Adhesive coatings for metal surfaces and related methods

Abstract

This disclosure describes curable coating compositions and methods for coating the surfaces of objects such as metal objects. The coating compositions may include organic and / or inorganic solid adsorbents and may provide a durable curable coating layer that can be used to adsorb specific molecules such as carbon dioxide or water onto the surface of a metal object.

Description

Technical Field

[0001] (Government Support) This invention was made under government support awarded by the U.S. Department of Energy under DE-FE0032099. The U.S. government has certain rights in this invention.

[0002] (Cross-Reference to Related Applications) This application claims the benefit of priority of U.S. Provisional Patent Application No. 63 / 463,274, filed on May 1, 2023, entitled "ADSORPTIVE COATINGS FOR METAL SURFACES AND RELATED METHODS", the entire contents of which are incorporated herein by reference.

[0003] (Technical Field) The subject matter of this disclosure relates to curable and cured coating compositions (e.g., for metal surfaces) and methods of coating surfaces with curable coating compositions. The coating compositions can include organic and inorganic materials, which can be selected to provide desired surface / coating properties or functionalities such as desired porosity and the ability to capture / adsorb specific molecules. Representative coating compositions include adsorbents such as polyamine-based linden dendrimers (P-dendrimers) for carbon dioxide capture or metal-organic frameworks (MOFs) for water adsorption. The subject matter of this disclosure further relates to methods of using the coated surfaces of this disclosure for carbon capture or water harvesting from the air.

Background Art

[0004] The coating process generally involves depositing organic and / or inorganic materials onto a surface (such as a metal rod, sheet, paper, or the surface of another object). It may be desirable to coat the surface of another object with different materials in a uniform manner, e.g., with a uniform pattern and / or thickness. Surface coatings may be desirable for a variety of reasons, including providing corrosion protection and / or a good appearance. The selection of a particular coating material may depend on various parameters, such as the shape of the surface to be coated, desired friction properties, hydrophilicity, thermal and / or electrical properties, and the cost and availability of the coating material. The coating material may be colored or uncolored and may be used to form a film of a desired thickness. Generally, it may be desirable for the coated surface to have good durability, for example, by minimizing loss of functionality and / or dimensionality.

[0005] In recent years, coating materials and processes have attracted attention for their use in the preparation of adsorbent coatings, such as carbon capture technology, water collection, and various other chemical separation / purification applications. For example, to provide carbon capture, it may be desirable to deposit or coat a carbon dioxide-adsorbent material onto a metal plate arranged in a designed structure to selectively adsorb carbon dioxide from gaseous mixtures such as mixed gas streams, exhaust gases, or the atmosphere. Materials capable of adsorbing water can be used for atmospheric water collection, i.e., to adsorb water vapor from the air and subsequently release or recover it as liquid water, an application of particular interest in arid regions.

[0006] Therefore, there is a continuing need for further coating formulations and processes for coating surfaces with materials that can selectively capture or adsorb specific molecules, particularly carbon dioxide or water. [Overview of the Initiative]

[0007] This summary lists several embodiments of the subject matter of the present disclosure and, in many cases, lists examples of variations and combinations of these embodiments. This summary is merely an example of the many diverse embodiments. References to representative features of a given embodiment are also illustrative. Such embodiments may or may not exist with or without the referenced features, and similarly, these features may apply to other embodiments of the present disclosure, whether or not they are described in this summary. To avoid excessive repetition, this summary does not list or suggest all possible combinations of such features.

[0008] In some embodiments, the subject of this disclosure provides a curable coating composition comprising (a) a solid adsorbent, (b) a liquid carrier, and (c) a curable binder. In some embodiments, the curable binder comprises an epoxy resin. In some embodiments, the epoxy resin comprises an alicyclic epoxy resin. In some embodiments, the curable binder further comprises a diamine. In some embodiments, the curable binder further comprises an epoxy modifier selected from the group comprising epoxy-functionalized alcohols, epoxy-functionalized diols, epoxy-functionalized polyols, and epoxy-functionalized carboxylic acids. In some embodiments, the curable binder further comprises an epoxy-functionalized silane.

[0009] In some embodiments, the liquid carrier is a polar organic solvent. In some embodiments, the polar organic solvent is isopropanol.

[0010] In some embodiments, the solid adsorbent is a polyamine-based lindendrimer (P-dendrimer). In some embodiments, the polyamine-based P-dendrimer is based on a polyamine selected from the group including branched polyethyleneimine (PEI) with a molecular weight (MW) of 800, branched PEI with MW600, branched PEI with MW1200, branched PEI with MW2500, branched PEI with MW10000, linear PEI with MW600, tetraethylenepentamine, triethylenebutamine, diethylenetriamine, 1,2-diaminoethane, 1,2-diaminopropane, and 2,2',2''-triaminotriethylamine.

[0011] In some embodiments, the solid adsorbent is a metal-organic structure (MOF). In some embodiments, the MOF is selected from the group including MOF-801, MOF-808, MOF-841, MOF-303, MOF-333, NbOFFIVE-1-Ni, FeFFIVE-1-Ni, and AlFFIVE-1-Ni.

[0012] In some embodiments, the curable coating composition contains at least about 5 wt% (wt%) of a curable binder compared to the weight of the solid adsorbent. In some embodiments, the curable coating composition contains about 5 wt% to about 45 wt% of a curable binder compared to the weight of the solid adsorbent.

[0013] In some embodiments, the curable coating composition further comprises a porosity control agent. In some embodiments, the porosity control agent comprises an inorganic solid additive that can be decomposed during heating at a temperature suitable for curing the curable binder solution. In some embodiments, the porosity control agent comprises one or more ammonium carbonate and ammonium bicarbonate. In some embodiments, the porosity control agent comprises a carbamate group formed between carbon dioxide gas and a reactive amine group in a polyamine-based P-dendrimer or another curable coating composition component containing a reactive amine group.

[0014] In some embodiments, the subject matter of the present disclosure provides a method for preparing a curable coating composition, the method comprising the steps of (a) preparing a slurry containing a solid adsorbent and a liquid carrier, (b) preparing a curable binder, and (c) bringing the curable binder into contact with the slurry to provide a curable coating composition. In some embodiments, the step of preparing the slurry includes bringing the solid adsorbent into contact with the liquid carrier and stirring the resulting mixture for a predetermined time. In some embodiments, the slurry contains a solid adsorbent and a liquid carrier in a weight ratio of about 1:2 to about 1:3.

[0015] In some embodiments, the step of preparing a curable binder includes mixing an epoxy resin with one or more of an epoxy modifier, a diamine, and an epoxy-functionalized silane. In some embodiments, the step of contacting the curable binder with a slurry includes adding the curable binder to the slurry and stirring the resulting composition for a predetermined time. In some embodiments, the contact includes contacting the slurry with an amount of curable binder having a weight of at least about 5% of the weight of the solid adsorbent in the slurry.

[0016] In some embodiments, the method further includes the step of incorporating a porosity control agent into a curable coating composition. In some embodiments, the porosity control agent comprises an inorganic solid additive which is decomposable when heated to a temperature suitable for curing the curable binder, and the incorporation of the porosity control agent comprises adding the inorganic solid additive to the curable coating composition, the inorganic solid additive optionally comprising one or more from the group comprising ammonium carbonate and ammonium bicarbonate. In some embodiments, the solid adsorbent comprises a polyamine-based P-dendrimer containing a reactive amine group, and the incorporation of the porosity control agent comprises bubbling carbon dioxide gas into the slurry prepared in step (a), the carbon dioxide reacting with the reactive amine group to form a carbamate group which can decompose and regenerate carbon dioxide gas when heated to a temperature suitable for curing the curable binder solution.

[0017] In some embodiments, the subject matter of the present disclosure provides a method for coating a metal object, the method comprising: (i) providing a curable coating composition of the present disclosure; (ii) pre-treating one or more surfaces of a metal object to obtain one or more pre-treated surfaces, the pre-treatment comprising cleaning, abrasive treatment and / or application of a primer; (iii) applying the coating composition to one or more pre-treated surfaces to thereby provide one or more treated surfaces; and (iv) curing the curable coating composition to thereby provide a metal object comprising one or more surfaces comprising a solid coating layer. In some embodiments, step (ii) comprises cleaning one or more surfaces of the metal object with acetone and / or isopropanol. In some embodiments, step (ii) comprises applying a primer to one or more surfaces of the metal object, the primer being an epoxy primer if necessary, and curing the primer. In some embodiments, step (iv) is carried out by heating one or more treated surfaces to a temperature of about 60°C to about 130°C for about 30 minutes to about 5 hours. In some embodiments, the metallic object is a metal sheet or metal plate, and optionally a stainless steel sheet or stainless steel plate.

[0018] In some embodiments, the subject matter of this disclosure provides a metallic object comprising one or more surfaces including a solid coating layer prepared according to the method described herein.

[0019] In some embodiments, the subject of this disclosure provides a metallic object comprising one or more surfaces coated with a solid coating layer containing an adsorbent trapped in a polymer matrix, wherein the adsorbent is a polyamine-based P-dendrimer or a metal-organic structure (MOF), and the polymer matrix is ​​a cured epoxy resin. In some embodiments, the coating layer is porous. In some embodiments, the solid coating layer has a thickness of about 0.01 mm to about 1.0 mm.

[0020] In some embodiments, the subject matter of the present disclosure provides a method for adsorbing carbon dioxide from a gaseous fluid, the method comprising contacting a gaseous fluid containing carbon dioxide with a coating object, the coating object comprising a metallic object comprising one or more surfaces comprising a solid coating layer, the solid coating layer comprising a polyamine-based P-dendrimer encapsulated in a polymer matrix. In some embodiments, the metallic object is a metal sheet or metal plate, optionally a stainless steel sheet or stainless steel plate. In some embodiments, the polymer matrix comprises epoxy.

[0021] In some embodiments, the solid coating layer has a thickness of about 0.01 mm to about 1.0 mm, and optionally about 0.1 mm to about 1.0 mm. In some embodiments, the polyamine-based P-dendrimer in the solid coating layer has a CO2 adsorption capacity of about 78% compared to the same amount of free polyamine-based P-dendrimer.

[0022] In some embodiments, the subject matter of the present disclosure provides a method for adsorbing water from a gaseous fluid, the method comprising the steps of (i) providing a metal object comprising one or more surfaces comprising a solid coating layer, the solid coating layer comprising a metal-organic structure (MOF) encapsulated in a polymer matrix, (ii) heating the metal object to about 100°C under a nitrogen atmosphere, and (iii) bringing a gaseous fluid containing water vapor into contact with the metal object. In some embodiments, the MOF is selected from the group comprising MOF-801, MOF-808, MOF-841, MOF-303, MOF-333, NbOFFIVE-1-Ni, FeOFFIVE-1-Ni, and AlOFFIVE-1-Ni. In some embodiments, the MOF is MOF-801, and the coating layer has a water adsorption capacity of about 20% to about 50% by weight relative to the weight of the MOF in the coating layer.

[0023] Therefore, an object of the subject matter of the present disclosure is to provide a curable coating composition, an object coated with the composition, a method for preparing a curable coating composition, a method for coating a metal surface, and a method for capturing carbon dioxide or water from a gaseous fluid.

[0024] The specific objects of the subject matter of the present disclosure described above in this specification are those that are solved in whole or in part by the subject matter of the present disclosure, and other objects and aspects will become clear as the description proceeds in conjunction with the examples described as the best mode below.

[0025] The subject matter of the present disclosure can be better understood by referring to the following drawings. The components in the drawings are not necessarily drawn to scale, and emphasis is placed on showing the principles of the subject matter of the present disclosure. The drawings are not intended to limit the scope of the subject matter of the present disclosure specified in the claims of this specification or corrected later, but merely to clarify and exemplify the subject matter of the present disclosure.

