Crown ether carbenes and methods of use

Abstract

The 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)" indicates an optionally present bond and / or structure, each X is an optionally present substituent, each * independently represents-H, = O or a bond attached to the remainder of the material, with the proviso that at least one * is a bond attached to the remainder of the material, and wherein the remainder of the material is bound via sp3-sp3 carbon-carbon bonds, methods of making the material and methods of using the material are also provided. # imgabs0 #

Description

Background Art

[0001] Crown ethers are cyclic organic molecules containing oxygen-based and carbon-based repeating units. It is known that crown ethers firmly bind specific cations to form complexes. In this regard, the oxygen atoms are oriented in a manner that coordinates with the metal cations located inside the ring, while the outside of the ring remains hydrophobic due to the repeating carbon units. Therefore, complexes containing crown ethers and cations can be dissolved in non-polar solvents. For this reason, crown ethers can be useful in phase transfer catalysis.

[0002] Due to the high utility of crown ether-based compounds, there is still a need to develop materials containing crown ether-based compounds and new and efficient ways to prepare such materials. The present invention provides such materials and methods of preparation. Additional benefits and aspects of the present invention will be apparent from the disclosure provided herein. Summary of the Invention

[0003] The present invention provides a material comprising: (i) a crown ether of formula (I):

[0004]

[0005] (ii) a crown ether of formula (II):

[0006]

[0007] (iii) a crown ether of formula (III):

[0008]

[0009] or a salt thereof, wherein each m is independently an integer from 1 to 8, p is an integer from 1 to 1000, each designates an optionally present bond and / or structure, each X is an optionally present substituent, each * independently represents -H, =O or a bond connecting to the remainder of the material, provided that at least one * is a bond connecting to the remainder of the material, and wherein the remainder of the material is bonded via sp3-sp3 carbon-carbon bonds.

[0010] The present invention also provides a material of the following formula, formula (IV):

[0011]

[0012]

[0013] or a salt thereof, wherein each m is independently an integer from 1 to 8, p is an integer from 1 to 1000, each Indicating optionally present keys and / or structures, each X is an optionally present substituent, each Y is hydrogen, oxygen or MS, provided that at least one Y is MS, and each MS is independently a macromolecular support selected from a membrane, a fibrous medium, a polymer coating or material, a metalorganic framework, a monolith support, a bead, a filter or a resin, and wherein MS is bonded via an sp3-sp3 carbon-carbon bond.

[0014] The present invention also provides a method for preparing the materials described herein, the method comprising (i) reacting a hydrazide or hydrazine with a crown ether of the following formula to form a hydrazone-containing compound:

[0015] Formula (VII):

[0016]

[0017] Formula (VIII):

[0018]

[0019] Formula (IX):

[0020]

[0021] and (ii) reacting the hydrazone-containing compound with a macromolecular support to form at least one C-C bond.

[0022] The present invention also provides a method for removing one or more metal ions from a solution, which comprises passing the solution through the materials described herein.

[0023] Description of the Drawings

[0024] The drawings provide a bar graph showing the percentage of metal removal efficiency (MRE) of lithium, magnesium, aluminum, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, cadmium, tin, barium, tungsten and lead as exhibited by nylon coated with crown ether carbene as described in Example 7. Detailed Description

[0025] The present invention provides a material comprising: (i) a crown ether of formula (I):

[0026]

[0027] (ii) a crown ether of formula (II):

[0028]

[0029] (iii) a crown ether of formula (III):

[0030]

[0031] or a salt thereof, wherein each m is independently an integer from 1 to 8 (such as 1, 2, 3, 4, 5, 6, 7, or 8), p is an integer from 1 to 1000 (such as from 1 to 500, from 1 to 100, 10 to 50, or 1 to 10), each designates an optionally present bond and / or structure, each X is an optionally present substituent, each * independently represents -H, =O, or a bond connecting to the remainder of the material, provided that at least one * is a bond connecting to the remainder of the material, and wherein the remainder of the material is bonded via an sp3-sp3 carbon-carbon bond.

[0032] In some embodiments, the material comprises a crown ether of formula (I):

[0033]

[0034] or a salt thereof, wherein each m is independently an integer from 1 to 8, each designates an optionally present bond and / or structure, each X is an optionally present substituent, and * represents a bond connecting to the remainder of the material, wherein the remainder of the material is bonded via an sp3-sp3 carbon-carbon bond.

[0035] In some embodiments, the material comprises a crown ether of formula (II):

[0036]

[0037] or a salt thereof, wherein each m is independently an integer from 1 to 8, each designates an optionally present bond, each X is an optionally present substituent, each * independently represents -H, =O, or a bond connecting to the remainder of the material, provided that at least one * is a bond connecting to the remainder of the material, and wherein the remainder of the material is bonded via an sp3-sp3 carbon-carbon bond.

