Crown ether carbenes and methods of use

Abstract

The present invention provides a material comprising (i) a crown ether of formula (I), (ii) a crown ether of formula (II), and / or (iii) a crown ether of formula (III), or a salt thereof, wherein each m is independently an integer from 1 to 8, p is an integer from 1 to 1000, each "(F)" represents an optional bond and / or structure, each X is an optional substituent, and each * independently represent -H, =O, or a bond to the remainder of the substance, provided that at least one * is the bond to the remainder of the material, and the remainder of the material is attached via an sp3-sp3 carbon-carbon bond, methods of making the material, and methods of using the material are provided. [Formula 1] JPEG2025535965000092.jpg69149

Description

Background of the Invention

[0001]

[0001] Crown ethers are cyclic organic molecules containing oxygen-based repeating units and carbon-based repeating units. Crown ethers are known to bind strongly to certain cations to form complexes. In this regard, the oxygen atoms are oriented to coordinate with metal cations located inside the ring, while the outside of the ring remains hydrophobic due to the repeating carbon units. As a result, complexes containing crown ethers and cations can be soluble in nonpolar solvents. For this reason, crown ethers can be useful in phase transfer catalysis.

[0002]

[0002] Due to the high utility of crown ether-based compounds, there remains a need for the development of materials comprising crown ether-based compounds and new, efficient methods for preparing such materials. The present invention provides such materials and methods of preparation. Further advantages and aspects of the present invention will be readily apparent from the disclosure provided herein. BRIEF SUMMARY OF THE INVENTION

[0003] The present invention provides (i) a compound of formula (I): [ka] (ii) a crown ether of formula (II): [ka] and / or (iii) a crown ether of formula (III): [ka] or a salt thereof, wherein each m is independently an integer of 1 to 8, and p is an integer of 1 to 1000, and each " [ka] " denotes an optionally present bond and / or structure, each X is an optionally present substituent, and each * independently represent -H, =O, or a bond to the remainder of the substance, provided that at least one * is the bond to the remainder of the substance, and the remainder of the substance is bonded via an sp3-sp3 carbon-carbon bond.

[0004] The present invention also provides a compound of formula (IV): [ka] , formula (V): [ka] or formula (VI): [ka] or a salt thereof, wherein each m is independently an integer of 1 to 8, p is an integer of 1 to 1000, and each " [ka] " denotes optional bonds and / or structures, each X is an optional substituent, and each Y is hydrogen, oxygen, or MS, with the proviso that at least one Y is MS, and each MS is independently a polymeric support selected from a membrane, a fibrous medium, a polymeric coating or material, a metal organic framework, a monolith support, a bead, a filter, or a resin, and wherein the MS are bonded via sp3-sp3 carbon-carbon bonds.

[0005] The present invention provides a method for making the materials described herein, comprising: (i) reacting a hydrazide or hydrazine with a compound of formula (VII): [ka] , formula (VIII): [ka] or formula (IX): [ka] to form a hydrazone-containing compound; and (ii) reacting the hydrazone-containing compound with a polymeric support to form at least one C-C bond.

[0006] The present invention further provides a method for removing one or more metal ions from a solution, the method comprising passing the solution through a material described herein. [Brief explanation of the drawings]

[0007] [Figure 1] 1 is a bar graph showing the metal removal efficiency (MRE) percentage of lithium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten, and lead exhibited by nylon coated with crown ether carbene as described in Example 7. Detailed Description of the Invention

[0008] The present invention provides (i) a compound of formula (I): [ka] (ii) a crown ether of formula (II): [ka] and / or (iii) a crown ether of formula (III): [ka] or a salt thereof, wherein each m is independently an integer of 1 to 8 (e.g., 1, 2, 3, 4, 5, 6, 7, or 8), and p is an integer of 1 to 1000 (e.g., 1 to 500, 1 to 100, 10 to 50, or 1 to 10), and each [ka] " denotes an optionally present bond and / or structure, each X is an optionally present substituent, and each * independently represent -H, =O, or a bond to the remainder of the substance, provided that at least one * is the bond to the remainder of the substance, and the remainder of the substance is bonded via an sp3-sp3 carbon-carbon bond.

[0009] In some embodiments, the substance has formula (I): [ka] In the formula, each m is independently an integer of 1 to 8, and each " [ka] " denotes an optional bond and / or structure, each X is an optional substituent, * represents the bond to the remainder of the substance, which is attached via an sp3-sp3 carbon-carbon bond.

[0010] In some embodiments, the substance has formula (II): [ka] In the formula, each m is independently an integer of 1 to 8, and each " [ka] " denotes an optionally present bond, each X is an optionally present substituent, and each * independently represent -H, =O, or a bond to the remainder of the substance, provided that at least one * is the bond to the rest of the substance, which is attached via an sp3-sp3 carbon-carbon bond.

[0011] In certain embodiments, the substance has formula (III): [ka] Each m is independently an integer of 1 to 8, and p is an integer of 1 to 1000, and each * independently represent -H, =O, or a bond to the remainder of the substance, provided that at least one * is the bond to the rest of the substance, which is attached via an sp3-sp3 carbon-carbon bond.

[0012] In any of the embodiments of the materials described herein, each m is independently an integer from 1 to 8 (e.g., 1, 2, 3, 4, 5, 6, 7, or 8). Generally, each m is selected from the integers 1 to 8 to form a crown ether selected from 12-crown-4, 15-crown-5, 18-crown-6, 21-crown-7, 24-crown-8, 27-crown-9, or 30-crown-10. For example, each m can be 2 to form 12-crown-4, each m can be 3 to form 18-crown-6, each m can be 4 to form 24-crown-8, or each m can be 5 to form 30-crown-10. Alternatively, or additionally, each m may be different to form 12-crown-4, 15-crown-5, 18-crown-6, 21-crown-7, 24-crown-8, 27-crown-9, or 30-crown-10. In some embodiments, each m is independently an integer from 1 to 4. In certain embodiments, each m is independently an integer selected from 1 or 2. In other embodiments, each m is 2.

