrix can be easily adjusted, the nanopore size is much smaller than the first pore by controlling the type and relative proportion of polymers constituting each block of the self-assembled block copolymer. The size of the second pore can also be easily and uniformly adjusted.

In addition, the method of manufacturing the hybrid porous structure according to the embodiment, by adjusting the concentration or content of the material forming the porous material having the second pore, the porous having the second pore in the first pore in the hybrid porous structure The position and content of the material can be controlled, and the permeation amount or impurity removal rate suitable for the intended application can be easily adjusted therefrom.

In particular, as can be seen from the results of the examples to be described later, according to the embodiment, the porous material having the second pores is present only in the connection portion with the adjacent first pores of the first pores, and in the form of blocking the connection portion When present, there is no obstacle in the hybrid porous structure that prevents the flow of material in the first pore serving as a bypass for the material, for example, when used as a water treatment membrane, the permeability is remarkably You can see that it can be improved. Specifically, in the case of a hybrid porous structure prepared using a solution containing 7% by weight of a polystyrene-polymethylmethacrylate block copolymer (PS-b-PMMA) according to Example 1, the water permeation amount at 1 bar pressure It was found to be over 2000 LMH, which is more than twice the water permeability of the existing ultrafiltration membrane. On the other hand, in the case of a hybrid porous structure in which a porous material having a second pore was formed using a solution containing the concentration of the block copolymer as 10% by weight (Example 2), the permeability was 700 LMH or less, and the block air In the case of a hybrid porous structure (Example 3) in which the concentration of the coalescence was increased to 14% by weight to form a porous material having second pores, the permeability was significantly lowered to 100 LMH.

In addition, as can be seen from FIG. 10, in the case of the separator comprising the hybrid porous structure according to Example 1, when the pressure was increased to 2.5 bar, the water permeability was further improved to 2,000 LMH or more, and the mechanical properties of the separator It can be seen that the strength is also sufficiently guaranteed.

On the other hand, in the case of using the hybrid porous structure according to Example 1, despite the high water permeability as described above, since it still exhibits a high impurity removal rate, it is considered to be very useful for use as a water treatment film having both high water permeability and removal rate. This effect, as described above, the porous structure having the second pores present in the connecting portion of the first pores of the hybrid porous structure according to an embodiment of the present invention, although present only in the connecting portion of the first pore, this is one This indicates that it can sufficiently perform a role as a microseive that prevents the movement of impurities from the first pore to the other second pore.

As described above, the hybrid porous structure according to the embodiment of the present invention, the size and porosity of the first and second pores can be easily controlled and uniformly maintained, and further having a second pore in the first pore Since the position of the porous material can also be controlled, it is possible to significantly improve the water permeation rate and the impurity removal rate of the separator including the hybrid porous structure prepared therefrom. At the same time, the hybrid porous structure can also maintain high mechanical strength due to the presence of a non-porous matrix.

Hereinafter, specific embodiments of the present invention are presented. However, the examples described below are only for specifically illustrating or describing the present invention, and the present invention is not limited thereto.

( Example )

Manufacturing example  1: Preparation of polystyrene colloid particles

Emulsion polymerization was chosen to synthesize polystyrene (PS) colloidal particles. First, add 25 ml of ethanol and 0.01 g of polyvinylpyrrolidone (PVP) to a beaker, then prepare 3 ml of distilled water and 0.0065 g of ammonium persulfate (APS) in another container, After stirring for several minutes each, the two solutions are mixed. Thereafter, 2.2 ml of styrene monomer was added to the mixed solution and reacted at 70 ° C. for 12 hours. After the reaction is completed, the centrifugation process and the sonication process are repeated 3 times using ethanol at 11,000 rpm to remove unreacted substances or impurities such as PVP from the reactants.