[0038] In certain embodiments, the material comprises a crown ether of formula (III):

[0039]

[0040] or a salt thereof, wherein each m is independently an integer from 1 to 8, p is an integer from 1 to 1000, and each * independently represents -H, =O, or a bond connecting to the remainder of the material, provided that at least one * is a bond connecting to the remainder of the material, and wherein the remainder of the material is bonded via an sp3-sp3 carbon-carbon bond.

[0041] In any embodiment 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 from 1 to 8 to provide 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 provide 12-crown-4, each m can be 3 to provide 18-crown-6, each m can be 4 to provide 24-crown-8, or each m can be 5 to provide 30-crown-10. Alternatively or additionally, the each m can be different to provide 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.

[0042] In any embodiment of the materials described herein, each X is an optionally present substituent. When X is present, it 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, -NO2, -NR2, -NHR, -NH2, -COOH, -F, -Cl, -Br, -I, -COOR, -CN, -R, where R is a C 1-6 alkyl group (such as methyl, ethyl, propyl, butyl, pentyl, or hexyl). In some embodiments, the substituent "X" is absent.

[0043] In any embodiment of the materials described herein, p is an integer from 1 to 1000 (e.g., 1 to 500, 1 to 100, 10 to 50, or 1 to 10). In some embodiments, p is an integer from 1 to 10 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10).

[0044] In any embodiment of the materials described herein, each designates an optionally present bond and / or structure. In other words, depending on whether the substituent X is present, a bond connected to the variable X is optionally present, and depending on whether Y is -H, =O, or MS, the bond connected to the variable Y can be a single bond or a double bond, such that optionally one of the bonds is present, and an optionally present benzene ring marked by a dashed line is present.

[0045] In any embodiment of the materials described herein, each * independently represents -H, =O, or a bond connecting to the remainder of the material, provided that at least one * is a bond connecting to the remainder of the material, and wherein the remainder of the material is bonded via sp3-sp3 carbon-carbon bonds. Without wishing to be bound by any particular theory, it is believed that the hydrazones utilized in the preparation of the materials described herein can (i) not form first such that a ketone remains, (ii) hydrolyze and / or decompose without undergoing C-H insertion with a macromolecular carrier such that a hydrogen or a ketone remains, or (iii) undergo C-H insertion with a macromolecular carrier to form at least one C-C bond. In some embodiments, the materials containing the crown ethers of formulae (I-III) have more than one C-C bond with the remainder of the material.

[0046] The crown ethers of formulae (I)-(III) can be incorporated into any suitable material (e.g., a chemical compound or a medium), provided that the crown ethers of formulae (I)-(III) are bonded to the remainder of the material via at least one carbon labeled * in formulae (I)-(III), wherein the remainder of the material is bonded via sp3-sp3 carbon-carbon bonds. The purpose of this application is to incorporate the crown ethers of formulae (I)-(III) into materials via C-H insertion using carbene chemistry. One of ordinary skill in the art will readily understand that the crown ethers of formulae (I)-(III) can be incorporated into a material any number of times at any number of positions. Thus, the material can be any suitable material (e.g., a chemical compound or a medium) containing aliphatic C-H bonds capable of undergoing C-H insertion. In some embodiments, the material is porous such that a liquid or a fluid can flow through the material.

[0047] In some embodiments, the remaining portion of the material to which the crown ethers of formulas (I)-(III) are bound is a macromolecular carrier selected from membranes (e.g., porous membranes or permeable membranes), fibrous media, polymer coatings (e.g., sheet products or sealants such as polyurethane coatings, epoxy coatings, acrylic coatings, etc.) or materials (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.), metal-organic frameworks, monolithic supports (e.g., catalyst supports), beads (e.g., polymer beads), filter media or resins (e.g., chromatographic resins). In some embodiments, the macromolecular carrier 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 combinations thereof. In certain embodiments, the macromolecular carrier comprises polyethylene, polypropylene, nylon, polyvinylidene fluoride, polyethylene oxide, polypropylene oxide, polyethylene / polypropylene oxide, polyacrylonitrile, cellulose or combinations thereof.

[0048] Accordingly, in some embodiments, the material has the following:

[0049] Formula (IV):

[0050]

[0051] Formula (V):

[0052]

[0053] Formula (VI):

[0054]

[0055] or salts thereof, where each m is independently an integer from 1 to 8, p is an integer from 1 to 1000, each Indicating optionally present bonds and / or structures, each X is an optionally present substituent, each Y is hydrogen, oxygen or MS, provided that at least one Y is MS, and each MS is independently a macromolecular carrier selected from membranes, fibrous media, polymer coatings or materials, metal-organic frameworks, monoliths, beads, filter media or resins, and wherein MS is bonded via an sp3-sp3 carbon-carbon bond. All other definitions and embodiments regarding the variables m, p and X and the macromolecular carrier are as described herein regarding the materials of the invention.

