WO2020096353A1 - Mof nanoparticles surface-treated with fatty acid and mof-polymer composite containing same - Google Patents

Abstract

The present invention provides: surface-modified metal-organic framework (MOF) particles which are surface-treated with a liquid fatty acid, wherein the carboxyl group of the fatty acid forms chemical bonds with hydrophilic groups exposed to MOF surfaces, a metal, or both, and the fatty acid is an unsaturated or saturated fatty acid; an MOF-polymer composite comprising a polymer and the surface-modified MOF particles which are uniformly distributed in the polymer; and an MOF-polymer composite molded product obtained by molding the MOF-polymer composite.

Description

MOF nanoparticles surface-treated with fatty acids and MOF-polymer complex containing the same

The present invention is a metal-organic framework (MOF) particle surface-treated with liquid fatty acids, wherein the carboxyl group of the unsaturated fatty acid forms a chemical bond with a hydrophilic group, metal, or both exposed on the MOF surface. Characterized by surface-modified MOF particles; A MOF-polymer composite comprising a polymer and the surface-modified MOF particles uniformly distributed in the polymer; And a MOF-polymer composite molded body obtained by molding the MOF-polymer composite (eg, fiber, film, membrane, etc.).

Organic-inorganic hybrid nanopores, so-called metal-organic frameworks (MOFs), are commonly referred to as "porous coordination polymers", or "porous organic-inorganic hybrids". The metal-organic skeletal body has recently begun to develop newly by the combination of molecular coordination and material science, and the metal-organic skeletal body has a high surface area and pores of a molecular size or a nano-scale, and thus an adsorbent and gas storage material , Sensors, membranes, functional thin films, drug delivery materials, catalysts, and catalyst carriers, as well as being applicable to collecting guest molecules smaller than the pore size or using pores to separate molecules according to the size of the molecules Therefore, it has been actively studied recently. In addition, the metal-organic framework has nano-sized pores, and thus has the advantage of providing a high surface area. Therefore, it is mainly used for adsorption of substances or supporting the composition in pores for delivery.

MOF is a porous material, and it is possible to simultaneously implement the function of an adsorbent and a function of a catalyst. When the conventional MOF is applied to the fiber, there is a problem in mass production or manufacturing in the form sprayed on the fiber. In addition, even if a method such as electrospinning is used, there is a problem in manufacturing that is not uniformly mixed or the nozzle is clogged.

The present invention is intended to provide a method for modifying MOF nanoparticles having excellent miscibility with organic solvents and / or polymers, in order to provide various MOF-polymer composite molded products including composite fiber products containing MOF nanoparticles.

The first aspect of the present invention is a metal-organic framework (MOF) particle surface-treated with a liquid fatty acid, wherein the carboxyl group of the fatty acid has a chemical bond with a hydrophilic group, metal or both exposed on the MOF surface. It provides surface-modified MOF particles characterized by being formed.

The second aspect of the present invention includes a polymer; And it provides a MOF-polymer complex comprising the surface-modified MOF particles of the first aspect uniformly distributed in the polymer.

The third aspect of the present invention provides a MOF-polymer composite molded body obtained by molding the MOF-polymer composite of the second aspect.

When the liquid fatty acid is used as the surface modifier of the MOF particles according to the present invention, not only can the dispersibility with the polymer be enhanced, but also the molecular size or nano-sized pores of the MOF that exhibit adsorption and catalytic activity are not blocked The pores can be coated in an orientation that does not interfere with the access of the desired molecules (eg, gas permeation) as much as possible.

Therefore, MOF particles surface-modified with liquid fatty acids according to the present invention; And MOF-polymer composite molded body made of MOF-polymer complex containing polymer uniformly, the adsorption and / or catalytic properties of the MOF natural combine with the functionality of the polymer, removing harmful gases, removing harmful substances, desalination, desalination It can be used in various separation, purification, adsorption, catalyst, and functional materials fields.

1 is a MOF-polymer composite of a typical MOF nanoparticle and a matrix polymer (top view) and a MOF of a MOF nanoparticle and a matrix polymer surface-modified with unsaturated or saturated fatty acids according to the present invention (bottom view) It is a conceptual diagram showing structural differences including aggregation and uniform dispersion of nanoparticles.

FIG. 2 is a TEM photograph of general MOF nanoparticles (left view) and MOF nanoparticles (right view) surface-modified with unsaturated fatty acids. In the right view, there is no aggregation between particles.

FIG. 3 is a photograph of surface-modified Zn-MOF and Co-MOF nanoparticles dispersed in a solvent and a TEM photograph of MOF nanoparticles.

4 is a photograph showing XRD crystallinity analysis before and after surface modification treatment with unsaturated fatty acids for Co-MOF nanoparticles.

5 is a TEM photograph of Zr-MOF nanoparticles before and after surface treatment with unsaturated or saturated fatty acids.

FIG. 6 is a photograph showing XRD crystallinity analysis before and after surface modification treatment for Zr-MOF nanoparticles.

7 is a photograph of a MOF-polymer composite fiber mat (20x30 cm) containing at least 55, 65, and 75 wt% of MOF, respectively, and a fiber SEM photograph thereof.

8 is a high-resolution SEM and TEM photograph of a composite fiber containing 55 wt% or more of MOF nanoparticles.

9 is an SEM photograph of fibers prepared using a polymer solution containing Zr-MOF surface-modified with OA as an unsaturated or saturated fatty acid.

FIG. 10 is a photograph of a fabric woven of fibers prepared using a polymer solution containing MOF surface-modified with unsaturated or saturated fatty acids.

FIG. 11 is a photograph of a film produced by a heat-extrusion process and a MOF-Polypropylene composite chip injection molded with Al-MOF nanoparticles containing 3 wt% and 10 wt% respectively.

12 is an SEM photograph of the MOF-Polypropylene composite film of FIG. 11. Here, it can be confirmed that the MOF nanoparticles are uniformly distributed and there are no defects at the interface.

