Crown etheramine and method 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 strongly bond to certain cations to form complexes. In this respect, the oxygen atoms are oriented to coordinate with metal cations located on the inside of 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 catalysts.

[0002]

[0002] Due to the high utility of crown ether-based compounds, there remains a need for the development of substances containing crown ether-based compounds and for new and efficient methods for preparing such substances. The present invention provides such substances and methods for their preparation. Further advantages and aspects of the present invention will be readily apparent from the disclosures provided herein. Brief Summary of the Invention

[0003]

[0003] The present invention is (i) Formula (I): [ka] The crown ether and / or (ii) formula (II): [ka] A substance comprising the crown ether of or a salt thereof, wherein each m is an integer from 1 to 8 independently, and each " [ka] " indicates the bonds and / or structures that exist of any choice, where each X independently has -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 - where each R1 is independently hydrogen or C 1~6 alkyl, and each Z is optionally present and independently a counterion for balancing the charge of nitrogen, * represents a bond to the remainder of the substance, providing a substance.

[0004]

[0004] The present invention also relates to a substance of formula (III):

Chemical formula

Chemical formula

Chemical formula

[0005]

[0005] The present invention relates to a method for producing the substances described herein, (i) React a benzo or dibenzo crown ether with an aminobenzoic acid compound to obtain (a) Formula (V): [ka] The crown ether or (b) formula (VI): [ka] The steps of forming the crown ether and (ii) A method further comprising the step of reacting a crown ether of formula (V) or a crown ether of formula (VI) with a polymer support to form at least one CN bond or C=N bond is provided.

[0006]

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

[0007] [Figure 1] This bar graph shows the metal removal efficiency (MRE) percentages for sodium, potassium, calcium, magnesium, and nickel for three tests (n=1-3) using the crown etheramine resin described in Example 5. Detailed description of the invention

[0008]

[0008] The present invention is (i) Formula (I): [ka] The crown ether and / or (ii) formula (II): [ka] A substance comprising the crown ether of or a salt thereof, wherein each m is an integer from 1 to 8 independently, and each " [ka] " indicates the bonds and / or structures that exist of any choice, where each X independently has -N(R1)2, -N * (R1), -N ** , -N * (R1)2 + Z - , or -N ** (R1) + Z - And, however, at least one X is -N * (R1), -N ** , -N * (R1)2 + Z - , or -N ** (R1) + Z - And each R1 is independently hydrogen or C 1~6 It is an alkyl group, and each Z is optionally present and independently acts as a counterion to balance the charge of nitrogen. * However, it provides a substance that represents bonding to the remainder of the substance.

[0009]

[0009] In some embodiments, the substance is of formula (I): [ka] It comprises the crown ether or a salt thereof, where each m is independently an integer from 1 to 8 (e.g., 1, 2, 3, 4, 5, 6, 7, or 8), and each " [ka] " indicates optional bonds and / or structures, where X is -N * (R1), -N ** , -N * (R1)2 + Z - , or -N **(R1) + Z - Each R1 is independently either hydrogen or C 1~6 It is an alkyl group, and Z is an optional counterion that exists to balance the charge of nitrogen. * This represents bonding to the remainder of the substance.

[0010]

[0010] In some embodiments, the substance is of formula (II): [ka] The crown ether of or a salt thereof, where 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 - And, however, at least one X is -N * (R1), -N ** , -N * (R1)2 + Z - , or -N ** (R1) + Z - Each R1 is independently either hydrogen or C 1~6 It is an alkyl group, and each Z is optionally present and independently acts as a counterion to balance the charge of nitrogen. * This represents bonding to the remainder of the substance.

[0011]

[0011] In any embodiment of the substance 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 an integer from 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 may be 2 to form 12-crown-4, each m may be 3 to form 18-crown-6, each m may be 4 to form 24-crown-8, or each m may be 5 to form 30-crown-10. Alternatively, or additionally, each m may differ 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 between 1 and 4. In certain embodiments, each m is independently an integer selected from 1 or 2. In other embodiments, each m is 2.