[0013] In any of the embodiments of the materials described herein, each X is an optionally present substituent. When present, X can be an electron-withdrawing substituent, an electron-donating substituent, or a neutral substituent. For example, each X can be independently selected from -OR, -OH, -NO, -NR, -NHR, -NH, -COOH, -F, -Cl, -Br, -I, -COOR, -CN, -R, where R is C 1~6 alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, or hexyl). In some embodiments, the substituent "X" is absent.

[0014] In any of the embodiments of the materials described herein, p is an integer between 1 and 1000 (e.g., between 1 and 500, between 1 and 100, between 1 and 50, or between 1 and 10). In some embodiments, p is an integer between 1 and 10 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10).

[0015] In any of the material embodiments described herein, each " [ka] " indicates an optionally present bond and / or structure. In other words, the bond to variable X is optional depending on whether substituent X is present, and the bond to variable Y can be a single or double bond depending on whether Y is -H, =O, or MS, so that one of the bonds is optional and the phenyl ring designated by the dashed line is optional.

[0016] In any of the embodiments of the material described herein, each * independently represent -H, =O, or a bond to the remainder of the substance, provided that at least one * is the bond to the remainder of the material, which is bonded via an sp3-sp3 carbon-carbon bond. Without wishing to be bound by any particular theory, it is believed that the hydrazones utilized to prepare the materials described herein (i) cannot form initially, thereby leaving a ketone, (ii) can be hydrolyzed and / or decomposed by the polymeric support without undergoing C-H insertion, thereby leaving a hydrogen or ketone, or (iii) can undergo C-H insertion by the polymeric support to form at least one C-C bond. In some embodiments, materials comprising crown ethers of formulas (I-III) have more than one C-C bond to the remainder of the material.

[0017]

[0017] The crown ethers of formulae (I) to (III) are *The crown ethers of formulas (I)-(III) can be incorporated into any suitable substance (e.g., a chemical compound or medium) so long as they are bonded to the remainder of the substance through at least one carbon designated by the symbol "(I)" and the remainder of the substance is bonded via an sp3-sp3 carbon-carbon bond. The objective of the present application is to incorporate the crown ethers of formulas (I)-(III) into a substance via C-H insertion using carbene chemistry. It will be readily apparent to those skilled in the art that the crown ethers of formulas (I)-(III) can be incorporated into a substance at any number of positions and any number of times. Thus, the substance can be any suitable substance (e.g., a chemical compound or medium) that contains an aliphatic C-H bond available for C-H insertion. In some embodiments, the substance is porous, thereby allowing a liquid or fluid to pass through the substance.

[0018]

[0018] In some embodiments, the remainder of the material to which the crown ether of formula (I)-(III) is attached is attached to a polymeric support selected from a membrane (e.g., a porous or permeable membrane), a fibrous medium, a polymer coating (e.g., a laminate or sealant such as a polyurethane coating, an epoxy coating, an acrylic coating, etc.) or a material (e.g., gelatin, alginate, starch, polyethylene, polypropylene, nylon, polyvinylidene fluoride, polyethylene oxide, polypropylene oxide, polyethylene / polypropylene oxide, polyacrylonitrile, poly(meth)acrylate, poly(meth)acrylamide, polyamide, polyimide, polyester, cellulose, polystyrene, etc.), a metal organic framework, a monolith support (e.g., a catalyst support), a bead (e.g., a polymeric bead), a filter, or a resin (e.g., a chromatography resin). In some embodiments, the polymeric support comprises gelatin, alginate, starch, polyethylene (e.g., high density polyethylene), polypropylene, nylon, polyvinylidene fluoride, polyethylene oxide, polypropylene oxide, polyethylene / polypropylene oxide, polyacrylonitrile, poly(meth)acrylate, poly(meth)acrylamide, polyamide (e.g., nylon), polyimide, polyester, cellulose, polystyrene, or a combination thereof. In certain embodiments, the polymeric support comprises polyethylene, polypropylene, nylon, polyvinylidene fluoride, polyethylene oxide, polypropylene oxide, polyethylene / polypropylene oxide, polyacrylonitrile, cellulose, or a combination thereof.

[0019]

[0019] Thus, in some embodiments, the substance has formula (IV): [ka] , formula (V): [ka] or formula (VI): [ka] or a salt thereof, wherein each m is independently an integer of 1 to 8, and p is an integer of 1 to 1000, and each " [ka] " denotes optional bonds and / or structures, each X is an optional substituent, each Y is hydrogen, oxygen, or MS, with the proviso that at least one Y is MS, and each MS is independently a polymeric support selected from a membrane, a fibrous medium, a polymeric coating or material, a metal-organic framework, a monolith support, a bead, a filter, or a resin, and wherein MS is bonded via an sp3-sp3 carbon-carbon bond. All other definitions and embodiments relating to the variables m, p, and X, and the polymeric support, are as described herein for the materials of the invention.

[0020] In any of the embodiments of the materials described herein, each Y is hydrogen, oxygen, or MS, provided that at least one Y is MS, and the MS is attached via an sp3-sp3 carbon-carbon bond. Without wishing to be bound by any particular theory, it is believed that the hydrazones utilized to prepare the materials described herein (i) cannot form ab initio, thereby leaving a ketone; (ii) can be hydrolyzed and / or decomposed by the polymeric support without undergoing C-H insertion, thereby leaving a hydrogen or ketone; or (iii) can undergo C-H insertion by the polymeric support to form at least one C-M-S bond via an sp3-sp3 carbon-carbon bond. In some embodiments, the materials of formulas (IV-VI) have more than one C-M-S bond.

