Monolithic bodies containing metal-organic frameworks

Abstract

The monolithic body may comprise a metal-organic framework (MOF) and a polymeric binder, the monolithic body may have a crush strength of at least 10 N, the amount of the polymeric binder is at least 3 wt % based on the total weight of the MOF and the polymeric binder, the polymeric binder comprises a first polymer and a second polymer, the first polymer has a solubility in water of 5 g / L or less at 25° C., and the second polymer has a solubility in water of at least 10 g / L at 25° C.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS The present disclosure relates to a monolithic body comprising a metal-organic framework (MOF) and a polymer binder. [Background technology]

[0002] Metal-organic frameworks (MOFs) are coordination networks of metal ions and organic ligands, a class of compounds known for their unique combination of properties such as large surface area, high porosity, and flexible adsorption / desorption behavior. MOFs can be tailored to adsorb desired types of molecules or ions with high selectivity.

[0003] There is a need to incorporate MOFs into objects suitable for industrial applications that can largely preserve the delicate network structure and properties of MOFs. [Brief description of the drawings]

[0004] The present disclosure may be better understood, and its numerous features and advantages made apparent to those skilled in the art by referencing the accompanying drawings. [Figure 1] 1 includes a scheme showing a method of making a body of the present disclosure, according to one embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0005] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," or any other variations thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that includes a list of features is not necessarily limited to only those features and may include other features that are not expressly listed or that are inherent to such process, method, article, or apparatus.

[0006] As used herein, unless clearly stated to the contrary, "or" refers to an inclusive or and not an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist).

[0007] Additionally, the use of "a" or "an" is used to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one, and the singular also includes the plural, unless it is clear that otherwise is meant.

[0008] The present disclosure relates to a monolithic body comprising a metal-organic framework (MOF) and a polymeric binder, the polymeric binder may comprise a first polymer and a second polymer, the first polymer being water-insoluble having a solubility of 5 g / L or less in water at 25° C., and the second polymer being water-soluble having a solubility of at least 10 g / L in water at 25° C. The amount of the polymeric binder may be at least 3 wt %, based on the total weight of the MOF and the polymeric binder, and the average crush strength of the monolithic body may be at least 10 N.

[0009] As used herein, the term "polymeric binder" refers to a combination of a first polymer and a second polymer, unless otherwise indicated. In one aspect, the first polymer and the second polymer may be at least partially crosslinked to each other.

[0010] The monolithic bodies can be designed for industrial applications to adsorb / desorb desired types of molecules or ions, for example, in non-limiting embodiments, the monolithic bodies can be used to adsorb carbon dioxide or methane, or for hydrogen storage, water and air purification, or in catalytic applications.

[0011] As used herein, the term "metal organic framework" (MOF) relates to any compound that forms a network of metal ions with coordinating organic ligands.

[0012] A method of forming a monolithic body of the present disclosure can include preparing a green body composition including a MOF (11), forming a green body from the green body composition (12), and curing the green body to obtain the monolithic body (13), as shown in FIG.

[0013] In an embodiment, forming the green body from the green body composition may include screen printing, extrusion, slip casting, or 3D printing.

[0014] The final shape and size of the monolithic body can vary widely. For example, the shape of the monolithic body can be a pellet, a tube, or a sheet, or it can be ball-shaped. In another aspect, the monolithic body can have an irregular shape.

[0015] The polymeric binder may comprise a combination of at least one first polymer (P1) and at least one second polymer (P2). In one embodiment, the first polymer may be a water-insoluble polymer having a solubility of 5 g / L or less, or 3 g / L or less, or 1 g / L or less, or 0.5 g / L or less in water at 25° C. In contrast to the first polymer, the second polymer may be a water-soluble polymer having a solubility of at least 10 g / L, or at least 30 g / L, or at least 50 g / L, or at least 100 g / L in water at 25° C. As used herein, unless otherwise indicated, the term "first polymer" (P1) relates to the water-insoluble polymer described above, and the term "second polymer" (P2) relates to the water-soluble polymer described above.

[0016] In one embodiment, a first polymer may include functional groups that may react with functional groups of a second polymer by forming covalent bonds, also referred to herein as crosslinks.

[0017] In one embodiment, non-limiting examples of functional groups of the first polymer may be amine, hydroxyl, acrylate, vinyl, thiol, carboxyl, or epoxy groups. In another embodiment, non-limiting examples of functional groups of the second polymer may be amine, hydroxyl, acrylate, vinyl, thiol, carboxyl, or epoxy groups, as long as the functional groups are different between the first and second polymers to allow crosslinking reactions between the functional groups. For example, the first polymer may include amine groups and the second polymer may include carboxyl groups, which can react with each other to form amide groups, thereby crosslinking the first and second polymers. In another embodiment, the first polymer may include hydroxyl groups and the second polymer may include carboxyl groups, which can combine to form ester groups.

[0018] In certain embodiments, the first polymer and the second polymer may react during curing of the green body to form an at least partially crosslinked polymer.

[0019] In one embodiment, the first polymer (the water insoluble polymer) can be a polyacrylate, a polystyrene, an epoxide polymer, a polyurethane, a polyester, a polyether, a polyamide, a polyimide, or any combination or copolymer thereof. In certain aspects, the first polymer can be an emulsion polymer.

[0020] The first polymer may further include graft substitutions that may introduce additional functional groups, for example, a polyacrylate may include substitutions with amine groups next to the acrylate groups, referred to herein as an amine-functionalized polyacrylate.

