Crown ether amines and methods of use

Abstract

The present invention provides a material comprising (i) a crown ether of formula (I) and / or (ii) a crown ether of formula (II), or a salt thereof, wherein each m is independently an integer from 1 to 8, each (A) represents an optionally present bond and / or structure, and each X is independently selected from the group consisting of -N(R1), -N * (R1), -N ** , -N * (R1)2 + Z - , or -N ** (R1) + Z - with the proviso that at least one X is -N * (R1), -N ** , -N * (R1)2 + Z - , or -N ** (R1) + Z - and each R is independently hydrogen or C 1~6 alkyl, and each Z is optionally present and independently a counterion to balance the charge on the nitrogen; * represents the bond to the remainder of the substance, methods of making the substance, and methods of using the substance are provided. [Formula 1] JPEG2025535518000064.jpg130149

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] and / or (ii) a crown ether of formula (II): [ka] or a salt thereof, wherein each m is independently an integer of 1 to 8, and each " [ka] " represents an optionally present bond and / or structure, and each X is independently -N(R1)2, -N * (R1), -N ** , -N * (R1)2+ Z - , or -N ** (R1) + Z - with the proviso that at least one X is -N * (R1), -N ** , -N * (R1)2 + Z - , or -N ** (R1) + Z - and each R is independently hydrogen or C 1~6 alkyl, and each Z is optionally present and independently a counterion to balance the charge on the nitrogen; * represents the bond to the remainder of the substance.

[0004] The present invention also provides a compound of formula (III): [ka] Or formula (IV): [ka] or a salt thereof, wherein each m is independently an integer from 1 to 8, and each R2 is optionally present and independently hydrogen or C 1~6 alkyl, and each " [ka] " denotes an optionally present bond and / or structure, and each R is optionally present and independently selected from hydrogen, C 1~6 alkyl, or MS; each Z is optionally present and independently a counterion to balance the charge of the nitrogen; and each Y is R 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, or a salt thereof.

[0005] The present invention provides a method for making the material described herein, comprising the steps of: (i) reacting a benzo or dibenzo crown ether with an aminobenzoic acid compound to form (a) a compound of formula (V): [ka] or (b) a crown ether of formula (VI): [ka] forming a crown ether of (ii) reacting a crown ether of formula (V) or a crown ether of formula (VI) with a polymeric support to form at least one C—N bond or C═N 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 for sodium, potassium, calcium, magnesium, and nickel for three tests (n=1-3) exhibited by the crown ether amine resin described in Example 5. Detailed Description of the Invention

[0008] The present invention provides (i) a compound of formula (I): [ka] and / or (ii) a crown ether of formula (II): [ka] or a salt thereof, wherein each m is independently an integer of 1 to 8, and each " [ka] " represents an optionally present bond and / or structure, and each X is independently -N(R1)2, -N * (R1), -N ** , -N * (R1)2 + Z - , or -N ** (R1) + Z - with the proviso that at least one X is -N * (R1), -N ** , -N * (R1)2 + Z - , or -N ** (R1) + Z - and each R is independently hydrogen or C 1~6 alkyl, and each Z is optionally present and independently a counterion to balance the charge on the nitrogen; * represents the bond to the remainder of the substance.

[0009] In some embodiments, the substance has formula (I): [ka] Each m is independently an integer from 1 to 8 (e.g., 1, 2, 3, 4, 5, 6, 7, or 8), and each " [ka] " denotes optionally present bonds and / or structures, and X is -N * (R1), -N ** , -N * (R1)2 + Z - , or -N **(R1) + Z - and each R is independently hydrogen or C 1~6 alkyl, and Z is an optional counterion to balance the charge on the nitrogen; * represents the bond to the rest of the substance.

[0010] In some embodiments, the substance has formula (II): [ka] 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), and each X is independently -N(R1)2, -N * (R1), -N ** , -N * (R1)2 + Z - , or -N ** (R1) + Z - where at least one X is -N * (R1), -N ** , -N * (R1)2 + Z - , or -N ** (R1) + Z - and each R is independently hydrogen or C 1~6 alkyl, and each Z is optionally present and independently a counterion to balance the charge on the nitrogen; * represents the bond to the rest of the substance.

[0011] 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.