[0021] In some embodiments, the substance has formula (IV): [ka] or a salt thereof, wherein each m is independently an integer of 1 to 8, and each " [ka] " denotes an optional bond and / or structure, each X is an optional substituent, and MS is a polymeric support selected from a membrane, a fibrous medium, a polymeric coating or material, a metal-organic framework, a monolith support, a bead, a filter, or a resin, and MS is attached via an sp3-sp3 carbon-carbon bond. All other definitions and embodiments of the variables m and X and the polymeric support are as described herein for the materials of the invention.

[0022] In another embodiment, the substance has the formula (V): [ka] or a salt thereof, wherein each m is independently an integer of 1 to 8, and each " [ka] " denotes an optionally present bond, each X is an optionally present substituent, and each Y is hydrogen, oxygen, or MS, with the proviso that at least one Y is MS, and each MS is independently a polymeric support selected from a membrane, a fibrous medium, a polymeric coating or material, a metal-organic framework, a monolith support, a bead, a filter, or a resin, and wherein MS is attached via an sp3-sp3 carbon-carbon bond. All other definitions and embodiments relating to the variables m, X, and Y, and the polymeric support, are as described herein for the materials of the invention.

[0023] In certain embodiments, the substance has formula (VI): [ka] or a salt thereof, wherein each m is independently an integer of 1 to 8, and p is an integer of 1 to 1000, and each " [ka] " denotes optionally present bonds and / or structures, and each Y is hydrogen, oxygen, or MS, with the proviso that at least one Y is MS, and each MS is independently a polymeric support selected from a membrane, a fibrous medium, a polymeric coating or material, a metal-organic framework, a monolith support, a bead, a filter, or a resin, and wherein the MS is bonded via an sp3-sp3 carbon-carbon bond. All other definitions and embodiments relating to the variables m, p, and Y, and to the polymeric support, are as described herein for the materials of the invention.

[0024] The aim of the present application is to incorporate crown ethers of formulae (I) to (III) into materials via C-H insertion using carbene chemistry. The present invention therefore provides a method for making the described materials, comprising: (i) reacting a hydrazide or hydrazine with a compound of formula (VII): [ka] , formula (VIII): [ka] or formula (IX): [ka] with a crown ether of formula (I) to form a hydrazone-containing compound; (ii) reacting the hydrazone-containing compound with a polymeric support selected from a membrane, a fibrous medium, a polymeric coating or material, a metal-organic framework, a monolith support, a bead, a filter, or a resin to form at least one C—C bond; All other definitions and embodiments relating to the variables m, p, and X and the polymeric support are as described herein for the materials of the invention.

[0025] The method includes reacting a hydrazide or hydrazine with a crown ether of formula (VII)-(VIII). For example, the hydrazide or hydrazine can be combined (e.g., contacted), mixed (e.g., shaken, stirred, etc.), heated, refluxed, or a combination thereof, with the crown ether of formula (VII)-(VIII) for any period of time so long as the desired hydrazone-containing compound is formed.

[0026] The hydrazide or hydrazine can be any suitable hydrazide or hydrazine known to those skilled in the art, so long as the hydrazide or hydrazine can decompose to form a reactive carbene when in the form of a hydrazone-containing compound. For example, the hydrazide or hydrazine can be p-toluenesulfonylhydrazide (i.e., tosylhydrazide), benzenesulfonylhydrazide, 2,4,6-triisopropylbenzenesulfonylhydrazide, etc. In some embodiments, the hydrazide or hydrazine is p-toluenesulfonylhydrazide.

[0027] The hydrazide or hydrazine can be used in any suitable amount. Generally, the hydrazide or hydrazine is added in a slight excess (e.g., about 1 molar equivalent, about 1.05 molar equivalents, about 1.1 molar equivalents, about 1.15 molar equivalents, or about 1.2 molar equivalents) relative to the number of desired hydrazone moieties. Thus, in some embodiments, the hydrazide or hydrazine is added in an amount of at least 1, at least 1.05, at least 1.1, at least 1.15, or at least 1.2 molar equivalents relative to the number of desired hydrazone moieties.

[0028] In some embodiments, the formation of the hydrazone-containing compound is carried out in a solvent. Thus, the reaction between a hydrazide or hydrazine and a crown ether of formula (VII)-(VIII) can be carried out in any suitable solvent. In some embodiments, the solvent is a high-boiling solvent (i.e., above 100°C), such as toluene. However, the formation of the hydrazone-containing compound can also be carried out in a low-boiling solvent (i.e., below 100°C), such as ethanol, methanol, etc., when promoted by an acid promoter.

[0029] In some embodiments, the formation of the hydrazone-containing compound is promoted by an acid promoter and / or heat. The acid promoter can be any suitable Bronsted acid or Lewis acid. For example, the formation of the hydrazone-containing compound can be promoted by p-toluenesulfonic acid, acetic acid, or formic acid. The reaction can be heated to any suitable temperature. Because the goal is to eliminate water, in some embodiments, the reaction between the hydrazide or hydrazine and the crown ether of Formula (VII)-(VIII) is heated to a temperature greater than 100°C, for example, by using a Dean-Stark apparatus.

[0030] The method further includes reacting the hydrazone-containing compound with a polymeric support selected from a membrane, a fibrous medium, a polymer coating or material, a metal-organic framework, a monolith support, a bead, a filter, or a resin to form at least one C-C bond. For example, the hydrazone-containing compound can be combined (e.g., contacted), mixed (e.g., shaken, stirred, etc.), heated, refluxed, or a combination thereof with the polymeric support for any period of time so long as the desired C-C bond is formed.