[0021] In another embodiment, the second polymer (water soluble polymer) can be, in non-limiting examples, a polysaccharide, a polyethylene glycol, a polyamide, a polyvinyl alcohol, or a polyacrylate.

[0022] In one embodiment, the second polymer can be a polysaccharide. Non-limiting examples of polysaccharides can be cellulose derivatives, starch derivatives, alginates, alginate derivatives, or any combination thereof. In certain embodiments, the cellulose derivative can be a salt of carboxymethylcellulose, such as sodium carboxymethylcellulose (NaCMC).

[0023] In certain embodiments, the first polymer can be a polyacrylate containing amine functional groups and the second polymer can be a salt of carboxymethylcellulose.

[0024] In embodiments, the weight percentage ratio of the first polymer to the second polymer (P1:P2) may range from 1:10 to 10:1, or from 1:5 to 5:1, or from 1:2 to 4:1, or from 1:2 to 2:1, or from 1:1 to 1:10, or from 1:1 to 1:4, or from 1:1 to 4:1, or from 2:1 to 5:1.

[0025] Depending on the type of first and second polymers of the polymeric binder, curing can be performed by heat or light radiation, for example UV radiation.

[0026] The polymeric binder of the monolithic body of the present disclosure may have a structure that may be permeable to analytes that may be adsorbed by the MOFs contained in the binder matrix. Non-limiting examples of analytes may be water, carbon dioxide, ozone, carbon monoxide, hydrogen, methane, ammonia, nitrogen dioxide, water pollutants, or air pollutants.

[0027] Surprisingly, it has been observed that green body compositions containing a particular combination of a water-insoluble first polymer and a water-soluble second polymer allow for the inclusion of large amounts of metal-organic frameworks (MOFs) such that monolithic bodies with good strength can be formed that are able to largely retain the properties of the MOFs (prior to use, the MOF powder).

[0028] The MOFs contained in the monolithic bodies of the present disclosure are not limited to a particular type of MOF. The choice of MOF may depend on the intended use of the bodies of the present disclosure. Non-limiting examples of MOFs can be networks containing metal or transition metal ions, aluminum, copper, iron, zirconium, zinc, or beryllium, and organic ligands, such as monovalent, divalent, trivalent, or tetravalent organic ligands. Examples of commercially available MOFs are MIL-100, MIL-101, Numat11, Numat25, HKUST-1, UIO-66, MOF-0, MOF-2, MOF-3, MOF-4, MOF-5, MOF-6, MOF-7, MOF-8, and the like. MOF-9, MOF-11, MOF-12, MOF-20, MOF-25, MOF-26, MOF-31, MOF-32, MOF-33, MOF-34, M OF-36, MOF-37, MOF-38, MOF-39, MOF-47, MOF-49, MOF-69a, MOF-69b, MOF-74, MOF-101 , MOF-102, MOF-107, MOF-108, MOF-110, MOF-177, MOF-j, MOF-n, IRMOF-1, IRMOF-2, IRMOF-3, IRMOF-4, IRMOF-5, IRMOF-6, IRMOF-7, IRMOF-8, IRMOF-9, IRMOF-10, IRMOF-11 , IRMOF-12, IRMOF-13, IRMOF-14, IRMOF-15, IRMOF-16, IRMOF-17, IRMOF-18, IRMOF-19, IRMOF-20, AS16, AS27-2, AS32, AS54-3, AS61-4, AS68-7, BPR43G2, BPR48A2, BPR49B1, BPR68D10, BPR69B1, BPR73E4, BPR76D5, BPR80D5, BPR92A2, BPR95C5, UiO-67, UiO-68, NO13, NO29, NO305, NO306A, NO330, NO332, NO333, NO335, NO336, or HKUST-1.

[0029] In one embodiment, the metal organic framework may have an average particle size of at least 0.020 μm, for example, at least 0.050 μm, at least 0.1 μm, at least 0.2 μm, at least 0.5 μm, at least 1 μm, at least 3 μm, at least 5 μm, at least 8 μm, or at least 10 μm. In another aspect, the average particle size of the MOFs may be 1000 microns or less, or 800 microns or less, or 500 microns or less, or 300 microns or less, or 200 microns or less, or 100 microns or less, or 50 microns or less, or 10 microns or less, or 7 microns or less, or 5 microns or less, or 1 micron or less, or 0.5 microns or less, or 0.1 microns or less. The average particle size of the MOFs may be a value between any of the above minimum and maximum values.

[0030] In certain embodiments, the MOFs can be shaped particles. In one aspect, the shaped particles can have a length to width aspect ratio of greater than 1.0, e.g., greater than 1.2, or greater than 1.5, or greater than 2.0, or greater than 3.0, or greater than 5.0, or greater than 10.0.

[0031] In one embodiment, the monolithic body may comprise MOFs as a majority of the total weight. In another aspect, the weight percent ratio of MOFs to polymer binder may be 2:1 or less, or 5:1 or less, or 10:1 or less, or 15:1 or less, or 20:1 or less, or 25:1 or less, or 30:1 or less. In another aspect, the weight percent ratio of MOFs to polymer binder may be at least 40:1, or at least 35:1, or at least 30:1, or at least 25:1. The weight percent ratio of MOFs to polymer binder may be within a range including any of the minimum and maximum values ​​listed above, such as 2:1 to 40:1, or 5:1 to 30:1, or 10:1 to 25:1, or 15:1 to 20:1.