Manufacturing example  2: Reverse opal Non-porous  Preparation of the matrix

Using the 600 nm-sized polystyrene nanoparticles prepared in Preparation Example 1, an opal structure having a highly crystalline lattice shape is formed by sedimentation. Polyurethane acrylate (PUA) is injected into the formed opal structure by a rotation coating method (1,000 rpm, 5 min). In order to form a free-standing thin film in which both sides of the reverse opal structure thin film are open, ethanol (30 v / v%, distilled water) is rotated (1,000 rpm, 30 sec) and is present in excess on the surface. The polyurethane acrylate is removed and the surface is flattened. Subsequently, an inverted opal-type polyurethane acrylate matrix is formed through curing for 30 minutes under ultraviolet light exposure conditions, and then supported by toluene for 2 hours to remove polystyrene particles therein.

Manufacturing example  3: Synthesis of block copolymer

Polystyrene-polymethyl methacrylate block copolymer (PS-b-PMMA) is synthesized on tetrahydrofuran (THF) solvent using styrene and methyl methacrylate monomers through anionic polymerization. In an argon atmosphere, the initiator was prepared using sec-butyllithium -78 The polymerization reaction is carried out at ° C. The number average molecular weight was confirmed to be 86 to 88 kg / mol (PDI <1.06), and the volume fraction of PMMA ( ? _PMMA ) was adjusted between 0.20 and 0.28.

Example  1: Preparation of hybrid porous structure

After incorporating a 7% by weight dilution solution of the PS-b-PMMA block copolymer (PS volume fraction = 80%) prepared in Preparation Example 3 into the reverse opal non-porous matrix prepared in Preparation Example 2, the solvent was vaporized. To form a thin film of the block copolymer therein, and again, applying a heat treatment process of 170 ° C. for 24 hours under vacuum to induce nanophase separation in the form of a cylinder. Thereafter, the chain of PMMA is decomposed through ultraviolet (UV) dimming in a vacuum for 5 hours, and then the decomposed PMMA is eluted using acetic acid to prepare a nanoporous structure of the block copolymer. Thus, a hybrid porous structure in which the nanoporous structure of the block copolymer was formed in a reverse opal non-porous matrix was prepared. FIG. 8 shows a scanning electron microscope (SEM) photograph of a cross section of the hybrid porous structure prepared according to the present embodiment.

As can be seen from Figure 8, the nanoporous structure formed from the 7% by weight dilution solution of the block copolymer, in the inverse opal non-porous matrix, the spherical pores are mainly formed at the site where they are connected to each other Able to know.

Example  2: Preparation of hybrid porous structures

Nanopores of the block copolymer in the same manner as in Example 1, except that a 10% by weight dilution solution of the PS-b-PMMA block copolymer (PS volume fraction = 80%) prepared in Preparation Example 3 was used. A hybrid porous structure including the structure is prepared. 9 is a scanning electron microscope (SEM) photograph of a cross section of a hybrid porous structure prepared according to the present embodiment.

Example  3: Preparation of hybrid porous structures

Nanopores of the block copolymer in the same manner as in Example 1, except that a 14% by weight dilution solution of the PS-b-PMMA block copolymer (PS volume fraction = 80%) prepared in Preparation Example 3 was used. A hybrid porous structure including the structure is prepared.

Example  4: Preparation of hybrid porous structure

Nanopores of the block copolymer in the same manner as in Example 1, except that a 7% by weight dilution solution of the PS-b-PMMA block copolymer (PS volume fraction = 72%) prepared in Preparation Example 3 was used. A hybrid porous structure including the structure is prepared.

Manufacturing example  4: Preparation of separator

In order to evaluate the permeability and impurity removal rate of the hybrid porous structures prepared in Examples 1 to 4, the hybrid porous structures (15 μm) and the cellulose acetate (CA: cellulose acetate) support membrane (0.45 μm) as a commercialized support After binding, assembled in a stirred cell to prepare an ultrafiltration (UF) membrane.