[0031] In some embodiments, the C—C bond is formed in a solvent. Thus, the reaction between the hydrazone-containing compound and the polymeric support can be carried out in any suitable solvent (e.g., an organic solvent). For example, the reaction between the hydrazone-containing compound and the polymeric support can be carried out in ethanol, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, methanol, isopropyl alcohol, tetrahydrofuran, acetonitrile, or a combination thereof.

[0032] In some embodiments, the reaction between the hydrazone-containing compound and the polymeric support is promoted by a base promoter. In other words, the formation of carbene can be promoted by a base promoter. The base promoter can be any suitable Bronsted base or Lewis base. For example, the base promoter can be sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, potassium tert-butoxide, or a combination thereof. In certain embodiments, the reaction between the hydrazone-containing compound and the polymeric support is carried out in ethanol and / or N-methyl-2-pyrrolidone in the presence of sodium hydroxide.

[0033] The base promoter can be used in any suitable amount. Generally, the base promoter is added in excess (e.g., at least about 1 molar equivalent, at least about 2 molar equivalents, at least about 5 molar equivalents, or at least about 10 molar equivalents) relative to the number of hydrazone moieties present in the hydrazone-containing molecule being reacted. Thus, in some embodiments, the base promoter is added in an amount that is at least 1-fold, at least 2-fold, at least 5-fold, or at least 10-fold molar equivalent relative to the number of hydrazone moieties present in the hydrazone-containing molecule being reacted.

[0034] In some embodiments, the formation of the carbene is further promoted by a metal catalyst. Suitable metal catalysts for forming and / or stabilizing the carbene moiety are known in the art. For example, the formation of the carbene can be promoted by a copper catalyst, a rhodium catalyst, an iron catalyst, a ruthenium catalyst, a molybdenum catalyst, or a combination thereof. In certain embodiments, the reaction between the hydrazone-containing compound and the polymeric support does not include a metal catalyst.

[0035] The reaction between the hydrazone-containing compound and the polymeric substrate can be heated and / or exposed to ultraviolet (UV) light. Without wishing to be bound by any particular theory, it is believed that C-C bond formation (e.g., via C-H insertion) can be promoted by elevated temperatures (e.g., above 50°C or above 75°C) and / or UV light. In certain embodiments, the reaction between the hydrazone-containing compound and the polymeric substrate is cured using patterned selective functionalization by UV light exposure.

[0036] The materials described herein can be used for any suitable purpose and in any suitable industrial application. For example, the materials described herein can be used in water purification applications, wastewater treatment applications, mining applications, electronic (e.g., microelectronics) applications, papermaking applications, pharmaceutical applications, biomedical applications, energy applications (e.g., as separators in fuel cells or batteries), or metallurgical applications. Generally, the materials described herein are used to selectively remove one or more metal ions from a fluid (i.e., a solution). The fluid can be any suitable liquid containing a solvent (e.g., water, alcohol, sulfoxide, sulfide, acetate, ether, amide, nitrile, or a combination thereof) and one or more metal ions. In certain embodiments, the fluid (i.e., the solution) is an aqueous solution.

[0037] In some embodiments, the materials described herein can be used in a method for removing one or more metal ions from a solution, the method comprising passing the solution through the material. For example, the material can be used as a filter, porous medium, chromatography resin, membrane, etc., through which a solution passes to remove one or more metal ions. Accordingly, the present invention provides a method for removing one or more metal ions from a solution, the method comprising: (i) treating the solution with a compound of formula (I): [ka] (ii) a crown ether of formula (II): [ka] and / or (iii) a crown ether of formula (III): [ka] or a salt thereof, wherein each m is independently an integer of 1 to 8 (e.g., 1, 2, 3, 4, 5, 6, 7, or 8), and p is an integer of 1 to 1000 (e.g., 1 to 500, 1 to 100, 10 to 50, or 1 to 10), and each [ka] " denotes an optionally present bond and / or structure, each X is an optionally present substituent, and each * independently represent -H, =O, or a bond to the remainder of the substance, provided that at least one * is the bond to the remainder of the material, wherein the remainder of the material is attached via an sp3-sp3 carbon-carbon bond. All other definitions and embodiments relating to the variables m, p, X, and Y and the polymeric support are as described herein for the materials of the invention.

[0038]

[0038] This method can be used to remove any suitable ions. Alternatively, or in addition, this method can be used to allow any suitable ions to pass through a material. For example, this method can be used to selectively remove one or more metal ions selected from sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten, lead, or combinations thereof. Alternatively, or in addition, this method can be used to selectively allow one or more metal ions selected from sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten, lead, or combinations thereof to pass through a material. In certain embodiments, the method selectively allows lithium to pass through the material and removes one or more metal ions selected from sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten, lead, or combinations thereof.

[0039] The method can remove any suitable amount of one or more metal ions from a solution. For example, the method can remove at least 40% of one or more metal ions from a solution, at least 50% of one or more metal ions from a solution, at least 60% of one or more metal ions from a solution, at least 70% of one or more metal ions from a solution, at least 80% of one or more metal ions from a solution, or at least 90% of one or more metal ions from a solution. In some embodiments, the method removes at least 50% of one or more metal ions selected from sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten, lead, or a combination thereof. In certain embodiments, the method removes at least 60% of one or more metal ions selected from sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten, lead, or combinations thereof. In preferred embodiments, the method removes at least 70% of one or more metal ions selected from sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten, lead, or combinations thereof.