[0012]

[0012] In any embodiment of the substance described herein, each X is independently -N(R1)2, -N * (R1), -N ** , -N * (R1)2 + Z - , or -N ** (R1) + Z - And, however, at least one X is -N * (R1), -N ** , -N * (R1)2 + Z - , or -N ** (R1) + Z - Each R1 is independently either hydrogen or C 1~6 It is an alkyl group, and Z is an optional counterion that exists to balance the charge of nitrogen. *represents the attachment to the remainder of the substance. In other words, 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, multiple single bonds, a double bond, 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 charge or a cationic charge. Alternatively, or additionally, 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 charge or a 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]

[0013] In some embodiments, each X is independently -N(R1)2, -N * (R1), or -N ** wherein at least one X is -N * (R1) or -N ** each R1 is independently hydrogen or C 1~6 alkyl, * represents the attachment to the remainder of the substance. For example, each X can be -N(R1)2 or -N * (R1), provided that at least one X is -N * (R1), and each R1 is independently hydrogen or C 1~6 alkyl, * represents the attachment to the remainder of the substance. In other embodiments, each X is independently -N(R1)2 or -N ** wherein at least one X is -N ** each R1 is independently hydrogen or C 1~6 alkyl, * represents the attachment to the remainder of the substance. In certain embodiments, each X is independently -N(R1)2 or -N * (R1), provided that at least one X is -N *(R1) is such that 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 (for example, to form an amine or amide).

[0014]

[0014] In other embodiments, each X is independently -N(R1)2, -N * (R1)2 + Z - , or -N ** (R1) + Z - And, however, at least one X is -N * (R1)2 + Z - or -N ** (R1) + Z - Each R1 is independently either hydrogen or C 1~6 It is an alkyl group, and Z is an optional counterion that exists to balance the charge of nitrogen. * This represents bonding to the remainder of the substance.

[0015]

[0015] In any embodiment of the substance described herein, each R1 is independently hydrogen or C 1~6 The alkyl group is (e.g., methyl, ethyl, propyl, butyl, pentyl, or hexyl). In some embodiments, each R1 is hydrogen. In other embodiments, each R1 is C 1~6 It is alkyl.

[0016]

[0016] In any of the embodiments of the substance described herein, each [ka] The dashed line indicates a bond and / or structure that is of optional nature. 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; therefore, one of the bonds is of optional nature, and the phenyl ring indicated by the dashed line is of optional nature.

[0017]

[0017] In any of the embodiments of the substance described herein, each * is independently a bond to the remainder of the substance, provided that at least one * There exists. The bonding to the remainder of the substance can be any suitable bond, as long as at least one bond is a CN bond or a C=N bond. In some embodiments, a substance comprising the crown ether of formula (I) or the crown ether of formula (II) has more than one CN bond or C=N bond with the remainder of the substance. For example, the crown ether has (i) (a) two distinct * or (b) two separate ** It can be bonded to the remainder of the substance via two separate nitrogen atoms as and / or (ii)(a) one single * (b) two separate * or (c) single ** It can be bonded to the remainder of the substance via a single nitrogen as a single nitrogen atom. Therefore, used herein ** This refers to two distinct single bonds or one single double bond.

[0018]

[0018] In any embodiment of the substance described herein, each Z is optionally present and independently a counterion for balancing the charge of nitrogen. Z can be any suitable counterion for balancing the cation charge of the nitrogen atom. For example, Z may be a halogen (e.g., chlorine, bromine, or iodine), NO3 - , OH - These may include, for example, chlorine or bromine in some embodiments.

[0019]

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

[0020]

[0020] In some embodiments, the remainder of the substance to which the crown ether of formula (I) or the crown ether of formula (II) is bonded is bonded to a polymer support selected from a membrane (e.g., a porous membrane or a permeable membrane), a fibrous medium, a polymer coating (e.g., a laminate or sealant such as a polyurethane coating, epoxy coating, or acrylic coating), or a substance (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 structure, a monolithic support (e.g., a catalytic support), beads (e.g., polymer beads), a filter, or a resin (e.g., a chromatography resin). In some embodiments, the polymer support includes 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 polymer support includes polyacrylonitrile, poly(meth)acrylate, poly(meth)acrylamide, polyimide, polyester, polystyrene, or a combination thereof.

[0021]

[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] Therefore, in some embodiments, the substance is of formula (III): [ka] Alternatively, equation (IV): [ka] It is a substance or a salt thereof, where each m is independently an integer from 1 to 8, and each R2 is optionally present and independently hydrogen or C 1~6 It is alkyl, and each " [ka] " indicates a bond and / or structure that is optionally present, where each R3 is optionally present and independently of hydrogen, C 1~6 The elements are alkyl or MS, where each Z is optionally present and independently a counterion for balancing the charge of nitrogen, each Y is R2 or MS, provided that at least one Y is MS, and each MS is independently a polymer support selected from membranes, fiber media, polymer coatings or materials, metal-organic structures, monolithic supports, beads, filters, or resins. All other definitions and embodiments relating to the variables m, R2, R3, Y and Z and polymer supports are as described herein with respect to the materials of the present invention.

[0023]

[0023] In any embodiment of the substance described herein, each Y is R2 or MS, wherein at least one Y is MS. In other words, the substance described herein has at least one CN bond or C=N bond formed together with the crown ether of formula (I) or the crown ether of formula (II).