[0026] To understand the subject matter of the present disclosure more fully, refer to the following drawings.

Brief Description of the Drawings

[0027] [Figure 1] Composite photographic image showing a metal plate coated with a coating layer prepared from a curable coating composition containing a polyamine-based dendrimer (P-dendrimer) adsorbent and an epoxy-based binder solution (BS). The amount of BS in the curable coating composition was varied to 15% (upper left), 20% (upper right), 30% (lower left), and 45% (lower right) with respect to the weight of the P-dendrimer. [Figure 2] (Upper) Schematic diagram of the process for pretreating the surface of a metal substrate before coating with a curable coating composition, and (lower) Schematic diagram with a photographic image showing the surface coating process according to the subject matter of the present disclosure, including pretreatment by sanding / primer application and coating with a curable coating composition. [Figure 3A]These are a series of microscopic images of polyamine-based lindendrimer (P-dendrimer) adsorbents. The scale bar in the lower right indicates 50 micrometers (μm). [Figure 3B] These are a series of microscopic images of polyamine-based lindendrimer (P-dendrimer) adsorbents. The scale bar in the lower right indicates 20 μm. [Figure 3C] These are a series of microscopic images of polyamine-based lindendrimer (P-dendrimer) adsorbents. The scale bar in the lower right indicates 5 μm. [Figure 3D] These are a series of microscopic images of coatings formed by curing a curable coating composition containing a p-dendrimer and an epoxy binder solution (BS), where the amount of BS is 30% relative to the weight of the p-dendrimer. The scale bar in the lower right indicates 200 μm. [Figure 3E] These are a series of microscopic images of coatings formed by curing a curable coating composition containing a p-dendrimer and an epoxy binder solution (BS), where the amount of BS is 30% relative to the weight of the p-dendrimer. The scale bar in the lower right indicates 20 μm. [Figure 3F] These are a series of microscopic images of coatings formed by curing a curable coating composition containing a p-dendrimer and an epoxy binder solution (BS), where the amount of BS is 30% relative to the weight of the p-dendrimer. The scale bar in the lower right indicates 5 μm. [Figure 4] This graph shows the infrared (IR) spectra of cured coating layers formed from curable coating compositions containing polyamine-based lindendrimers (P-dendrimers) and various amounts of epoxy-based binder solution (BS) (15% by weight, 20% by weight, 30% by weight, or 45% by weight of P-dendrimers). For comparison, the spectra of P-dendrimers alone are also shown. [Figure 5A]This is one of a pair of graphs showing carbon dioxide (CO2) isotherms (adsorption amount at standard temperature and pressure (STP) (grams per cubic centimeter (cc / g STP)) versus absolute pressure (millimeters of mercury (mmHg))). Figure 5A shows the isotherms of polyamine lindendrimers (P-dendrimers). [Figure 5B] This is one of a pair of graphs showing carbon dioxide (CO2) isotherms (adsorption amount (grams per cubic centimeter (cc / g STP)) versus absolute pressure (millimeters of mercury (mmHg)) at standard temperature and pressure (STP)). Figure 5C shows the isotherms of coatings formed from a coating composition containing p-dendrimers and 30% epoxy binder solution (BS) relative to the weight of the p-dendrimers. [Figure 6] This graph shows the time-resolved adsorption behavior of carbon dioxide (CO2) at a relative humidity of 75% (RH) (i.e., mass (measured as weight percentage (wt.%)) versus time (hours)), and illustrates coatings prepared by curing a coating composition containing a polyamine-based lindendrimer (P-dendrimer) and a 30% epoxy-based binder solution (BS) relative to the weight of the P-dendrimer. [Figure 7] This is a photographic image of a substrate coated with a coating formed from a curable coating composition containing a polyamine-based lindendrimer (P-dendrimer), an epoxy-based binder solution (BS), and a solid additive for controlling porosity. In particular, the image shows a coating prepared from a composition containing 40% BS and ammonium carbonate relative to the weight of the P-dendrimer. The coating was cured at 65°C for 4 hours. [Figure 8] These are a series of scanning electron microscope (SEM) images of a coating obtained by bubbling carbon dioxide (CO2) into an isopropanol (IPA)-polyamine lindendrimer slurry before mixing with an epoxy binder solution (BS) and curing. The magnification of the images increases from left to right. [Figure 9]These are a series of images of metal-organic frame (MOF) adsorbents, namely MOF-801 and coating materials containing MOF. The image on the left is a photographic image of a coated plate prepared with a MOF-801-containing coating layer according to the method of the subject of this disclosure. The image in the center is a scanning electron microscope (SEM) image of untreated MOF-801, and the image on the right is an SEM image of a coating layer prepared from a curable coating composition of the subject of this disclosure containing MOF-801. [Figure 10] These are a series of images of niobium metal-organic structure (Nb-MOF) adsorbents and coating materials containing Nb-MOF. The image on the left is a photographic image of a coated plate prepared with an Nb-MOF-containing coating layer according to the method of the subject of this disclosure. The image in the center is a scanning electron microscope (SEM) image of untreated Nb-MOF. The image on the right is an SEM image of a coating layer prepared from a curable coating composition of the subject of this disclosure containing Nb-MOF. [Figure 11A] Figure 11A is an intelligent gravimetric analysis (IGA) graph of a cured coating layer of the subject matter of this disclosure, which contains a metal-organic structure (MOF), namely MOF-801, as an adsorbent. The graph shows the time-resolved adsorption behavior of water vapor (i.e., mass (measured as weight percent (wt.%)) versus time (minutes)). [Figure 11B] Figure 11B is an intelligent gravimetric analysis (IGA) graph of a cured coating layer of the subject matter of this disclosure, which contains a metal-organic structure (MOF), namely MOF-801, as an adsorbent. The graph shows the mass increase (expressed as weight percentage (wt.%)) as a function of relative humidity (RH; expressed as percentage (%)). [Modes for carrying out the invention]

[0028] The subject matter of this disclosure will be described in more detail below with reference to representative embodiments, along with the accompanying drawings and examples. However, the subject matter of this disclosure may be carried out in different forms and should not be construed as being limited to the embodiments described herein. Rather, these embodiments are provided to make this disclosure complete and to fully convey the scope of the embodiments to those skilled in the art.

[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art. All publications, patent applications, patents, and other documents mentioned herein are incorporated herein by reference in their entirety.

[0030] In this specification and in the claims, unless otherwise specified, any particular chemical formula or name shall encompass all optical isomers, stereoisomers, and racemic mixtures where isomers and racemic mixtures exist.

[0031] (I. Definition) In accordance with long-standing patent law convention, the terms “a,” “an,” and “the” in this specification mean “one or more,” including in the claims. Therefore, a reference to “solvent,” for example, includes one or more solvents, a mixture of two or more solvents, and so on.

[0032] Unless otherwise specified, all numerical values ​​such as component amounts and reaction conditions used in this specification and the claims are understood to be modified by the term "approximately." Therefore, unless otherwise stated, the numerical parameters described herein and in the appended claims are approximations that may vary depending on the properties to be desired from the disclosed subject matter.

[0033] In this specification, the term "about" when used with respect to measurable values ​​such as weight, molar equivalent, time, and temperature means to include variations of, for example, ±20% or ±10%, ±5%, ±1%, and ±0.1%, such that these variations are appropriate for carrying out the disclosed method.

[0034] In this specification, the term "and / or" is used to describe two or more activities, conditions, or results, and applies whether both of the listed conditions are included or only one of the two is included.

[0035] In this specification, the term “contains” is synonymous with “contains,” “includes,” or “characterized,” and is comprehensive or open-ended and does not exclude additional elements or method steps not described. “Contains” is a technical term used in the claims and means that the elements described are essential, but other elements may be added to still form the components of the claims.

[0036] In this specification, the phrase "consisting of" means to exclude any element, step, or component not specified in the claim. When the phrase "consisting of" appears in a section of the body of a claim, it limits only the elements defined in that section, rather than immediately following the preamble, and other elements are not excluded from the claim as a whole.

[0037] In this specification, the phrase "essentially consisting of" means limiting the scope of the claim to specified materials or steps, with the addition of which does not substantially affect the basic and novel properties of the claimed subject matter.

[0038] With regard to the terms “including,” “consisting of,” and “essentially consisting of,” if any of these three terms is used herein, the subject matter to be disclosed and claimed may also include any of the other two terms.

[0039] In this specification, the term “alkyl” means a C1-C20 linear (i.e., “linear”), branched, or cyclic hydrocarbon chain that is saturated or at least partially, and possibly fully unsaturated (i.e., alkenyl and alkynyl), including, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, octenyl, butadienyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, and allenyl groups. “Branched” means an alkyl group in which a lower alkyl group, such as methyl, ethyl, or propyl, is bonded to a linear alkyl chain. “Lower alkyl” means an alkyl group having 1 to about 8 carbon atoms (i.e., C1-C8 alkyl), for example, one, two, three, four, five, six, seven, or eight carbon atoms. In some embodiments, “lower alkyl” may mean a C1-C6 or C1-C5 alkyl group. "Higher alkyl" refers to alkyl groups having approximately 10 to approximately 20 carbon atoms, for example, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. In certain embodiments, "alkyl" refers specifically to linear or branched alkyl groups of C1-C8 or C1-C6.

[0040] Alkyl groups may be optionally substituted with one or more alkyl substituents, which may be the same or different ("substituted alkyl"). The term "alkyl substituent" includes, but is not limited to, alkyl, substituted alkyl, halo, nitro, cyano, amino, arylamino, acyl, hydroxy, aryloxy, alkoxy, alkylthio, arylthio, aralkyloxy, aralkylthio, carboxyl, alkoxycarbonyl, oxo, and cycloalkyl. One or more oxygen, sulfur, or substituted or unsubstituted nitrogen atoms may be inserted into the alkyl chain, and the substituents on the nitrogen may be hydrogen, lower alkyl (also referred to herein as "alkylaminoalkyl"), or aryl.

[0041] Therefore, in this specification, the term "substituted alkyl" includes alkyl groups as defined herein in which one or more atoms or functional groups are substituted with other atoms or functional groups, such as alkyl, substituted alkyl, halogen, aryl, substituted aryl, alkoxy, hydroxy, nitro, cyano, amino, alkylamino, dialkylamino, ester, acyl, amide, sulfonyl, sulfate, mercapto, and the like.

[0042] The term "alkenyl" refers to an alkyl group as defined above that contains at least one carbon-carbon double bond. Typical alkenyl groups include, but are not limited to, ethenyl, propenyl, butenyl, pentenyl, hexenyl, octenyl, butadienyl, and allenyl groups. Alkenyl groups may be substituted as needed with one or more identical or different alkyl substituents, which may include, but are not limited to, saturated or unsaturated alkyls, substituted alkyls (e.g., halo-substituted and perfluoro-substituted alkyls, e.g., -CF3), cycloalkyls, halo, nitro, hydroxy, carbonyl, carboxyl, acyl, alkoxy, aryloxy, aralkoxy, thioalkyl, thioaryl, thioaralkyl, amino (e.g., aminoalkyl, aminodialkyl, aminoaryl, etc.), sulfonyl, and sulfinyl groups.

[0043] "Cyclic" and "cycloalkyl" refer to non-aromatic monocyclic or polycyclic ring systems having about 3 to about 10 carbon atoms, e.g., 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms. In some embodiments, the cycloalkyl ring system contains 3 to 6 carbon atoms. Cycloalkyl groups may be partially unsaturated as needed. Cycloalkyl groups may be optionally substituted with alkyl substituents as defined herein. One or more oxygen, sulfur, or substituted or unsubstituted nitrogen atoms may be inserted into the cyclic alkyl chain, and the nitrogen substituents may be hydrogen, alkyl, substituted alkyl, aryl, or substituted aryl, thereby yielding heterocyclic groups. Typical monocyclic cycloalkyl rings include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl. Furthermore, cycloalkyl groups may be optionally substituted with linking groups such as alkylene groups as defined below, e.g., methylene, ethylene, and propylene. In such cases, the cycloalkyl group may be called, for example, cyclopropylmethyl, cyclobutylmethyl, etc. In addition, polycyclic cycloalkyl rings include adamantyl, octahydronaphthyl, decalin, camphor, camphan, and noadamantyl.