[0032] In another embodiment, the amount of MOF in the monolithic body can be at least 70 wt%, e.g., at least 75 wt%, at least 80 wt%, at least 85 wt%, at least 90 wt%, or at least 95 wt%, or at least 97 wt%, based on the total weight of the monolithic body. In further embodiments, the amount of MOF in the monolithic can be 98 wt% or less, 97 wt% or less, or 95 wt% or less, based on the total weight of the functional layer. The amount of MOF in the monolithic body can be within a range including any of the minimum and maximum values ​​above.

[0033] In another embodiment, the amount of polymer binder contained in the monolithic body may be at least 1 wt%, or at least 3 wt%, or at least 5 wt%, or at least 8 wt%, or at least 10 wt%, or at least 12 wt%, or at least 15 wt%, or at least 18 wt%, or at least 20 wt%, based on the total weight of the polymer binder and the MOF. In another aspect, the amount of polymer binder may be 30 wt% or less, for example, 25 wt% or less, 20 wt% or less, 15 wt% or less, 10 wt% or less, or 5 wt% or less, based on the total weight of the polymer binder and the MOF. In a particular aspect, the amount of polymer binder may be at least 5 wt% and 15 wt% or less, based on the total weight of the polymer binder and the MOF. The amount of polymer binder may be a value between any of the minimum and maximum values ​​above.

[0034] In one embodiment, the monolithic body of the present disclosure may have a normalized functionality ratio (NFR) of at least 0.5. As used herein, normalized functionality ratio (NFR) is defined as the ratio of a property of the monolithic body to the respective property of the MOFs prior to inclusion in the monolithic body. In one aspect, the property may be specific surface area (SSA), or adsorption capacity of an analyte, or porosity, or pore volume.

[0035] In certain embodiments, the NFR can be at least 0.55, or at least 0.60, or at least 0.65, or at least 0.7, or at least 0.75, or at least 0.8, or at least 0.85, or at least 0.9, or at least 0.92, or at least 0.94, or at least 0.95, or at least 0.96, or at least 0.97, or at least 0.99.

[0036] In another embodiment, the monolithic body has a specific surface area (SSA) of at least 850 m 2 / g, or at least 900m 2 / g, or at least 950m 2 / g, or at least 1000m 2 / g, or at least 1050m 2 / g, or at least 1100m 2 / g, or at least 1150m 2 / g, or at least 1200m 2 / g, or at least 1250m 2 / g, or at least 1300m 2 / g, or at least 1350m 2 / g, or at least 1400m 2 In another embodiment, the SSA of the monolithic body can be 2500 m 2 / g or less, or 2000m 2 / g or less, or 1800m 2 / g or less, or 1500m 2 / g or less.

[0037] In further embodiments, the monolithic body may have a water adsorption capacity at a temperature of 25° C. and a relative humidity of 30% of at least 0.10 g HO / g MOF, or at least 0.15 g HO / g MOF, or at least 0.17 g HO / g MOF, or at least 0.20 g HO / g MOF, or at least 0.25 g HO / g MOF, or at least 0.30 g HO / g MOF.

[0038] In another embodiment, the monolithic body may have a water adsorption capacity at a temperature of 25° C. and a relative humidity of 80% of at least 0.15 g HO / g MOF, or at least 0.17 g HO / g MOF, or at least 0.20 g HO / g MOF, or at least 0.25 g HO / g MOF, or at least 0.30 g HO / g MOF.

[0039] In one embodiment, the method of preparing a monolithic body of the present disclosure can include forming a green body composition as a first step. In one aspect, forming the green body composition can include combining a MOF, a polymer binder (a first polymer and a second polymer), and a solvent, where the second polymer is dissolved in the solvent and the first polymer is not dissolved in the solvent or only a small portion of the first polymer is dissolved in the solvent. In a particular aspect, the first polymer can be an emulsion polymer.

[0040] In one embodiment, the weight percent ratio of MOFs to polymer binder in the composition can range from 2:1 to 50:1. In certain embodiments, the weight percent ratio of MOFs to polymer binder can range from 5:1 to 30:1, 10:1 to 25:1, or 15:1 to 20:1.

[0041] In certain embodiments, the solvent of the green body composition can include water, hi certain embodiments, the solvent can consist essentially of water, except for unavoidable impurities.

[0042] In further particular embodiments, the green body composition may include one or more optional additives, such as a surfactant, a dispersant, a pH adjuster, a buffer, a filler, or a viscosity modifier.

[0043] In further embodiments, the green body composition can have a pH of 1 to 12, particularly 3 to 11. In particular embodiments, the pH is at least 4.5 and no more than 10, or at least 7 and no more than 10.

[0044] In one embodiment, the amount of MOFs in the green body composition can be at least 10 wt%, or at least 15 wt%, or at least 20 wt%, or at least 25 wt%, or at least 30 wt%, or at least 50 wt%, or at least 70 wt%, or at least 80 wt%. In another embodiment, the amount of MOFs can be 90 wt% or less, or 80 wt% or less, or 70 wt% or less, or 60 wt% or less, or 50 wt% or less, or 40 wt% or less, or 30 wt% or less, or 25 wt% or less, or 20 wt% or less. The amount of MOFs in the green body composition can be a value between any of the minimum and maximum values ​​above.

[0045] In further embodiments, the amount of polymeric binder in the green body composition can be at least 2 wt%, or at least 5 wt%, or at least 10 wt%, or at least 20 wt%, based on the total weight of the green body composition. In other embodiments, the amount of polymeric binder in the green body composition can be 50 wt% or less, or 30 wt% or less, or 20 wt% or less, or 10 wt% or less. The amount of binder in the green body composition can be any value between any of the minimum and maximum numbers listed above.