[0024]

[0024] In any embodiment of the substance described herein, each R2 is optionally present and independently of hydrogen or C 1~6The R2 is an alkyl group (e.g., methyl, ethyl, propyl, butyl, pentyl, or hexyl). In some embodiments, each R2 is hydrogen. In other embodiments, each R2 is C 1~6 It is alkyl. In certain embodiments, R2 is absent.

[0025]

[0025] In any embodiment of the substance described herein, each R3 is optionally present and independently of hydrogen, C 1~6 Alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, or hexyl), or MS. In some embodiments, each R3 is absent. In other embodiments, each R3 is C 1~6 It is alkyl. If R3 is present, the nitrogen atom of the crown ether may have a positive charge. This positive charge may or may not be balanced with the anionic charge provided by the counterion Z, as described herein. While we do not wish to be bound by any particular theory, charged variants of the crown ether are thought to modify the material to behave like an exchange resin, and this behavior may be desirable for certain applications.

[0026]

[0026] In some embodiments, the substance is of formula (III): [ka] It is a substance or a salt thereof, where each m is an integer from 1 to 8 independently, and R2 is optionally present, either hydrogen or C 1~6 It is alkyl, and each " [ka] " indicates a bond and / or structure that is optionally present, where R3 is optionally present, hydrogen, C 1~6The material is alkyl or MS, where Z is optionally present and is a counterion for balancing the charge of nitrogen, and each MS is independently a polymeric support selected from membranes, fiber media, polymer coatings or materials, metal-organic structures, monolithic supports, beads, filters, or resins. All other definitions and embodiments relating to the variables m, R2, R3, and Z, as well as the polymeric support, are as described herein with respect to the material of the present invention.

[0027]

[0027] In other embodiments, the substance is of formula (IV): [ka] It is a substance or a salt thereof, where each m is independently an integer from 1 to 8, and each R2 is optionally present and independently hydrogen or C 1~6 It is alkyl, and each " [ka] " indicates a bond and / or structure that is optionally present, where each R3 is optionally present and independently of hydrogen, C 1~6 The elements are alkyl or MS, where each Z is optionally present and independently a counterion for balancing the charge of nitrogen, each Y is R2 or MS, provided that at least one Y is MS, and each MS is independently a polymer support selected from membranes, fiber media, polymer coatings or materials, metal-organic structures, monolithic supports, beads, filters, or resins. All other definitions and embodiments relating to the variables m, R2, R3, Y and Z and polymer supports are as described herein with respect to the materials of the present invention.

[0028]

[0028] The object of this application is to incorporate a crown ether of formula (I) or a crown ether of formula (II) into a substance via a CN bond or a C=N bond. Accordingly, the present invention also relates to a method for producing the described substance, (i) React a benzo or dibenzo crown ether with an aminobenzoic acid compound to obtain (a) Formula (V): [ka] The crown ether or (b) formula (VI): [ka] The steps of forming the crown ether and (ii) A step of reacting a crown ether of formula (V) or a crown ether of formula (VI) with a polymer support selected from a film, fiber medium, polymer coating or substance, metal-organic structure, monolithic support, beads, filter, or resin to form at least one CN bond or C=N bond. The present invention provides a method including the following. All other definitions and embodiments relating to the variables m and R2, as well as the polymer support, are as described herein with respect to the substance of the present invention.

[0029]

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

[0030]

[0030] The aminobenzoic acid compound can be any suitable benzoic acid as long as the aryl ring has an amine-based substituent. For example, the aminobenzoic acid compound may 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 a particular embodiment, the aminobenzoic acid compound is 4-aminobenzoic acid. In other embodiments, the aminobenzoic acid compound is 4-(methylamino)benzoic acid.

[0031]

[0031] The aminobenzoic acid compound can be used in any suitable amount. Generally, the aminobenzoic acid compound is added in a slightly excess amount relative to the desired number of ketone moieties (e.g., about 1 molar equivalent, about 1.05 molar equivalent, about 1.1 molar equivalent, about 1.15 molar equivalent, or about 1.2 molar equivalent). Therefore, 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 times the number of molar equivalents relative to the desired number of ketone moieties.

[0032]

[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 point 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 point solvent (i.e., below 100°C), such as diethyl ether, tetrahydrofuran, ethanol, methanol, acetonitrile, or dichloromethane.