[0040] In some embodiments, the solution that passes through the material is the desired product of the methods described herein. Accordingly, in such embodiments, the method may further include recovering the solution (e.g., aqueous solution) that has passed through the material. Without wishing to be bound by any particular theory, it is believed that when smaller metal ions, such as lithium and / or sodium, are desired, the recovered solution is the desired product because smaller metal ions, such as lithium and / or sodium, pass through the materials described herein more easily.

[0041] In other embodiments, the one or more metal ions removed from the solution are a desired product of the methods described herein. Accordingly, in these embodiments, the methods may further include recovering the one or more metal ions removed from the solution. The one or more metal ions may be recovered by any suitable means. For example, the material containing the one or more metal ions may be washed with the recovery solution. Without wishing to be bound by any particular theory, it is believed that when larger metal ions, such as magnesium, aluminum, potassium, calcium, manganese, iron, barium, etc., are desired, these desired metal ions remain in the material because the larger metal ions pass less easily through the materials described herein.

[0042] Aspects of the invention described herein, including embodiments, may be useful alone or in combination with one or more other aspects or embodiments. Without limiting the foregoing, certain non-limiting embodiments of the present disclosure, numbered 1 through 22, are set forth below. As will be apparent to one of ordinary skill in the art upon reading this disclosure, each individually numbered embodiment can be used or combined with any preceding or subsequent individually numbered embodiment. This is intended to cover all such combinations of embodiments, and is not limited to the combinations of embodiments explicitly set forth below:

[0043] (1) In embodiment (1), (i) a compound of formula (I): [ka] (ii) a crown ether of formula (II): [ka] and / or (iii) a crown ether of formula (III): [ka] or a salt thereof, wherein each m is independently an integer of 1 to 8, and p is an integer of 1 to 1000, and each " [ka] " denotes an optionally present bond and / or structure, each X is an optionally present substituent, and each * independently represent -H, =O, or a bond to the remainder of the substance, provided that at least one * is the bond to the remainder of the substance, and the remainder of the substance is bonded via an sp3-sp3 carbon-carbon bond.

[0044] (2) In embodiment (2), the substance is of formula (I): [ka] or a salt thereof, wherein each m is independently an integer of 1 to 8, and each " [ka] " represents an optional bond and / or structure, each X is an optional substituent, * represents a bond to the remainder of the substance, and the remainder of the substance is bonded via an sp3-sp3 carbon-carbon bond.

[0045] (3) In embodiment (3), the substance is of formula (II): [ka] or a salt thereof, wherein each m is independently an integer of 1 to 8, and each " [ka] " denotes an optionally present bond, each X is an optionally present substituent, and each * independently represent -H, =O, or a bond to the remainder of the substance, provided that at least one * is the bond to the remainder of the substance, and the remainder of the substance is bonded via an sp3-sp3 carbon-carbon bond.

[0046] (4) In embodiment (4), the substance is of formula (III): [ka] or a salt thereof, wherein each m is independently an integer of 1 to 8, and p is an integer of 1 to 1000, and each * independently represent -H, =O, or a bond to the remainder of the substance, provided that at least one * is the bond to the remainder of the substance, and the remainder of the substance is bonded via an sp3-sp3 carbon-carbon bond.

[0047] (5) In embodiment (5), the material of embodiments (1)-(4) is provided, wherein each m is independently an integer from 1 to 4.

[0048] (6) In embodiment (6), there is provided the material of any one of embodiments (1) through (5), wherein each m is independently an integer selected from 1 or 2.

[0049] (7) In embodiment (7), the substance of any one of embodiments (1) to (6) is provided, wherein each m is 2.

[0050] (8) In embodiment (8), the substance has the formula (IV): [ka] , formula (V): [ka] or formula (VI): [ka] or a salt thereof, wherein each m is independently an integer of 1 to 8, and p is an integer of 1 to 1000, and each " [ka] " denotes an optional bond and / or structure, each X is an optional substituent, each Y is hydrogen, oxygen, or MS, with the proviso that at least one Y is MS, and each MS is independently a polymeric support selected from a membrane, a fiber medium, a polymeric coating or material, a metal organic framework, a monolith support, a bead, a filter, or a resin, and the MS are bonded via an sp3-sp3 carbon-carbon bond.

[0051] (9) In embodiment (9), the substance has the formula (IV): [ka] or a salt thereof, wherein each m is independently an integer of 1 to 8, and each " [ka] " denotes an optional bond and / or structure, each X is an optional substituent, and MS is a polymeric support selected from a membrane, a fibrous medium, a polymeric coating or material, a metal organic framework, a monolith support, a bead, a filter, or a resin, and MS is bonded via an sp3-sp3 carbon-carbon bond.

[0052] (10) In embodiment (10), the substance has the formula (V): [ka] or a salt thereof, wherein each m is independently an integer of 1 to 8, and each " [ka] " indicates an optional bond, each X is an optional substituent, and each Y is hydrogen, oxygen, or MS, with the proviso that at least one Y is MS, and each MS is independently a polymeric support selected from a membrane, a fiber medium, a polymeric coating or material, a metal organic framework, a monolith support, a bead, a filter, or a resin, and the MS is bonded via an sp3-sp3 carbon-carbon bond.

[0053] (11) In embodiment (11), the substance has the formula (VI): [ka] or a salt thereof, wherein each m is independently an integer of 1 to 8, and p is an integer of 1 to 1000, and each " [ka] " denotes optionally present bonds and / or structures, and each Y is hydrogen, oxygen, or MS, with the proviso that at least one Y is MS, and each MS is independently a polymeric support selected from a membrane, a fiber medium, a polymeric coating or material, a metal organic framework, a monolith support, a bead, a filter, or a resin, and the MS are bonded via sp3-sp3 carbon-carbon bonds.