[0056] In any embodiment of the materials described herein, each Y is hydrogen, oxygen or MS, provided that at least one Y is MS, wherein MS is bonded via an sp3-sp3 carbon-carbon bond. Without wishing to be bound by any particular theory, it is believed that the hydrazone utilized in the preparation of the materials described herein can (i) not form first such that a ketone remains, (ii) hydrolyze and / or decompose without undergoing C-H insertion with the macromolecular carrier such that hydrogen or a ketone remains, or (iii) undergo C-H insertion with the macromolecular carrier to form at least one C-MS bond via an sp3-sp3 carbon-carbon bond. In some embodiments, the materials of formulas (IV-VI) have more than one C-MS bond.

[0057] In some embodiments, the material has the formula (IV):

[0058]

[0059] or a salt thereof, wherein each m is independently an integer from 1 to 8, each Indicating optionally present bonds and / or structures, each X is an optionally present substituent, and MS is a macromolecular carrier selected from membranes, fibrous media, polymer coatings or materials, metal-organic frameworks, monoliths, beads, filter media or resins, and wherein MS is bonded via an sp3-sp3 carbon-carbon bond. All other definitions and embodiments regarding the variables m and X and the macromolecular carrier are as described herein regarding the materials of the invention.

[0060] In other embodiments, the material has the formula (V):

[0061]

[0062] or a salt thereof, wherein each m is independently an integer from 1 to 8, each Indicating an optionally present bond, each X is an optionally present substituent, each Y is hydrogen, oxygen or MS, provided that at least one Y is MS, and each MS is independently a macromolecular carrier selected from membranes, fibrous media, polymer coatings or materials, metal-organic frameworks, monoliths, beads, filter media or resins, and wherein MS is bonded via an sp3-sp3 carbon-carbon bond. All other definitions and embodiments regarding the variables m, X and Y and the macromolecular carrier are as described herein regarding the materials of the present invention.

[0063] In certain embodiments, the material has the formula (VI):

[0064]

[0065] or a salt thereof, wherein each m is independently an integer from 1 to 8, p is an integer from 1 to 1000, each Indicating an optionally present bond and / or structure, each Y is hydrogen, oxygen or MS, provided that at least one Y is MS, and each MS is independently a macromolecular carrier selected from membranes, fibrous media, polymer coatings or materials, metal-organic frameworks, monoliths, beads, filter media or resins, and wherein MS is bonded via an sp3-sp3 carbon-carbon bond. All other definitions and embodiments regarding the variables m, p and Y and the macromolecular carrier are as described herein regarding the materials of the present invention.

[0066] The object of the present application is to incorporate crown ethers of formula (I)-(III) into the material via C-H insertion using carbene chemistry. Accordingly, the present invention also provides a method for preparing the described materials, the method comprising:

[0067] (i) Reacting an acylhydrazide or hydrazine with a crown ether of the following formula to form a hydrazone-containing compound,

[0068] Formula (VII):

[0069]

[0070] Formula (VIII):

[0071]

[0072] Formula (IX):

[0073]

[0074] (ii) Reacting the hydrazone-containing compound with a macromolecular carrier selected from membranes, fibrous media, polymer coatings or materials, metal-organic frameworks, monoliths, beads, filter media or resins to form at least one C-C bond. All other definitions and embodiments regarding the variables m, p and X and the macromolecular carrier are as described herein regarding the materials of the present invention.

[0075] 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), as long as the desired hydrazone-containing compound is formed.

[0076] The hydrazide or hydrazine can be any suitable hydrazide or hydrazine known to those of ordinary skill in the art, as 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-toluenesulfonyl hydrazide (i.e., p-toluenesulfonyl hydrazine), benzenesulfonyl hydrazide, or 2,4,6-triisopropylbenzenesulfonyl hydrazide, etc. In some embodiments, the hydrazide or hydrazine is p-toluenesulfonyl hydrazide.

[0077] The hydrazide or hydrazine can be used in any suitable amount. Generally, the hydrazide or hydrazine is added in an amount slightly in excess of the number of hydrazone moieties required (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). Thus, in some embodiments, the hydrazide or hydrazine is added in an amount of at least 1x, at least 1.05x, at least 1.1x, at least 1.15x, or at least 1.2x molar equivalents relative to the number of hydrazone moieties required.

[0078] In some embodiments, the formation of the hydrazone-containing compound is carried out in a solvent. Thus, the reaction between the hydrazide or hydrazine and the 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., greater than 100 °C) such as toluene, etc. However, if promoted by an acid promoter, 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 or methanol, etc.

[0079] 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. Since the goal is to distill out 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.

[0080] The method further includes reacting the hydrazone-containing compound with a macromolecular carrier selected from a membrane, a fibrous medium, a polymer coating or material, a metal-organic framework, a monolith, beads, a filter medium 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 macromolecular carrier for any period of time as long as the desired C-C bond is formed.