Experimental Example  1: Membrane performance evaluation

(One) Pitching  evaluation

In order to evaluate the membrane performance for each separator prepared in Preparation Example 4, the degree of purification was evaluated after passing through a feed solution.

The effective membrane area of the Stirred cell of Preparation Example 4 was 4.1 cm 2. In order to measure the permeability, pressure is applied using nitrogen gas, and the permeability is calculated by measuring the volume over time. The permeation amount is calculated according to Equation 1 below.

(Equation 1)

F = V / (A * t)

In Equation 1, V represents the permeate flow rate, A represents the membrane area, and t represents the measurement time.

The permeability of the separators prepared from the hybrid porous structures according to Examples 1 to 3 is as shown in Table 1 below.

Example 1 Example 2 Example 3 Pitching 2,000 LMH 700 LMH 100 LMH or less

On the other hand, by measuring the change in the permeability according to the pressure increase of the separation membrane is shown in the graph of FIG.

As can be seen from Table 1, the separation membrane comprising a hybrid porous structure prepared by setting the concentration of the PS-b-PMMA block copolymer to about 7% by weight has a water permeability of 2,000 LMH, and the concentration of the block copolymer is 10% by weight. Or it can be seen that the permeability is significantly increased compared to the separation membrane comprising a hybrid porous structure in which a nanoporous structure is prepared using a solution increased to 14% by weight.

In addition, it can be seen from FIG. 10 that the permeability increases more rapidly than the separator comprising the hybrid porous structures of Example 2 and Example 3 when the pressure is increased. It can be seen that, even when high pressure is applied, mechanical strength is also sufficient. In particular, when the pressure increases by 2.5 bar or more, the permeation rate increases to 3,000 LMH or more.

On the other hand, the separation membrane containing the hybrid porous structure of Example 3, despite the pressure increase, the permeability increase was very small, even if the pressure was increased to 2.5 bar or more, the permeability was less than 500 LMH. The separation membrane comprising the hybrid porous structure of Example 2 also does not have a large increase in permeability despite increasing pressure, but when increasing the pressure to 2.5 bar, shows a permeation amount of about 1,000 LMH, similar to that of a commercially available ultrafiltration separation membrane. Can be seen.

(2) Impurity removal rate evaluation

In addition, in order to evaluate the removal rate of impurities, gold nanoparticles were prepared at 5, 10, 20, and 30 nm, and tested under 1 bar. In addition, the removal rate is measured by checking the concentration change of the influent solution and the product water solution using UV-vis spectroscopy.

For the removal rate test, a separation membrane including the hybrid porous structure according to Example 1 and a separation membrane including the hybrid porous structure according to Example 4 were used. In the hybrid porous structure according to Example 1, the PMMA volume fraction of the block copolymer forming the nanoporous structure is 20%, and the pore size of the block copolymer formed therefrom is about 16 nm. On the other hand, in the hybrid porous structure according to Example 4, the PMMA volume fraction of the block copolymer forming the nanoporous structure is about 28%, and the pore size of the block copolymer formed therefrom is about 22 nm.

The results of evaluating the removal rate of gold particles having the particle size using these separators are shown in Table 2 below.

 Removal rate (%) / gold (Au) diameter 5 10 20 30 Example 1 (nanopore size: 16 nm) 30 77 100 100 Example 4 (nanopore size: 22 nm) 25 68 89 100

As can be seen from Table 2, the separation membrane according to the embodiment of the present invention can easily adjust the size of the nanopores in the hybrid porous structure by adjusting the volume fraction of the polymer forming each block of the block copolymer, etc. , As a result, selectivity and removal rate according to the material to be removed can be significantly increased.

Although preferred embodiments of the present invention have been described in detail above, the scope of rights of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concept of the present invention defined in the following claims are also provided. It belongs to the scope of the invention.