[0046] In still further embodiments, the amount of solvent in the green body composition can be at least 10 wt%, e.g., at least 20 wt%, or at least 30 wt%, or at least 40 wt%, or at least 50 wt%, or at least 60 wt%, based on the total weight of the green body composition. In other embodiments, the amount of solvent can be 80 wt% or less, or 60 wt% or less, or 50 wt% or less, or 30 wt% or less, based on the total weight of the green body composition. The amount of solvent in the green body composition can be a value between any of the minimum and maximum values ​​recited above.

[0047] In certain embodiments, the green body composition may be a paste adapted to be suitable for filling a mold, passing through a sieve, or extrusion molding. In certain aspects, the paste may be filled into a mold to form a shaped green body, such as a belt having a shaped aperture, and the shaped green body may be cured at an elevated temperature to form a monolithic body.

[0048] The temperature for curing the green body can be at least 60° C., or at least 80° C., or at least 100° C., or at least 130° C. In alternative embodiments, the temperature for curing can be 250° C. or less, or 200° C. or less, or 150° C. or less.

[0049] In one particular embodiment, the monolithic body of the present disclosure may be a filter or filter material adapted to filter gases or fluids by adsorbing specific analytes.

[0050] The monolithic body of the present disclosure may have good strength. In one embodiment, the average crush strength of the monolithic body may be at least 5N, or at least 10N, or at least 15N, or at least 20N, or at least 15N, or at least 30N, or at least 35N. In another aspect, the crush strength may be 150N or less, or 100N or less, or 50N or less, or 40N or less. The average crush strength may be a value between any of the minimum and maximum numbers listed above, such as 10N to 100N, or 20N to 50N, or 25N to 45N. As used herein, the crush strength is determined by testing pellets having a diameter of 1.60 mm and a thickness of 0.76 mm.

[0051] Many different aspects and embodiments are possible. Some of these aspects and embodiments are described herein. After reading this specification, a person skilled in the art will understand that these aspects and embodiments are merely illustrative and do not limit the scope of the present invention. The embodiment may be according to any one or more of the embodiments listed below.

[0052] Embodiment Embodiment 1. A monolithic body comprising a metal organic framework (MOF) and a polymeric binder, the polymeric binder comprising a first polymer and a second polymer, the first polymer being water insoluble having a solubility of 5 g / L or less in water at 25° C., the second polymer being water soluble having a solubility of at least 10 g / L in water at 25° C., the amount of the polymeric binder being at least 3 wt. %, based on the total weight of the MOF and the polymeric binder, and the average crush strength of the monolithic body being at least 10 N.

[0053] Embodiment 2. The monolithic body of embodiment 1, wherein the monolithic body has a normalized functionality ratio (NFR) of at least 0.5, the NFR being the ratio of a property of the monolithic body to a property of the MOF prior to inclusion in the monolithic body.

[0054] Embodiment 3. The monolithic body of embodiment 2, wherein the property of the NFR is selected from specific surface area (SSA), adsorption capacity of an analyte, pore volume, porosity, or a combination thereof.

[0055] Embodiment 4. The monolithic body of embodiment 4, wherein the NFR is at least 0.55, or at least 0.6, or at least 0.65, or at least 0.7, or at least 0.75, or at least 0.8, or at least 0.85, or at least 0.9, or at least 0.95, or at least 0.98.

[0056] Embodiment 5. A monolithic body according to embodiment 3 or 4, wherein the property of the NFR is specific surface area (SSA).

[0057] Embodiment 6. The monolithic body of any one of the preceding embodiments, wherein the specific surface area (SSA) of the monolithic body is at least 850 m2 / g, or at least 900 m2 / g, or at least 950 m2 / g, or at least 1000 m2 / g, or at least 1050 m2 / g, or at least 1100 m2 / g, or at least 1150 m2 / g, or at least 1200 m2 / g, or at least 1250 m2 / g, or at least 1300 m2 / g, or at least 1350 m2 / g, or at least 1400 m2 / g.

[0058] Embodiment 7. The monolithic body of any one of the preceding embodiments, wherein the specific surface area (SSA) is 2500 m2 / g or less, or 2000 m2 / g or less, or 1500 m2 / g or less.

[0059] Embodiment 8. The monolithic body of embodiment 3, wherein the analyte comprises at least one of water, carbon dioxide, methane, ammonia, hydrogen, a water pollutant, or an air pollutant.

[0060] Embodiment 9. The monolithic body of embodiment 8, wherein the NFR of the analyte adsorption capacity is at least 0.6, or at least 0.65, or at least 0.7, or at least 0.75, or at least 0.8, or at least 0.85, or at least 0.9, or at least 0.95, or at least 0.96, or at least 0.97, or at least 0.98, or at least 0.99.

[0061] Embodiment 10. The monolithic body of any one of the preceding embodiments, wherein the monolithic body comprises a water adsorption capacity at a temperature of 25° C. and a relative humidity of 30% of at least 0.10 g HO / g MOF, or 0.15 g HO / g MOF, or at least 0.17 g HO / g MOF, or at least 0.20 g HO / g MOF, or at least 0.25 g HO / g MOF, or at least 0.30 g HO / g MOF.

[0062] Embodiment 11. The monolithic body of any one of the preceding embodiments, wherein the monolithic body comprises a water adsorption capacity at a temperature of 25° C. and a relative humidity of 80% of at least 0.15 g HO / g MOF, or at least 0.17 g HO / g MOF, or at least 0.20 g HO / g MOF, or at least 0.25 g HO / g MOF, or at least 0.30 g HO / g MOF.