[0081] In some embodiments, the C-C bond is formed in a solvent. Thus, the reaction between the hydrazone-containing compound and the macromolecular carrier can be carried out in any suitable solvent (e.g., an organic solvent). For example, the reaction between the hydrazone-containing compound and the macromolecular carrier can be carried out in ethanol, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, methanol, isopropanol, tetrahydrofuran, acetonitrile, or a combination thereof.

[0082] In some embodiments, the reaction between the hydrazone-containing compound and the macromolecular carrier is promoted by a base promoter. In other words, the formation of the carbene can be promoted by a base promoter. The base promoter can be any suitable Brønsted 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 a particular embodiment, the reaction between the hydrazone-containing compound and the macromolecular carrier is carried out in ethanol and / or N-methyl-2-pyrrolidone in the presence of sodium hydroxide.

[0083] The base promoter can be used in any suitable amount. Generally, the base promoter is added in an amount that exceeds the number of hydrazone moieties present in the reacting hydrazone-containing molecules (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). Thus, in some embodiments, the base promoter is added in an amount of at least 1x, at least 2x, at least 5x, at least 10x the molar equivalent of the number of hydrazone moieties present in the reacting hydrazone-containing molecules.

[0084] In some embodiments, the formation of the carbene is further promoted by a metal catalyst. Metal catalysts suitable for the formation and / or stabilization of 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 a particular embodiment, the reaction between the hydrazone-containing compound and the macromolecular carrier does not contain a metal catalyst.

[0085] The reaction between a hydrazone-containing compound and a macromolecular carrier can be heated or subjected to ultraviolet (UV) light. Without wishing to be bound by any particular theory, it is believed that the formation of C-C bonds (e.g., via C-H insertion) can be promoted by elevated temperature (e.g., above 50 °C or above 75 °C) and / or UV light. In certain embodiments, patterned selective functionalization and UV light irradiation are used to cure the reaction between the hydrazone-containing compound and the macromolecular carrier.

[0086] The materials described herein can be used for any suitable industrial application for any suitable purpose. For example, the materials described herein can be used in water purification applications, wastewater treatment applications, mining applications, electronic (e.g., microelectronic) applications, paper-making 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 for the selective removal of 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 combinations thereof) and one or more metal ions. In certain embodiments, the fluid (i.e., the solution) is an aqueous solution.

[0087] 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 flowing the solution through the material. For example, the material can be used as a filter media, a porous medium, a chromatographic resin, or a membrane, etc., through which the solution flows to remove one or more metal ions. Accordingly, the present invention also provides a method for removing one or more metal ions from a solution, which comprises flowing the solution through a material, the material comprising: (i) a crown ether of formula (I):

[0088]

[0089] (ii) a crown ether of formula (II):

[0090]

[0091] (iii) a crown ether of formula (III):

[0092]

[0093] or a salt thereof, wherein each m is independently an integer from 1 to 8 (e.g., 1, 2, 3, 4, 5, 6, 7, or 8), p is an integer from 1 to 1000 (e.g., 1 to 500, 1 to 100, 10 to 50, or 1 to 10), each Designate optionally present bonds and / or structures, each X is an optionally present substituent, each * independently represents -H, =O or a bond connecting to the remainder of the material, provided that at least one * is a bond connecting to the remainder of the material, and wherein the remainder of the material is bonded via sp3-sp3 carbon-carbon bonds. All other definitions and embodiments regarding the variables m, p, X and Y and the macromolecular carrier are as described herein for the materials of the present invention.

[0094] The method can be used to remove any suitable ions. Alternatively or additionally, the method can be used to allow any suitable ions to flow through the material. For example, the 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 additionally, the 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 the material. In certain embodiments, the method selectively allows lithium to flow 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.

[0095] 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 the solution, remove at least 50% of one or more metal ions from the solution, remove at least 60% of one or more metal ions from the solution, remove at least 70% of one or more metal ions from the solution, remove at least 80% of one or more metal ions from the solution or remove at least 90% of one or more metal ions from the 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 combinations 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.

[0096] In some embodiments, the solution that has flowed through the material is the desired product of the methods described herein. Thus, in such embodiments, the method may further include recovering the solution (e.g., aqueous solution) that has flowed 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 will be the desired product since smaller metal ions such as lithium and / or sodium are more likely to flow through the materials described herein.

[0097] In other embodiments, one or more metal ions removed from the solution are the desired products of the methods described herein. Thus, in these embodiments, the method may further include recovering one or more metal ions removed from the solution. The one or more metal ions can be recovered by any suitable means. For example, the material containing one or more metal ions can be washed with the recovered 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 will remain in the material since larger metal ions are less likely to flow through the materials described herein.