13 is an XRD analysis result for the MOF-Polypropylene composite film of FIG. 11.

14 is a photograph of a composite membrane of MOF-Polyimide containing 40 wt% or more of Zr-MOF nanoparticles.

15 is an SEM photograph of the MOF-Polyimide composite separation membrane of FIG. 14. At this time, it can be confirmed that the MOF nanoparticles are uniformly distributed and there are no defects at the interface.

One aspect to achieve the above object is a metal-organic framework (MOF) particles surface-treated with liquid fatty acids, the carboxyl group of the fatty acid being exposed to the surface of the MOF hydrophilic group, metal or both It provides surface-modified MOF particles characterized by forming chemical bonds.

In this specification, “adsorption” is a concept that includes both adsorption and sorption, as well as narrow adsorption.

A metal-organic framework (MOF) is a porous organic-inorganic polymer compound formed by binding of a central metal ion with an organic ligand through molecular coordination bonding, and includes both organic and inorganic substances in the framework structure, and has a molecular size or nano It is a crystalline compound having a pore structure of size. The framework of the MOF is formed by covalent bonding between metal-organic clusters (SBUs), which are secondary buiding units (SBUs), and organic ligands, and the metal-organic clusters have nodes in the MOF framework. Can be. MOF are the geometry of the various coordination bond (coordination geometries), poly linker of topics (polytopic linkers), and the auxiliary ligand is composed of a ^{(ancillary ligands (F -, H} 2 O among others) -, OH).

Therefore, the MOF design starts with selecting the right metal ion and the right organic ligand. For example, reacting metal ions (eg, Zn ²⁺ ) with various acetates produces Zn ₄ O (CH ₃ COO) ₆ clusters, and combining these clusters with organic ligands produces MOF structures. At this time, the organic ligand portion of the benzene structure may be a spacer, and a Zn ₄ O (CH ₃ COO) ₆ cluster portion may be a node.

The central metal ion of the MOF is Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Be ²⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Sc ³⁺ , Y ³⁺ , Ti ⁴⁺ , Zr ⁴⁺ , Hf ⁺ , V ⁴⁺ , V ³⁺ , V ²⁺ , Nb ³⁺ , Ta ³⁺ , Cr ³⁺ , Mo ³⁺ , W ³⁺ , Mn ³⁺ , Mn ²⁺ , Re ^{3 +} , Re ²⁺ , Fe ³⁺ , Fe ²⁺ , Ru ³⁺ , Ru ²⁺ , Os ³⁺ , Os ²⁺ , Co ³⁺ , Co ²⁺ , Rh ²⁺ , Rh ⁺ , Ir ²⁺ , Ir ⁺ , Ni ²⁺ , Ni ⁺ , Pd ²⁺ , Pd ⁺ , Pt ²⁺ , Pt ⁺ , Cu ²⁺ , Cu ⁺ , Ag ⁺ , Au ⁺ , Zn ²⁺ , Cd ²⁺ , Hg ²⁺ , Al ^{3 +} , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Si ⁴⁺ , Si ²⁺ , Ge ⁴⁺ , Ge ²⁺ , Sn ⁴⁺ , Sn ²⁺ , Pb ⁴⁺ , Pb ²⁺ , As ⁵⁺ , As ³⁺ , As ⁺ , Sb ⁵⁺ , Sb ³⁺ , Sb ⁺ , Bi ⁵⁺ , Bi ³⁺ and Bi ⁺ may be selected from the group consisting of, but are not limited thereto.

The organic ligand is also referred to as a linker (linker), can be any organic compound having a functional group capable of coordination bond, and, for example, the organic ligand is a carboxyl group (-COOH), a carboxylic acid anion group (-COO ^-), amine Group (-NH ₂ ) and imino group (-NH), nitro group (-NO ₂ ), hydroxy group (-OH), halogen group (-X) and sulfonic acid group (-SO ₃ H), sulfonic acid anion group (-SO ₃ ^-), methane dithiol Osan group (-CS ₂ H), methane dithiol Osan anion group (-CS ₂ ^- may be used), a pyridine group and a compound or a mixture thereof having at least one functional group selected from the group consisting of a pyrazine . MOF may be a dicyclic anion of a heterocyclic ring as a ligand. Preferably, the ligand is from the group consisting of terephthalate anion, furandicarboxylic acid anion, pyridinedicarboxylic acid anion, benzenetricarboxylic acid, thiophenedicarboxylic acid anion and pyrazoledicarboxylic acid anion. It may be one or more selected, but is not limited thereto.

The MOF in which the crystalline skeleton contains polar metal ions and carboxylic acid oxygen anions and co-existing non-polar aromatic compound groups can have both hydrophilicity and hydrophobicity.