Claims (20)

A hybrid porous structure comprising a matrix comprising a plurality of first pores interconnected in a three-dimensional direction and a porous material having a second pore filling part or all of each of the plurality of first pores,
The matrix is made of a non-porous material,
The porous material having the second pore is derived from a self-assembled block copolymer, and includes nanopores formed by removing some or all of the polymers forming at least one block of the self-assembled block copolymer. Hybrid porous structure. In claim 1,
The plurality of first pores are spherical (spherical) hybrid porous structures connected to each other in a three-dimensional direction. In claim 1,
The non-porous material is a hybrid porous structure selected from inorganic oxides, thermoplastic resins, curable resins, and combinations thereof. In claim 1,
The porous material having the second pores is a hybrid porous structure that occupies 70% or less of the total volume of the plurality of first pores in the matrix. In claim 1,
The porous material having the second pores is a hybrid porous structure in the plurality of first pores, wherein the first pores exist in a form of blocking a portion interconnected with adjacent first pores. In claim 1,
The porous material having the second pores is a hybrid porous structure present in the form of coating the inner walls of the plurality of first pores. delete delete In claim 1,
The self-assembled block copolymer is a polystyrene-polymethylmethacrylate block copolymer (PS-b-PMMA), a polystyrene-polybutadiene block copolymer (PS-b-PB), a polystyrene-polyethylene oxide block copolymer (PS -b-PEO), polystyrene-polyvinylpyridine block copolymer (PS-b-PVP), polystyrene-polyethylene-alt-propylene block copolymer (PS-b-PEP), polystyrene-polyisoprene block The hybrid porous structure is selected from copolymers (PS-b-PI) and combinations thereof. In claim 1,
The plurality of first pores is a hybrid porous structure having an average diameter of 5nm to 100㎛. In claim 1,
The second pore is a hybrid porous structure having an average diameter of 1nm to 100nm. In claim 1,
The hybrid porous structure is in the form of a film having two opposing surfaces and a thickness, and the two opposing surfaces are hybrid porous structures each occupying 5 to 99% of the total surface area. In claim 12,
In the hybrid porous structure having the form of the membrane, the thickness of the membrane is 10 nm to 1000 ㎛ hybrid porous structure. Separator comprising the hybrid porous structure of any one of claims 1 to 6 and 9 to 13. In claim 14,
A separation membrane in the form of a composite membrane further comprising a support membrane. Stacking a plurality of spherical particles for forming the first pores to contact each other in a three-dimensional direction;
Filling a gap between the stacked plurality of spherical particles, and injecting and curing a liquid non-porous material to coat the outer surfaces of the spherical particles;
Dissolving and removing the plurality of spherical particles for forming the first pores in the cured non-porous material, thereby forming a matrix comprising a plurality of first pores that are connected in a three-dimensional direction;
Forming a hybrid structure by injecting a self-assembled block copolymer in which at least two or more polymers are covalently linked into a plurality of first pores in the matrix; And
Forming a porous material having second pores by partially or completely eluting a polymer forming at least one block in the self-assembled block copolymer among the hybrid structures.
Containing,
A method of manufacturing a hybrid porous structure in which a porous material having a second pore fills part or all of each of the plurality of first pores. In claim 16,
The step of stacking the plurality of spherical particles for forming the first pores so as to contact each other in a three-dimensional direction comprises: stacking the spherical particles so that they are stacked in a closest packing structure. Manufacturing method. In claim 16,
The plurality of spherical particles for forming the first pore is a method for producing a hybrid porous structure that is a colloidal particle. In claim 16,
The step of forming a hybrid structure by injecting the self-assembled block copolymer into a plurality of first pores in the matrix includes adjusting and injecting the concentration of the self-assembled block copolymer, and the self-assembled block A method of manufacturing a hybrid porous structure that controls the position of the porous material having the second pores in the plurality of first pores by adjusting and injecting the concentration of the copolymer. In claim 16,
The size of the second pores of the porous material having the second pores, the method of manufacturing a hybrid porous structure is controlled by adjusting the type of the at least two polymers of the self-assembled block copolymer or the relative proportion of the polymers.

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