[0033]

[0033] In some embodiments, the formation of the crown ether of formula (V) or the crown ether of formula (VI) is accelerated by an acid accelerator and / or heat. The acid accelerator can be any suitable Brønsted acid or Lewis acid. For example, the formation of the crown ether of formula (V) or the crown ether of formula (VI) can be accelerated by polyphosphate, 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 accelerated 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]

[0034] This method further includes the step of reacting a crown ether of formula (V) or a crown ether of formula (VI) with a polymer support selected from a film, fiber medium, polymer coating or substance, metal-organic structure, monolithic support, beads, filter, or resin to form at least one CN bond or C=N bond. For example, the crown ether of formula (V) or a crown ether of formula (VI) can be brought into contact with the polymer support, mixed (e.g., shaken, stirred, etc.), heated, refluxed, or a combination thereof, for any period of time, as long as the desired CN bond or C=N bond is formed. The desired CN bond or C=N bond can be formed by any suitable means, many of which are known in the art. For example, the CN bond or C=N bond can be formed by substitution, condensation, or reduction amination reactions.

[0035]

[0035] The substances described herein can be used for any suitable purpose in any suitable industrial application. For example, the substances described herein can be used in water purification, wastewater treatment, mining, electronic (e.g., microelectronics), papermaking, pharmaceutical, biomedical, energy (e.g., as separators in fuel cells or batteries), or metallurgical applications. Generally, the substances 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]

[0036] In some embodiments, the substances described herein can be used in a method for removing one or more metal ions from a solution, comprising the step of passing the solution through the substance. For example, the substance can be used as a filter, porous medium, chromatographic resin, membrane, etc., through which a solution passes to remove one or more metal ions. Thus, the present invention relates to a method for removing one or more metal ions from a solution, comprising passing the solution through (i) Formula (I): [ka] The crown ether and / or (ii) formula (II): [ka] A substance containing the crown ether of or a salt thereof, where each m is an integer from 1 to 8 independently, and each " [ka] " indicates the bonds and / or structures that exist of any choice, where each X independently has -N(R1)2, -N *(R1), -N ** , -N * (R1)2 + Z - , or -N ** (R1) + Z - And, however, at least one X is -N * (R1), -N ** , -N * (R1)2 + Z - , or -N ** (R1) + Z - And each R1 is independently hydrogen or C 1~6 It is an alkyl group, and Z is an optional counterion that exists to balance the charge of nitrogen. * However, it represents bonding to the remainder of the substance. The present invention further provides a method including the step of passing a substance through it. All other definitions and embodiments relating to the variables m and X are as described herein with respect to the substance of the present invention.

[0037]

[0037] This method can be used to remove any suitable ions. Alternatively, or additionally, this method can be used to allow any suitable ions to pass through a substance. 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 additionally, 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 substance. In certain embodiments, this method selectively allows lithium to pass through a 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]

[0038] This method can remove any appropriate amount of one or more metal ions from a solution. For example, this 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, this 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 a particular embodiment, this 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 a preferred embodiment, this 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]

[0039] In some embodiments, the solution through which the substance has passed is the desired product of the method described herein. Thus, in such embodiments, the method may further include the step of recovering the solution through which the substance has passed (e.g., an aqueous solution). While we do not wish to be bound by any particular theory, if smaller metal ions such as lithium and / or sodium are desired, it is assumed that the recovered solution will be the desired product because smaller metal ions such as lithium and / or sodium pass through the substance described herein more readily.

[0040]

[0040] In other embodiments, one or more metal ions removed from the solution are desired products of the method described herein. Thus, in these embodiments, the method may further include recovering one or more metal ions removed from the solution. One or more metal ions can be recovered by any suitable means. For example, a substance containing one or more metal ions can be washed with the recovery solution. While we do not wish to be bound by any particular theory, if larger metal ions such as magnesium, aluminum, potassium, calcium, manganese, iron, and barium are desired, it is assumed that these desired metal ions will remain in the substance because larger metal ions are less likely to pass through the substance described herein.

[0041]

[0041] The aspects of the present invention described herein, including embodiments, may be useful individually or in combination with one or more other aspects or embodiments. Without limiting the foregoing description, certain non-limiting embodiments of this disclosure, numbered 1 to 26, are described below. As will be apparent to those skilled in the art upon reading this disclosure, each individually numbered embodiment may be used or combined with any preceding or succeeding individually numbered embodiment. This is intended to cover all such combinations of embodiments and is not limited to the combinations of embodiments expressly described below: Embodiments

[0042]

[0042] (1) In embodiment (1), (i) formula (I): [ka] The crown ether and / or (ii) formula (II): [ka] A substance comprising the crown ether of or a salt thereof, wherein each m is an integer from 1 to 8 independently, and each " [ka] " indicates the bonds and / or structures that exist of any choice, where each X independently has -N(R1)2, -N * (R1), -N ** , -N * (R1)2 + Z - , or -N ** (R1) + Z - And, however, at least one X is -N * (R1), -N ** , -N * (R1)2 + Z - , or -N ** (R1) + Z - And each R1 is independently hydrogen or C 1~6 It is an alkyl group, and each Z is optionally present and independently acts as a counterion to balance the charge of nitrogen. * However, a substance is presented that represents the bonding to the remainder of the substance.