[0012] In any of the embodiments of the materials described herein, each X is independently -N(R1)2, -N * (R1), -N ** , -N * (R1)2 + Z - , or -N ** (R1) + Z - where at least one X is -N * (R1), -N ** , -N * (R1)2 + Z - , or -N ** (R1) + Z - and each R is independently hydrogen or C 1~6 alkyl, and Z is an optional counterion to balance the charge on the nitrogen; *represents the bond to the remainder of the substance. In other words, the crown ether of formula (I) or the crown ether of formula (II) can be bonded to the remainder of the substance via a single bond, multiple single bonds, double bonds, or multiple double bonds, thereby forming structures such as amines, imines, amides, etc. For example, the crown ether of formula (I) or the crown ether of formula (II) can be incorporated into the substance at a single position via one or two bonds, such that the nitrogen atom has a neutral or cationic charge. Alternatively, or in addition, the crown ether of formula (I) or the crown ether of formula (II) can be incorporated into the substance at multiple positions via one or two bonds at each position, such that the nitrogen atom has a neutral or cationic charge. It will be readily understood by those skilled in the art that multiple crown ethers of formula (I) or crown ethers of formula (II) can be incorporated into the substance.

[0013] In some embodiments, each X is independently —N(R 1 ) 2 , —N * (R1), or -N ** where at least one X is -N * (R1) or -N ** and each R is independently hydrogen or C 1~6 is alkyl, * represents a bond to the remainder of the substance. For example, each X can be -N(R1)2 or -N * (R1), with the proviso that at least one X is -N * (R1), where each R1 is independently hydrogen or C 1~6 is alkyl, * represents a bond to the remainder of the substance. In other embodiments, each X is independently -N(R1)2 or -N ** where at least one X is -N ** and each R is independently hydrogen or C 1~6 is alkyl, * represents a bond to the remainder of the substance. In certain embodiments, each X is independently -N(R1)2 or -N * (R1), with the proviso that at least one X is -N *(R1), so that the crown ether of formula (I) or the crown ether of formula (II) can be attached to the remainder of the substance via a single bond (for example, to form an amine or amide).

[0014] In other embodiments, each X is independently -N(R1)2, -N * (R1)2 + Z - , or -N ** (R1) + Z - where at least one X is -N * (R1)2 + Z - or -N ** (R1) + Z - and each R is independently hydrogen or C 1~6 alkyl, and Z is an optional counterion to balance the charge on the nitrogen; * represents the bond to the rest of the substance.

[0015] In any of the embodiments of the materials described herein, each R1 is independently hydrogen or C 1~6 In some embodiments, each R is hydrogen. In other embodiments, each R is C 1~6 It is alkyl.

[0016] 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 Y can be a single or double bond depending on whether Y is R2 or MS, and the bond to MS can be a single or double bond, so that one of the bonds is optional and the phenyl ring designated by the dashed line is optional.

[0017] In any of the embodiments of the material described herein, each * are independently bonds to the remainder of the substance, provided that at least one * The bond to the remainder of the substance can be any suitable bond, so long as at least one bond is a C-N bond or a C=N bond. In some embodiments, the substance comprising a crown ether of formula (I) or a crown ether of formula (II) has more than one C-N or C=N bond to the remainder of the substance. For example, the crown ether can be (i) (a) two separate * or (b) two separate ** and / or (ii) (a) one single * , (b) two separate * or (c) a single ** As used herein, the term "a" refers to a group of atoms that can be attached to the remainder of a substance via a single nitrogen atom as a ** refers to two separate single bonds or one single double bond.

[0018] In any of the embodiments of the materials described herein, each Z is optionally present and independently is a counterion to balance the charge of the nitrogen. Z can be any suitable counterion to balance the cationic charge of the nitrogen atom. For example, Z can be a halogen (e.g., chlorine, bromine, or iodine), NO3 - , O.H. - etc. In some embodiments, Z is a halogen (e.g., chlorine or bromine).

[0019]

[0019] The crown ether of formula (I) or the crown ether of formula (II) is *The crown ether of formula (I) or the crown ether of formula (II) can be incorporated into any suitable material (e.g., a chemical compound or medium) so long as it is bonded to the remainder of the material via at least one C-N bond or C=N bond as specified in (I). It will be readily understood by those skilled in the art that the crown ether of formula (I) or the crown ether of formula (II) can be incorporated into the material at any number of positions and any number of times. Thus, the material can be any suitable material (e.g., a chemical compound or medium) that can form at least one C-N bond or C=N bond with the crown ether of formula (I) or the crown ether of formula (II). In some embodiments, the material is porous, allowing liquids or fluids to pass through the material.