[0063] Embodiment 12. A monolithic body according to any one of the preceding embodiments, wherein the MOF has an average particle size (D50) of at least 0.020 μm, or at least 0.050 μm, or at least 0.1 μm, or at least 0.2 μm, or at least 0.5 μm, or at least 1 μm, or at least 3 μm, or at least 5 μm, or at least 8 μm, or at least 10 μm.

[0064] Embodiment 13. A monolithic body according to any one of the preceding embodiments, wherein the MOF has an average particle size (D50) of 1000 μm or less, or 800 μm or less, or 500 μm or less, or 300 μm or less, or 200 μm or less, or 100 μm or less, or 50 μm or less, or 10 μm or less, or 7 μm or less, or 5 μm or less, or 1 μm or less, or 0.5 μm or less, or 0.1 μm or less.

[0065] Embodiment 14. The monolithic body of any one of the preceding embodiments, wherein the MOFs can be shaped MOF particles.

[0066] Embodiment 15. A monolithic body as described in embodiment 14, wherein the shaped MOF particles have a length-to-width aspect ratio greater than 1.0.

[0067] Embodiment 16. A monolithic body according to embodiment 14 or 15, wherein the aspect ratio of the length to width of the shaped MOF particles is at least 1.1, or at least 1.5, or at least 2.0, or at least 3.0, or at least 5.0, or at least 10.0.

[0068] Embodiment 17. The MOF is aluminum fumarate, or MIL-100, or MIL-101, or Numat-11, or Numat-25, or UIO-66, or a transition metal-based MOF, or MOF-0, MOF-2, MOF-3, MOF-4, MOF-5, MOF-6, MOF-7, MOF-8, MOF-9, MOF-11, MOF-12, MOF-20, MOF-25, MOF-26, MOF-31, MOF-32, MOF-33, MOF-34, MOF-36, MOF-37, MOF-38, MOF-39, MOF-47, MOF-49, MOF-69a, MOF-69b, MOF-74, MOF-101, MOF-102, MOF -107, MOF-108, MOF-110, MOF-177, MOF-j, MOF-n, IRMOF-1, IRMOF-2, IRMOF-3, IRMOF-4, IRM OF-5, IRMOF-6, IRMOF-7, IRMOF-8, IRMOF-9, IRMOF-10, IRMOF-11, IRMOF-12, IRMOF-13, IRMO 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145,

[0069] Embodiment 18. The monolithic body of any one of the preceding embodiments, wherein the weight percent ratio of MOF to binder in the monolithic body is at least 5:1, or at least 8:1, or at least 10:1, or at least 15:1, or at least 20:1, or at least 30:1, or at least 40:1, or at least 50:1.

[0070] Embodiment 19. The monolithic body of any one of the preceding embodiments, wherein the weight percent ratio of MOF to binder in the monolithic body is 100:1 or less, or 70:1 or less, or 50:1 or less, or 30:1 or less, or 20:1 or less, or 15:1 or less, or 10:1 or less.

[0071] Embodiment 20. A monolithic body according to any one of the preceding embodiments, wherein the amount of MOF is at least 70% by weight, or at least 75% by weight, or at least 80% by weight, or at least 85% by weight, or at least 90% by weight, or at least 95% by weight, or at least 98% by weight, based on the total weight of the monolithic body.

[0072] Embodiment 21. A monolithic body according to any one of the preceding embodiments, wherein the amount of MOF is 99.5% by weight or less, for example 99% by weight or less, or 97% by weight or less, based on the total weight of the monolithic body.

[0073] Embodiment 22. A monolithic body according to any one of the preceding embodiments, wherein the amount of binder is 30% by weight or less, or 25% by weight or less, or 20% by weight or less, or 15% by weight or less, or 10% by weight or less, or 5% by weight or less, or 3% by weight or less, based on the total weight of the monolithic body.

[0074] Embodiment 23. A monolithic body according to any one of the preceding embodiments, wherein the amount of binder is at least 0.5% by weight, or at least 1% by weight, or at least 3% by weight, or at least 5% by weight, based on the total weight of the monolithic body.

[0075] Embodiment 24. The monolithic body of any one of the preceding embodiments, wherein the monolithic body is a pellet, a tube, a sheet, has a round shape, or has an irregular shape.

[0076] Embodiment 25. The monolithic body of embodiment 24, wherein the monolithic body is a pellet.

[0077] Embodiment 26. The monolithic body of embodiment 25, wherein the pellet has an aspect ratio of length to thickness of 1:1 to 10:1.

[0078] Embodiment 27. The monolithic body of embodiment 24 or 25, wherein the pellet has a thickness of at least 0.1 mm, or at least 0.3 mm, or at least 0.5 mm, or at least 0.8 mm, or at least 1.0 mm, or at least 1.2 mm, or at least 1.4 mm, or at least 1.6 mm, or at least 1.8 mm, or at least 2.0 mm.

[0079] Embodiment 28. The monolithic body of embodiment 24 or 25, wherein the pellet has a thickness of 5.0 mm or less, or 4.0 mm or less, or 3.0 mm or less, or 2.0 mm or less, or 1.0 mm or less.

[0080] Embodiment 29. A monolithic body according to any one of embodiments 24 to 28, wherein the length of the pellet is at least 0.5 mm, or at least 1.0 mm, or at least 1.3 mm, or at least 1.5 mm, or at least 2.0 mm, or at least 3 mm, or at least 5 mm.

[0081] Embodiment 30. The monolithic body of any one of embodiments 24 to 28, wherein the length of the pellet is 10 mm or less, or 8 mm or less, or 5 mm or less, or 3.0 mm or less, or 2.0 mm or less.