[0043]

[0043] (2) In embodiment (2), the substance is of formula (I): [ka] The formula contains the crown ether of or a salt thereof, where each m is an integer from 1 to 8 independently, and each " [ka] " indicates optional bonds and / or structures, where X is -N * (R1), -N ** , -N * (R1)2 + Z - , or -N ** (R1) + Z- And each R1 is independently hydrogen or C 1~6 It is an alkyl group, and Z is an optional counterion that exists to balance the charge of nitrogen. * However, the substance of embodiment (1) is presented, which represents bonding to the remainder of the substance.

[0044]

[0044] (3) In embodiment (3), the substance is of formula (II): [ka] The crown ether of or a salt thereof, where each m is an integer from 1 to 8 independently, and each X is an integer from -N(R1)², -N * (R1), -N ** , -N * (R1)2 + Z - , or -N ** (R1) + Z - And, however, at least one X is -N * (R1), -N ** , -N * (R1)2 + Z, or -N ** (R1) + Z is such that each R1 is independently either hydrogen or C 1~6 It is an alkyl group, and each Z is optionally present and independently acts as a counterion to balance the charge of nitrogen. * However, the substance of embodiment (1) is presented, which represents bonding to the remainder of the substance.

[0045]

[0045] (4) Embodiment (4) presents one of the substances from Embodiments (1) to (3), in which each m is an integer from 1 to 4 independently.

[0046]

[0046] (5) Embodiment (5) presents the substances of Embodiments (1) to (4), wherein each m is an integer independently selected from 1 or 2.

[0047]

[0047] (6) Embodiment (6) presents one of the substances from Embodiments (1) to (5), where each m is 2.

[0048]

[0048] (7) In embodiment (7), each X independently has -N(R1)2, -N * (R1), or -N ** And, however, at least one X is -N * (R1) or -N ** And each R1 is independently hydrogen or C 1~6 It is alkyl, * However, one of the substances in embodiments (1) to (6) is presented that represents bonding to the remainder of the substance.

[0049]

[0049] (8) Embodiment (8) presents the substance of Embodiment (7) in which each R1 is hydrogen.

[0050]

[0050] (9) In embodiment (9), each R1 is C 1~6 A substance of embodiment (7) that is alkyl is presented.

[0051]

[0051] (10) In embodiment (10), the substance is of formula (III): [ka] Alternatively, equation (IV): [ka] It is a substance or a salt thereof, where each m is independently an integer from 1 to 8, and each R2 is arbitrarily selected and independently hydrogen or C 1~6 It is alkyl, and each " [ka] This indicates a bond and / or structure that exists by choice, where each R3 is present by choice and independently of hydrogen and C. 1~6A substance of Embodiment (1) is presented, wherein each Z is optionally present and independently a counterion for balancing the charge of nitrogen, each Y is R2 or MS, provided that at least one Y is MS, and each MS is independently a polymer support selected from films, fiber media, polymer coatings or materials, metal-organic structures, monolithic supports, beads, filters, or resins.

[0052]

[0052] (11) In embodiment (11), the substance is of formula (III): [ka] It is a substance or a salt thereof, where each m is an integer from 1 to 8 independently, and R2 is optionally present, and hydrogen or C 1~6 It is alkyl, and each " [ka] " indicates a bond and / or structure that is optionally present, where R3 is optionally present, and hydrogen, C 1~6 A substance of Embodiment (10) is presented, which is alkyl or MS, where Z is optionally present and is a counterion for balancing the charge of nitrogen, and each MS is independently a polymeric support selected from membranes, fiber media, polymer coatings or materials, metal-organic structures, monolithic supports, beads, filters, or resins.

[0053]

[0053] (12) In embodiment (12), the substance is of formula (IV): [ka] It is a substance or a salt thereof, where each m is independently an integer from 1 to 8, and each R2 is arbitrarily selected and independently hydrogen or C 1~6 It is alkyl, and each " [ka] This indicates a bond and / or structure that exists by choice, where each R3 is present by choice and independently of hydrogen and C. 1~6 A substance of Embodiment (10) is presented, wherein each Z is optionally present and independently a counterion for balancing the charge of nitrogen, each Y is R2 or MS, provided that at least one Y is MS, and each MS is independently a polymer support selected from films, fiber media, polymer coatings or materials, metal-organic structures, monolithic supports, beads, filters, or resins.

[0054]

[0054] (13) Embodiment (13) presents one of the substances from Embodiments (10) to (12), in which each m is an integer from 1 to 4 independently.