[0020]

[0020] In some embodiments, the remainder of the material to which the crown ether of formula (I) or the crown ether of formula (II) 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 polyacrylonitrile, poly(meth)acrylate, poly(meth)acrylamide, polyimide, polyester, polystyrene, or a combination thereof.

[0021] In certain embodiments, the crown ether compounds described herein are used to functionalize coatings, such as coatings containing benzyl chloride groups. Alternatively, or additionally, the crown ether compounds described herein can be directly converted to polyamides or polyimides by polymerization reactions.

[0022]

[0022] Thus, in some embodiments, the substance has formula (III): [ka] Or formula (IV): [ka] or a salt thereof, wherein each m is independently an integer from 1 to 8; and each R2 is optionally present and independently hydrogen or C 1~6 alkyl, and each " [ka] " denotes an optionally present bond and / or structure, and each R is optionally present and independently represents hydrogen, C 1~6 m is an alkyl, or MS, each Z is optionally present and independently a counterion to balance the charge of the nitrogen, each Y is R 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. All other definitions and embodiments of the variables m, R, R, Y, and Z, and the polymeric support, are as described herein for the materials of the invention.

[0023] In any of the embodiments of the materials described herein, each Y is R2 or MS, with the proviso that at least one Y is MS. In other words, the materials described herein have at least one C-N bond or C=N bond formed with a crown ether of formula (I) or a crown ether of formula (II).

[0024] In any of the embodiments of the materials described herein, each R2 is optionally present and independently represents hydrogen or C 1~6In some embodiments, each R is hydrogen. In other embodiments, each R is C 1~6 In certain embodiments, R2 is absent.

[0025] In any of the embodiments of the materials described herein, each R3 is optionally present and independently represents hydrogen, C 1~6 alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, or hexyl), or MS. In some embodiments, each R is absent. In other embodiments, each R is C 1~6 The nitrogen atom of the crown ether may be alkyl. When R3 is present, the nitrogen atom of the crown ether may have a positive charge. The positive charge may or may not be balanced by an anionic charge provided by the counterion Z, as described herein. Without wishing to be bound by any particular theory, it is believed that the charge variants of the crown ether modify the material to behave like an exchange resin, which may be desirable for certain applications.

[0026] In some embodiments, the substance has formula (III): [ka] or a salt thereof, wherein each m is independently an integer from 1 to 8; R2 is optionally present and is hydrogen or C 1~6 alkyl, and each " [ka] " denotes an optionally present bond and / or structure, and R3 is optionally present and can be hydrogen, C 1~6alkyl, or MS, Z is an optionally present counterion to balance the charge of the nitrogen, 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. All other definitions and embodiments of the variables m, R2, R3, and Z, and the polymeric support, are as described herein for the materials of the invention.

[0027] In another embodiment, the substance has formula (IV): [ka] or a salt thereof, wherein each m is independently an integer from 1 to 8; and each R2 is optionally present and independently hydrogen or C 1~6 alkyl, and each " [ka] " denotes an optionally present bond and / or structure, and each R is optionally present and independently represents hydrogen, C 1~6 m is an alkyl, or MS, each Z is optionally present and independently a counterion to balance the charge of the nitrogen, each Y is R 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. All other definitions and embodiments of the variables m, R, R, Y, and Z, and the polymeric support, are as described herein for the materials of the invention.

[0028] The object of the present application is to incorporate a crown ether of formula (I) or a crown ether of formula (II) into a material via a C-N or C=N bond. The present invention therefore also relates to a method for preparing the material described, which comprises: (i) reacting a benzo or dibenzo crown ether with an aminobenzoic acid compound to form (a) a compound of formula (V): [ka] or (b) a crown ether of formula (VI): [ka] forming a crown ether of (ii) reacting the crown ether of formula (V) or the crown ether of formula (VI) 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-N bond or a C=N bond; The variables m and R2 and all other definitions and embodiments relating to the polymeric support are as described herein for the materials of the invention.

[0029] A method of reacting a benzo- or dibenzo crown ether with an aminobenzoic acid compound to form a crown ether of formula (V) or a crown ether of formula (VI). For example, the aminobenzoic acid compound can be combined (e.g., contacted), mixed (e.g., shaken, stirred, etc.), heated, refluxed, or a combination thereof with the benzo- or dibenzo crown ether for any period of time so long as the desired crown ether of formula (V) or crown ether of formula (VI) is formed.