[0098] Aspects of the invention described herein, including embodiments, may be advantageous alone or in combination with one or more other aspects or embodiments. Without being limited by the foregoing description, specific non-limiting embodiments of Publication Nos. 1 - 22 are provided below. As will be apparent to those skilled in the art upon reading this disclosure, each individually numbered embodiment can be used or combined with any preceding or following individually numbered embodiment. This is intended to provide support for all such combinations of embodiments and is not limited to the combinations of embodiments explicitly provided below:

[0099] Embodiment

[0100] (1) In Embodiment (1), there is a material that comprises (i) a crown ether of Formula (I):

[0101]

[0102] (ii) a crown ether of Formula (II):

[0103]

[0104] (iii) a crown ether of Formula (III):

[0105]

[0106] or a salt thereof, wherein each m is independently an integer from 1 to 8, p is an integer from 1 to 1000, each Indicating optionally present bonds and / or structures, each X is an optionally present substituent, each * independently represents -H, =O or a bond connecting to the remainder of the material, provided that at least one * is a bond connecting to the remainder of the material, and wherein the remainder of the material is bonded via an sp3-sp3 carbon-carbon bond.

[0107] (2) The material of embodiment (1) is present in embodiment (2), wherein the material comprises a crown ether of formula (I):

[0108]

[0109] or a salt thereof, wherein each m is independently an integer from 1 to 8, each Indicating optionally present bonds and / or structures, each X is an optionally present substituent, and * represents a bond connecting to the remainder of the material, wherein the remainder of the material is bonded via an sp3-sp3 carbon-carbon bond.

[0110] (3) The material of embodiment (1) is present in embodiment (3), wherein the material comprises a crown ether of formula (II):

[0111]

[0112] or a salt thereof, wherein each m is independently an integer from 1 to 8, each Indicating optionally present bonds, each X is an optionally present substituent, each * independently represents -H, =O or a bond connecting to the remainder of the material, provided that at least one * is a bond connecting to the remainder of the material, and wherein the remainder of the material is bonded via an sp3-sp3 carbon-carbon bond.

[0113] (4) The material of embodiment (1) is present in embodiment (4), wherein the material comprises a crown ether of formula (III):

[0114]

[0115] or a salt thereof, wherein each m is independently an integer from 1 to 8, p is an integer from 1 to 1000, and each * independently represents -H, =O or a bond connecting to the remainder of the material, provided that at least one * is a bond connecting to the remainder of the material, and wherein the remainder of the material is bonded via an sp3-sp3 carbon-carbon bond.

[0116] (5) The materials of embodiments (1)-(4) are present in embodiment (5), wherein each m is independently an integer from 1 to 4.

[0117] (6) The material of any one of embodiments (1)-(5) is present in embodiment (6), wherein each m is independently an integer selected from 1 or 2.

[0118] (7) In embodiment (7), there is a material of any one of embodiments (1)-(6), where each m is 2.

[0119] (8) In embodiment (8), there is a material of embodiment (1), where the material has the following:

[0120] Formula (IV):

[0121]

[0122] Formula (V):

[0123]

[0124] Formula (VI):

[0125]

[0126] or a salt thereof, where each m is independently an integer from 1 to 8, p is an integer from 1 to 1000, each designates an optionally present bond and / or structure, each X is an optionally present substituent, each Y is hydrogen, oxygen, or MS, provided that at least one Y is MS, and each MS is independently a macromolecular carrier selected from a membrane, fibrous medium, polymer coating or material, metal-organic framework, monolithic support, bead, filter media, or resin, and where MS is bonded via an sp3-sp3 carbon-carbon bond.

[0127] (9) In embodiment (9), there is a material of embodiment (8), where the material has Formula (IV):

[0128]

[0129] or a salt thereof, where each m is independently an integer from 1 to 8, each designates an optionally present bond and / or structure, each X is an optionally present substituent, and MS is a macromolecular carrier selected from a membrane, fibrous medium, polymer coating or material, metal-organic framework, monolithic support, bead, filter media, or resin, and where MS is bonded via an sp3-sp3 carbon-carbon bond.

[0130] (10) In embodiment (10), there is a material of embodiment (8), where the material has Formula (V):

[0131]

[0132] or a salt thereof, where each m is independently an integer from 1 to 8, each Indicating an optionally present bond, each X is an optionally present substituent, each Y is hydrogen, oxygen or MS, provided that at least one Y is MS, and each MS is independently a macromolecular carrier selected from membranes, fibrous media, polymer coatings or materials, metal-organic frameworks, monoliths, beads, filter media or resins, and wherein MS is bonded via an sp3-sp3 carbon-carbon bond.

[0133] (11) The material of embodiment (8) is present in embodiment (11), wherein the material has formula (VI):

[0134]

[0135] or a salt thereof, wherein each m is independently an integer from 1 to 8, p is an integer from 1 to 1000, each Indicating an optionally present bond and / or structure, each Y is hydrogen, oxygen or MS, provided that at least one Y is MS, and each MS is independently a macromolecular carrier selected from membranes, fibrous media, polymer coatings or materials, metal-organic frameworks, monoliths, beads, filter media or resins, and wherein MS is bonded via an sp3-sp3 carbon-carbon bond.