[0044] Therefore, in this specification, the term "substituted cycloalkyl" includes cycloalkyl groups as defined herein in which one or more atoms or functional groups are substituted with other atoms or functional groups, such as alkyl, substituted alkyl, halogen, aryl, substituted aryl, alkoxy, hydroxy, nitro, cyano, amino, alkylamino, dialkylamino, ester, acyl, amide, sulfonyl, sulfate, mercapto, etc.

[0045] As used herein, the term “aryl” refers to an aromatic substituent consisting of a single aromatic ring or multiple aromatic rings linked by condensation, covalent bonds, or a common group such as a methylene or ethylene moiety. The common linking group may be carbonyl in benzophenone, oxygen in diphenyl ether, nitrogen in diphenylamine, etc. The term “aryl” particularly encompasses heterocyclic aromatic compounds (i.e., “heteroaryls”). Aromatic rings may include phenyl, naphthyl, biphenyl, diphenyl ether, diphenylamine, benzophenone, etc. In certain embodiments, the term “aryl” means a cyclic aromatic compound containing about 5 to about 10 carbon atoms, e.g., 5, 6, 7, 8, 9, or 10 carbon atoms, and including 5-membered and 6-membered hydrocarbon rings and heterocyclic aromatic rings.

[0046] The aryl group may be substituted with one or more aryl group substituents (which may be the same or different) as needed ("substituted aryl"), and the "aryl group substituents" include alkyl, substituted alkyl, aryl, substituted aryl, aralkyl, hydroxyl, alkoxy, aryloxy, aralkyloxy, carboxyl, acyl, halo, nitro, alkoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl, acyloxy, acylamino, aroylamino, carbamoyl, alkylcarbamoyl, dialkylcarbamoyl, arylthio, alkylthio, alkylene, and -NR'R'', where R' and R'' can independently be hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, and aralkyl, respectively.

[0047] Accordingly, the term "substituted aryl" as used herein includes aryl groups in which one or more atoms or functional groups are substituted with other atoms or functional groups, such as alkyl, substituted alkyl, halogen, aryl, substituted aryl, alkoxy, hydroxyl, nitro, amino, alkylamino, dialkylamino, sulfate, and mercapto.

[0048] Specific examples of aryl groups include, but are not limited to, cyclopentadienyl, phenyl, furan, thiophene, pyrrole, pyridine, imidazole, benzimidazole, isothiazole, isoxazole, pyrazole, pyrazine, triazine, thiazole, pyrimidine, quinoline, isoquinoline, indole, carbazole, naphthyl, etc.

[0049] In this specification, as used alone or as part of another group, “heterocycle,” “heterocyclic group,” or “heterocyclic formula” refers to an aliphatic (e.g., fully or partially saturated heterocyclic formula) or aromatic (e.g., heteroaromatic ring) monocyclic or bicyclic ring system containing one or more heteroatoms (e.g., 1, 2, or 3 heteroatoms selected from oxygen, sulfur, and substituted or unsubstituted nitrogen) inserted into a cyclic alkyl or aryl carbon chain. Examples of monocyclic ring systems include any 5-membered or 6-membered ring containing 1, 2, 3, or 4 heteroatoms independently selected from oxygen, nitrogen, and sulfur. A 5-membered ring has 0 to 2 double bonds, and a 6-membered ring has 0 to 3 double bonds. Representative examples of monocyclic ring systems include ethylene oxide, azetidine, azepine, aziridine, 1,3-dioxolane, dioxane, dithiane, furan, imidazole, imidazoline, imidazolidine, isothiazole, isothiazolin, isothiazolidine, isoxazole, isosazoline, isosazolidin, morpholine, oxadiazole, oxadiazoline, oxadiazolidin, oxazole, oxazoline, oxazolidine, piperazine, piperidine, pyran, pyrazine, pyrazol Examples of monocyclic ring systems include, but are not limited to, aryl groups, pyrazolin, pyrazolidine, pyridine, pyrimidine, pyridazine, pyrrole, pyrroline, pyrrolidine, tetrahydrofuran, tetrahydropyran, tetrahydrothiophene (also called thiolan), tetrazine, tetrazole, thiadiazole, thiadiazoleline, thiadiazolidine, thiazoleline, thiazolidine, thiazoline, thiazolidine, thiophene, thiomorpholine, thiomorpholine sulfone, thiopyran, triazine, triazole, trithiane, etc. Examples of bicyclic ring systems include those in which any of the above monocyclic ring systems are condensed with an aryl group, cycloalkyl group, or other monocyclic ring system as defined herein.Representative examples of bicyclic ring systems include, but are not limited to, benzimidazole, benzothiazole, benzothiadiazole, benzothiophene, benzoxadiazole, benzoxazole, benzofuran, benzopyran, benzothiopyran, benzodioxin, 1,3-benzodioxol, carbazole, cinnoline, indazole, indole, indoline, indidine, naphthyridine, isobenzofuran, isobenzothiophene, isoindole, isoindoline, isoquinoline, phthalazine, purine, pyranopyridine, quinoline, quinolidine, quinoxaline, quinazoline, tetrahydroisoquinoline, tetrahydroquinoline, and thiopyranopyridine. These rings include quaternized derivatives and may be substituted with one or more alkyl and / or aryl group substituents as needed.

[0050] As used herein, "substituted heterocycle" refers to a heterocyclic group in which one or more hydrogen atoms are substituted with alkyl or aryl substituents.

[0051] The term "heteroaromatic ring" refers to an aromatic monocyclic or bicyclic (condensed, bridging, or spirocyclic) ring system containing one or more heteroatoms (e.g., 1, 2, or 3 heteroatoms selected from oxygen, sulfur, and substituted or unsubstituted nitrogen, with N-oxides, sulfur oxides, and dioxides also being acceptable heteroatomic substitutions) inserted into a cyclic aryl carbon chain. In some embodiments, the monocyclic heteroaromatic ring group is a 5- to 7-membered aromatic ring. Representative heteroaromatic ring groups include, but are not limited to, furan, thiophene, pyrrole, imidazole, pyrazole, triazole, tetrazole, oxazole, isoxazole, oxadiazole, thiaciaazole, isothiazole, pyridine, pyridazine, pyrazine, pyrimidine, quinoline, isoquinoline, benzofuran, benzoxazole, benzothiophene, indole, indazole, benzimidazole, imidazopyridine, pyrazolopyridine, and pyrazolopyrimidine.

[0052] The term "substituted heteroaromatic ring" refers to a heteroaromatic ring group as defined herein in which one or more hydrogen atoms are substituted with an aryl substituent.

[0053] "Aralkyl" refers to an aryl-alkyl- or -alkyl-aryl group, where aryl and alkyl are as described above, and may include substituted aryl and substituted alkyl groups. Therefore, "substituted aralkyl" may refer to an aralkyl group containing one or more alkyl or aryl group substituents. Examples of aralkyl groups include benzyl, phenylethyl, and naphthylmethyl.

[0054] "Alkylene" can refer to a linear or branched divalent aliphatic hydrocarbon group having 1 to about 20 carbon atoms, for example, having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. Alkylene groups can be linear, branched, or cyclic. Alkylene groups can also be unsaturated (i.e., including alkene or alkyne groups) as needed, and can be substituted with one or more "alkyl group substituents". One or more oxygen, sulfur, or substituted or unsubstituted nitrogen atoms (also referred to herein as "alkylaminoalkyl") may be inserted into the alkylene group as needed, and the nitrogen substituents are alkyl as described above. Examples of alkylene groups include methylene (-CH2-), ethylene (-CH2-CH2-), propylene (-(CH2)3-), and cyclohexylene (-C6H 10 -), -CH=CH-CH=CH-, -CH=CH-CH2-, -(CH2) q -N(R)-(CH2) r -, where q and r are integers from 0 to about 20, for example 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20, and R is hydrogen or a lower alkyl group, such as methylenedioxy(-O-CH2-O-) or ethylenedioxy(-O-(CH2)2-O-). The alkylene group has about 2 to about 3 carbon atoms and may have an additional 6 to 20 carbon atoms.

[0055] "Arylene" refers to a divalent aryl group that may be substituted or unsubstituted.

[0056] The term "aralkylene" refers to a divalent group that includes a combination of an alkylene group and an arylene group (for example, -arylene-alkylene-, alkylene-arylene-alkylene-, arylene-alkylene-arylene-, etc.).

[0057] Similarly, the terms “cycloalkylene,” “heterocycloalkylene,” and “heteroarylene” refer to divalent cycloalkyl, heterocyclic, and heteroaryl groups that may be optionally substituted with one or more alkyl or aryl substituents.

[0058] As used herein, the term "acyl" refers to an organic carboxylic acid group in which the -OH group of the carboxylic acid group is substituted with another substituent. Thus, an acyl group may be represented as RC(=O)-, where R is an alkyl, substituted alkyl, aralkyl, substituted aralkyl, aryl, or substituted aryl group as defined herein. Therefore, the term "acyl" particularly includes arylacyl groups such as the phenacyl group. Specific examples of acyl groups include acetyl (i.e., -C(=O)CH3) and benzoyl.

[0059] "Alkoxyl" refers to an alkyl-O-group, including substituted alkyls, where the alkyl group is as described above. In this specification, "alkoxyl" may refer to, for example, methoxyl, ethoxyl, propoxyl, isopropoxyl, butoxyl, t-butoxyl, and pentoxyl. The terms "oxyalkyl" and "alkoxy" may be used synonymously with "alkoxyl."

[0060] "Aryloxyl" and "aryloxy" refer to aryl-O-groups, including substituted aryls, in which the aryl group is as described above. In this specification, the term "aryloxyl" may refer to phenyloxyl or hexyloxyl, as well as phenyloxyl or hexyloxyl substituted with alkyl, substituted alkyl, or alkoxyl.

[0061] "Aralkyloxyl" or "aralkyloxy" refers to the aralkyl-O- group, as described above. A typical example of an aralkyloxyl group is benzyloxyl.

[0062] The term "carbonyl" refers to a -C(=O)- group. The term "carbonyl carbon" refers to the carbon atom of the carbonyl group. Other groups, including but not limited to acyl groups, anhydrides, aldehydes, esters, lactones, amides, ketones, carbonates, and carboxylic acids, contain carbonyl groups.

[0063] The terms "carboxyl" and "carboxylic acid" refer to the -C(=O)OH or -C(=O)O- group. In some embodiments, the term "carboxylate" refers to the C(=O)O- group.

[0064] As used herein, the terms "halo" or "halogen" refer to fluoro, chloro, bromo, and iodine groups.

[0065] The term "amine" refers to a molecule having formula N(R)3, or its protonated form, or a group having formula -N(R)2, where each R is independently H, alkyl, substituted alkyl, aryl, substituted aryl, aralkyl, substituted aralkyl, or two R groups together form an alkylene or arylene group. The term "primary amine" refers to an amine in which at least two R groups are H. The term "secondary amine" refers to an amine in which only one R group is H.

[0066] The terms "hydroxyl" and "hydroxy" refer to the -OH group.

[0067] The terms "mercapto" and "thiol" refer to the -SH group.

[0068] The term "oxo" in this specification refers to a compound in which a carbon atom is replaced by an oxygen atom, as described above.