[0030] The aminobenzoic acid compound can be any suitable benzoic acid, so long as the aryl ring has an amine-based substituent. For example, the aminobenzoic acid compound can be 2-aminobenzoic acid, 2-(methylamino)benzoic acid, 2-(dimethylamino)benzoic acid, 3-aminobenzoic acid, 3-(methylamino)benzoic acid, 3-(dimethylamino)benzoic acid, 4-aminobenzoic acid, 4-(methylamino)benzoic acid, 4-(dimethylamino)benzoic acid, or a combination thereof. In some embodiments, the aminobenzoic acid compound is 4-aminobenzoic acid, 4-(methylamino)benzoic acid, 4-(dimethylamino)benzoic acid, or a combination thereof. In certain embodiments, the aminobenzoic acid compound is 4-aminobenzoic acid. In other embodiments, the aminobenzoic acid compound is 4-(methylamino)benzoic acid.

[0031] The aminobenzoic acid compound can be used in any suitable amount. Generally, the aminobenzoic acid compound 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 ketone moieties. Thus, in some embodiments, the aminobenzoic acid compound 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 ketone moieties.

[0032] In some embodiments, the crown ether of formula (V) or the crown ether of formula (VI) is formed in a solvent. Thus, the reaction between the benzo- or dibenzo crown ether and the aminobenzoic acid compound 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. In other embodiments, the formation of the crown ether of formula (V) or the crown ether of formula (VI) is carried out in a low-boiling solvent (i.e., below 100° C.) such as diethyl ether, tetrahydrofuran, ethanol, methanol, acetonitrile, dichloromethane, etc.

[0033] In some embodiments, the formation of the crown ether of formula (V) or the crown ether of formula (VI) 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 crown ether of formula (V) or the crown ether of formula (VI) can be promoted by polyphosphoric acid, phosphorus pentoxide, boron trifluoride, sulfuric acid, aluminum chloride, Eaton's reagent, etc. In certain embodiments, the formation of the crown ether of formula (V) or the crown ether of formula (VI) is promoted by Eaton's reagent. The reaction can be heated to any suitable temperature. For example, the reaction between a benzo- or dibenzo crown ether and an aminobenzoic acid compound can be heated to about 25° C. or higher, about 50° C. or higher, or about 75° C. or higher. In certain embodiments, the reaction between a benzo- or dibenzo crown ether and an aminobenzoic acid compound is heated to a temperature of about 25° C. to about 100° C.

[0034] The method further includes reacting the crown ether of formula (V) or the crown ether of formula (VI) with a polymeric support selected from a membrane, a fibrous medium, a polymer coating or material, a metal-organic framework, a monolith support, beads, a filter, or a resin to form at least one C-N bond or C=N bond. For example, the crown ether of formula (V) or the crown ether of formula (VI) 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-N bond or C=N bond is formed. The desired C-N bond or C=N bond can be formed by any suitable means, many of which are known in the art. For example, the C-N bond or C=N bond can be formed by a substitution reaction, a condensation reaction, or a reductive amination reaction.

[0035] 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. In general, 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.

[0036] 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 the 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] and / or (ii) a crown ether of formula (II): [ka] In the formula, each m is independently an integer of 1 to 8, and each " [ka] " represents an optionally present bond and / or structure, and each X is independently -N(R1)2, -N *(R1), -N ** , -N * (R1)2 + Z - , or -N ** (R1) + Z - with the proviso that at least one X is -N * (R1), -N ** , -N * (R1)2 + Z - , or -N ** (R1) + Z - and each R is independently hydrogen or C 1~6 alkyl, and Z is an optional counterion to balance the charge on the nitrogen; * represents the bond to the rest of the substance, Further provided is a method comprising passing a material through the method. All other definitions and embodiments for the variables m and X are as described herein for the material of the invention.

[0037]

[0037] 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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 26, are set forth below. As will be apparent to one of 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:

[0042] (1) In embodiment (1), (i) a compound of formula (I): [ka] and / or (ii) a crown ether of formula (II): [ka] or a salt thereof, wherein each m is independently an integer of 1 to 8, and each " [ka] " represents an optionally present bond and / or structure, and each X is independently -N(R1)2, -N * (R1), -N ** , -N * (R1)2 + Z - , or -N ** (R1) + Z - with the proviso that at least one X is -N * (R1), -N ** , -N * (R1)2 + Z - , or -N ** (R1) + Z - and each R is independently hydrogen or C 1~6 alkyl, and each Z is optionally present and independently a counterion to balance the charge on the nitrogen; * represents the bond to the remainder of the substance, the substance is presented.