[0136] (12) The material of any one of embodiments (8)-(11) is present in embodiment (12), wherein each m is independently an integer from 1 to 4.

[0137] (13) The material of any one of embodiments (8)-(12) is present in embodiment (13), wherein each m is independently an integer selected from 1 or 2.

[0138] (14) The material of any one of embodiments (8)-(13) is present in embodiment (14), wherein each m is 2.

[0139] (15) The material of any one of embodiments (8)-(14) is present in embodiment (15), wherein the macromolecular carrier comprises gelatin, alginate / ester, 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.

[0140] (16) A method for preparing the material of any one of embodiments (8)-(15) is present in embodiment (16), the method comprising:

[0141] (i) Reacting an acylhydrazide or hydrazine with a crown ether of the following formula to form a hydrazone-containing compound,

[0142] Formula (VII):

[0143]

[0144] Formula (VIII):

[0145]

[0146] Formula (IX):

[0147]

[0148] (ii) Reacting the hydrazone-containing compound with a macromolecular carrier selected from membranes, fibrous media, polymer coatings or materials, metal-organic frameworks, monolithic supports, beads, filter media or resins to form at least one C-C bond.

[0149] (17) The method of embodiment (16) is present in embodiment (17), wherein the hydrazide or hydrazine is p-toluenesulfonyl hydrazide.

[0150] (18) The method of removing one or more metal ions from a solution is present in embodiment (18), which includes flowing the solution through the material of any one of embodiments (1)-(15) or its salt.

[0151] (19) The method of embodiment (18) is present in embodiment (19), wherein the solution is an aqueous solution.

[0152] (20) The method of embodiment (18) or embodiment (19) is present in embodiment (20), 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.

[0153] (21) The method of embodiment (18) or embodiment (19) is present in embodiment (22), 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.

[0154] (22) The method of embodiment (18) or embodiment (19) is present in embodiment (22), 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.

[0155] Examples

[0156] The following examples further illustrate the present invention but should not be construed as limiting its scope in any way.

[0157] Example 1

[0158] This example provides an exemplary experimental procedure for preparing the crown ether of formula (VII) described herein, which is summarized in Scheme 1.

[0159] Scheme 1.

[0160]

[0161] Dissolve benzo crown ether 1 (5 g, 18.6 mmol, 1 eq) in Eaton's Reagent (35 g) at 50 °C. Once completely dissolved, add 4-aminobenzoic acid 2 (2.8 g, 20.5 mmol, 1.1 eq) and heat the reaction at 50 °C for 16 h. Pour the resulting mixture onto ice, filter, and wash with water. After allowing the resulting solid product to dry on the filter, recrystallize the product from ethanol to obtain 2.23 g (31%) of aminobenzo crown ether 3.

[0162] Example 2

[0163] This example provides an exemplary experimental procedure for preparing the crown ether of formula (VII) described herein, which is summarized in Scheme 2.

[0164] Scheme 2.

[0165]

[0166] Dissolve dibenzo crown ether 4 (24.0 g, 66.5 mmol) in Eaton's Reagent (110 mL) at 50 °C. Once completely dissolved, add 4-(methylamino)benzoic acid 5 (10.0 g, 66.5 mmol, 1 eq) and heat the reaction at 50 °C for 4 h. Pour the resulting mixture onto ice, filter, and wash with water. After allowing the resulting solid product to dry on the filter, recover the crude aminodibenzo crown ether 6 (30 g). Nuclear magnetic resonance (NMR) spectroscopy indicates that the crude product is >85% of the desired product 6, with the remaining mass being a mixture of starting material 4 and the di-addition product.

[0167] Example 3

[0168] This example provides an exemplary experimental procedure for preparing the crown ether of formula (VIII) described herein, which is summarized in Scheme 3.

[0169] Scheme 3.

[0170]

[0171] Dibenzo crown ether 4 (5.0 g, 13.8 mmol, 1 eq) 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 eq) 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 allowing the resulting solid product to dry on the filter, the product was recrystallized from ethanol to afford 4.1 g (50%) of diamino dibenzo crown ether 7.

[0172] Example 4

[0173] This example provides an exemplary experimental procedure for preparing the crown ether of formula (VIII) described herein, which is summarized in Scheme 4.

[0174] Scheme 4.

[0175]

[0176] Dibenzo crown ether 4 (5.0 g, 13.8 mmol, 1 eq) 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 eq) 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 allowing the resulting solid product to dry on the filter, the product was recrystallized from ethanol to afford 7.25 g (92%) of dibenzoyl-benzo-18-crown-6 (9).

[0177] Example 5

[0178] This example provides an exemplary experimental procedure for preparing the crown ether of formula (IX) described herein, which is summarized in Scheme 5.

[0179] Scheme 5.