[0082] Embodiment 31. A monolithic body according to any one of the preceding embodiments, wherein the crush strength of the monolithic body is at least 5N, or at least 10N, or at least 15N, or at least 20N, or at least 15N, or at least 30N, or at least 35N.

[0083] Embodiment 32. A monolithic body according to any one of the preceding embodiments, wherein the crush strength of the monolithic body is 150N or less, or 100N or less, or 50N or less, or 40N or less.

[0084] Embodiment 33. The monolithic body of any one of the preceding embodiments, wherein the first polymer comprises a functional group and the second polymer comprises a functional group, and the functional group of the first polymer is capable of forming a covalent bond with the functional group of the second polymer.

[0085] Embodiment 34. The monolithic body of embodiment 33, wherein the functional groups of the first polymer are selected from amine groups, hydroxyl groups, acrylate groups, vinyl groups, thiol groups, carboxyl groups, or epoxy groups.

[0086] Embodiment 35. The monolithic body of embodiment 33 or 34, wherein the functional groups of the second polymer are selected from carboxyl groups, hydroxyl groups, amine groups, acrylate groups, or vinyl groups.

[0087] Embodiment 36. The monolithic body of any one of the preceding embodiments, wherein the first polymer comprises at least one polyacrylate, polystyrene, epoxide polymer, polyurethane, polyester, polyether, polyamide, polyimide, or any combination or copolymer thereof.

[0088] Embodiment 37. The monolithic body of embodiment 36, wherein the first polymer is an emulsion polymer.

[0089] Embodiment 38. The monolithic body of embodiment 36 or 37, wherein the first polymer comprises a polyacrylate containing amine functional groups.

[0090] Embodiment 39. The monolithic body of any one of the preceding embodiments, wherein the second polymer comprises a polysaccharide, a polyethylene glycol, a polyamide, a polyvinyl alcohol, or a polyacrylate.

[0091] Embodiment 40. The monolith of embodiment 39, wherein the second polymer comprises a polysaccharide, the polysaccharide being selected from a cellulose derivative, or a starch derivative, an alginate, or an alginate derivative.

[0092] Embodiment 41. The monolithic body of embodiment 40, wherein the polysaccharide comprises a salt of carboxymethylcellulose.

[0093] Embodiment 42. The monolithic body of any one of the preceding embodiments, wherein the polymer binder comprises an at least partially crosslinked polymer of Polymer 1 and Polymer 2.

[0094] Embodiment 43. The monolithic body of embodiment 42, wherein the first polymer comprises a polyacrylate comprising amine functional groups, the second polymer comprises sodium carboxymethylcellulose, and the polyacrylate comprising amine functional groups is at least partially crosslinked with sodium carboxymethylcellulose (NaCMC).

[0095] Embodiment 44. The monolithic body of any one of the preceding embodiments, wherein the weight percentage ratio of polymer 1 to polymer 2 (P1P2) is in the range of 1:10 to 10:1, or 1:5 to 5:1, or 1:2 to 4:1, or 1:1 to 3:1.

[0096] Embodiment 45. The monolithic body of any one of the preceding embodiments, wherein the monolithic body further comprises an inorganic binder.

[0097] Embodiment 46. The monolithic body of embodiment 45, wherein the inorganic binder comprises a hydroxyl group.

[0098] Embodiment 47. The monolithic body of embodiment 45 or 46, wherein the inorganic binder comprises aluminum hydroxide.

[0099] Embodiment 48. The monolithic body of embodiment 47, wherein the inorganic binder comprises gibbsite boehmite.

[0100] Embodiment 49. A monolithic body according to any one of the preceding embodiments, wherein the monolithic body comprises a first pore structure and a second pore structure, the first pore structure being associated with the open pores of the particles of the MOF, and the second pore structure being associated with the open pores formed within the binder and between the binder and the particles of the MOF.

[0101] Embodiment 50. The monolithic body of embodiment 49, wherein the average pore size of the first pore structure is different from the average pore size of the second pore structure.

[0102] Embodiment 51. The monolithic body of embodiment 50, wherein the average pore size of the second pore structure is greater than the average pore size of the first pore structure.

[0103] Embodiment 52. The monolithic body of any one of the preceding embodiments, wherein the binding agent is permeable to an analyte that can be adsorbed by the MOF.

[0104] Embodiment 53. The monolithic body of embodiment 52, wherein the analyte comprises at least one of water, carbon dioxide, hydrogen, methane, ammonia, a water pollutant, or an air pollutant.

[0105] Embodiment 54. The density of the monolithic body is at least 1.5 g / cm 3 , or at least 1.8 g / cm 3 , or at least 2.0 g / cm 3 , or at least 2.2 g / cm 3 , or at least 2.3 g / cm 3 3. The monolithic body of any one of the preceding embodiments, wherein

[0106] Embodiment 55. The density of the monolithic body is 3.5 g / cm 3 or less than 3.0g / cm 3 or less than 2.8g / cm 3 or less than 2.6g / cm 3 13. The monolithic body of any one of the preceding embodiments, wherein:

[0107] Embodiment 56. A method for preparing a monolithic body comprising a metal-organic framework (MOF), comprising: preparing a green body composition comprising a MOF, a first polymer, and a second polymer, wherein the first polymer has a solubility in water of 5 g / L or less at 25° C., and the second polymer has a solubility in water of at least 10 g / L at 25° C.; forming a shaped green body from the green body composition; and curing the shaped green body to obtain a monolithic body.

[0108] Embodiment 57. The method of embodiment 56, wherein curing comprises heat treating at a temperature of at least 60°C, or at least 80°C, or at least 100°C, or at least 130°C.