[0043] (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] " denotes an optionally present bond and / or structure, and X is -N * (R1), -N ** , -N * (R1)2 + Z - , or -N ** (R1) + Z- and each R is independently hydrogen or C 1~6 alkyl, and Z is an optional counterion to balance the charge on the nitrogen; * represents a bond to the remainder of the substance.

[0044] (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 X is independently -N(R1)2, -N * (R1), -N ** , -N * (R1)2 + Z - , or -N ** (R1) + Z - with the proviso that at least one X is -N * (R1), -N ** , -N * (R1)2 + Z or -N ** (R1) + Z, and each R is independently hydrogen or C 1~6 alkyl, and each Z is optionally present and independently a counterion to balance the charge on the nitrogen; * represents a bond to the remainder of the substance.

[0045] (4) In embodiment (4), the material of any one of embodiments (1) through (3) is provided, wherein each m is independently an integer from 1 to 4.

[0046] (5) In embodiment (5), the material of embodiments (1)-(4) is provided, wherein each m is independently an integer selected from 1 or 2.

[0047] (6) In embodiment (6), the substance of any one of embodiments (1) to (5) is provided, wherein each m is 2.

[0048] (7) In embodiment (7), each X is independently -N(R1)2, -N * (R1), or -N ** with the proviso that at least one X is -N * (R1) or -N ** and each R is independently hydrogen or C 1~6 is alkyl, * represents a bond to the remainder of the substance.

[0049] (8) In embodiment (8), the material of embodiment (7) is provided, wherein each R1 is hydrogen.

[0050] (9) In embodiment (9), each R1 is C 1~6 The substance of embodiment (7) is provided, wherein the alkyl is:

[0051] (10) In embodiment (10), the substance is of formula (III): [ka] Or formula (IV): [ka] or a salt thereof, wherein each m is independently an integer from 1 to 8, and each R2 is optionally present and independently hydrogen or C 1~6 alkyl, and each " [ka] " denotes an optionally present bond and / or structure, and each R is optionally present and independently selected from hydrogen, C 1~6and each Y is R 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.

[0052] (11) In embodiment (11), the substance has the formula (III): [ka] or a salt thereof, wherein each m is independently an integer from 1 to 8; R2 is optionally present and is hydrogen or C 1~6 alkyl, and each " [ka] " denotes an optionally present bond and / or structure, and R3 is optionally present and can be hydrogen, C 1~6 The material of embodiment (10) is provided, wherein Z is an alkyl, or MS; Z is an optionally present counterion to balance the charge of the nitrogen; 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.

[0053] (12) In embodiment (12), the substance has the formula (IV): [ka] or a salt thereof, wherein each m is independently an integer from 1 to 8, and each R2 is optionally present and independently hydrogen or C 1~6 alkyl, and each " [ka] " denotes an optionally present bond and / or structure, and each R is optionally present and independently selected from hydrogen, C 1~6 and each Y is R 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.

[0054] (13) In embodiment (13), the material of any one of embodiments (10)-(12) is provided, wherein each m is independently an integer from 1 to 4.

[0055] (14) In embodiment (14), the material of any one of embodiments (10)-(13) is provided, wherein each m is independently an integer selected from 1 or 2.

[0056] (15) In embodiment (15), the material of any one of embodiments (10) to (14) is provided, wherein each m is 2.

[0057] (16) In embodiment (16), each R2 is independently hydrogen or C 1~6 The substance of any one of embodiments (10) to (15) is provided, wherein the alkyl is alkyl.

[0058] (17) In embodiment (17), the material of embodiment (16) is provided, wherein each R2 is hydrogen.

[0059] (18) In embodiment (18), each R2 is C 1~6 The substance of embodiment (16) is provided, wherein the alkyl is alkyl.

[0060] (19) In embodiment (19), any one of embodiments (10) to (18) 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.