[0180]

[0181] Dibenzo crown ether 4 (2.29 g, 13.8 mmol 1 eq) was dissolved in Eaton's reagent (70 g) at 50 °C. Once completely dissolved, 1,4-phthalic acid 10 (5.00 g, 13.8 mmol, 1 eq) 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 and then with methanol. After allowing the resulting solid product to dry on the filter, 4.21 g (62%) of the polymeric product 11 was recovered, which had a degree of polymerization of approximately 20 as estimated by nuclear magnetic resonance (NMR) spectroscopy.

[0182] Example 6

[0183] This example provides an exemplary experimental procedure for preparing the materials of formula (V) described herein, the first step of which is summarized in Scheme 6.

[0184] Scheme 6.

[0185]

[0186] Dibenzoyl-benzo-18-crown-6 (9) (3.52 g, 6 mmol, 1 eq), p-toluenesulfonyl (i.e., p-toluenesulfonyl) hydrazide (2.23 g, 12 mmol, 2 eq), and p-toluenesulfonic acid (10 mg, 1 mol%) were heated in refluxing toluene (100 mL) with a Dean-Stark separator for 16 h. The resulting mixture was cooled in a cold storage and filtered to afford a powder, which was washed with ethanol and then dried. Nuclear magnetic resonance (NMR) spectroscopy was used to confirm the desired conversion to the imine, and the yield was approximately 76% of the crude product 12. The isolated hydrazone 12 was then linked to nylon as shown in Scheme 7.

[0187] Scheme 7.

[0188]

[0189] A coating solution of 1 wt% or 3 wt% containing hydrazone 12 (0.41 g or 1.24 g) and NaOH (6 mmol, added as a 50% aqueous solution) in N-methyl-2-pyrrolidone (21 mL) and ethanol (21 mL) was prepared. A 4.5” by 10” nylon strip was coated with the 1 wt% or 3 wt% coating solution on a bench-top dip coater using an 8 mils gap height. The coated nylon was cured in an oven at 85 °C for 2 h. The initial uptake percentage was measured and then the coated nylon was cleaned by immersing the coated nylon in 3% HCl for 1 h and then immersing the coated nylon in deionized water for 1 h. The coated nylon was then drip washed with deionized water for 10 min and dried in an oven at 85 °C for 2 h. The uptake percentage after cleaning and the critical weight surface tension (CWST) of the coated nylon were measured. The results are listed in Table 1.

[0190] Table 1. Crown Ether Coated Nylon Results

[0191] Coating solution Initial coating absorption Cleaning coating absorption <![CDATA[CWST (dyn / cm 2 )]]> Test 1 (1 wt%) 6.7％ 2.8％ 73 Test 2 (1 wt%) 5.6％ 2.6％ 73 Test 3 (3 wt%) 14.3％ 8.4％ 65 Test 4 (3 wt%) 17.3％ 10.7％ 63

[0192] It is clear from the results listed in Table 1 that a more concentrated hydrazone solution provides better crown ether uptake of the coated nylon. In addition, Table 1 shows that as the uptake increases, the critical weight surface tension (CWST) of the coated nylon decreases.

[0193] Example 7

[0194] This example shows the metal removal efficiency of the materials of formula (V) described herein.

[0195] Metal removal efficiency (MRE) testing was performed using a perforated 47 mm disc of the nylon-coated material from Test 4 of Example 6, which had been cleaned using 5% HCl solution and deionized water. A 20 - 30 mL or 30 - 40 mL solution of propylene glycol monomethyl 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 disc, and the resulting metal ion concentration was measured by inductively coupled plasma - mass spectrometry (ICP - MS). The metal removal efficiency (i.e., the percentage concentration removed) was calculated, and the results for the 20 - 30 mL test (left) or 30 - 40 mL (right) were plotted in the figures.

[0196] As is clear from the results listed in the figures, the nylon - coated material from Test 4 of Example 6 removes more than 50% of magnesium, aluminum, potassium, calcium, manganese, iron, and barium, while selectively allowing ions such as lithium and sodium to flow through. In addition, the nylon - coated material from Test 4 of Example 6 is particularly effective at removing magnesium and barium, showing an MRE greater than 90% in both cases.

[0197] All citations referred to herein, including publications, patent applications, and patents, are incorporated herein by reference to the same extent as if each citation were individually and specifically indicated to be incorporated by reference and were set forth in full herein.

[0198] In the context of describing the present invention (especially in the context of the following claims), the use of the terms "a", "an", "the", "at least one", and similar referents should be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by the context. The use of the term "at least one" followed by a list of one or more items (such as "at least one of A and B") should be construed to mean one of 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 the 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 specified. The recitation of a range 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 into the specification as if it were individually recited herein. All methods described herein may be performed in any suitable order, unless otherwise indicated herein or clearly contradicted by the context. The use of any and all examples or exemplary language (such as "for example") provided herein is merely intended to better illuminate the invention and does not impose a limitation on the scope of the invention, unless otherwise stated. No language in the specification should be construed as indicating any non-recited element as essential to the practice of the invention.