[0054] (12) In embodiment (12), the material of any one of embodiments (8) through (11) is provided, wherein each m is independently an integer from 1 to 4.

[0055] (13) In embodiment (13), the material of any one of embodiments (8)-(12) is provided, wherein each m is independently an integer selected from 1 or 2.

[0056] (14) In embodiment (14), the material of any one of embodiments (8) to (13) is provided, wherein each m is 2.

[0057] (15) In embodiment (15), any one of embodiments (8) to (14) is provided, wherein the polymeric support comprises gelatin, alginate, starch, polyethylene, polypropylene, nylon, polyvinylidene fluoride, polyethylene oxide, polypropylene oxide, polyethylene / polypropylene oxide, polyacrylonitrile, poly(meth)acrylate, poly(meth)acrylamide, polyamide, polyimide, polyester, cellulose, polystyrene, or a combination thereof.

[0058] (16) In embodiment (16), there is provided a method for making the material of any one of embodiments (8) to (15), comprising the steps of: (i) reacting a hydrazide or hydrazine with a compound of formula (VII): [ka] , formula (VIII): [ka] or formula (IX): [ka] with a crown ether of formula (I) to form a hydrazone-containing compound; (ii) reacting the hydrazone-containing compound with a polymeric support selected from a membrane, a fibrous medium, a polymeric coating or material, a metal-organic framework, a monolith support, a bead, a filter, or a resin to form at least one C—C bond; A method is presented, including:

[0059] (17) In embodiment (17), the method of embodiment (16) is provided, wherein the hydrazide or hydrazine is p-toluenesulfonylhydrazide.

[0060] (18) In embodiment (18), a method for removing one or more metal ions from a solution is provided, comprising passing the solution through a substance or salt thereof according to any one of embodiments (1) to (15).

[0061] (19) In embodiment (19), the method of embodiment (18) is provided, wherein the solution is an aqueous solution.

[0062] (20) In embodiment (20), the method of embodiment (18) or embodiment (19) is provided, wherein the method removes at least 50% of one or more metal ions selected from sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten, lead, or a combination thereof.

[0063] (21) In embodiment (22), the method of embodiment (18) or embodiment (19) is presented, wherein the method removes at least 60% of one or more metal ions selected from sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten, lead, or a combination thereof.

[0064] (22) In embodiment (22), the method of embodiment (18) or embodiment (19) is provided, wherein the method removes at least 70% of one or more metal ions selected from sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten, lead, or a combination thereof. [Example]

[0065] These following examples further illustrate the present invention but, of course, should not be construed as in any way limiting its scope.

[0066] Example 1 This example provides an exemplary experimental procedure for preparing the crown ethers of formula (VII) described herein, which is summarized in Scheme 1. [ka]

[0067] Benzocrown ether 1 (5 g, 18.6 mmol, 1 equiv.) was dissolved in Eaton's reagent (35 g) at 50° C. Once completely dissolved, 4-aminobenzoic acid 2 (2.8 g, 20.5 mmol, 1.1 equiv.) was added and the reaction was heated at 50° C. for 16 h. The resulting mixture was poured onto ice, filtered, and washed with water. After drying the resulting solid product on the filter, the product was recrystallized from ethanol to yield 2.23 g (31%) of aminobenzocrown ether 3.

[0068] Example 2 This example provides an exemplary experimental procedure for preparing the crown ethers of formula (VII) described herein, which is summarized in Scheme 2. [ka]

[0069] Dibenzocrown ether 4 (24.0 g, 66.5 mmol) was dissolved in Eaton's reagent (110 mL) at 50° C. Once completely dissolved, 4-(methylamino)benzoic acid 5 (10.0 g, 66.5 mmol, 1 equiv.) was added and the reaction was heated at 50° C. for 4 h. The resulting mixture was poured onto ice, filtered, and washed with water. After drying the resulting solid product on a filter, crude aminodibenzocrown ether 6 (30 g) was recovered. Nuclear magnetic resonance (NMR) spectroscopy indicated that the crude product was >85% of the desired product 6, with the mass balance being a mixture of starting material 4 and the double addition product.

[0070] Example 3 This example provides an exemplary experimental procedure for preparing the crown ethers of formula (VIII) described herein, which is summarized in Scheme 3. [ka]

[0071] Dibenzocrown ether 4 (5.0 g, 13.8 mmol, 1 equiv.) was dissolved in Eaton's reagent (35 g) at 50° C. Once completely dissolved, 4-aminobenzoic acid 2 (4.16 g, 30.4 mmol, 2.2 equiv.) was added and the reaction was heated at 50° C. for 4 h. The resulting mixture was poured onto ice, filtered, and washed with water. After drying the resulting solid product on the filter, the product was recrystallized from ethanol to yield 4.1 g (50%) of diaminodibenzocrown ether 7.

[0072] Example 4 This example provides an exemplary experimental procedure for preparing the crown ethers of formula (VIII) described herein, which is summarized in Scheme 4. [ka]

[0073] Dibenzocrown ether 4 (5.0 g, 13.8 mmol, 1 equiv.) was dissolved in Eaton's reagent (35 g) at 50° C. Once completely dissolved, benzoic acid 8 (3.71 g, 30.4 mmol, 2.2 equiv.) was added and the reaction was heated at 50° C. for 4 h. The resulting mixture was poured onto ice, filtered, and washed with water. After drying the resulting solid product on the filter, the product was recrystallized from ethanol to yield 7.25 g (92%) of dibenzoic acid-benzo-18-crown-6 (9).