[0069] The terms “joined” or “joined” and their variations can refer to either a covalent or non-covalent bond. In some cases, the term “joined” refers to a bond by a coordinate covalent bond. The term “conjugation” can refer to a bonding process such as the formation of a covalent link or a coordinate covalent bond.

[0070] In this specification, the term “metal-organic structure” refers to a solid network (e.g., a two-dimensional or three-dimensional network) containing both metallic and organic components, where the organic component contains at least one, and usually multiple, carbon atoms. In some embodiments, the metal-organic matrix material is a coordination polymer, which comprises repeating units of coordination complexes containing metallic components (also called “secondary building units” or “SBUs”) and polydentate organic ligands. Suitable SBUs include, for example, metal ions, metal clusters, and metal-oxoclusters. Suitable organic ligands include bidentate, tridentate, or other polydentate organic ligands, i.e., molecules containing at least two functional groups capable of forming coordination bonds with a metal. Thus, a single organic ligand can interact with or crosslink at least two SBUs. In some embodiments, the MOF contains multiple types of SBUs. In some embodiments, the MOF may contain multiple types of organic crosslinking ligands.

[0071] A "coordination complex" is a compound in which a coordination bond exists between a metal ion and an electron pair donor, ligand, or chelating group. Therefore, the ligand or chelating group is generally an electron pair donor, a molecule or molecular ion that has a lone pair of electrons that can be donated to the metal ion.

[0072] The term "coordinate bond" refers to the interaction between an electron pair donor and a coordination site on a metal ion, creating an attractive force between the electron pair donor and the metal ion. The use of this term is not limited, and certain coordinate bonds may be classified as having more covalent properties (including entirely covalent bonds) depending on the characteristics of the metal ion and electron pair donor.

[0073] In this specification, the term “ligand” generally refers to a species, such as a molecule or ion, that interacts with, for example, another species in some way, such as by bonding. More specifically, in this specification, “ligand” may refer to a molecule or ion that bonds with a metal ion in solution to form a “coordination complex.” See Martell, AE, and Hancock, RD, Metal Complexes in Aqueous Solutions, Plenum: New York (1996), which is incorporated herein by reference in its entirety. The terms “ligand” and “chelating group” may be used synonymously. The term “bridged ligand” may refer to a group that bonds to multiple metal ions or complexes and provides a “bridge” between them. Organic bridged ligands may have groups having two or more lone pairs of electrons separated by, for example, alkylene or arylene groups. Groups with lone pairs of electrons include, but are not limited to, -CO2H, -NO2, amino groups, hydroxyl groups, thio groups, thioalkyl groups, -B(OH)2, -SO3H, PO3H, phosphonic acid groups, and heteroatoms in heterocycles (e.g., nitrogen, oxygen, and sulfur).

[0074] In this specification, the term “coordination site,” when used in reference to a ligand, such as a bridging ligand, refers to a lone pair of electrons, a negative charge, or an atom or functional group capable of forming a lone pair of electrons or a negative charge (e.g., by deprotonation under a specific pH).

[0075] "Embedded" can refer to an agent (e.g., an adsorbent) that is bonded to the interior of a porous material (e.g., a porous polymer network or "matrix") by bonds, for example, covalent or coordination bonds. The "embedded" agent may be "isolated," "enclosed," or "trapped" (i.e., non-covalently embedded, "encapsulated") within pores, cavities, or channels in the porous material, and may interact with the components of the matrix through hydrogen bonds, London dispersion forces, or other non-covalent interactions.

[0076] The terms "polymer" and "polymeric" refer to chemical structures having repeating units (i.e., multiple copies of a given chemical moiety). Polymers can be formed from polymerizable monomers. A polymerizable monomer is a molecule or complex that contains one or more moieties that can react or interact with other molecules or parts of a complex to form bonds (e.g., covalent or coordination bonds). In some embodiments, each polymerizable monomer may bond with two or more other molecules / moieties. In some cases, a polymerizable monomer bonds with only one other molecule to form the ends of a polymer material.

[0077] Polymers can be organic, inorganic, or a combination thereof. In this specification, the term "inorganic" refers to a compound or composition containing at least several atoms other than carbon, hydrogen, nitrogen, oxygen, sulfur, phosphorus, or halogens. Therefore, for example, an inorganic compound or composition may contain one or more silicon atoms and / or one or more metal atoms.

[0078] The term "curable" refers to a composition that can be cured, that is, converted from a liquid or viscous state to a solid state. For example, the terms "cured" and "cured" may refer to the joining of monomers, oligomers, or polymer chains by covalent or non-covalent bonds, for example, via crosslinking molecules or groups, to form a polymer network. In this specification, a curable coating composition may contain curable components (e.g., "resins," "binders," or "binder systems") and non-curable components (e.g., solid adsorbents and / or solid inorganic porosity control agents). Thus, in some embodiments, crosslinking may occur via reactions including reactions of co-reactive functional groups and self-condensation. Crosslinking is usually activated by temperature (i.e., thermally). "Thermal activation" means that crosslinking proceeds at room temperature or usually higher, within a reasonable time frame (e.g., minutes or hours) that fits the overall manufacturing process of the surface coating. Alternatively, curing / crosslinking may be initiated by ultraviolet (UV) or electron beam (EB) irradiation.

[0079] (II. General discussion) As described above, coating materials and processes have recently attracted attention in relation to carbon capture technology and in other applications involving the selective adsorption / collection of specific molecules. A variety of organic and / or inorganic adsorbent materials (e.g., organic and / or inorganic solid adsorbent materials) are known and desirable in the field for functional coatings used in adsorption applications. For example, solid amine adsorbents can adsorb carbon dioxide (CO2) gas via chemiadsorption, binding the CO2 gas as a carbamate. One type of solid amine-containing adsorbent, used for CO2 adsorption in carbon capture and storage (CCS) applications, is prepared by reacting polyamines with polyaldehyde dendrimers. These materials are more commonly referred to herein as "polyamine-based P-dendrimers" or simply "P-dendrimers." The polyamine-based P-dendrimers and methods for their preparation described herein are described in U.S. Patent No. 10,994,261, the entire disclosure of which is incorporated herein by reference. Solid materials containing many metal-organic structures (MOFs), or metal ions or clusters linked via polydentate organic ligands, can function as adsorbents for, for example, water, carbon dioxide, hydrogen sulfide (H2S), and hydrocarbons (e.g., paraffins and aromatics). However, incorporating solid adsorbents into compositions suitable for effective and durable coating of surfaces can be challenging. For example, since most organic oligomers, polymers, and dendrimers have rubbery properties, coating P-dendrimer materials onto surfaces such as metal plates or paper can be difficult. Cracking and subsequent delamination of solid or solidified coating materials containing solid adsorbents from the surface are also challenges.

[0080] In this field, several coating methods are known, including, but are not limited to, microarc oxidation (MAO), chemical vapor deposition (CVD), physical vapor deposition (PVD), and spray technology. For example, PVD is carried out under extremely low pressure, where the material is evaporated and deposited by the condensation of metal vapor, forming a thin film. This process can be repeated many times to obtain a thicker coating. However, the PVD process requires expensive equipment and can be energy-intensive [Non-Patent Literature 1, 2]. CVD is carried out under high vacuum and is widely used in the semiconductor manufacturing industry. CVD can involve vapor-phase chemical reactions that produce byproducts. This method can yield coatings on the order of micrometers in thickness [Non-Patent Literature 3, 4]. The MAO process generates microarc plasma channels, melting specific portions of the substrate surface. Oxygen in the electrolyte can cause oxidation of the material, leading to the formation of byproducts. Therefore, not all of these methods can provide coatings on the order of millimeters to centimeters in thickness [Non-Patent Literature 5, 6].

[0081] The subject matter of this disclosure provides a modular method for coating surfaces with adsorbent coating layers, such as polyamine-based P-dendrimers and / or MOFs, embedded in polymer networks / matrices, i.e., solid coating layers containing adsorbents (e.g., solid adsorbents). The subject matter of this disclosure further provides curable coating compositions containing solid adsorbents. The curable coating compositions described herein may optionally contain additional components that can improve the porosity of the corresponding cured coating layer. Such additional components include, for example, pyrolytic inorganic compounds and degradable chemical functional groups (e.g., carbamate groups formed by bubbling carbon dioxide gas into a curable coating composition containing a polyamine-based P-dendrimer containing a reactive amine group). The methods and curable coating compositions of this disclosure can coat a metal plate with an adsorbent coating layer (e.g., including organic dendrimers, oligomers, polymers) to a thickness of up to 0.5 mm or more (e.g., a uniform, crack-free coating). Furthermore, objects coated using the coating method and / or curable coating composition of the Disclosure (i.e., objects having at least one surface cured / solid coating layer in which an adsorbent is incorporated in a polymer matrix) and their applications, such as carbon capture (e.g., direct air capture (DAC)) or water vapor capture (e.g., atmospheric moisture collection), are also provided. For example, as described below, the carbon capture capability of the polyamine-based P-dendrimer coating formulations of the Disclosure was measured via an intelligent gravimetric analyzer (IGA), and the surface properties of the thereby coated materials were investigated by scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) surface area analysis, as well as CO2 isotherm experiments. Moisture adsorption of the MOF-containing coating composition of the Disclosure is also described.

[0082] (III. Curable and pre-cured coating compositions) In some embodiments, the subject matter disclosed herein provides curable coating compositions comprising an adsorbent (e.g., a solid adsorbent), a liquid carrier, and a curable binder (hereinafter also referred to herein as “binder solution” or “BS”). In some embodiments, the composition may comprise several different adsorbents. The composition may be prepared by mixing a slurry containing the adsorbent (or more adsorbents) and liquid carrier with the curable binder. Thus, when the curable coating composition is cured, the adsorbent (or more adsorbents) is embedded in a solid polymer matrix layer formed by the curing of the binder.

[0083] In this specification, the term “curable binder” refers to a molecule or mixture of molecules that is liquid or semi-liquid (e.g., “viscous”) but can form a solid polymer matrix upon curing. Typically, a “curable binder” may contain or consist of one or more “resins.” Synthetic resins include, but are not limited to, epoxy resins, polyester resins, phenolic resins, alkyd resins, polycarbonate resins, polyamide resins, polyurethane resins, and silicone resins. When a cured resin forms part of a copolymer, the binder may contain multiple monomers, oligomers, or liquid polymers that can be cured. In some embodiments, in a binder capable of forming a copolymer, one monomer, oligomer, or liquid polymer may be called a “resin,” and the others may be called a “curing agent.” For example, liquid polyglycidyl ethers of polyhydroxyphenol or other polyols capable of forming a solid epoxy polymer are commonly referred to as “epoxy resins” (although these may also be called “prepolymers”). Binders containing epoxy resins typically also contain comonomers or co-reactants, often referred to as "curing agents." Suitable curing agents for use with epoxy resins include, but are not limited to, polyfunctional amines, polyfunctional carboxylic acids or acid anhydrides, polyfunctional phenols, aliphatic polyols, and polyfunctional thiols.

[0084] In some embodiments, the curable coating compositions disclosed herein include an epoxy resin, i.e., the curable binder includes an epoxy resin. In some embodiments, the curable binder includes a non-aromatic epoxy resin. In this specification, the term “non-aromatic epoxy resin” refers to a compound, oligomer, polymer, or “prepolymer” that includes a reactive epoxide group and does not contain an aromatic ring. In addition to the epoxide group, the non-aromatic epoxy resin may include groups such as alkyl groups, alkylene groups, alkoxy groups, alkenyl groups, alkenylene groups, alkynyl groups, cycloalkyl groups, cycloalkylene groups, heterocycloalkyl groups, heterocycloalkylene groups, cycloalkenyl groups (e.g., cyclic groups with a double bond in the ring and that are not aromatic), cycloalkenylene groups, heterocycloalkenyl groups, heterocycloalkenylene groups, and / or non-aromatic condensed polycyclic groups. Therefore, the non-aromatic epoxy resin may include any suitable aliphatic epoxy resin, cycloaliphatic epoxy resin, or mixtures thereof. The non-aromatic epoxy resin may have one or more, for example, two or more reactive epoxy groups. A "reactive epoxy group" refers to an epoxy group that can react with other compounds, such as amines. In some embodiments, the epoxide group of a non-aromatic resin may be bonded to other functional groups via single or multiple bonds. For example, the oxygen atom of the epoxide group may be bonded to two distinct and adjacent carbon atoms of a cycloaliphatic ring, for instance, when the non-aromatic epoxy resin includes a cycloaliphatic epoxy resin.