Non-limiting examples of organic-inorganic hybrid nanoporous materials include NU-1000, MIL-100, MIL-101, extended MOF-74, PCN-222, DUT-32, Al-BDC (benzene dicarboxylate), Fe-BDC, Cr-BDC, V-BDC, Al-BTC, Cr-BTC, Fe-BTC, Al-BDC, Cr-BDC, Zr-BPDC, Cu-BTC (L1) (L1 = 5-nitro-1,3-dicarboxylate , Or 5-cyanide-1,3-dicarboxylate or 5-hydroxyl-1,3-dicarboxylate or pyridine-3,5-dicarboxylate), UiO-67, UiO-68, MOF-808, DUT-37, HKUST-1 (Cu ₃ (btc) ₂ , btc: benzene-1,3,5-tricarboxylate) (tbo), MOF-14 (Cu ₃ (btb) ₂ , btb: benzene-1,3,5-tribenzoate) (pto) , DUT-34 (Cu ₃ (btb) ₂ ), DUT-23 ([Cu ₂ (bipy)] ₃ (btb) ₄ ), MOF-14, DUT-34, DUT-33, MOF-74 (CPO-27 ), UMCM-1, UMCM-2, DUT-6 (MOF-205), UMCM-3, UMCM-4, UMCM-5, MOF-210, DUT-32 (Zn ₄ O (bpdc) (btctb) _{4 / 3} , btctb: 4,4 ', 4 “-[benzene-1,3,5-triyltris (carbonylimino)] trisbenzoate, bpdc: 4,4'-biphenylendicarboxylate), DUT-6, PCN-21, DUT-68, MOP-1, DUT-49, UMCM-1, DUT-7, DUT-28 (Co ₂₂ (BTB) ₁₂ (NO ₃ ) ₈ (DEF) _x (H ₂ O) _y ), NU-109, NU-110 , DUT-13 (Zn ₄ O- (BenzTB ) _3/2 , BenzTB: N, N, N ', N'-benzidinetetrabenzoate), PCN-69, HKUST-1, MIL-101 (Cr), UMCM-1; Ligand functionalized materials (Wina Zhang, Yayuan Liu, Guang Lu, Yong Wang, Shaozhou Li, Chenlong Cui, Jin Wu, Zhiling Xu, Danbi Tian, Wei Huang, Joseph S. DuCheneu, W. David Wei, Hongyu Chen) , Yanhui Yang, and Fengwei Huo, Adv. Mater. 2015, 27, 2923-2929); Mixtures thereof.

The MOF is a porous material, and can function as an adsorbent and / or as a catalyst by pores. However, as the content of MOF increases, the adsorption and / or catalytic effect increases, while the defects or gaps between the matrix polymer and the MOF are large (FIG. 1), and the MOF particles have good dispersibility when preparing a composite with the polymer. There is no uniform characteristic, and MOF content is limited. In addition, since the mixing properties are not good and the dispersibility is not good, a heterogeneous mixture or precipitation occurs. Therefore, when molding the final product (fiber products, membranes, injection molded products, etc.), there are difficulties due to clogging of nozzles and cracks.

For example, MOFs often include M (Metal) -O or M-OH structures in the central metal or polar functional groups in ligands, such as the ZIF series, and are highly hydrophilic and organic solvents or organic materials. Dispersion is difficult due to poor miscibility. Therefore, when the MOF nanoparticles are dispersed in a solvent and used as a solution, there is a disadvantage that the size of the MOF particles increases due to agglomeration. In addition, when the particle size of the MOF is increased, miscibility with each other is reduced when manufactured in a masterbatch with a polymer, and as a result, product quality such as cracks in the molding process may be deteriorated. Therefore, even if spinning by electrospinning, etc., only MOF nanoparticles are agglomerated, and it is not uniformly mixed with the polymer. As a result, it is difficult to manufacture fibers (mat mat) of sufficient size due to problems such as clogging and precipitation and clogging of the nozzle. , It is virtually impossible to manufacture a textile product (nonwoven fabric, fabric, etc.) in which the MOF is uniformly dispersed. Also, it was only possible to include a small amount of MOF, if possible. Therefore, it was manufactured by attaching MOF to the fiber surface once produced, and as a result, there is a problem in that mass production is difficult and MOF is easily detached from the product.

The present invention liquidifies the MOF particles to provide surface-modified MOF particles to prevent agglomeration between MOF particles and increase miscibility with organic solvents and / or polymers, while maintaining various functions exerted by pores in the final product. It is characterized by surface treatment with unsaturated or saturated fatty acids.

Surface treatment of MOF particles with liquid unsaturated or saturated fatty acids according to the present invention to increase miscibility with organic solvents and / or polymers can also be applied to nanoscale (e.g., 5 nm to 1000 nm) MOF particles with much greater cohesion problems. 2 (FIGS. 2, 3, 5, and 7-9).

In the present invention, the MOF particles to be subjected to the surface treatment, preferably in a uniform size, may be surface treated with liquid unsaturated or saturated fatty acids after grinding.

The term “fatty acid” of the present invention is a material containing a hydrocarbon chain and a carboxyl group (-COOH) at its end, and the hydrocarbon chain has hydrophobicity but can interact with a hydrophilic material through a terminal carboxyl group.

The 'fatty acid' of the present invention may be an unsaturated or saturated fatty acid.

The unsaturated fatty acid is preferably C5 to C50 in terms of miscibility with the organic solvent and / or polymer of MOF.

Unsaturated fatty acid is COOH or COO in the end with a fatty acid having at least one double ^bond is a hydrophilic group, for example, MO / M-OH structures which are exposed to the MOF surface of the particles (M is a central metal ion); Ancillary ligand ^{(ancillary ligands (F -, OH} -, H 2 O among others)); And / or an organic ligand of the carboxyl group (-COOH), a carboxylic acid anion group (-COO ^-), an amine group (-NH _2), and an imino group (-NH), a nitro group (-NO _2), a hydroxy group (-OH ), a halogen group (-X), and a sulfonic acid group (-SO ₃ H), a sulfonic acid anion group (-SO ₃ ^-), methane dithiol Osan group (-CS ₂ H), methane dithiol Osan anion group (-CS ₂ ^-) , Pyridine group and pyrazine group; And / or hydrogen bonds, ionic bonds, covalent bonds, etc. with the unsaturated coordination sites of the MOF, while the curved carbon chain of the unsaturated fatty acid is oriented toward the outside of the MOF particles due to the double bond, thereby accessing desired molecules into the pores (e.g., gas permeation) ) Can form a hydrophobic channel in an orientation that does not interfere as much as possible. Therefore, even if the surface of MOF particles is modified using unsaturated fatty acids according to the present invention, it is possible to access and / or release desired molecules into the pores (eg, gas permeation) without blocking the pores of the MOF. Thus, adsorption and / or catalytic activity of MOF can be exhibited.