[0061] (20) In embodiment (20), there is provided a method for making the material of any one of embodiments (10) to (19), comprising the steps of: (i) reacting a benzo or dibenzo crown ether with an aminobenzoic acid compound to form (a) a compound of formula (V): [ka] or (b) a crown ether of formula (VI): [ka] forming a crown ether of (ii) reacting the crown ether of formula (V) or the crown ether of formula (VI) 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-N bond or a C=N bond; A method is presented, including:

[0062] (21) In embodiment (21), the method of embodiment (20) is provided, wherein the aminobenzoic acid is 4-aminobenzoic acid, 4-(methylamino)benzoic acid, 4-(dimethylamino)benzoic acid, or a combination thereof.

[0063] (22) In embodiment (22), 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 (19).

[0064] (23) In embodiment (23), the method of embodiment (22) is provided, wherein the solution is an aqueous solution.

[0065] (24) In embodiment (24), the method of embodiment (22) or embodiment (23) 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.

[0066] (25) In embodiment (25), the method of embodiment (22) or embodiment (23) is provided, 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.

[0067] (26) In embodiment (26), the method of embodiment (22) or embodiment (23) 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]

[0068] These following examples further illustrate the present invention but, of course, should not be construed as in any way limiting its scope.

[0069] Example 1 This example provides an exemplary experimental procedure for preparing the crown ethers of formula (V) described herein, which is summarized in Scheme 1. [ka]

[0070] 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.

[0071] Example 2 This example provides an exemplary experimental procedure for preparing the crown ethers of formula (V) described herein, which is summarized in Scheme 2. [ka]

[0072] 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.

[0073] Example 3 This example provides an exemplary experimental procedure for preparing the crown ethers of formula (VI) described herein, which is summarized in Scheme 3. [ka]

[0074] 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.

[0075] Example 4 This example provides an exemplary experimental procedure for preparing materials of formula (III) described herein, which is summarized in Scheme 4. [ka]

[0076] Aminodibenzocrown ether 6 (30 g, 60 mmol, 1.67 equiv.) was added to a solution of chloromethylated polystyrene:1% divinylbenzene copolymer beads 8 (15 g, 36 mmol, 2.4 mmol / g) dissolved in DMF, and the resulting solution was heated to 100° C. for 60 h. The resulting mixture was poured onto ice, filtered, and washed with water. After drying the resulting solid product on the filter, aminodibenzocrown ether-modified polystyrene / divinylbenzene resin 9 (22.94 g, approximately 0.7 molar equivalents / g) was obtained.

[0077] Example 5 This example demonstrates the metal removal efficiency of the materials of formula (III) described herein.

[0078] Metal removal efficiency (MRE) tests were conducted using 100 mg of the crown ether amine resin of Example 4, which had been washed with a 5% HCl solution and deionized water. A water solution (50 mL) containing 6% LiOH and the initial concentrations of sodium, potassium, calcium, magnesium, or nickel listed in Table 1, maintained at 94°C in an oven, was passed through the resin at a rate of 7 mL / min using nitrogen gas. The challenge solution was collected in a vial, and the resulting metal ion concentrations were measured by inductively coupled plasma optical emission spectroscopy (ICP-OES). The metal ion concentrations of three separate tests (n = 1-3) are listed in Table 1, and the metal removal efficiency (i.e., percent concentration removed) was calculated. The metal removal efficiency results are listed in Table 1 and plotted in the figure.

[0079] [Table 1]

[0080] As is evident from the results set forth in Table 1 and the figures, the crown ether amine resin of Example 4 removed over 50% of magnesium and nickel at 94° C., while selectively allowing ions such as lithium, sodium, potassium, and calcium to pass through. In other words, the crown ether amine resin of Example 4 was more effective at removing divalent cations than monovalent cations at 94° C.

[0081]

[0080] 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.

[0082] 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.

[0083] Preferred embodiments of the present 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): 【Chemical 1】 and / or (ii) a crown ether of formula (II): 【Chemistry 2】 or a salt thereof, wherein each m is independently an integer from 1 to 8, and each " 【Chemistry 3】 " represents an optionally present bond and / or structure, and each X independently represents -N(R １ ) ２ , -N ＊ (R １ ), -N ＊＊ , -N ＊ (R １ ) ２ ＋ Z － , or -N ＊＊ (R １ ) ＋ Z － and wherein at least one X is -N ＊ (R １ ), -N ＊＊ , -N ＊ (R １ ) ２ ＋ Z － , or -N ＊＊ (R １ ) ＋ Z － and each R １ are independently hydrogen or C １～６ alkyl, and each Z is optionally present and independently a counterion to balance the charge on the nitrogen; ＊ represents a bond to the remainder of said substance.