[0085] Examples of suitable non-aromatic epoxy resins include acrylic polymers or oligomers containing glycidyl methacrylate, aliphatic epoxy resins prepared from hydrogenated bisphenol A (e.g., EPONEX® Resin 1510, available from Hexion Inc. in Columbus, Ohio, USA), aliphatic monoglycidyl ethers (e.g., HELOXY® Modifier 8, HELOXY® Modifier 61, HELOXY® Modifier 62, HELOXY® Modifier 65, HELOXY® Modifier 116, available from Hexion Inc.), reaction products of reactants containing epichlorohydrin and C12-C14 alcohols (e.g., Dow DER® 721, available from Dow Chemical Company in Midland, Michigan, USA), and reaction products of reactants containing epichlorohydrin and 2-ethylhexyl alcohol (e.g., Dow DER® 721, available from Dow Chemical Company). 728), cycloaliphatic epoxy resin (e.g., Dow DER® 3391 available from Dow Chemical Company), aliphatic liquid epoxy resin (e.g., Dow DER® 3912 from Dow Chemical Company), reaction products of a reaction containing epichlorohydrin and cyclohexanedimethanol (e.g., Dow DER® 737 available from Dow Chemical Company), reaction products of a reaction containing epichlorohydrin and neopentyl glycol (e.g., Dow DER® 738 available from Dow Chemical Company), reaction products of a reaction containing epichlorohydrin and trimethylolpropane (e.g., Dow DER® 741 available from Dow Chemical Company), triglycidyl ether of trimethylolpropane (e.g., HELOXY® Modifier 48 from Hexion Inc.), diglycidyl ether of 1,4-butanediol (e.g., Hexion Inc.HELOXY® Modifier 67 (available from Hexion Inc.), diglycidyl ether of neopentyl glycol (e.g., HELOXY® Modifier 68, available from Hexion Inc.), diglycidyl ether of cyclohexanedimethanol (e.g., HELOXY® Modifier 107, manufactured by Hexion Inc.), diglycidyl ester of dimer acid (e.g., HELOXY® Modifier 71, available from Momentive), polyglycidyl ether of castor oil (e.g., HELOXY® Modifier 505, available from Momentive), triglycidyl ether of glycerol propoxylate, reaction products of reactants including propylene glycol and / or dipropylene glycol and epichlorohydrin (e.g., DER® 732 and DER® (registered trademark) available from Dow Chemical Company). Examples include, but are not limited to, 3,4-epoxycyclohexylmethyl, 3,4-epoxycyclohexanecarboxylate, and bis((3,4-epoxycyclohexyl)methyl) adipate. In some embodiments, the epoxy resin includes a cycloaliphatic epoxy resin. In some embodiments, the epoxy resin is a glycidyl ether prepared from hydrogenated bisphenol A (e.g., EPONEX® 1510).

[0086] In some embodiments, the curable binder further comprises a curing agent or copolymer suitable for reacting with and curing the epoxy resin. In some embodiments, the curable binder comprises an amine, such as a diamine or other polyamine, as the curing agent. Those skilled in the art will understand that the amine reacts with epoxy functional groups on the non-aromatic epoxy resin, thereby playing a role in curing the coating composition. Any suitable amines that can be used may include, for example, aliphatic amines, adducts of aliphatic amines, alicyclic amines, amidoamines, polyamides, polyamides having one or more amine groups, or mixtures thereof. In some embodiments, the curing agent may comprise one or more primary or secondary diamines or polyamines in which the group bonded to the amine nitrogen atom may be saturated or unsaturated, aliphatic, alicyclic, aromatic, aromatic-substituted aliphatic, aliphatic-substituted aromatic, or heterocyclic. The curing agent may comprise a mixed amine with different groups attached to the amine nitrogen atom. For example, the mixed amine may comprise an aromatic group and an aliphatic group. The amine may also comprise other nonreactive groups bonded to the carbon atoms of the group attached to the amine nitrogen atom. For example, other nonreactive groups may include oxygen, sulfur, halogens, or nitroso. Suitable examples of aliphatic and alicyclic diamines include 1,2-ethylenediamine, 1,2-propylenediamine, isophoronediamine, propane-2,2-cyclohexylamine, and methane-bis-(4-cyclohexylamine). Examples of suitable commercially available amines, but not limited to these, include ANCAMINES® and ANCAMIDES® available from Evonik (Essen, Germany), LONZACURE® curing agent available from Lonza (Basel, Switzerland), JEFFAMINE® polyetheramine available from Huntsman (Salt Lake City, Utah, USA), LAROMIN® curing agent available from BASF (Ludwigshafen, Germany), DYTEK® Idea Intermediates available from INVISTA (Wichita, Kansas, USA), and VERSAMINE® polyamine available from BASF (Ludwigshafen, Germany).In some embodiments, the amine-based curing agent is a diamine (i.e., the curable binder contains a diamine). In some embodiments, the diamine is an aliphatic or alicyclic diamine. In some embodiments, the diamine is C3-C. 12 It is an alkane or a C3-C6 alkane diamine. In some embodiments, the diamine is 1,3-pentanediamine.

[0087] In some embodiments, the curable binder further comprises one or more epoxy modifiers, including but not limited to epoxy-functionalized alcohols, epoxy-functionalized diols, epoxy-functionalized polyols, and epoxy-functionalized carboxylic acids. In some embodiments, the epoxy modifier is one or more of the epoxy resins described above, for example, any of the epoxy modifiers marketed under the trademark HELOXY® (available from Hexion Inc., Columbus, Ohio, USA).

[0088] In some embodiments, the curable binder further comprises an adhesion promoter, i.e., a polyfunctional monomer or oligomer containing functional groups that can chemically or physically interact with the target substrate (e.g., a metal substrate) and functional groups that can chemically or physically interact with the resin or curing agent in the binder. In some embodiments, the adhesion promoter is an epoxy-functionalized silane. In some embodiments, the epoxy-functionalized silane is glycidoxypropyltrimethoxysilane (GPS).

[0089] In some embodiments, the liquid carrier is an organic solvent. The liquid carrier may be provided, for example, to help disperse a solid adsorbent in a curable binder. In some embodiments, the liquid carrier is selected to have a boiling point similar to the temperature used for curing the curable binder (e.g., within about 10°C or about 20°C) and low reactivity with the curable binder. Suitable solvents include, but are not limited to, alkanes (e.g., cyclohexane, hexane, etc.), ethers (e.g., tetrahydrofuran (THF), dioxane, etc.), ketones (e.g., 2-butanone, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (e.g., ethyl acetate, butyl acetate), nitriles (e.g., acetonitrile), and alcohols (e.g., methanol, ethanol, propanol (e.g., isopropanol (IPA)), butanol (e.g., 1-butanol, 2-butanol, tert-butanol, etc.)). In some embodiments, the solvent is a polar organic solvent, e.g., alcohol, acetonitrile, or ethyl acetate. In some embodiments, the liquid carrier is an alcohol. In some embodiments, the liquid carrier includes or consists of IPA.

[0090] The adsorbent may comprise any solid adsorbent capable of chemically or physically adsorbing target molecules (e.g., from a gas mixture). In some embodiments, the solid adsorbent comprises or comprises an amine-containing solid adsorbent. In some embodiments, the adsorbent is a polyamine-based P-dendrimer. As described above, this type of solid amine adsorbent is described in U.S. Patent No. 10,994,261, the entirety of which is incorporated herein by reference. More specifically, the polyamine-based P-dendrimer is produced as a result of a crosslinking reaction between a polyaldehyde-containing lindendrimer core compound and polyethyleneimine (PEI) or other polyamines (e.g., ethylenediamine or tetraethylenepentamine (TEPA)). The polyaldehyde-containing lindendrimer core may be a thiophosphoryl, phosphazene, or cyclophosphazatetraene compound. In some embodiments, polyaldehyde P-dendrimer cores can be prepared by reacting a phosphorus core compound containing a P-Cl bond with 4-hydroxybenzaldehyde (this yields a "zero generation" (G0) polyaldehyde-containing P-dendrimer core compound). If necessary, more complex cores can be formed by first reacting the G0 core with dichlorophosphonomethylhydrazide (which reacts with the aldehyde group of the G0 core to form a -C=NN(Me)-P(=S)(Cl)2 group), and then reacting it with 4-hydroxybenzaldehyde, in which case the chlorine is replaced with a new aldehyde-terminated phenoxy substituent, thereby forming a "G1" dendrimer. The G1 compound can be further modified by repeating the reaction of dichlorophosphonomethylhydrazide and 4-hydroxybenzaldehyde one or more times to obtain more complex "higher generation" (e.g., G2, G3, etc.) compounds, which can increase the structural complexity and aldehyde functionality of the core. The core structures can also be linked to each other via a bifunctional organic linker such as 4,4'-dihydroxydiphenyl.

[0091] In some embodiments, polyamine-based P-dendrimers are prepared by reacting a polyamine with an aldehyde-containing P-dendrimer core selected from hexa(4-formylphenoxy)cyclotriphosphazene (referred to herein as "1-G0") and o,o,o-tris(4-formylphenyl)phosphorothioate (TPPT) (referred to herein as "2-G0"). In some embodiments, the aldehyde-containing P-dendrimer core is a high-grade core (e.g., G1, G2 or higher). The polyamine may comprise one or more polyamines, including but not limited to PEI (e.g., branched PEI with a molecular weight of approximately 600 to 70,000), tetraethylenepentamine, triethylenebutamine, diethylenetriamine, 1,2-diaminoethane, 1,2-diaminopentane, and 2,2',2”-triaminotriethylamine. In some embodiments, the polyamine comprises one or more polyamines selected from the group including MW600 branched PEI, MW800 branched PEI, MW1200 branched PEI, MW2500 branched PEI, MW10000 branched PEI, MW600 straight-chain PEI, tetraethylenepentamine, triethylenebutamine, diethylenetriamine, 1,2-diaminoethane, 1,2-diaminopentane, and 2,2',2”-triaminotriethylamine. In some embodiments, the polyamine-based P-dendrimer is a crosslinked product of 1-G0 and branched PEI. In some embodiments, the polyamine-based P-dendrimer is a crosslinked product of 1-G0 and MW800 branched PEI, i.e., "800PEI".

[0092] Alternatively, in some embodiments, the solid adsorbent includes or consists of an inorganic material or a material containing both inorganic and organic components, such as a metal-organic frame (MOF). MOFs are a material classification containing metal ions or clusters (e.g., metal oxoclusters) periodically linked by polydentate organic ligands to form one-dimensional, two-dimensional, or three-dimensional arrangements. In some embodiments, MOFs are crystalline porous solid materials. MOFs capable of adsorbing various small molecules are known to those skilled in the art. The surface chemistry and structure of MOFs can be tailored for specific applications depending on performance criteria such as the adsorption / desorption rate of the target, capacity to pressure, and operating temperature. More specifically, in some embodiments, the pore size and / or shape of the MOF can be tailored to provide selective adsorption of different gas molecules. Thus, for example, an MOF can function as a physicoadsorbent that achieves adsorption of selected molecules through molecular interactions with the MOF pore surface. In some embodiments, e.g., a water-adsorbing coating, the MOF includes polydentate organic ligands containing carboxylic acid and / or amine functional groups. In some embodiments, the organic ligand includes a carboxylic acid group.