The saturated fatty acid preferably has C4 to C40 in terms of miscibility with MOF's organic solvent and / or polymer. Specifically Butyric acid, caprylic acid, caprylic acid, capric acid, lauric acid, myristic acid and palmitic acid acid), stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melic acid (Melissic acid) and corinomycolic acid (Corynomycolic acid) may be one or more selected from the group consisting of, but is not limited now.

Furthermore, when the surface of MOF particles is modified using liquid fatty acids according to the present invention, MOF particles have hydrophobicity due to the carbon chain of fatty acids, and thus not only suppress aggregation between MOF particles surface-modified with liquid fatty acids ( 2), it is possible to impart mixing / dispersibility with an organic solvent and / or a polymer (FIGS. 3, 5, 7 and 9). For this reason, the mixing properties with various polymers are very excellent, and at this time, the MOF particles can be contained in a uniformly dispersed state and 90 wt% or more by mass ratio is also possible. Since excellent dispersibility provides a uniform structure and improves the mixing property with a polymer, for example, in the case of fiber production, spinning for a long time is possible, so that large-area fiber production is possible.

On the other hand, fatty acids having COOH or COO ^- functional groups can chemically bond with hydrophilic groups and / or metals exposed on the surface of MOF particles (e.g., hydrogen bonds, ionic bonds, covalent bonds), and thus It is also within the scope of the present invention to use saturated fatty acids (eg, stearic acid) as surface modifiers as long as they are compatible.

Another aspect of the present invention, the present invention is a polymer; And MOF particles uniformly distributed in the polymer, and MOF particles surface-modified with liquid fatty acids.

In this case, the MOF particle content may be 0.5 to 95 parts by weight based on 100 parts by weight of the total MOF-polymer composite. In addition, in the MOF-polymer composite of the present invention, the polymer may be a binder or a moldable resin.

Since MOF is a material containing a large number of pores, its density is very low at a level of approximately 0.5 g / cm ³ or less, whereas for polyimide mainly used as a matrix polymer, for example, since the density is 1 g / cm ³ or more, MOF 30 In the case of wt%, the volume occupied by the MOF itself in the matrix occupies at least 60% (FIGS. 7 and 8).

Therefore, based on 100 parts by weight of the total MOF-polymer complex, MOF-polymer complex containing 30 parts by weight to 95 parts by weight of MOF nanoparticles surface-modified with unsaturated or saturated fatty acids, preferably 40 parts by weight to 75 parts by weight, is It is possible to provide a MOF-based molded body that acts as a binder for the surface-modified MOF particles rather than the polymer matrix resin (FIG. 8).

Non-limiting examples of the MOF-polymer composite may be a MOF particle-containing polymer solution (eg, ink, paint, paste) or a MOF particle-containing polymer master batch.

MOF particles surface-modified with fatty acids are uniformly intercalated between the entangled chains of the polymer dissolved in the organic solvent in a state of being uniformly dispersed in the organic solvent, so that the polymer solution containing the homogeneous MOF particles can be easily provided.

The solvent capable of dispersing the surface-modified MOF particles with liquid fatty acids is not limited in its kind as long as it can break the bonds between the carbon chains of unsaturated or saturated fatty acids, but the solvent is N-methyl-2-pyrrolidone , Dioxane, dimethylacetamide, dimethylformamide, dimethylsulfoxide, acetone, methylethylketone, r-butyrolactone, C1-6 alcohol, ethyl acetate, and glycol ether.

In order to prepare a homogeneous MOF particle-containing polymer solution, it may be performed through ultrasonic treatment, stirring, or both, but is not limited thereto.

In addition, the present invention can provide a homogeneous MOF particle-containing polymer masterbatch through compounding with a moldable polymer in a state uniformly dispersed in an organic solvent or without an organic solvent.

The master batch may mean a pellet-shaped raw material in which various additives are previously dispersed in order to improve kneading properties of various additives during extrusion / injection molding of a plastic resin or the like. In particular, the master batch of the present invention may be for manufacturing molded bodies of various shapes.

The polymer master batch containing MOF particles may be compounded in the form of powders of MOF particles surface-modified with unsaturated fatty acids. In this case, MOF nanoparticles surface-modified with an unsaturated fatty acid according to the present invention can be dispersed in a matrix polymer resin without aggregation. As an example, the moldable matrix resin and the MOF particles surface-modified with the unsaturated fatty acid are well mixed, and then compounded by introducing them into the twin-screw extruder through a hopper. The melt-blending resin inside the extruder can be processed into filaments or pellets after air cooling. In order to remove water absorbed during the cooling process, a masterbatch can be prepared by drying in a vacuum oven.

Furthermore, another aspect of the present invention provides a MOF-polymer composite molded body obtained by molding the MOF-polymer composite of the present invention.

The MOF-polymer composite molded article of the present invention may provide a molded article (eg, film) molded from a polymer solution containing MOF particles or a polymer masterbatch containing MOF particles to provide a molded article (eg, injection molding, melt spinning). .

Accordingly, the MOF-polymer composite molded body may be in the form of a membrane, a coating film, a wrapping paper, a container, a sheet, a part, or some layer of a laminate. For example, the MOF-polymer composite can be prepared by coating, 3D printing, spinning, blow molding, injection molding or extrusion molding the MOF-polymer composite material.

Specifically, in one embodiment of the present invention, it was confirmed that agglomeration between MOF nanoparticles surface-modified with unsaturated or saturated fatty acids does not occur and that a molded body having a small particle size in the original size range of the MOF nanoparticles can be produced (FIG. 11) , FIGS. 12, 14 and 15).

Since the MOF-polymer composite molded article according to the present invention exhibits adsorption and / or catalytic activity of the MOF nanoparticles itself, non-limiting examples of various MOF-polymer composite molded articles are functional fibers, membranes, filters, thin film coatings, and injection molding. Functional products (wearable devices, etc.), display bags, packaging materials, and the like. In addition, the MOF-based molded article according to the present invention may be protective clothing, safety clothing, work clothing, military clothing, exhaust filters, vehicle hoses, separators, special clothing, industrial materials, insulation materials, electrical insulation materials, automobile high heat resistant non-woven fabrics, industrial filters, and the like.