[0055]

[0055] (14) Embodiment (14) presents one of the substances from Embodiments (10) to (13), in which each m is an integer independently selected from 1 or 2.

[0056]

[0056] (15) Embodiment (15) presents one of the substances from Embodiments (10) to (14), where each m is 2.

[0057]

[0057] (16) In embodiment (16), each R2 is independently hydrogen or C 1~6 One of the substances in embodiments (10) to (15) is an alkyl group.

[0058]

[0058] (17) Embodiment (17) presents the substance of Embodiment (16) in which each R2 is hydrogen.

[0059]

[0059] (18) In embodiment (18), each R2 is C 1~6 A substance of embodiment (16) that is alkyl is presented.

[0060]

[0060] (19) Embodiment (19) presents any one of the materials from Embodiments (10) to (18) in which the polymer support is 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]

[0061] (20) Embodiment (20) is a method for producing any one of the substances of Embodiments (10) to (19), (i) React a benzo or dibenzo crown ether with an aminobenzoic acid compound to obtain (a) Formula (V): [ka] The crown ether or (b) formula (VI): [ka] The steps of forming the crown ether and (ii) A step of reacting a crown ether of formula (V) or a crown ether of formula (VI) with a polymer support selected from a film, fiber medium, polymer coating or substance, metal-organic structure, monolithic support, beads, filter, or resin to form at least one CN bond or C=N bond. Methods including this are presented.

[0062]

[0062] (21) Embodiment (21) presents the method of Embodiment (20) in which the aminobenzoic acid is 4-aminobenzoic acid, 4-(methylamino)benzoic acid, 4-(dimethylamino)benzoic acid, or a combination thereof.

[0063]

[0063] (22) Embodiment (22) presents a method for removing one or more metal ions from a solution, comprising the step of passing the solution through one of the substances or salts thereof of Embodiments (1) to (19).

[0064]

[0064] (23) Embodiment (23) presents the method of Embodiment (22) in which the solution is an aqueous solution.

[0065]

[0065] (24) Embodiment (24) presents the method of Embodiment (22) or Embodiment (23) for removing 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.

[0066]

[0066] (25) Embodiment (25) presents the method of Embodiment (22) or Embodiment (23) for removing 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.

[0067]

[0067] (26) Embodiment (26) presents the method of Embodiment (22) or Embodiment (23) for removing 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. [Examples]

[0068]

[0068] These following embodiments further illustrate the present invention, but should not be interpreted as limiting its scope.

[0069] Example 1

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

[0070]

[0070] Benzocrown ether 1 (5 g, 18.6 mmol, 1 equivalent) 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 equivalents) was added, and the reaction was heated at 50°C for 16 hours. The resulting mixture was poured over ice, filtered, and washed with water. After drying the resulting solid product through a filter, the product was recrystallized from ethanol to produce 2.23 g (31%) of aminobenzocrown ether 3.

[0071] Example 2

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

[0072]

[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 equivalent) was added, and the reaction was heated at 50°C for 4 hours. The resulting mixture was poured onto ice, filtered, and washed with water. After drying the resulting solid product through a filter, crude aminodibenzocrown ether 6 (30 g) was recovered. Nuclear magnetic resonance (NMR) spectroscopy showed that the crude product was more than 85% of the desired product 6, and that the mass balance was a mixture of starting material 4 and the doubling product.

[0073] Example 3

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

[0074]

[0074] Dibenzocrown ether 4 (5.0 g, 13.8 mmol, 1 equivalent) 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 equivalents) was added, and the reaction was heated at 50°C for 4 hours. The resulting mixture was poured onto ice, filtered, and washed with water. After drying the resulting solid product through a filter, the product was recrystallized from ethanol to produce 4.1 g (50%) of diaminodibenzocrown ether 7.

[0075] Example 4

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

[0076]

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

[0077] Example 5

[0077] This embodiment demonstrates the metal removal efficiency of the substance of formula (III) described herein.

[0078]

[0078] A metal removal efficiency (MRE) test was performed using 100 mg of the crown etheramine resin from Example 4, which had been washed with a 5% HCl solution and deionized water. A solution (50 mL) of water containing 6% LiOH and the initial concentrations of sodium, potassium, calcium, magnesium, or nickel listed in Table 1, kept 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 concentration was measured by inductively coupled plasma atomic emission spectrometry (ICP-OES). The metal ion concentrations from three individual tests (n=1-3) are listed in Table 1, and the metal removal efficiency (i.e., the percentage concentration removed) was calculated. The results of the metal removal efficiency are listed in Table 1 and plotted in the figure.

[0079] [Table 1]

[0080]

[0079] As is evident from the results shown in Table 1 and the Figures, the crown etheramine resin of Example 4 removed more than 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 etheramine resin of Example 4 was more effective at removing divalent cations than monovalent cations at 94°C.