[0093] Representative water-adsorbing and desorbing MOFs that can be used in the coating materials disclosed herein include, but are not limited to, those described by Furukawa et al. [Non-Patent Literature 7]. In some embodiments, the MOF comprises a polydentate coordinating organic ligand selected from the group including fumaric acid, 1H-pyrazole-3,5-dicarboxylic acid (HPDC), isophthalic acid (IPA), franzicarboxylic acid (FDC), terephthalic acid (TPA), 1,3,5-benzenetricarboxylic acid (BTC), and methanetetrayltetrabenzoic acid (MTB). In some embodiments, the MOF comprises one or more metal ions selected from elements including, but not limited to, Na, K, Li, Ca, Mg, Fe, Zn, Zr, Al, Ti, Cu, Mn, Ag, and Nb. Suitable water-adsorbing MOFs include MOF-303 (i.e., Al(OH)(HPDC)), CAU-10 (i.e., Al(OH)(IPA)), MOF-801 (i.e., Zr6O4(OH)4(fumarate)6), MOF-808 (i.e., Zr6O4(OH)4(BTC)2(HCOO)6), MOF-841 (i.e., Zr6O4(OH)4(MTB)6(HCOO)4(H2O)2), and aluminum fumarate. Examples include, but are not limited to, Al(OH)(fumaric acid) (i.e., Al(OH)(FDA)), MIL-160 (i.e., Al(OH)(TPA)), MIL-53 (i.e., Al(OH)(TPA)), MOF-573 (i.e., [Al(OH)(C5H2O4N2)(H2O)], which is composed of an aluminum(III) ion linked to 3,5-pyrazole dicarboxylic acid), and aluminum phosphate AlPO4-LTA.Further MOFs that may be used include CAU-8 (i.e., an organometallic structure containing an Al ion as a metal ion and benzophenone dicarboxylic acid as an organic ligand), HKUST-1 (MOF-199; containing a Cu ion as a metal ion and 1,3,5-benzenetricarboxylic acid as an organic ligand), MOF-333 which has the same structure as MOF-303 except that the HPDC ligand is substituted with 2,4-franzicarboxylic acid (FDC), and Nb-MOFs having the structural formula [Nb2(TPA)2(naphthalenetetracarboxydiimide)], as well as pillar-type MOFs such as those described in U.S. Patent Publication No. 2020 / 0114301, the entirety of which disclosure is incorporated herein by reference. Representative pillar-type MOFs include, but are not limited to, NbOFFIVE-1-Ni (chemical formula NiNbOF5(pyrazine)2), FeFFIVE-1-Ni (chemical formula NiFeF5(pyrazine)2), and AlFFIVE-1-Ni (chemical formula NiAlF5(pyrazine)2). In some variations, the MOF has a pore size of about 0.5 nm to about 1 nm (e.g., about 0.5 nm, about 0.6 nm, about 0.7 nm, about 0.8 nm, about 0.9 nm, or about 1 nm). In some embodiments, the MOF is selected from the group including MOF-801, MOF-808, MOF-841, MOF-303, MOF-333, NbOFFIVE-1-Ni, FeFFIVE-1-Ni, and AlFFIVE-1-Ni. In some embodiments, the MOF is selected from MOF-801 and NbOFFIVE-1-Ni. In some embodiments, the MOF is MOF-801.

[0094] In some embodiments, the curable coating composition contains at least about 5 wt% (wt%) of a curable binder compared to the weight of the adsorbent in the curable coating composition. In some embodiments, the curable coating composition contains about 5 wt% to about 45 wt% (e.g., about 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, or about 45 wt%) of a curable binder compared to the weight of the adsorbent in the curable coating composition. In some embodiments, the curable coating composition contains at least about 20 wt% (e.g., about 20 wt% to about 45 wt% curable binder) of curable binder relative to the weight of the adsorbent in the curable coating composition.

[0095] In some embodiments, the curable coating composition further includes a porosity control agent to enhance the porosity of the solid coating layer prepared, for example, by curing the curable coating. In some embodiments, the porosity control agent is a molecule or group that forms a gas by decomposition or other reaction. The gas may form additional pores in the cured coating as it escapes from the coating layer during the curing process. In some embodiments, the porosity control agent is an inorganic solid additive that decomposes upon heating to produce a gas. In some embodiments, the inorganic solid porosity control agent may be selected as a solid that decomposes at approximately the same temperature used to cure the curable coating composition (i.e., the curing temperature of the curable binder). For example, the porosity control agent may be a solid that decomposes at the same temperature as, or slightly lower than, the curing temperature used to cure the curable coating composition (e.g., within about 20°C, about 15°C, about 10°C, or about 5°C of the curing temperature). Suitable pyrolytic inorganic solids include, but are not limited to, ammonium carbonate and ammonium bicarbonate. In some embodiments, the porosity control agent is either or both of ammonium carbonate and ammonium bicarbonate.

[0096] Alternatively, pyrolytically decomposable functional groups can be incorporated into the components of a curable coating composition. For example, free / reactive amine groups in polyamine-based P-dendrimers can be converted to pyrolytically decomposable carbamate groups before adding the curable composition by bubbling carbon dioxide gas through a slurry containing the polyamine-based P-dendrimer. Upon heating, the carbamate groups can release carbon dioxide gas and regenerate free amine groups. Free / reactive amine groups in other components of the curable coating composition, such as free / reactive amine groups in the curing agent in the binder solution, can also be converted to pyrolytically decomposable carbamate groups.

[0097] In some embodiments, the subject disclosed herein provides a solid material embedded in a polymer matrix material containing an adsorbent, for example, a solid coating layer (e.g., a polyamine-based P-dendrimer or MOF (e.g., a water-adsorbent MOF)). In some embodiments, the adsorbent may comprise two or more different adsorbents. In some embodiments, the polymer matrix material is epoxy. In some embodiments, the coating material contains about 55% or more (e.g., about 55% to about 95%) of the adsorbent by weight. Thus, in some embodiments, the coating material contains about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, or about 95% of the adsorbent by weight. In some embodiments, the solid material is formed by curing a curable coating composition described herein.

[0098] In some embodiments, the subject disclosed herein provides a coating substrate (e.g., a metallic object) in which one or more surfaces of the substrate are coated with a solid coating layer prepared by coating the curable coating composition described herein and curing the curable coating composition. In some embodiments, the subject disclosed herein provides a substrate (e.g., a metallic object) comprising one or more surfaces coated with a solid coating layer containing an adsorbent encapsulated in a polymer matrix. For example, the adsorbent may be a polyamine-based P-dendrimer or MOF. In some embodiments, the polymer matrix is ​​epoxy (i.e., a curable epoxy resin or binder). In some embodiments, the metallic object is a metallic sheet (e.g., a stainless steel sheet). In some embodiments, the solid coating layer is porous. In some embodiments, the thickness of the solid coating layer is about 0.01 millimeters (mm) or more. In some embodiments, the solid coating layer has a thickness of about 0.01 mm to about 1.0 mm. In some embodiments, the thickness of the solid coating layer is about 0.1 mm to about 1.0 mm (e.g., about 0.1 mm, about 0.2 mm, about 0.3 mm, about 0.4 mm, about 0.5 mm, about 0.6 mm, about 0.7 mm, about 0.8 mm, about 0.9 mm, or about 1.0 mm). In some embodiments, the solid coating layer contains about 55% by weight or more of adsorbent (e.g., about 55% to about 95% adsorbent).

[0099] (IV. Methods for preparing curable coating compositions and coated objects, and their uses) In some embodiments, the subject matter of this disclosure provides a method for preparing a curable coating composition, the method comprising: (a) preparing a slurry containing a solid adsorbent and a liquid carrier; (b) preparing a curable binder; and (c) contacting the curable binder with the slurry to provide a curable coating composition. Suitable solid adsorbents, liquid carriers, and curable binders are described above.

[0100] In some embodiments, the step of preparing a slurry includes contacting a solid adsorbent (e.g., a polyamine-based P-dendrimer or MOF) with a liquid carrier and stirring the resulting mixture for a predetermined time. In some embodiments, the liquid carrier is IPA. In some embodiments, the slurry has a weight ratio of solid adsorbent to liquid carrier of about 1:2 to about 1:3. In some embodiments, the slurry contains MOF and liquid carrier (e.g., IPA) in a weight ratio of about 1:3. In some embodiments, the slurry contains polyamine-based P-dendrimer and liquid carrier (e.g., IPA) in a weight ratio of about 1:2.

[0101] In some embodiments, the step of preparing a curable binder includes mixing an epoxy resin with one or more (or each of) epoxy modifiers, diamines or other curing agents, epoxy-functionalized silanes or other adhesion promoters. Mixing may be carried out using a vortex mixer or other mixing device. In some embodiments, mixing is carried out for about 15 seconds to about 5 minutes (e.g., about 15 seconds, about 30 seconds, about 60 seconds, 90 seconds, about 120 seconds, about 180 seconds, about 240 seconds, or about 300 seconds). Suitable resins, modifiers, curing agents and adhesion promoters are as described above. In some embodiments, the step of contacting the curable binder with a slurry includes adding the curable binder to the slurry and stirring the resulting composition for a predetermined time (e.g., about 10 minutes, about 30 minutes, about 45 minutes, about 60 minutes, about 90 minutes, about 2 hours, about 4 hours, etc.). Mixing may be carried out using a vortex mixer or other mixing device. In some embodiments, the contact in step (c) involves contacting the slurry with an amount of curable binder having a weight of curable binder of at least about 5% (e.g., about 5% to about 45%) of the weight of the solid adsorbent in the slurry. In some embodiments, the curable binder is about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, or about 45% of the weight of the solid adsorbent.

[0102] In some embodiments, the method further includes incorporating a porosity control agent into the curable coating composition. For example, when the porosity control agent includes an inorganic solid additive (e.g., ammonium carbonate and / or ammonium bicarbonate) that decomposes thermally to produce gas, the incorporation of the porosity control agent may include adding the inorganic solid additive to the curable coating composition in step (c). Alternatively, the porosity control agent may be added to the slurry in step (a) or the binder in step (b). In some embodiments, the porosity control agent is an inorganic solid additive that decomposes thermally to release carbon dioxide gas. Porosity control agents such as ammonium carbonate or ammonium bicarbonate may be used in amounts ranging from about 1% to about 5% by weight (e.g., about 1% by weight, about 2% by weight, about 3% by weight, about 4% by weight, or about 5% by weight) relative to the adsorbent.

[0103] In some embodiments, the porosity control agent includes a carbamate group that can decompose to produce carbon dioxide gas and amine groups. The carbamate group can be incorporated into a curable coating composition by bubbling carbon dioxide gas into a composition containing a polyamine-based P-dendrimer containing a free / reactive amine group (e.g., a primary amine group), or into a binder solution containing a composition component (e.g., a curing agent) containing a free / reactive amine group. Thus, in some embodiments, the incorporation of the porosity control agent includes bubbling carbon dioxide gas into the slurry in step (a), where the carbon dioxide reacts with the reactive amine group in the polyamine-based P-dendrimer adsorbent to form a carbamate group that can decompose to regenerate carbon dioxide gas when heated to a temperature suitable for curing the curable binder solution. In some embodiments, the incorporation of the porosity control agent includes bubbling carbon dioxide gas during contact in step (b) or step (c). Carbamate groups can also be generated when other porous control agents (e.g., thermally decomposable inorganic solid additives such as ammonium carbonate or ammonium bicarbonate) decompose and generate carbon dioxide gas, which can form carbamate groups with reactive amine groups in the curable binder solution (e.g., other components such as polyamine-based P-dendrimers or amine-containing curing agents).