[0074] Example 5 This example provides an exemplary experimental procedure for preparing the crown ethers of formula (IX) described herein, which is summarized in Scheme 5. [ka]

[0075] Dibenzocrown ether 4 (2.29 g, 13.8 mmol, 1 equiv.) is dissolved in Eaton's reagent (70 g) at 50° C. Once completely dissolved, 1,4-benzenedicarboxylic acid 10 (5.00 g, 13.8 mmol, 1 equiv.) is added and the reaction is heated at 50° C. for 4 h. The resulting mixture is poured onto ice, filtered, and washed with water and then methanol. After drying the resulting solid product on the filter, 4.21 g (62%) of polymer product 11 is recovered with a degree of polymerization of approximately 20, as estimated using nuclear magnetic resonance (NMR) spectroscopy.

[0076] Example 6 This example provides an exemplary experimental procedure for preparing materials of formula (V) described herein, the first step of which is summarized in Scheme 6. [ka]

[0077] Dibenzoic acid-benzo-18-crown-6 (9) (3.52 g, 6 mmol, 1 equiv.), p-toluenesulfonyl (i.e., tosyl) hydrazide (2.23 g, 12 mmol, 2 equiv.), and p-toluenesulfonic acid (10 mg, 1 mol%) were heated in toluene (100 mL) at reflux for 16 h with a Dean-Stark trap. The resulting mixture was cooled in a freezer and filtered to give a powder, which was washed with ethanol and then dried. Nuclear magnetic resonance (NMR) spectroscopy confirmed the desired conversion to the imine with a crude product 12 yield of approximately 76%. The isolated hydrazone 12 was then coupled to nylon as shown in Scheme 7. [ka]

[0078] A 1 wt % or 3 wt % coating solution containing hydrazone 12 (0.41 g or 1.24 g) and NaOH (6 mmol, added as a 50% aqueous solution) was prepared in N-methyl-2-pyrrolidone (21 mL) and ethanol (21 mL). A 4.5 inch x 10 inch strip of nylon was coated with the 1 wt % or 3 wt % coating solution using a benchtop dip coater with an 8 mil gap height. The coated nylon was cured in an oven at 85°C for 2 hours. The initial absorption percentage was measured, and then the coated nylon was washed by immersing it in 3% HCl for 1 hour, followed by immersing it in deionized water for 1 hour. The coated nylon was then trickle washed with deionized water for 10 minutes and dried in an oven at 85°C for 2 hours. The post-wash absorption percentage and the critical gravimetric surface tension (CWST) of the coated nylon were measured. The results are listed in Table 1.

[0079] [Table 1]

[0080] As is evident from the results reported in Table 1, more concentrated hydrazone solutions achieved better crown ether absorption on the coated nylon. Furthermore, Table 1 shows that as absorption increased, the critical weight surface tension (CWST) of the coated nylon decreased.

[0081] Example 7 This example demonstrates the metal removal efficiency of the materials of formula (V) described herein.

[0082] Metal removal efficiency (MRE) tests were conducted using 47 mm die-cut disks of the nylon-coated material from Example 6, Test 4, which had been washed with 5% HCl solution and deionized water. A 20-30 mL or 30-40 mL solution of propylene glycol methyl ether acetate (i.e., OK73 fluid) containing 1 ppb of each metal impurity (i.e., lithium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten, and lead) was passed through the disk, and the resulting metal ion concentrations were measured by inductively coupled plasma mass spectrometry (ICP-MS). Metal removal efficiencies (i.e., percent concentration removed) were calculated, and the results for the 20-30 mL test (left) or the 30-40 mL test (right) are plotted in the figure.

[0083] As is evident from the results depicted in the figures, the nylon-coated material of Example 6, Test 4 removed greater than 50% of magnesium, aluminum, potassium, calcium, manganese, iron, and barium, while selectively allowing ions such as lithium and sodium to pass through. Furthermore, the nylon-coated material of Example 6, Test 4 was particularly effective at removing magnesium and barium, exhibiting an MRE of greater than 90% in both cases.

[0084]

[0083] All references, including publications, patent applications, and patents, cited in this specification are incorporated by reference herein to the same extent as if each reference was individually and specifically indicated to be incorporated by reference and as if set forth in its entirety herein.

[0085] The use of the terms "a," "an," "the," and "at least one," and similar referents in the context of describing the invention (particularly in the context of the claims below) should be construed to encompass both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The use of the term "at least one" followed by a list of one or more items (e.g., "at least one of A and B") should be construed to mean one item selected from the listed items (A or B), or any combination of two or more of the listed items (A and B), unless otherwise indicated herein or clearly contradicted by context. The terms "comprising," "having," "including," and "containing" should be construed as open-ended terms (i.e., meaning "including, but not limited to"), unless otherwise noted. The recitation of ranges of values ​​herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated herein as if it were individually set forth herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. Any examples described herein, or the use of exemplary language (e.g., "such as"), are intended merely to facilitate the invention and do not limit the scope of the invention unless specifically claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

[0086] Preferred embodiments of the invention are described herein, including the best mode known to the inventors for carrying out the invention. Variations of these preferred embodiments will become apparent to those skilled in the art upon reading the foregoing description. The inventors expect those skilled in the art to employ such variations as they see fit, and the inventors intend the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, this invention includes any combination of the above-described elements in all possible variations thereof unless otherwise indicated herein or otherwise clearly contradicted by context.

Claims

1. (i) Formula (I): 【Chemistry 1】 (ii) a crown ether of formula (II): 【Chemistry 2】 and / or (iii) a crown ether of formula (III): 【Transformation 3】 or a salt thereof, wherein each m is independently an integer from 1 to 8, and p is an integer from 1 to 1000, and each " 【Chemistry 4】 " represents an optional bond and / or structure, each X is an optional substituent, and each ＊ independently represent -H, =O, or a bond to the remainder of the substance, provided that at least one ＊ is the bond to the remainder of the substance, and the remainder of the substance is bonded via an sp3-sp3 carbon-carbon bond.