[0109] Embodiment 58. The method of embodiment 56, wherein curing comprises heat treating at a temperature of 350°C or less, or 300°C or less, or 250°C or less, or 200°C or less, or 160°C or less, or 130°C or less.

[0110] Embodiment 59. The method of any one of embodiments 56-58, wherein forming the shaped green body comprises screen printing, extrusion, slip casting, injection molding, or 3D printing.

[0111] Embodiment 60. The method of any one of embodiments 56-59, wherein the green body composition is a paste.

[0112] Embodiment 61. The method of embodiment 60, wherein the paste has a moisture content of 50% by weight or less, or 40% by weight or less, or 30% by weight or less, or 25% by weight or less, based on the total weight of the green body composition.

[0113] Embodiment 62. The method of any one of embodiments 56-61, wherein the polymeric binder is selected from any of the polymeric binders of embodiments 33-44. EXAMPLES

[0114] The following non-limiting examples illustrate the invention.

[0115] Example 1 A two-component polymer binder system containing a water-insoluble polymer (Polymer 1) and a water-soluble polymer (Polymer 2) was used with the following polymer combinations: As the water-insoluble polymer, Rhoplex GL-618, an acrylic polymer emulsion, was used with sodium carboxymethylcellulose (NaCMC) (product 12M8P from Ashland), a water-soluble cellulose derivative, having a molecular weight of 90,000 g / mol.

[0116] First, a paste was prepared by mixing 10 g of MOF powder of type UTSA-16, a cobalt citrate type compound suitable for absorbing CO2, with a D50 particle size of about 5 microns, 2.12 g of Rhoplex GL-618 (with a solid content of 47 wt%), 2 g of NaCMC, and a 10 wt% NaCMC aqueous solution, and kneading by hand for 3 minutes. The paste, also referred to herein as green body composition, was further subjected to forming a pellet-shaped green body by screen printing, followed by curing the molded green body. The total amount of polymer binder in the cured pellet was about 11 wt% based on the total weight of the polymer binder and MOF.

[0117] The screen printing was performed using a 0.76 mm thick PEEK belt with 1.6 mm diameter circular through holes. The through holes of the belt were filled with paste using a spatula. The screen printed pellets were dried by heating at 100°C for 1 hour.

[0118] Crushing strength measurement The pellets were subjected to crush strength testing using an MTS Sintech 2 / G system with load cell sensitivity down to 0.01 N. The head of the measurement unit was positioned to just touch the test pellet and crushing was performed using a constant displacement. The displacement was set at 2 μm / s until pellet breakage occurred. Breakage was indicated by the instrument by a sudden drop in load from maximum load.

[0119] The average crush strength obtained for the pellets containing the polymer binder combination of Rhoplex GL618 and NaCMC was 37N.

[0120] A summary of the crushing strength test results is shown in Table 1.

[0121] [Table 1]

[0122] MOF-containing pellets with boehmite binder A paste was formed by combining 5 g of MOF (UTSA-16), 0.68 g of boehmite (P2 Disperal from Sasol) and 3 g of deionized water and kneading the mixture by hand for 3 minutes.

[0123] Screen printing was carried out in the same manner as described above for the polymeric binder-containing pellets, except that heating was at 150° C. for 2 hours.

[0124] The results of the crush strength test (Sample S2) are also summarized in Table 1. It can be seen that the pellets formed using the boehmite binder had lower crush strength compared to the pellets made using the polymer binder combination of Polymer 1 and Polymer 2.

[0125] MOF-containing pellets with alginate binder A paste was formed by hand mixing 6.41 g of MOF (UTSA-16, a CO2-adsorbing MOF with a D50 size of approximately 5 microns) with 3.14 g of ammonium alginate (4 wt% ammonium alginate in water) for 3 minutes.

[0126] Screen printing was performed in the same manner as described above for the polymer binder-containing pellets, except that after filling the belt holes, the paste in the belt holes was exposed to a 30% calcium chloride solution by wiping the surface with a paper towel moistened with calcium chloride solution. The calcium chloride treatment (which causes cross-linking of the alginate) was followed by heating at 100°C for 15 minutes.

[0127] Crush strength test results showed an average crush strength of 13N for pellets made with alginate as the binder, which was lower than the crush strength of pellets containing a polymer binder combination or a boehmite binder.

[0128] Example 2 As used in Example 1, a series of MOF-containing pellets were prepared by combining a binary polymer binder combination of Rhoplex GL-618 (polymer 1) and NaCMC (polymer 2) with a metal organic framework powder of type MIL-100(Fe) (from AEOL). MIL-100(Fe) is an iron(III)-based compound with trimesic acid ligands and has a D50 particle size of about 9.4 microns (measured with a Horiba LA-950 laser scattering particle size analyzer). Samples were varied by the total amount of polymer binder (5 wt%, 10 wt%, 15 wt%, and 20 wt%, based on the total weight of MOF and polymer binder) and by varying the ratio of Rhoplex GL-618 (polymer 1) to NaCMC (polymer 2). The weight percentage ratios of Polymer 1 to Polymer 2 (P1 to P2) were 1.5 to 1.0, 1.0 to 1.0, 1.0 to 1.5, 1.0 to 2.33, and 1 to 4. Each sample was hand mixed for 3 minutes, with small amounts of water added as needed to form a paste (green body composition), screen printed and cured as described in Example 1.

[0129] The specific surface area (SSA) of the resulting pellets was measured using a Micromeritics TriStar II Plus gas adsorption analyzer according to the BET method, using nitrogen gas as the adsorbent.