Method of manufacturing a MOF-polymer composite molding according to the present invention

A first step of uniformly dispersing MOF particles surface-modified with liquid fatty acids according to the present invention in a polymer to form a MOF-polymer complex; And

And a second step of shaping the MOF-polymer complex to obtain a MOF-polymer complex.

Preferably, after the second step may further include a third step of heat treatment or vacuum treatment of the MOF-polymer composite. These pre-treatment and / or post-treatment steps include heat treatment or vacuum treatment, in which MOF particles are activated or may affect defects or densities between the MOF particles and the polymer.

If the liquid fatty acid according to the present invention is used as a surface modifier for MOF particles and contains 70 wt% or more of MOF, this corresponds to MOF molding technology.

Polymers capable of producing MOF-polymer composites may serve as a matrix and / or binder.

When the MOF-polymer composite is a fiber, the polymer is a molecule capable of producing fibers, for example, after dissolving in a solvent, electrospinning, wet spinning, conjugate spinning, melt blown. It may be a molecule capable of producing fibers when spun by conventional spinning methods including melt blown spinning or flash spinning. Examples of typical polymers used as fibers include polyethylene, polypropylene, nylon, polyester, Kevlar and Nomee, cellulose, and poly There is a polyurethane (polyurethane).

The MOF-polymer composite molded article according to the present invention may be, for example, a film layer having a film thickness of 1 μm to 300 μm, preferably 2 μm to 30 μm. The film layer may serve as a gas barrier and / or a protective film, as well as various sensors, membranes, functional thin films, drug delivery materials, catalysts, and catalyst carriers. Non-limiting examples of film-forming polymers include polyimide, polyacetylene, cellulose acetate, polysulfone, polyethylene oxide, poly (4-methylpentene-1), poly (2,6-dimethyl phenylene oxide), polydimethylsiloxane, Polyethylene, polyvinylidene chloride, polytetrafluoroethylene oxide, polyacrylonitrile, poly (vinyl alcohol), polystyrene, nylon 6, and the like.

Non-limiting examples of transparent film-forming polymers include ester polymers such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN); Cellulose-based polymers such as diacetyl cellulose and triacetyl cellulose; Carbonate-based polymers such as polycarbonate (PC); Acrylic polymers such as poly (methyl) methacrylate; Acrylic resins such as acrylic resins having an aromatic ring or lactone-modified acrylic resins; Styrene-based polymers such as polystyrene or acrylonitrile-styrene copolymer; Olefin polymers such as polyethylene, polypropylene, cyclo-olefin polymers (COP), and ethylene / propylene copolymers; Vinyl chloride polymers; Amide polymers such as nylon or aromatic polyamides; Imide-based polymers; Sulfone-based polymers; Polyether sulfone polymers; Polyether ether ketone-based polymers; Polyphenylene sulfide polymers; Vinyl alcohol-based polymers; Vinylidene chloride-based polymers; Vinyl butyl aldehyde polymers; Arylate-based polymers; Polyoxymethylene polymers; Epoxy polymers; Or blend polymers in which these are mixed. Preferably, polyethylene terephthalate, which is advantageous in price as a transparent film, or poly (methyl) methacrylate or triacetyl cellulose, which is advantageous in light resistance and weather resistance, can be used as a raw material.

In addition, the polymer can be a conductive polymer such as polyacetylene, polypyrrole, polythiophene, polyethylenedioxythiophene, polyphenylenevinylene, polyphenylene, polysilane, polyfluorene, polyaniline and polysulfur nitride. .

The second step may be a step of obtaining the MOF-polymer composite molded body by molding the polymer solution.

In order to form a transparent film layer or fiber, it is preferable to maintain a state in which MOF particles surface-modified with liquid fatty acids are dispersed in a nanoparticle size during the manufacturing process.

When the MOF-polymer composite is in the form of a membrane, the second step of molding is knife casting, tape casting, spinning, slip coating, spray coating, ultrasonic coating, roll coating, slot die coating, and bar ( Bar) may be performed by coating, dip coating, or spin coating, but is not limited thereto. Knife casting and tape casting may be performed by forming a polymer solution into a flat plate such as a film using a knife or tape, respectively, and then removing the solvent by heat treatment or the like.

Film layer formation can be carried out by applying a coating solution in which MOF particles surface-modified with unsaturated or saturated fatty acids are uniformly dispersed in a monomer, oligomer, or polymer of an organic solvent or a binder resin. At this time, the monomer or oligomer of the binder resin may be UV-curable, and may be filmed through a curing process through UV irradiation after coating.

When the MOF-polymer composite molded body is in the form of a fiber, the molding method in the second step may be a spinning method for drawing a thread.

There are three types of spinning methods: : (1) The wet method is to solidify the contents dissolved in a suitable solvent by pushing them into a coagulation bath through a fine hole .; (2) The dry method is a solvent that is easy to vaporize, and the melted matter is pushed into the air through a fine hole. When the solvent evaporates, it becomes a thread and remains; (3) The melting method heats the polymer to make it melt, and pushes it out of a thin hole. When cooled and hardened, a thread is produced.

When spinning synthetic fibers, many types of unique fibers can be made by changing the shape of the fine holes into different shapes.

The fibers may be short fibers cut into a short form of cotton and long fibers in the form of a thread after undergoing a process of spinning to extract threads from the MOF particle-containing polymer solution and stretching to give various properties. The fabric may be woven into a fabric-like fabric.