[0104] In some embodiments, the subject matter of the present disclosure provides a method for coating an object (e.g., a metal object), the method comprising: (i) providing the curable coating composition described above; (ii) pre-treating one or more surfaces of the object (e.g., a metal object) to obtain one or more pre-treated surfaces, the pre-treatment comprising at least one of cleaning, abrasive treatment and / or application of a primer; (iii) applying the coating composition to one or more pre-treated surfaces to thereby provide one or more treated surfaces; and (iv) curing the curable coating composition to thereby provide a metal object comprising one or more surfaces including a solid coating layer. In some embodiments, the pre-treatment comprises cleaning the one or more surfaces of the object (e.g., the metal object) with an organic solvent such as acetone and / or IPA. In some embodiments, the pre-treatment comprises applying a primer to the one or more surfaces of the metal object. The primer may be, for example, a commercially available epoxy primer (e.g., one sold by RUST-OLEUM® (Rust-Oleum Corporation, Vernon Hills, Illinois, USA)). The pretreatment may further include curing of the primer. In some embodiments, curing of the primer yields a surface having free hydroxyl groups. Alternatively, in some embodiments, the pretreatment may be omitted.

[0105] Step (iii) can be carried out by any suitable technique, e.g., application of the curable coating composition to a pre-treated surface, pouring of the curable coating composition onto the surface, application with a doctor blade, or spin coating. The curing method in step (iv) may depend on the type of curable binder used in the curable coating solution. In some embodiments, curing includes heating the object or the surface of the object (e.g., placing the object in an oven). In some embodiments, curing is carried out by heating one or more treated surfaces to about 60°C to about 130°C (e.g., about 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C or about 130°C) for about 30 minutes to about 5 hours (e.g., about 30 minutes, about 1 hour, about 2 hours, about 3 hours, about 4 hours, or about 5 hours).

[0106] In some embodiments, the object is a metallic object. In some embodiments, the metallic object is a metallic sheet or plate. In some embodiments, the metallic object contains or consists of stainless steel (for example, it may be a stainless steel sheet or plate). However, the object may have any shape, including irregular shapes.

[0107] The coatings prepared herein may have diverse applications, for example, in the purification, recovery, or separation of various gases. Specific applications of the coatings may depend on the selectivity of the adsorbent present in the solid / cured coating layer.

[0108] In some embodiments, the subject matter of this disclosure provides a method for adsorbing carbon dioxide from a gaseous fluid (e.g., air, optionally from a specific location near a high-concentration carbon dioxide emission site). In some embodiments, the method comprises bringing a gaseous fluid containing carbon dioxide (e.g., air) into contact with a coating object, the coating object comprising a metal object having a solid coating layer on one or more surfaces, the solid coating layer comprising a polyamine-based P-dendrimer encapsulated in a polymer matrix (e.g., epoxy). In some embodiments, the metal object is a metal sheet or metal plate. In some embodiments, the metal object is a stainless steel sheet or stainless steel plate. In some embodiments, the polymer matrix comprises epoxy. In some embodiments, the thickness of the solid coating layer is at least about 0.01 mm. In some embodiments, the thickness of the solid coating layer is about 0.01 mm to about 1.0 mm. In some embodiments, the thickness of the solid coating layer is about 0.1 mm to about 1.0 mm (e.g., about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or about 1.0 mm). In some embodiments, the solid coating layer contains about 55% by weight or more (e.g., about 55% to about 95%) of polyamine-based P-dendrimers. In some embodiments, the polyamine-based P-dendrimers are formed by crosslinking of 1-G0 and 800PEI. In some embodiments, the polyamine-based P-dendrimers in the solid coating layer have about 78% of the CO2 adsorption capacity compared to the same amount of free polyamine-based P-dendrimers (i.e., the same amount of the same polyamine-based P-dendrimers except that they are not encapsulated in a polymer matrix).

[0109] In some embodiments, the subject matter of the present disclosure provides a method for adsorbing water (i.e., water vapor) from a gaseous fluid (e.g., air). In some embodiments, the method includes the steps of (i) providing a metal object comprising one or more surfaces comprising a solid coating layer, wherein the solid coating layer comprises an MOF (i.e., a water-adsorbing MOF) encapsulated in a polymer matrix (e.g., epoxy); (ii) heating the metal object to about 100°C under a nitrogen atmosphere (e.g., to release already adsorbed water); and (iii) bringing a gaseous fluid containing water vapor into contact with the metal object. In some embodiments, the MOF is selected from the group comprising MOF-801, MOF-808, MOF-841, MOF-303, MOF-333, NbOFFIVE-1-Ni, FeOFFIVE-1-Ni, and AlOFFIVE-1-Ni. The water adsorption capacity of the coating layer may vary depending on the thickness of the layer, the amount of MOF packed in, and the relative humidity (RH). In some embodiments, the water adsorption capacity of the coating layer may be about 20% to about 50% by weight (e.g., about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, or about 50% by weight) relative to the weight of the MOF in the coating layer. In some embodiments, the MOF is MOF-801, and the coating layer has a water adsorption capacity of about 20% by weight (e.g., at 75% RH) relative to the weight of the MOF in the coating layer. In some embodiments, the method further includes the step of recovering the water adsorbed in step (iii) by, for example, heating a metal object to release the adsorbed water, and cooling the adsorbed water to condense it and form liquid water. [Examples]

[0110] The following embodiments are included to provide guidance to those skilled in the art for carrying out typical embodiments of the subject matter of this disclosure. In light of the current disclosure and the general state of the art for those skilled in the art, the following embodiments are illustrative only, and those skilled in the art will understand that numerous changes, modifications, and alterations are possible without departing from the scope of the subject matter of this disclosure.

[0111] (Example 1) (Carbon-scavenging coating) (Preparation of curable coating composition)

[0112] Six grams of p-dendrimer adsorbent were added to a 250 mL round-bottom flask equipped with a magnetic stirrer. Twelve grams of isopropanol (IPA) were added to the flask, and the mixture was stirred at room temperature for two hours. This yielded a smooth p-dendrimer slurry.

[0113] For the preparation of a standard epoxy binder solution (BS), 2.67 grams of low-to-medium viscosity epoxy resin sold under the trademark EPONEX® 1510 (Hexion, Columbus, Ohio, USA), 0.874 grams of glycidyl ether epoxy modifier sold under the trademark HELOXY® 67 (Hexion, Columbus, Ohio, USA), 0.489 grams of 1,3-pentanediamine sold under the trademark DYTEK® EP (INVISTA, Wichita, Kansas, USA), and 3 drops of glycidoxypropylsilane (3-GPS) were mixed in a 20 mL glass vial and stirred with a vortex mixer for 30 seconds.

[0114] The coating compositions were prepared by adding BS (30% of the weight of the P-dendrimer) to a P-dendrimer slurry. The resulting curable coating compositions were stirred separately for 45 minutes. Curable coating compositions containing 15%, 20%, and 45% BS were prepared in the same manner, by changing only the amount of BS to achieve the desired weight percentage relative to the P-dendrimer.

[0115] (Preparation of metal plates) A 6-inch x 6-inch stainless steel sheet was purchased from McMASTER-CARR (Elhurst, Illinois, USA, part number 8983K115) and prepared for coating as shown in the upper part of Figure 2. A thin plastic protective layer was removed, and the surface was cleaned by mechanical polishing. The sheet was cleaned with IPA and acetone. The sheet was dried in air for 10 minutes. To improve the adhesion of the metal sheet, a white primer sold by the trademark RUST-OLEUM® (Rust-Oleum, Vernon Hills, Illinois, USA) was applied, dried in air for 10 minutes, and then cured at 120°C for 10 minutes. The sheet was cooled to room temperature before applying the curable coating composition. See the lower part of Figure 2.

[0116] (coating) A curable coating composition was uniformly applied to the surface of a pre-treated metal plate using a doctor blade. The plate was slowly dried in air and IPA vapor. After the coating composition was dry and complete, it was cured at 120°C for 1.5 hours to obtain a crack-free coating. The quality of the coating was evaluated by tape testing. Figure 1 shows plates coated with P-dendrimer curable coating compositions containing 15%, 20%, 30%, and 45% BS. Of the four different coating formulations, the one containing 30% BS was found to contain the minimum amount of BS required to obtain a crack-free coating that passed the tape testing.

[0117] The surface structure of the curable coating composition was investigated by SEM. SEM revealed that a rough surface (see Figures 3A-3C) resulting from the spherical structure of P-dendrimers was retained within the coating composition, indicating a porous network (see Figures 3D-3F).

[0118] Chemical characterization of the coating compositions was performed using infrared (IR) spectroscopy. All coating compositions retained characteristic peaks present in the P-dendrimer in the IR spectrum. See Figure 4. The chemical composition of the coating compositions containing the P-dendrimer and 30% BS was investigated by elemental analysis. Elemental analysis of the coating compositions revealed 46.035% carbon, 12.431% nitrogen, and 7.489% hydrogen, while the composition of the P-dendrimer alone was 50.035% carbon, 17.204% nitrogen, and 8.234% hydrogen. This indicates that the coating compositions retain 72.27% of the nitrogen (N) content of the parent P-dendrimer.

[0119] The porous structure of P-dendrimers and coating compositions was investigated using an accelerated surface area and pore size measurement system sold under the trademark ASAP® 2020 V4.03 (Micromeritics Instruments, Norcross, Georgia, USA). Both materials exhibited increased adsorption capacity with increasing absolute pressure, demonstrating the exothermic nature of adsorption. See Figures 5A and 5B.

[0120] The carbon capture capacity of p-dendrimers and formulations was measured using intelligent gravimetric analysis (IGA). Adsorption was performed at 20°C, using air containing 400 ppm CO2 gas at 75% relative humidity (RH) and a flow rate of 300 standard cubic centimeters per minute (sccm). Desorption was performed at 80°C using dry N2 gas for 150 minutes. Under these conditions, the amount of CO2 adsorbed by the untreated p-dendrimer was 1.62 wt% CO2 / g after 0.5 hours and reached 4.39 wt% CO2 / g after 8 hours. The curable composition adsorbed 1.75 wt% CO2 per gram of adsorbent after 0.5 hours and 3.44 wt% CO2 per gram after 8 hours. This corresponds to 78% of the untreated adsorbent. See Table 1 below. Also see Figure 6.

[0121] [Table 1]

[0122] (Example 2) (Porousness control) The direct air capture (DAC) performance of a surface-coated material may be related to the coating's porosity. Porous materials accelerate the diffusion of gases (e.g., air) into the coating, increasing the surface area for gas-adsorbent interactions and leading to improved adsorption capacity. Therefore, increasing the porosity of a coating may be desirable. To introduce additional porosity to the coatings disclosed herein, porosity control agents were added to the coating compositions. For example, porosity control agents include those that decompose upon heating to generate gases. Desirable porosity control agents include compounds that do not chemically react with the adsorbent in the composition and those that decompose at the temperature used during coating curing.

[0123] Chemicals with different decomposition temperatures were screened. Additives with moderate decomposition temperatures, such as ammonium carbonate, showed good performance. For example, a composition containing 40% BS yielded a crack-free coating that passed tape tests when cured at two different temperatures. See Table 2 below. Also see Figure 7.