[0130] Additionally, the crushing strength (CS) of pellets having polymer ratios of 1.5 to 1.0, 1.0 to 1.0, and 1.0 to 4.0 were measured at different total binder concentrations in the same manner as described in Example 1.

[0131] A summary of the SSA values, calculated NFR, and crushing strength for the pellets is given in Tables 2, 3, and 4.

[0132] [Table 2]

[0133] [Table 3]

[0134] [Table 4]

[0135] The above table shows a pellet (sample S16) (1135 m) with a P1:P2 ratio of 1:2.33 and a total binder content of 15 wt.%. 2 / g SSA was measured) and pellets with a P1:P2 ratio of 1:1.5 (sample 17) (SSA at 5 mg total binder was 1296 m 2 / g) and pellets (sample 18) (SSA was 1006 m for a total binder amount of 15 wt.%. 2 / g) is not shown.

[0136] From the summarized data, it can be seen that the highest SSA was obtained when the weight percent ratio of Rhoplex to NaCMC (P1 to P2) was 1:1. Very close SSA values ​​could be obtained with a binder ratio of P1 to P2 of 1.5:1, which has the advantage of improving the crush strength.

[0137] A comparative example was made by preparing pellets made only of Rhoplex GL618 (Polymer 1) and Mil-100 (Fe). Pellets containing 32 wt. % Rhoplex (Polymer 1) and Mil-100 (Fe) as the only binder were 82 mm thick. 2 In addition, the pellets made with only water, without a binder, maintained their pellet shape after drying, but had a very low crush strength of 2.4 N and an SSA of 1251 m 2 / g SSA.

[0138] The experiments further show that using a specific weight percent ratio combination of polymer 1 and polymer 2 and total amount of polymer binder, a high normalized functionality ratio (NFR) can be obtained.

[0139] Comparative Polymer Binder Combinations Pellets are prepared as described above for the binder combination of Rhoplex GL618 and NaCMC, but using a combination of different types of polymers in a 1:1 weight percent ratio with a total amount of polymer binder of 10 wt %.

[0140] The following combinations of polymer binders are tested: 1) Zusoplast PS1 (water soluble) and polyethylene oxide (water insoluble at 25° C.), 2) NaCMC (water soluble) and polyethyleneimine (water soluble), 3) Rhoplex GL618 (water insoluble) and Maincote 5045 (water insoluble).

[0141] It is observed that the pellets produced with the comparative binder combination have either a lower SSA or poorer crush strength compared to the pellets containing the binder combination Rhoplex GL618 / NaCMC.

[0142] In the foregoing specification, the concepts have been described with reference to specific embodiments. However, those skilled in the art will recognize that various modifications and changes can be made without departing from the scope of the invention as set forth in the following claims. The specification and figures are therefore to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of the invention.

Claims

1. 1. A monolithic body comprising a metal-organic framework (MOF) and a polymer binder, the polymeric binder comprises a first polymer and a second polymer, the first polymer being water-insoluble having a solubility in water of 5 g / L or less at 25° C., and the second polymer being water-soluble having a solubility in water of at least 10 g / L at 25° C.; the amount of the polymer binder is at least 3 wt.%, based on the total weight of the MOF and the polymer binder; A monolithic body, the average crush strength of which is at least 10 N.

2. The specific surface area (SSA) of the monolithic body is at least 850 m ２ 2. The monolithic body of claim 1, wherein the molecular weight is 1 / g.

3. 3. The monolithic body of claim 1 or 2, wherein the weight percent ratio of the MOF to the polymer binder in the monolithic body is at least 5:

1.

4. 3. The monolithic body of claim 1 or 2, wherein the amount of the polymer binder is at least 3.0 wt.% and no more than 20 wt.%, based on the total weight of the polymer binder and the MOF.

5. 3. The monolithic body according to claim 1 or 2, wherein the crush strength of the monolithic body is at least 25N.

6. 3. The monolithic body of claim 1 or 2, wherein the first polymer comprises a functional group and the second polymer comprises a functional group, the functional group of the first polymer capable of forming a covalent bond with the functional group of the second polymer.

7. 3. The monolithic body of claim 1 or 2, wherein the first polymer comprises at least one of polyacrylate, polystyrene, epoxide polymer, polyurethane, polyester, polyether, polyamide, polyimide, or any combination or copolymer thereof.

8. The monolithic body of claim 7 , wherein the first polymer comprises a polyacrylate containing amine functional groups.

9. The monolithic body of claim 1 or 2, wherein the second polymer comprises a polysaccharide, a polyethylene glycol, a polyamide, a polyvinyl alcohol, or a polyacrylate.

10. 10. The monolithic body of claim 9, wherein the second polymer comprises a polysaccharide, the polysaccharide being selected from a cellulose derivative, or a starch derivative, an alginate, or an alginate derivative.

11. 11. The monolithic body of claim 10, wherein the polysaccharide comprises a salt of carboxymethyl cellulose.

12. The monolithic body of claim 1 or 2, wherein the polymer binder comprises an at least partially crosslinked polymer of polymer 1 and polymer 2.

13. 13. The monolithic body of claim 12, wherein the first polymer comprises a polyacrylate containing amine functional groups and the second polymer comprises a salt of carboxymethyl cellulose.

14. 3. The monolithic body of claim 1 or 2, wherein the polymeric binder is permeable to an analyte that can be adsorbed by the MOF, the analyte being selected from the group of water, carbon dioxide, hydrogen, methane, ammonia, water pollutants, or air pollutants.

15. The density of the monolithic body is at least 1.5 g / cm ３ 3. The monolithic body according to claim 1 or 2,

Images