In addition, the fibers may be in the form of a nonwoven fabric. Non-woven fabric refers to a planar structure made by tangling various fibers such as natural, synthetic, glass, and metal according to mutual characteristics and forming a sheet-like web and combining them with mechanical or physical methods. The non-woven fabric may be a fiber aggregate or a film, which is not bound to spinning or weaving, by physical or chemical means, or may be bonded to each other by suitable moisture or heat. Various nonwoven fabric manufacturing methods are illustrated in Table 1 below.

Process		Recipe	Characteristic	Main purpose
Wet nonwoven fabric		The same process as the papermaking process, which is a papermaking process, but only raw materials are not used as pulp and manufactured using various fibers	Very freely changeable properties	Wiper, towel, wheel, towel, diaper cover
Dry Dry Nonwoven	Chemical bond	When bonding the web, the adhesive penetrates the fiber and is manufactured through a drying process.	Very flexible and breathable	Wick, coating bubble
	Thermal Bond	Manufactured by mixing low melting point plastic synthetic fibers and igniting or melting them with heat, pressure, solvent, etc.	Hygienic because no adhesive is used	Diapers, hygiene, naphkin, etc.
	Air Ray	Manufactured using compressed air and adhesives at the same time	There is no tension difference between horizontal and vertical directions	Battery filter, wick, carpet foam material, wiper sponge, insulation material
Spanless		Manufactured by combining fibers using high pressure water flow	Excellent flexibility and breathability	For medical, wick, household goods, coating bubble, roofing material, Wiper
Spunbond		Self-adhesive bonding by spinning molten fiber	Easy fabric design according to use	Packaging materials, physiological naphkin, civil construction materials, filters, wicks, carpet foam materials, coating materials, etc.
Melt blown		Synthetic polymers are spun into ultrafine fibers by high-pressure hot air to produce uniform melted fiber webs.	Excellent flexibility, impermeability and insulation	Filter, insulating material, absorbent sheet, wiper, absorbent sheet, physiological naphkin
Needle punch		Manufactured by mechanically (special needle) bonding of web	Easy thickness adjustment	Carpet, blanket, filter, coating foam material, wick
Stitch Bond		Manufactured by knitting the formed web into threads without using adhesives using knitting needles	Thin but high tensile strength	Wick, automobile interior material, etc.

Hereinafter, the present invention will be described in more detail through examples. These examples are only intended to illustrate the present invention in more detail, and the scope of the present invention is not limited by these examples.

Preparation Example 1: Preparation of MIL-100 (Fe) nanoparticles

For microwave synthesis of MIL-100 (Fe) nanoparticles, 30 mL of H ₂ O, iron (III) chloride hexahydrate (2.43 g, 9.00 mmol) and trimesic acid (0.84 g, 4.00 mmol) were placed in a microwave reactor. I put it. The mixture was heated to 130 ° C. under solvothermal conditions (p = 2.5 bar) within 30 seconds, maintained at 4 ° C. to 130 ° C., and then cooled to room temperature. To purify, the reaction mixture was centrifuged at about 20,000 rpm and the solvent was removed, and if necessary, filtration and purification were repeated and dried to obtain nanoparticles.

Preparation Example 2: Preparation of MIL-101 (Cr) nanoparticles

For microwave synthesis of MIL-101 (Cr) nanoparticles, H ₂ O 20 mL (1.11 mol), terephthalic acid 615 mg (3.70 mmol) and Cr (NO ₃ ) ₃ · 9H ₂ O (3.70 mmol) in a microwave reactor ) 1.48 g was added. A lamp of 4 minutes at 180 ° C and a holding time of 2 minutes at 180 ° C were applied. After cooling to room temperature, it was filtered and washed with 50 ml EtOH to remove residues such as terephthalic acid. The filtration and purification were repeated and dried as necessary to obtain nanoparticles.

Preparation Example 3: Preparation of MIL-88 (Fe) nanoparticles

1 mmol of ferric chloride (FeCl ₃ ), 5 mL of dimethyl formamide (DMF, 98%), anhydrous ethanol (1 mL) and 1 mmol of fumaric acid were reacted in an autoclave at a temperature of 150 ° C. for 30 minutes. The obtained precipitate was collected by centrifugation at 5000 rpm for 10 minutes. The filtration and purification were repeated and dried as necessary to obtain nanoparticles.

Preparation Example 4: Preparation of MIL-53 (Fe) ＿NH ₂ nanoparticles

As a low-temperature synthetic route, 9 mL of an ethanol solution containing 0.1 mmol FeCl ₃ · 6H ₂ O and 0.1 mmol 2-amino terephthalic acid (NH ₂ -H ₂ BDC) was mixed in a round bottom flask (25 mL) and 2 hours at 40 ° C. While stirring. The obtained reaction product was filtered and purified as necessary and dried to obtain nanoparticles.

Preparation Example 5: Preparation of MIL-68 (Al) nanoparticles

1.4 g Al (NO ₃ ) ₃ · 9H ₂ O and 0.6 g H ₂ BDC (benzene-1,4-dicarboxylic acid) are added as solvent to 16 mL of tetrahydrofuran (THF) and the mixture is stirred Heated to 70 ° C. for 3 days. The product was obtained by centrifugation, washed three times with fresh THF, and repeated and dried by filtration and purification as needed to obtain nanoparticles.

Preparation Example 6: Preparation of MOF-808 (Zr) nanoparticles

To a solvent mixture of DMF / formic acid (270 mL / 360 mL) was added H ₃ BTC (3.3 g, 15.7 mmol) and ZrOCl ₂ · 8H ₂ O (5.06 g, 15.7 mmol). The reaction mixture was heated with an autoclave at 135 ° C. for 48 hours. The white precipitate was collected by centrifugation, and, if necessary, filtration and purification were repeated and dried to obtain nanoparticles.