2. The substance has formula (I): 【Transformation 5】 or a salt thereof, wherein each m is independently an integer from 1 to 8, and each " 【Transformation 6】 " represents an optional bond and / or structure, each X is an optional substituent, ＊ 10. The substance of claim 1, wherein represents a bond to the remainder of the substance, and the remainder of the substance is bonded via an sp3-sp3 carbon-carbon bond.

3. The substance has the formula (II): 【Transformation 7】 or a salt thereof, wherein each m is independently an integer from 1 to 8, and each " 【Transformation 8】 " denotes an optionally present bond, each X is an optionally present substituent, and each ＊ independently represent -H, =O, or a bond to the remainder of the substance, provided that at least one ＊ is the bond to the remainder of the material, and the remainder of the material is bonded via an sp3-sp3 carbon-carbon bond.

4. The substance has the formula (III): 【Chemistry 9】 or a salt thereof, wherein each m is independently an integer from 1 to 8, and p is an integer from 1 to 1000; ＊ independently represent -H, =O, or a bond to the remainder of the substance, provided that at least one ＊ is the bond to the remainder of the material, and the remainder of the material is bonded via an sp3-sp3 carbon-carbon bond.

5. 5. The material of any one of claims 1 to 4, wherein each m is independently an integer from 1 to 4.

6. 6. The material of any one of claims 1 to 5, wherein each m is independently an integer selected from 1 or 2.

7. A material according to any one of claims 1 to 6, wherein each m is 2.

8. The substance has formula (IV): 【Chemistry 10】 , formula (V): 【Chemistry 11】 or formula (VI): 【Chemistry 12】 or a salt thereof, wherein each m is independently an integer from 1 to 8, and p is an integer from 1 to 1000, and each " 【Chemistry 13】 " denotes optional bonds and / or structures, each X is an optional substituent, each Y is hydrogen, oxygen, or MS, with the proviso that at least one Y is MS, and each MS is independently a polymeric support selected from a membrane, a fiber medium, a polymeric coating or material, a metal organic framework, a monolith support, a bead, a filter, or a resin, and wherein the MS is attached via an sp3-sp3 carbon-carbon bond.

9. The substance has formula (IV): 【Chemistry 14】 or a salt thereof, wherein each m is independently an integer from 1 to 8; 【Chemistry 15】 " represents an optional bond and / or structure, each X is an optional substituent, and MS is a polymeric support selected from a membrane, a fibrous medium, a polymeric coating or material, a metal organic framework, a monolith support, a bead, a filter, or a resin, and MS is attached via an sp3-sp3 carbon-carbon bond.

10. The substance has the formula (V): 【Chemistry 16】 or a salt thereof, wherein each m is independently an integer from 1 to 8; 【Chemistry 17】 " indicates an optional bond, each X is an optional substituent, and each Y is hydrogen, oxygen, or MS, with the proviso that at least one Y is MS, and each MS is independently a polymeric support selected from a membrane, a fiber medium, a polymeric coating or material, a metal organic framework, a monolith support, a bead, a filter, or a resin, and wherein the MS is attached via an sp3-sp3 carbon-carbon bond.

11. The substance has the formula (VI): [Chemistry 18] or a salt thereof, wherein each m is independently an integer from 1 to 8, and p is an integer from 1 to 1000, and each " 【Chemistry 19】 " denotes optionally present bonds and / or structures, and each Y is hydrogen, oxygen, or MS, with the proviso that at least one Y is MS, and each MS is independently a polymeric support selected from a membrane, a fiber medium, a polymeric coating or material, a metal organic framework, a monolith support, a bead, a filter, or a resin, and wherein the MS is attached via an sp3-sp3 carbon-carbon bond.

12. 12. The material of any one of claims 8 to 11, wherein each m is independently an integer from 1 to 4.

13. 13. The material of any one of claims 8 to 12, wherein each m is independently an integer selected from 1 or 2.

14. A material according to any one of claims 8 to 13, wherein each m is 2.

15. 15. The material of any one of claims 8 to 14, wherein the polymeric support comprises gelatin, alginate, starch, polyethylene, polypropylene, nylon, polyvinylidene fluoride, polyethylene oxide, polypropylene oxide, polyethylene / polypropylene oxide, polyacrylonitrile, poly(meth)acrylate, poly(meth)acrylamide, polyamide, polyimide, polyester, cellulose, polystyrene, or a combination thereof.

16. A method for producing a material according to any one of claims 8 to 15, comprising the steps of: (i) reacting a hydrazide or hydrazine with a compound of formula (VII): 【Chemistry 20】 , formula (VIII): 【Chemistry 21】 or formula (IX): 【Chemistry 22】 with a crown ether of formula (I) to form a hydrazone-containing compound; (ii) reacting the hydrazone-containing compound with a polymeric support selected from a membrane, a fibrous medium, a polymeric coating or material, a metal organic framework, a monolith support, a bead, a filter, or a resin to form at least one C—C bond; A method comprising:

17. 17. The method of claim 16, wherein the hydrazide or hydrazides is p-toluenesulfonylhydrazide.

18. 16. A method for removing one or more metal ions from a solution, the method comprising passing the solution through a substance or salt thereof according to any one of claims 1 to 15.

19. 20. The method of claim 18, wherein the solution is an aqueous solution.

20. 20. The method of claim 18 or 19, wherein at least 50% of one or more metal ions selected from sodium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten, lead, or combinations thereof are removed.

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