[0081]

[0080] All references cited herein, including publications, patent applications and patents, are incorporated herein by reference to the same extent as each reference is individually and specifically indicated as being incorporated by reference, and as if it were included herein in whole.

[0082]

[0081] In the context describing the present invention (particularly in the context of the following claims), the use of the terms “a,” “an,” “the,” and “at least one,” and similar demonstrative pronouns, should be interpreted as encompassing both singular and plural, unless otherwise specifically indicated herein or unless clearly contradicted by the context. The use of the term “at least one” following an enumeration of one or more items (e.g., “at least one A and B”) should be interpreted as meaning one item selected from the enumerated items (A or B), or any combination of two or more of the enumerated items (A and B), unless otherwise specifically indicated herein or unless clearly contradicted by the context. The terms “equip,” “have,” “include,” and “contain” should be interpreted as open-ended terms unless otherwise specifically mentioned (i.e., “include, but not limited to”). The enumeration of value ranges in this specification is intended merely as a simplified method for referring individually to each distinct value within the range, unless otherwise specifically indicated herein, and each distinct value is incorporated herein as if it were listed individually. All methods described herein may be carried out in any suitable order, unless otherwise specifically indicated herein or unless it is clearly inconsistent with the context. Any embodiments or use of exemplary language (e.g., “like”) described herein is intended merely to improve the invention and does not limit the scope of the invention unless specifically asserted otherwise. No language herein should be construed as indicating an element not claimed as essential to the practice of the invention.

[0083]

[0082] Preferred embodiments of the Invention, including the best mode known to the inventors for carrying out the Invention, are described herein. Variations of these preferred embodiments will become apparent to those skilled in the art by reading the preceding description. The inventors expect that those skilled in the art will use such variations appropriately, and the inventors intend that the Invention may be practiced in ways other than those specifically described herein. Accordingly, the Invention includes all modifications and equivalents of the subject matter listed in the claims appended herein, as permitted by applicable law. Furthermore, unless otherwise specifically indicated herein, or unless otherwise clearly inconsistent with the context, any combination of the above elements in all possible variations is incorporated into the Invention. In certain embodiments, for example, the following items are provided: (Item 1) (i) Equation (I): [ka] The crown ether and / or (ii) formula (II): [ka] A substance comprising the crown ether of or a salt thereof, wherein each m is an integer from 1 to 8 independently, and each " [ka] " indicates a bond and / or structure that exists by choice, where each X independently has -N(R 1 ) 2 、-N * (R 1 )、-N ** 、-N * (R 1 ) 2 + Z - , or -N ** (R 1 ) + Z - And, however, at least one X is -N * (R 1 )、-N** 、-N * (R 1 ) 2 + Z - , or -N ** (R 1 ) + Z - And each R 1 However, hydrogen or C 1~6 It is an alkyl group, and each Z is optionally present and independently acts as a counterion to balance the charge of nitrogen. * However, a substance that represents bonding to the remainder of the aforementioned substance. (Item 2) The aforementioned substance is given by formula (I):

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Claims

1. (i) Equation (I): 【Chemistry 1】 The crown ether and / or formula (ii) (II): 【Chemistry 2】 A substance comprising a crown ether or a salt thereof, wherein each m is an integer from 1 to 8, and each " 【Transformation 3】 」 indicates an optionally present bond and / or structure, and each X is independently -N(R １ ), -N ２ (R ＊ ), -N １ (R ＊ ), １ ), ２ ＋ Z － or -N ＊＊ (R １ ), ＋ Z － provided that at least one X is -N ＊ (R １ ), -N ＊ (R １ ), ２ ＋ Z － or -N ＊＊ (R １ ), ＋ Z － each R １ is independently hydrogen or C １～６ alkyl, each Z is optionally present and independently a counterion for balancing the charge of nitrogen, ＊ represents a bond to the remainder of the substance, and the remainder of the substance is a polymeric support selected from a membrane, a fibrous medium, a polymer coating or substance, a metal organic framework, a monolithic support, beads, a filter, or a resin.

2. The aforementioned substance is given by formula (I): 【Chemistry 4】 The formula comprises a crown ether or a salt thereof, where each m is an integer from 1 to 8, and each " 【Transformation 5】 " indicates optional bonds and / or structures, where X is -N ＊ (R １ ), -N ＊ (R １ ) ２ ＋ Z － , or -N ＊＊ (R １ ) ＋ Z － And each R １ However, hydrogen or C １～６ It is an alkyl group, and Z is an optional counterion that exists to balance the charge of nitrogen. ＊ The substance according to claim 1, wherein the substance is bonded to the remainder of the aforementioned substance.