[0199] Preferred embodiments of the invention are described herein, including the best mode known to the inventors for practicing the invention. Variations of these preferred embodiments will become apparent to those skilled in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, the invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. In addition, the invention covers any combination of all viable variations of the elements described above, unless otherwise indicated herein or clearly contradicted by the context.

Claims

1. 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, where each m is independently an integer from 1 to 8, p is an integer from 1 to 1000, each designates an optionally present bond and / or structure, each X is an optionally present substituent, each * independently represents -H, =O or a bond to the remainder of the material, provided that at least one * is a bond to the remainder of the material, and where the remainder of the material is bonded via an sp3-sp3 carbon-carbon bond.

2. The material according to claim 1, wherein the material comprises a crown ether of formula (I): or a salt thereof, wherein each m is independently an integer from 1 to 8, each designates an optionally present bond and / or structure, each X is an optionally present substituent, and * represents a bond to the remainder of the material, wherein the remainder of the material is bonded via an sp3-sp3 carbon-carbon bond.

3. The material according to claim 1, wherein the material comprises a crown ether of formula (II): or a salt thereof, wherein each m is independently an integer from 1 to 8, each designates an optionally present bond, each X is an optionally present substituent, each * independently represents -H, =O or a bond connecting to the remainder of the material, provided that at least one * is a bond connecting to the remainder of the material, and wherein the remainder of the material is bonded via an sp3-sp3 carbon-carbon bond.

4. The material according to claim 1, wherein the material comprises 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, and each * independently represents -H, =O or a bond connecting to the remainder of the material, provided that at least one * is a bond connecting to the remainder of the material, and wherein the remainder of the material is bonded via an sp3-sp3 carbon-carbon bond.

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

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

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

8. The material according to claim 1, wherein the material has the following: Formula (IV): Formula (V): or formula (VI): or a salt thereof, wherein each m is independently an integer from 1 to 8, p is an integer from 1 to 1000, each designates an optionally present bond and / or structure, each X is an optionally present substituent, each Y is hydrogen, oxygen or MS, provided that at least one Y is MS, and each MS is independently a macromolecular carrier selected from membranes, fibrous media, polymer coatings or materials, metal-organic frameworks, monoliths, beads, filter media or resins, and wherein MS is bonded via an sp3-sp3 carbon-carbon bond.

9. The material according to claim 8, wherein the material has formula (IV): or a salt thereof, wherein each m is independently an integer from 1 to 8, each designates an optionally present bond and / or structure, each X is an optionally present substituent, and MS is a macromolecular support selected from membranes, fibrous media, polymer coatings or materials, metal-organic frameworks, monolithic supports, beads, filter media or resins, and wherein MS is bonded via an sp3-sp3 carbon-carbon bond.

10. The material according to claim 8, wherein the material has formula (V): or a salt thereof, wherein each m is independently an integer from 1 to 8, each designates an optionally present bond, each X is an optionally present substituent, each Y is hydrogen, oxygen or MS, provided that at least one Y is MS, and each MS is independently a macromolecular support selected from membranes, fibrous media, polymer coatings or materials, metal-organic frameworks, monoliths, beads, filter media or resins, and wherein MS is bonded via an sp3-sp3 carbon-carbon bond.

11. The material according to claim 8, wherein the material has formula (VI): or a salt thereof, wherein each m is independently an integer from 1 to 8, p is an integer from 1 to 1000, each designates an optionally present bond and / or structure, each Y is hydrogen, oxygen or MS, provided that at least one Y is MS, and each MS is independently a macromolecular carrier selected from membranes, fibrous media, polymer coatings or materials, metal-organic frameworks, monolithic supports, beads, filter media or resins, and wherein MS is bonded via an sp3-sp3 carbon-carbon bond.

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

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

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

15. The material according to any one of claims 8-14, wherein the macromolecular carrier comprises gelatin, alginate / ester, 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 preparing the material according to any one of claims 8-15, the method comprising: (i) reacting an acyl hydrazide or hydrazine with a crown ether of the following formula to form a hydrazone-containing compound, Formula (VII): Formula (VIII): or Formula (IX): and (ii) reacting the hydrazone-containing compound with a macromolecular carrier selected from a membrane, a fibrous medium, a polymer coating or material, a metal-organic framework, a monolithic support, beads, a filter material or a resin to form at least one C-C bond.

17. The method according to claim 16, wherein the acyl hydrazide or hydrazine is p-toluenesulfonyl hydrazide.

18. A method for removing one or more metal ions from a solution, which comprises passing the solution through the material according to any one of claims 1-15 or a salt thereof.

19. The method according to claim 18, wherein the solution is an aqueous solution.

20. The method according to claim 18 or claim 19, 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.

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