[0124] [Table 2]

[0125] Another approach to controlling porosity involves pre-saturating the adsorbent coating composition with carbon dioxide gas. This allows for in-situ formation of carbamate bonds through the reaction of free amine groups in the p-dendrimer adsorbent with gaseous carbon dioxide. During the curing of the coating composition (e.g., after applying the coating composition to a surface), the carbamate bonds decompose to generate gaseous carbon dioxide and free amine groups, regenerating the active adsorbent (i.e., p-dendrimer). For example, carbon dioxide gas can be bubbling into an isopropanol (IPA) solution of p-dendrimer before BS addition. Formation of degradable carbamates by bubbling with carbon dioxide gas is economical, and SEM images show that a coating with improved porosity is obtained compared to a coating prepared without pre-saturating the p-dendrimer solution with carbon dioxide gas. See Figure 8. (Example 3)

[0126] (Water-adsorbing coating) A coating capable of adsorbing water from the air was prepared using a method similar to that described in Example 1 for the preparation of a carbon-capturing coating. More specifically, a coating composition was prepared in which the p-dendrimer adsorbent was replaced with an MOF. For example, a coating containing MOF-801 or Nb MOF (prepared by the method described above [Non-Patent Literature 8, 9]) was prepared on a metal plate pre-coated with a primer for collecting water from the air. The usual procedure involved stirring an MOF slurry (weight ratio 1:3) in IPA for 2 hours, then adding epoxy-based BS (30% relative to the MOF) and stirring for a further 45 minutes. The resulting MOF composition was cast onto a 6-inch x 6-inch metal plate pre-coated with a primer, followed by air drying for 2 hours and curing at 80°C for 2 hours. The cured coating had a maximum thickness of 1 millimeter (mm) and held 8 grams of MOF. The quality of the coating was evaluated by tape testing. Images of the coated plate, SEM images of the coating composition, and images of the untreated MOF are shown in Figures 9 and 10.

[0127] The water adsorption capacity of the MOF-801 coating composition was measured using an IGA apparatus with 100 milligrams (mg) of the coating composition (pre-activated by heating at 80°C under a nitrogen atmosphere) at 283K and in a relative humidity range of 5%RH to 75%RH. See Figures 11A and 11B. Water vapor was generated using dynamic flow of dry and wet nitrogen streams at a total flow rate of 300 sccm. Relative humidity was increased at regular intervals from dry conditions to 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, and 95%. The increase in mass was recorded at each pressure interval, and equilibrium was considered reached when the mass change / time change was less than ±0.001 mg / min for 60 seconds. Under these conditions, the water adsorption capacity of the coating composition was found to be 20% wt / wt at 75%RH.

[0128] (References) All references described herein, including but not limited to patents, patent applications and their publications, scientific journal articles, and database entries, are incorporated herein by reference in their entirety and apply to the extent that they supplement, explain, provide background to, or teach the methodologies, techniques, and compositions used herein. The references are provided merely to summarize the claims of their authors. No designation is made that any reference (or any part thereof) constitutes relevant prior art. The applicant reserves the right to challenge the accuracy and relevance of any cited references. [Prior art documents] [Non-patent literature]

[0129] [Non-Patent Document 1] Klokholm, E.; Berry, BS Intrinsic Stress in Evaporated Metal Films. J. Electrochem. Soc. 1968, 115(8), 823. [Non-Patent Document 2] D'Heurle,FMAluminum Films Deposited by Rf Sputtering.Metall.Mater.Trans.B 1970,1(3),725-732. [Non-licensed document 3] I.On Electrostriction.Proc.R.Soc.Lond.1878,26(179-184),504-512.

Non-licensed Document 4

Non-licensed Document 5

Non-licensed Document 6

Non-licensed Document 7

[0130] Please understand that various details of the subject matter of this disclosure may be changed without exceeding the scope of the subject matter of this disclosure. Furthermore, the above description is for illustrative purposes only and not for limitation.

Claims

1. (a) Solid adsorbent and (b) Liquid carrier and (c) A hardening binder, A curable coating composition containing the following.

2. The curable coating composition according to claim 1, wherein the curable binder comprises an epoxy resin.

3. The curable coating composition according to claim 2, wherein the epoxy resin includes an alicyclic epoxy resin.

4. The curable coating composition according to claim 2, wherein the curable binder further comprises a diamine.

5. The curable coating composition according to claim 2, wherein the curable binder further comprises an epoxy modifier selected from the group consisting of epoxy-functionalized alcohols, epoxy-functionalized diols, epoxy-functionalized polyols, and epoxy-functionalized carboxylic acids.

6. The curable coating composition according to claim 2, wherein the curable binder further comprises an epoxy-functionalized silane.

7. The curable coating composition according to claim 1, wherein the liquid carrier is a polar organic solvent.

8. The curable coating composition according to claim 7, wherein the polar organic solvent is isopropanol.

9. The curable coating composition according to claim 1, wherein the solid adsorbent is a polyamine-based lindendrimer (P-dendrimer).

10. The curable coating composition according to claim 1, wherein the polyamine-based P-dendrimer is based on a polyamine selected from the group consisting of branched polyethyleneimine (PEI) with a molecular weight (MW) of 800, branched PEI with a molecular weight (MW) of 600, branched PEI with a molecular weight of 1200, branched PEI with a molecular weight of 2500, branched PEI with a molecular weight of 10000, linear PEI with a molecular weight (MW) of 600, tetraethylenepentamine, triethylenebutamine, diethylenetriamine, 1,2-diaminoethane, 1,2-diaminopropane, and 2,2',2''-triaminotriethylamine.

11. The curable coating composition according to claim 1, wherein the solid adsorbent is a metal-organic frame (MOF).

12. The curable coating composition according to claim 11, wherein the MOF is selected from the group consisting of MOF-801, MOF-808, MOF-841, MOF-303, MOF-333, NbOFFIVE-1-Ni, FeFFIVE-1-Ni, and AlFFIVE-1-Ni.

13. The curable coating composition according to claim 1, wherein the curable coating composition comprises at least about 5 weight percent (wt%) of the curable binder compared to the weight of the solid adsorbent.

14. The curable coating composition according to claim 13, wherein the curable coating composition comprises about 5 wt% to about 45 wt% of a curable binder compared to the weight of the solid adsorbent.

15. The curable coating composition according to claim 1, further comprising a porosity control agent.

16. The curable coating composition according to claim 15, wherein the porous control agent includes an inorganic solid additive that can be decomposed during heating at a temperature suitable for curing the curable binder solution.

17. The curable coating composition according to claim 16, wherein the porous control agent comprises one or more ammonium carbonate and ammonium bicarbonate.

18. The curable coating composition according to claim 15, wherein the porous control agent comprises a carbamate group formed between carbon dioxide gas and a reactive amine group in a polyamine-based P-dendrimer or another curable coating composition component containing the reactive amine group.

19. (a) A step of preparing a slurry containing a solid adsorbent and a liquid carrier, (b) A step of preparing a curable binder, (c) A step of preparing a curable coating composition by bringing the curable binder into contact with the slurry, A method for preparing a curable coating composition, including the following.

20. The method according to claim 19, wherein the step of preparing the slurry includes bringing the solid adsorbent into contact with the liquid carrier and stirring the resulting mixture for a predetermined time.

21. The method according to claim 19, wherein the slurry has a weight ratio of solid adsorbent to liquid carrier of about 1:2 to about 1:

3.

22. The method according to claim 19, wherein the step of preparing the curable binder comprises mixing an epoxy resin with one or more of an epoxy modifier, a diamine, and an epoxy-functionalized silane.

23. The method according to claim 19, wherein the step of bringing the curable binder into contact with the slurry includes adding the curable binder to the slurry and stirring the resulting composition for a predetermined time.

24. The method according to claim 19, wherein the contact comprises bringing a curable binder in a weight of at least about 5% of the weight of the solid adsorbent in the slurry into contact with the slurry.

25. The method according to claim 19, further comprising the step of incorporating a porous control agent into the curable coating composition.

26. The method according to claim 25, wherein the porous control agent comprises an inorganic solid additive, the inorganic solid additive is decomposable when heated to a temperature suitable for curing of the curable binder, and the step of incorporating the porous control agent comprises adding the inorganic solid additive to the curable coating composition, wherein optionally the inorganic solid additive comprises one or more from the group consisting of ammonium carbonate and ammonium bicarbonate.

27. The method according to claim 25, wherein the solid adsorbent comprises a polyamine-based P-dendrimer containing a reactive amine group, and the step of incorporating a porous control agent comprises bubbling carbon dioxide gas into the slurry prepared in step (a), wherein the carbon dioxide reacts with the reactive amine group to form a carbamate group that can decompose and regenerate carbon dioxide gas when heated to a temperature suitable for curing the curable binder solution.

28. (i) the step of preparing the curable coating composition according to claim 1, (ii) A step of obtaining one or more pre-treated surfaces by pre-treating one or more surfaces of a metal object, wherein the pre-treatment includes cleaning, treatment with an abrasive and / or application of a primer, (iii) The step of applying the coating composition to one or more pre-treated surfaces to prepare one or more treated surfaces, (iv) The step of curing the curable coating composition to provide a metallic object having one or more surfaces including a solid coating layer, A method for coating a metallic object, including [the specified element].

29. The method according to claim 28, wherein step (ii) comprises cleaning one or more surfaces of the metal object with acetone and / or isopropanol.

30. The method according to claim 28, wherein step (ii) comprises applying a primer to one or more surfaces of the metal object, optionally the primer being an epoxy primer, and comprising curing the primer.

31. The method according to claim 28, wherein step (iv) is carried out by heating one or more of the treatment surfaces to a temperature of about 60°C to about 130°C for about 30 minutes to about 5 hours.

32. The method according to claim 28, wherein the metal object is a metal sheet or metal plate, and optionally a stainless steel sheet or stainless steel plate.

33. A metallic object comprising one or more surfaces including a solid coating layer prepared according to the method of claim 28.

34. A metallic object comprising one or more surfaces coated with a solid coating layer containing an adsorbent trapped in a polymer matrix, wherein the adsorbent is a polyamine-based P-dendrimer or a metal-organic structure (MOF), and the polymer matrix is ​​a cured epoxy resin.

35. The metal object according to claim 34, wherein the coating layer is porous.

36. The metal object according to claim 34, wherein the solid coating layer has a thickness of about 0.01 millimeters (mm) to about 1.0 mm.

37. A method for adsorbing carbon dioxide from a gaseous fluid, the method comprising the step of bringing a gaseous fluid containing carbon dioxide into contact with a coating object, the coating object comprising a metallic object comprising one or more surfaces comprising a solid coating layer, the solid coating layer comprising a polyamine-based P-dendrimer encapsulated in a polymer matrix.

38. The method according to claim 37, wherein the metal object is a metal sheet or metal plate, and optionally a stainless steel sheet or stainless steel plate.

39. The method according to claim 37, wherein the polymer matrix comprises epoxy.

40. The method according to claim 37, wherein the solid coating layer has a thickness of 0.01 mm to about 1.0 mm, and optionally has a thickness of about 0.1 mm to about 1.0 mm.

41. The polyamine-based P-dendrimer in the solid coating layer contains approximately 78% CO2 compared to the same amount of free polyamine-based P-dendrimer. ２ The method according to claim 37, having adsorption capacity.

42. A method for adsorbing water from a gaseous fluid, wherein the method is (i) A step of preparing a metallic object comprising one or more surfaces including a solid coating layer, wherein the solid coating layer comprises a metal-organic structure (MOF) encapsulated in a polymer matrix, (ii) The step of heating the metal object to about 100°C in a nitrogen atmosphere, (iii) The step of bringing a gaseous fluid containing water vapor into contact with the metal object, A method for adsorbing water from a gaseous fluid, including [a specific substance].

43. The method according to claim 42, wherein the MOF is selected from the group consisting of MOF-801, MOF-808, MOF-841, MOF-303, MOF-333, NbOFFIVE-1-Ni, FeOFFIVE-1-Ni, and AlOFFIVE-1-Ni.

44. The method according to claim 42, wherein the MOF is MOF-801, and the coating layer has a water adsorption capacity of about 20% to about 50% by weight compared to the weight of the MOF in the coating layer.

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