Preparation Example 7: Preparation of UiO-66 (Zr) nanoparticles

1 L of N, N'-dimethylformamide (DMF) solvent was added to 14 mmol of ZrOCl ₂ · 8H ₂ O and 14 mmol of terephthalic acid (H ₂ BDC). 0.78 g of a 37% HCl aqueous solution was further added to the mixture, and the reaction mixture was mixed with stirring at 50 rpm for 20 minutes at room temperature.

The reactant is transferred to a glass reactor capable of reflux reaction, and raised to a temperature of 5 ° C. per minute from room temperature to 90 ° C. to form an organic gel. The mixture was decelerated and maintained for 3 hours while stirring. Then, the reactant was raised to 120 ° C again and maintained for 12 hours to perform a crystallization reaction, followed by cooling to room temperature at a cooling rate of 1 ° C or less per minute.

After synthesis, the slurry solution containing the porous organic-inorganic hybrid material was filtered through a pressure filter at room temperature once, and repeated and dried as necessary to obtain nanoparticles.

Preparation Example 8: Preparation of UiO-66 (Zr) ＿NH ₂ nanoparticles

UiO-66 nanoparticles prepared in Preparation Example 7 were reacted at 155 ° C. for 28 hours while stirring with 10 mmol of 2-aminoterephthalic acid. The resulting solid powder was filtered and, if necessary, repeated and dried by filtration and purification to obtain nanoparticles.

Preparation Example 9: Preparation of ZIF-8 (Zn) nanoparticles

After dissolving 0.893 g (3.0 mmol) of Zn (NO ₃ ) ₂ · 6H ₂ O and 0.985 g (12.0 mmol) of 2-methylimidazole in 10 mL of DMSO, respectively, the latter clear solution was added to a magnetic oil bath. Stir at 313K. After stirring for 30 minutes, the white solid was recovered by centrifugation from the milky white colloidal dispersion, washed with fresh MeOH, and the centrifugation was repeated 3 times, followed by filtration and purification as necessary and drying to obtain nanoparticles. Did.

Preparation Example 10: Preparation of ZIF-7 (Zn) nanoparticles

Zn (NO ₃ ) ₂ · 6H ₂ O (1.25 g, 4.2 mmol) and benzimidazole (1.54 g, 13 mmol) were dissolved in 100 mL of DMF, respectively. Once dissolved, the two solutions were mixed in a round bottom flask and stirred continuously at 35 ° C. for 72 hours. After the elapsed time, crystalline ZIF-7 was obtained in 70% yield and then separated by centrifugation at 6,000 rpm for 20 minutes. The mother liquor was discarded, and if necessary, filtration and purification were repeated and dried to obtain nanoparticles.

Preparation Example 11: Preparation of ZIF-67 (Co) nanoparticles

After dissolving Co (NO ₃ ) ₂ · 6H ₂ O (5.88 g) in 500 mL of methanol and dissolving 2-methylimidazole (6.626 g) and triethylamine (0.4 mL) in another 500 mL of methanol solution , Mixed and stirred and reacted at room temperature for 24 hours. The product was collected by centrifugation and, if necessary, repeated and dried by filtration and purification to obtain nanoparticles.

Preparation Example 12: Preparation of ZIF-11 (Zn) nanoparticles

0.21 g bIm (2 mmol) was dissolved in 6.4 g methanol (400 mmol) with 9.2 g toluene (100 mmol) and 2.4 g ammonium hydroxide (40 mmol). 0.22 g of zinc acetate dehydrate (1 mmol) was dissolved in 3.2 g of methanol (200 mmol). The two solutions were mixed and reacted. After cooling to 18 ° C., 50 mL centrifugation was performed at 10000 rpm at the same temperature. The collected powder was washed 3 times with methanol to completely remove toluene and dried at 100 ° C. for 12 hours. The filtration and purification were repeated and dried as necessary to obtain nanoparticles.

Preparation Example 13: Preparation of ZIF-90 (Zn) nanoparticles

Zn (NO ₃ ) ₂ · 6H ₂ O (1.25 mmol) and imidazole-2-carboxaldehyde (5 mmol) were added to DMF (12.5 mL) and the mixture was stirred at 80 ° C. for 4 hours. After the solution was cooled to room temperature, methanol (12.5 mL) was added to the solution while stirring, followed by further stirring at room temperature for 30 minutes. The resulting particles were centrifuged (14000 rpm) and sonicated-the centrifugation cycle was repeated several times to wash with methanol. The filtration and purification were repeated and dried as necessary to obtain nanoparticles.

Example 1. Surface treatment of MOF nanoparticles using fatty acids (core-shell structure formation or hydrophobic coating)

The MOF nanoparticles prepared in Preparation Examples 1 to 13, and the nanoparticles prepared as described above were added with stirring to each other by adding stearic acid (SA) as saturated fatty acid and oleic acid (OA) as unsaturated fatty acid, respectively. The reaction mixture was centrifuged and washed to obtain nanoparticles whose surface has been modified with SA and OA.

As shown in Figure 2 (right view), Co-MOF nanoparticles obtained by modifying the surface of Co-MOF nanoparticles (ZIF-67 (Co)) prepared in Preparation Example 11 with oleic acid are aggregated between particles in a dispersed solvent. There was no phenomenon. On the other hand, the co-MOF nanoparticles that were not surface-modified had a large number of intergranular particles (left view in FIG. 2). The same was true for MOF nanoparticles prepared in other preparations by modifying oleic acid.

XRD crystallinity analysis was performed on Co-MOF nanoparticles before and after surface treatment with oleic acid, and the results are shown in FIG. 4, respectively. As shown in Fig. 4, there was no difference in the XRD pattern before and after surface modification, indicating that the same crystal structure as the untreated sample was maintained even after the surface treatment with OA.

Furthermore, as shown in FIG. 3, it was confirmed that the MOF nanoparticles are maintained in a separate nanoparticle state from the dispersion state photograph and TEM image of the surface-modified Zn-MOF nanoparticles and the surface-modified Co-MOF nanoparticles. I could confirm.