2. The substance has formula (I): 【Chemistry 4】 or a salt thereof, wherein each m is independently an integer from 1 to 8, and each " 【Chemistry 5】 " denotes an optionally present bond and / or structure, and X is -N ＊ (R １ ), -N ＊＊ , -N ＊ (R １ ) ２ ＋ Z － , or -N ＊＊ (R １ ) ＋ Z, and each R １ are independently hydrogen or C １～６ alkyl, and Z is an optional counterion to balance the charge on the nitrogen; ＊ The substance of claim 1 , wherein represents a bond to the remainder of the substance.

3. The substance has the formula (II): 【Chemistry 6】 or a salt thereof, wherein each m is independently an integer from 1 to 8, and each X is independently —N(R １ ) ２ , -N ＊ (R １ ), -N ＊＊ , -N ＊ (R １ ) ２ ＋ Z － , or -N ＊＊ (R １ ) １ Z － and wherein at least one X is -N ＊ (R １ ), -N ＊＊ , -N ＊ (R １ ) ２ ＋ Z － , or -N ＊＊ (R １ ) ＋ Z － and each R １ are independently hydrogen or C １～６ alkyl, and each Z is optionally present and independently a counterion to balance the charge on the nitrogen; ＊ The substance of claim 1 , wherein represents a bond to the remainder of the substance.

4. 4. The material of any one of claims 1 to 3, wherein each m is independently an integer from 1 to 4.

5. 5. The material of any one of claims 1 to 4, wherein each m is independently an integer selected from 1 or 2.

6. A material according to any one of claims 1 to 5, wherein each m is 2.

7. Each X is independently —N(R １ ) ２ , -N ＊ (R １ ), or -N ＊＊ and wherein at least one X is -N ＊ (R １ ) or -N ＊＊ and each R １ are independently hydrogen or C １～６ is alkyl, ＊ A substance according to any one of claims 1 to 6, wherein represents the bond to the remainder of the substance.

8. The substance has the formula (III): 【Chemistry 7】 Or formula (IV): 【Chemistry 8】 or a salt thereof, wherein each m is independently an integer from 1 to 8; and each R ２ is optionally present and independently hydrogen or C １～６ alkyl, and each " 【Chemistry 9】 " represents an optionally present bond and / or structure, and each R ３ is optionally present and independently hydrogen, C １～６ alkyl, or MS; each Z is optionally present and independently a counterion to balance the charge on the nitrogen; and each Y is R ２ 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.

9. The substance has the formula (III): 【Chemistry 10】 or a salt thereof, wherein each m is independently an integer from 1 to 8; ２ is optionally present and is hydrogen or C １～６ alkyl, and each " 【Chemistry 11】 " denotes optionally present bonds and / or structures, and R ３ is optionally present, hydrogen, C １～６ 9. The material of claim 8, wherein Z is an alkyl, or MS, Z is optionally present and is a counterion to balance the charge of the nitrogen, 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.

10. The substance has formula (IV): 【Chemistry 12】 or a salt thereof, wherein each m is independently an integer from 1 to 8; and each R ２ is optionally present and independently hydrogen or C １～６ alkyl, and each " 【Chemistry 13】 " represents an optionally present bond and / or structure, and each R ３ is optionally present and independently hydrogen, C １～６ alkyl, or MS; each Z is optionally present and independently a counterion to balance the charge on the nitrogen; and each Y is R ２ 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.

11. 11. The material of any one of claims 8 to 10, wherein each m is independently an integer from 1 to 4.

12. 12. The material of any one of claims 8 to 11, wherein each m is independently an integer selected from 1 or 2.

13. 13. A material according to any one of claims 8 to 12, wherein each m is 2.

14. Each R ２ are independently hydrogen or C １～６ A substance according to any one of claims 8 to 13, which is alkyl.

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 benzo or dibenzo crown ether with an aminobenzoic acid compound to (a) produce a compound of formula (V): 【Chemistry 14】 or (b) a crown ether of formula (VI): 【Chemistry 15】 forming a crown ether of (ii) reacting said crown ether of formula (V) or said crown ether of formula (VI) 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—N bond or C═N bond; A method comprising:

17. 17. The method of claim 16, wherein the aminobenzoic acid is 4-aminobenzoic acid, 4-(methylamino)benzoic acid, 4-(dimethylamino)benzoic acid, or a combination thereof.

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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