3. The aforementioned substance is given by formula (II): 【Transformation 6】 The formula comprises a crown ether or a salt thereof, where each m is an integer from 1 to 8, and each X is an integer from -N(R) １ ) ２ , -N ＊ (R １ ), -N ＊ (R １ ) ２ ＋ Z － , or -N ＊＊ (R １ ) ＋ Z － And, however, at least one X is -N ＊ (R １ ), -N ＊ (R １ ) ２ ＋ Z － , or -N ＊＊ (R １ ) ＋ Z － And each R １ However, hydrogen or C １～６ It is an alkyl group, and each Z is optionally present and independently acts as a counterion to balance the charge of nitrogen. ＊ The substance according to claim 1, wherein the substance is bonded to the remainder of the aforementioned substance.

4. The substance according to claim 1 or 2, wherein each m is an integer from 1 to 4 independently.

5. The substance according to claim 1 or 2, wherein each m is an integer independently selected from 1 or 2.

6. The substance according to claim 1 or 2, wherein each m is 2.

7. Each X independently, -N(R) １ ) ２ , or -N ＊ (R １ ) and, however, at least one X is -N ＊ (R １ ) and each R １ However, hydrogen or C １～６ It is alkyl, ＊ The substance according to claim 1 or 2, which represents bonding to the remainder of the aforementioned substance.

8. The substance is of formula (III): 【Transformation 7】 Alternatively, formula (IV): 【Transformation 8】 It is a substance or a salt thereof, where each m is an integer from 1 to 8 independently, and each R ２ However, they exist by choice and independently of hydrogen or C １～６ It is alkyl, and each " 【Chemistry 9】 " indicates the bonds and / or structures that exist at will, and each R ３ However, they exist by choice and independently of hydrogen and C. １～６ It is an alkyl or MS, where each Z is optionally present and independently acts as a counterion to balance the charge of nitrogen, and each Y is R ２ The substance according to claim 1, or an MS, wherein at least one Y is an MS, and each MS is independently a polymer support selected from a film, a fiber medium, a polymer coating or substance, a metal-organic structure, a monolithic support, beads, a filter, or a resin.

9. The substance is of formula (III): 【Chemistry 10】 It is a substance or a salt thereof, where each m is an integer from 1 to 8 independently, and R ２ However, they exist by choice, and hydrogen or C １～６ It is alkyl, and each " 【Chemistry 11】 " indicates the optional bonds and / or structures, R ３ However, they exist by choice, and hydrogen, C １～６ The substance according to claim 8, wherein the MS is alkyl or MS, Z is optionally present and is a counterion for balancing the charge of nitrogen, and each MS is independently a polymer support selected from a film, fiber medium, polymer coating or substance, metal-organic structure, monolithic support, beads, filter, or resin.

10. The substance is of formula (IV): 【Chemistry 12】 It is a substance or a salt thereof, where each m is an integer from 1 to 8 independently, and each R ２ However, they exist by choice and independently of hydrogen or C １～６ It is alkyl, and each " 【Chemistry 13】 」 indicates an optionally present bond and / or structure, each R ３ is optionally present and independently is hydrogen, C １～６ alkyl, or MS, each Z is optionally present and independently is a counter ion for balancing the charge of nitrogen, each Y is R ２ or MS, provided that at least one Y is MS, each MS is independently a polymeric support selected from a membrane, a fibrous medium, a polymer coating or substance, a metal organic framework, a monolithic support, beads, a filter, or a resin, the substance according to claim 8.

11. The substance according to claim 8 or 9, wherein each m is an integer from 1 to 4 independently.

12. The substance according to claim 8 or 9, wherein each m is an integer independently selected from 1 or 2.

13. The substance according to claim 8 or 9, wherein each m is 2.

14. Each R ２ However, hydrogen or C １～６ The substance according to claim 8 or 9, which is alkyl.

15. The substance according to claim 8 or 9, wherein the polymer 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 the substance described in claim 8 or 9, (i) Reacting a benzo or dibenzo crown ether with an aminobenzoic acid compound to obtain (a) formula (V): 【Chemistry 14】 The crown ether or (b) formula (VI): 【Chemistry 15】 A step of forming a crown ether, wherein -N(R2)2 is in the para position with respect to the -C(O)- group, (ii) The step of reacting the crown ether of formula (V) or the crown ether of formula (VI) with a polymer support selected from a film, fiber medium, polymer coating or substance, metal-organic structure, monolithic support, beads, filter, or resin to form at least one C-N bond or C=N bond. Methods that include...

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

18. A method for removing one or more metal ions from a solution, comprising the step of passing the solution through a substance or salt thereof as described in claim 1 or 2.

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

20. The method according to claim 18, 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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