On the other hand, the surface of Zr-MOF prepared in Preparation Example 8, such as UiO-66 (Zr) _NH ₂ nanoparticles, is modified with saturated fatty acid stearic acid (SA) and unsaturated fatty acid oleic acid (OA). 5 is shown. As shown in FIG. 5, MOF nanoparticles are separated and maintained in each nanoparticle state compared to Zr-MOF before surface treatment, such as UiO-66 (Zr) _NH ₂ , from the TEM image of Zr-MOF nanoparticles after surface treatment. It was confirmed that it was.

Furthermore, XRD crystallinity analysis was performed on the surface of Zr-MOF before and after modification with SA and OA such as UiO-66 (Zr) _NH ₂ nanoparticles, and the results are shown in FIG. 6, respectively. As shown in FIG. 6, there was no difference in the XRD pattern before and after surface modification, indicating that the same crystal structure as the untreated sample was maintained even after surface treatment with SA and OA.

Example 2. Preparation of polymer composite containing MOF nanoparticles surface-treated by electrospinning

1 g of NMP solvent was mixed with 0.7 g of polyacrylonitrile (PAN) and 0.38 g of the surface-treated MOF sample prepared in Example 1 and added to a spinning device (equipment including a syringe-shaped nozzle) at a constant rate. Then, a fiber mat (web of MOF-polymer composite fibers containing MOF 55 wt%, 65 w% and 75 wt%, respectively) was obtained by uniformly dispersing MOF nanoparticles in the polymer using an electrospinning method (FIG. 7).

8 is a high-resolution SEM and TEM photograph of a composite fiber containing 55 wt% or more of MOF nanoparticles surface-treated with oleic acid, an unsaturated fatty acid.

Furthermore, Zr- surface-modified with a polymer solution containing unmodified MOF and saturated fatty acid stearic acid (SA) and unsaturated fatty acid oleic acid (OA) according to Example 1 of the present invention. The shape of the fibers prepared using a polymer solution containing MOF such as UiO-66 (Zr) _NH ₂ was observed by SEM, and the results are shown in FIG. 9. As shown in Fig. 9, fibers prepared from a polymer solution containing MOF that is not surface-modified do not evenly distribute MOF particles throughout the fiber and aggregate with each other, whereas polymers containing MOF surface-modified with SA and OA The fibers produced using the solution had evenly distributed and adsorbed MOF particles throughout the fibers.

Fabrics are fabricated by weaving fibers prepared using a polymer solution containing Zr-MOF surface-modified with SA and OA, such as UiO-66 (Zr) _NH ₂ , and photographed It is shown in FIG. 10.

On the other hand, Figure 11 is a polypropylene (PE) injection molded body containing 3 wt% and 10 wt% of the surface-modified Al-MOF nanoparticles, respectively, and the results of the production of a film produced by a heat extrusion process. In the case of Al-MOF that is not surface-modified, injection is not possible when 5 wt% or more is contained, or an injection molded body in a normal state as shown in FIG. 11 cannot be manufactured, but in the case of surface modification, even if it is contained at 10 wt% or more, uniform quality It was possible to manufacture an injection molded body of, it was also possible to manufacture in a film state by a heat extrusion method using the injection molded body. FIG. 12 shows Al-MOF nanoparticles uniformly dispersed in the film containing 10 wt%, and FIG. 13 shows the XRD results according to the Al-MOF nanoparticle content in the MOF-Polypropylene composite film of FIG. 11.

FIG. 14 is a mixed substrate film (MMM) photograph prepared by mixing Matrimid 5218 and Zr-MOF nanoparticles, confirming that it is possible to manufacture nanoparticles in an amount of 40 wt% or more. 15 is a SEM photograph of the MOF-Polyimide composite separation membrane of FIG. 14, from which it can be confirmed that the nanoparticles are uniformly dispersed.

Claims (12)

1. Metal-organic framework (MOF) particles surface-treated with liquid fatty acids, characterized in that the carboxyl groups of the fatty acids form chemical bonds with hydrophilic groups, metals, or both exposed on the MOF surface. Modified MOF particles.
2. According to claim 1,

   The chemical bond is hydrogen-bonded, ion-bonded, covalent-bonded or a combination thereof, characterized in that the surface modified MOF particles.
3. According to claim 1,

   The fatty acid is an unsaturated or saturated fatty acid surface modified MOF particles.
4. According to claim 3,

   The unsaturated fatty acid is C5 to C50 surface-modified MOF particles, characterized in that.
5. According to claim 3,

   The saturated fatty acid is a surface modified MOF particles, characterized in that the carbon number is C4 to C40.
6. The surface-modified MOF particle according to any one of claims 1 to 5, wherein the surface-treated MOF particles are nanoparticles having an average particle diameter of 5 to 1000 nm.
7. Polymers; And MOF-polymer composite comprising the surface-modified MOF particles of any one of claims 1 to 5 uniformly distributed in the polymer.
8. The method of claim 7,

   The MOF particle content, MOF-polymer composite, characterized in that 0.5 to 95 parts by weight based on 100 parts by weight of the total MOF-polymer composite.
9. The method of claim 7,

   The MOF-polymer composite is a MOF-polymer composite characterized in that the polymer solution containing MOF particles or a polymer master batch containing MOF particles.
10. A MOF-polymer composite molded article obtained by molding the MOF-polymer composite of claim 7.
11. The method of claim 10,

    The MOF-polymer composite molded body is a MOF-polymer composite molded body characterized by being a molded body molded from a polymer masterbatch containing a MOF nanoparticle or a molded body molded from a polymer solution containing MOF nanoparticles.
12. The method of claim 10,

    The polymer is a MOF-polymer composite molded body which is a MOF-based molded body containing 30 to 95 parts by weight of MOF particles based on 100 parts by weight of the total MOF-polymer composite molded body as a binder of surface-modified MOF particles.

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